Thesis advisor: Dunwei Wang / Metal nanocrystals with size and shape control have great potential in heterogeneous catalysis. Controllable encapsulation of well-defined metal nanoparticles into the novel porous materials results in new multifunctional nanomaterials. The core-shell nanostructure can enhance the selectivity, durability, or reactivity of the catalysts and even provide additional functionalities. Metal-organic frameworks (MOFs) are a class of novel crystalline nanoporous materials, with well-defined pore structures and distinctive chemical properties. Using MOFs as the encapsulating porous materials has drawn great interest recently due to their tunable structures and properties. However, it could be challenging to grow another porous material layer on metal surface due to the unfavorable interfacial energy. In this work we develop a new concept of colloidal synthesis to synthesize the metal@MOF core-shell nanostructures, in which a layer of self-assembled molecules directed the growth and alignment between two materials. Surfactant cetyltrimethylammonium bromide (CTAB) is designated to facilitate the overgrowth of MOF onto metal surface, and an alignment between the {100} planes of the metal and {110} planes of the MOF can be observed. By utilizing the same concept, a third layer of mesoporous silica could also be coated on the MOF shell with assistance of CTAB. And our method could be a general strategy to fabricate multiple-layer MOF materials. / Thesis (MS) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Submitted by Celso Magalhaes (celsomagalhaes@ufrrj.br) on 2017-05-09T14:28:22Z No. of bitstreams: 1 2016 - Leonardo Santos de Barros.pdf: 6766023 bytes, checksum: 16ce8cf6e87d3cfab0a3d73fc9a6e46c (MD5) / Made available in DSpace on 2017-05-09T14:28:22Z (GMT). No. of bitstreams: 1 2016 - Leonardo Santos de Barros.pdf: 6766023 bytes, checksum: 16ce8cf6e87d3cfab0a3d73fc9a6e46c (MD5) Previous issue date: 2016-11-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior - CAPES / The photochemical reactivity of chalcone (CH) nanocrystals and its fluorinated derivatives (CH4F, CH23F, CH25F, CH26F, CH34F, CH35F, PFCB and the DFC) in a suspension of aqueous CTAB (0.04 mM) was studied by ultraviolet spectroscopy (UV), hydrogen nuclear magnetic resonance (H1NMR) and dynamic light scattering (DLS). The suspension of chalcone nanocrystals was prepared by the reprecipitation method in an aqueous solution of CTAB. The ultraviolet spectrum for the chalcone nanocrystals prior to irradiation showed hypochromic and bathochromic effects when compared to the methanolic solution. The DLS spectrum for CH CH23F, CH25F, CH26F and PFCB nanocrystals in aqueous CTAB showed a polydispersed system containing three different particle sizes, whereas CH34F, CH35F and DFC nanocrystals showed a clear monodispersivity. After irradiation, the DLS spectrum for these nanocrystals did not show significant changes, however for the monodispersed chalcones a shift towards larger particle sizes was observed. After irradiation the UV spectrum for the chalcone nanocrystals indicated a hypochromic effect on the longer wavelength band, which may be related to the consumption of their E-isomer. The kinetic monitoring of the E-isomer consumption for the chalcones CH, CH4F, CH23F, CH25F, CH26F CH34F, CH35F, PFCB and DFC as a function of irradiation time indicated that after a certain time the reaction reaches a steady state, with no more changes on their absorbance. The H1NMR spectrum for the irradiation product of CH4F and CH23F showed the formation of a mixture of ?-, ??-, and ?-truxillic dimers. On the other hand, irradiation of CH25F and CH26F derivatives led to the formation of the ?-truxinic dimer. Photolysis of CH34F and CH35F nanocrystals showed the conversion of the reactant to a cyclobutane through a stereospecific reaction. For CH35F only the ?-truxillic dimer has been formed, in nearly 100% conversion. However, for nanocrystals of the chalcone CH34F the Z-isomer is formed together with the ?-truxillic dimer CH34F, which may be related to a chalcone fraction that was solubilized in the CTAB containing aqueous phase. Irradiation of DFC nanocrystals occurred at a conversion of almost 100% to the cycloaddition product, the ?-truxillic dimer. For chalcone (CH) a high yield formation of the Z-chalcone isomer and dimers that are not formed from its E-isomer was observed, while PFCB appeared as a stable molecule during the irradiation process, and the presence of the five fluorine atoms on the benzyl ring can account for its stability / A reatividade fotoqu?mica de nanocristais de chalcona (CH) e seus derivados fluorados (CH4F, CH23F, CH25F, CH26F, CH34F, CH35F, PFCB e DFC) foi estudada por espectroscopia de ultravioleta (UV), Resson?ncia magn?tica nuclear de hidrog?nio (RMN1H) e Espalhamento de luz din?mico (DLS). A suspens?o dos nanocristais das chalconas foi preparada pelo m?todo de reprecipita??o em uma solu??o aquosa de CTAB. Os espectros no ultravioleta para a suspens?o dos nanocristais das chalconas antes da irradia??o mostraram um efeito hipocr?mico e batocr?mico em rela??o ? solu??o metan?lica. Os espectros de DLS para os nanocristais da suspens?o das chalconas em solu??o aquosa de CTAB se apresentaram como um sistema polidisperso apresentando 3 tamanhos de part?culas para CH, CH23F, CH25F, CH26F, PFCB e monodisperso para CH34F, CH35F e DFC. Ap?s a irradia??o n?o se observou mudan?as significativas na estrutura dos espectros de DLS para os nanocristais, ocorrendo um deslocamento para tamanhos de part?culas maiores nas chalconas monodispersas. O espectro de UV para a suspens?o dos nanocristais das chalconas ap?s a irradia??o indicou um efeito hipocr?mico da banda de maior absor??o, o que pode estar relacionado ao consumo dos compostos de configura??o E. O acompanhamento cin?tico do consumo do is?mero E das chalconas CH, CH4F, CH23F, CH25F, CH26F CH34F, CH35F, PFCB e DFC contra tempo de irradia??o de uma suspens?o dos nanocristais destas chalconas em solu??o aquosa de CTAB (0,04 mM) indicou que a partir de um determinado tempo a rea??o atinge um estado estacion?rio, n?o apresentando mais mudan?as em sua absorb?ncia. Os espectros de RMN1H para o produto da irradia??o dos nanocristais das chalconas contendo fl?or na posi??o 4 (CH4F) e nas posi??es 2 e 3 (CH23F) mostraram a forma??o de uma mistura de d?meros ?????? e ?-trux?licos. A irradia??o dos derivados CH25F e CH26F levou ? forma??o do d?mero do tipo ?-trux?nico. Para os derivados CH34F e CH35F a convers?o dos reagentes ao fotociclobutano foi feita em uma forma estereoespec?fica, tendo sido formado somente o d?mero ?-trux?lico, com uma convers?o de quase 100% para o CH35F. No entanto, para os nanocristais da chalcona CH34F o is?mero Z-CH34F foi formado juntamente com o d?mero ?-trux?lico, o que pode estar relacionado a fra??es da chalcona que ficaram solubilizadas na fase aquosa contendo CTAB e n?o formaram suspens?o de nanocristais. A irradia??o dos nanocristais da chalcona DFC ocorreu com uma convers?o de quase 100% ao produto de fotocicloadi??o, sendo o d?mero formado o do tipo ?-trux?lico. Para chalcona (CH) observou-se um elevado rendimento de forma??o do is?mero Z-chalcona e de d?meros que n?o s?o provenientes do is?mero E, enquanto que PFCB apresentou-se como uma mol?cula est?vel durante o processo de irradia??o, com a presen?a dos cinco ?tomos de fl?or no anel benz?lico podendo ser respons?vel pela sua estabilidade

Os nanocristais são partículas de fármacos cristalinos, com tamanho médio na faixa de submicrons, geralmente entre 200 e 500 nm, estabilizados por agentes estéricos ou eletrostáticos adsorvidos na superfície das partículas do fármaco. Sua dimensão reduzida proporciona propriedades especiais, como a adesividade às mucosas e o aumento de área superficial e da solubilidade de saturação, o que melhora significativamente a biodisponibilidade de fármacos pouco solúveis em água. Outra aplicação emergente dos nanocristais é na melhoria da entrega e da retenção de fármacos em tecidos e células tumorais. Estudos demonstraram que o flubendazol é um fármaco capaz de induzir a morte celular em tumores malignos e retardar o seu crescimento, por meio da alteração que provoca na estrutura dos microtúbulos e pela inibição da polimerização da tubulina. Foi demonstrada sua atividade antiproliferativa em linhagens de leucemia, mieloma, câncer intestinal, câncer de mama e neuroblastoma. O flubendazol é também um fármaco eficaz contra os helmintos, demonstrando atividade superior na eliminação dos vermes adultos, quando comparado com a dietilcarbamazina. Embora o flubendazol pareça ser uma molécula promissora, é um fármaco praticamente insolúvel em água (0,005 mg/mL). Para atingir o efeito terapêutico desejado, é necessário o desenvolvimento de uma formulação com melhores solubilidade e biodisponibilidade. Nesse sentido, o presente trabalho apresenta o preparo e a caracterização físico-química de nanocristais de flubendazol por meio da microfluidização. Foram realizados ensaios exploratórios para avaliar a performance de diferentes agentes estabilizantes nas suspensões: o polissorbato 80, o polaxamer 188 e o D-α tocoferol polietilenoglicol 1.000 succinato (TPGS). A avaliação da distribuição do tamanho de partícula foi realizada por espalhamento de luz laser (LLS), espalhamento de luz dinâmica (DLS), análise de rastreamento de nanopartículas (NTA) e microscopia eletrônica de varredura (MEV). A utilização do TPGS favoreceu a obtenção de uma nanossuspensão com o menor diâmetro hidrodinâmico médio das partículas, de 253,9 ± 3,0 nm. Nos estudos exploratórios, também foram determinados os parâmetros ótimos de moagem do microfluidizador, sendo estabelecidos: 35.000 psi de pressão, temperatura do produto de 30°C (± 5°C) e tempo de recirculação de 2 horas/100 gramas. Objetivando alcançar o menor diâmetro hidrodinâmico médio dos nanocristais, executou-se um planejamento estatístico no qual foi avaliada a influência da concentração de flubendazol (% p/p) e de TPGS (% p/p) na formulação. A análise revelou a significativa influência da concentração do TPGS na redução do tamanho de partícula e na estabilidade físico-química da nanossuspensão. Ensaios complementares de solubilidade demonstraram que o nanocristal proporcionou incremento na solubilidade de 2,3 e 3,2 e 5,2 vezes em HCl 0,1 N, tampão fosfato pH 6,8 e tampão fosfato salino pH 7,4, respectivamente. No ensaio de dissolução conduzido em HCl 0,1 N e 0,1% TPGS, observou-se significativo incremento, de 41% de fármaco dissolvido após 60 minutos, quando comparado com o flubendazol micronizado. As características do estado sólido do nanocristal foram avaliadas por meio de análise térmica (calorimetria exploratória diferencial e termogravimetria) e difratometria de raios X, não sendo observadas significativas alterações da estrutura cristalina. O presente trabalho também avaliou a efetividade dos nanocristais de flubendazol em tumores de pulmão, demonstrando sua expressiva capacidade de retardar o crescimento e diminuir o tamanho desses tumores em camundongos xenotransplantados. / Nanocrystals are drug particles with an average size in the sub-micron range, generally between 200 and 500 nm, stabilized by steric or electrostatic agents adsorbed on the surface of the drug particles. The reduced size provides special properties such as mucosal adhesiveness, increase in surface area and saturation solubility, which significantly improves the bioavailability of poorly water-soluble drugs. Another emerging application of nanocrystals is in the enhancement of drug delivery and retention in tumor tissues. Studies have shown that flubendazole is a drug capable of inducing cell death in malignant tumors and decelerating their growth, by altering the structure of the microtubules and inhibiting the tubulin polymerization. Antiproliferative activity has been demonstrated in leukemia, myeloma, intestinal cancer, breast cancer and neuroblastoma lines. In addition, flubendazole is also an effective drug against helminths, demonstrating superior activity in eliminating adult worms when compared to diethylcarbamazine. Although flubendazole appears to be a promising molecule, it is an insoluble drug in water (0.005 mg / mL). To achieve the desired therapeutic effect, it is necessary the development of a formulation with better solubility and bioavailability. In this context, the present research reports the physico-chemical preparation and characterization of flubendazole nanocrystals through microfluidization. Exploratory experiments were carried out to evaluate the performance of different stabilizing agents in formulations: polysorbate 80, polaxamer 188 and D-α tocopherol polyethylene glycol 1000 succinate (TPGS). The determination of the particle size distribution determination was performed by laser light scattering (LLS), dynamic light scattering (DLS), nanoparticle scanning (NTA) and scanning electron microscopy (SEM). The use of TPGS favored the preparation of a nanosuspension with the lowest mean hydrodynamic size of the particles, of 253.9 ± 3 nm. In the exploratory studies, the optimum grinding parameters were also determined: 35,000 psi of microfluidizer pressure, product temperature of 30 ° C (± 5 ° C) and recirculation time of 2 hours for each 100 grams of suspension. In order to reach the lowest average hydrodynamic diameter, a statistical design was applied in which the influence of flubendazole concentration (% w / w) and TPGS (% w / w) on the formulation was evaluated. The analysis revealed a significant influence of TPGS concentration on the particle size reduction and on the physicochemical stability of the nanosuspension. Complementary solubility tests showed that the nanocrystal provided an increase in solubility of 2.3, 3.2 and 5.2-fold in 0.1 N HCl, phosphate buffer pH 6.8 and phosphate buffer saline pH 7.4, respectively. In the dissolution test performed in 0.1 N HCl with 0.1% TPGS, a 41% increase of the drug dissolved after 60 minutes was achieved, when compared to micronized flubendazole. The solid-state characteristics of the nanocrystal were accessed through thermal analysis (differential scanning calorimetry and thermogravimetry) and X-ray diffraction and the results indicated that the crystal structure was not significantly altered. This research also evaluated the action of flubendazole nanocrystals in lung tumors, demonstrating expressive ability to retard growth and decrease the size of these tumors in xenotransplanted mice.

The multi-scale modeling of ion-solid interactions presented can lead to a fundamentally new approach for understanding temperature evolution and damage formation. A coupling of the Monte Carlo code, SRIM, to a C FEM heat transfer code was performed, enabling a link between the damage cascade event to the subsequent heat transfer. Modeling results indicate that for 1 MeV Ni ion irradiation in Ni52.5Nb10Zr15Ti15Pt7.5, the heat transfer rate is too large for direct crystallization. Although the damage cascade induces a peak temperature of 5300 K, within 6 picoseconds the temperature is below the glass transition temperature. This result implies that there is a cooling rate of 10^14 K/s, which is much greater than the critical cooling rate for this material. Ion irradiation was performed to compare modeling with experiment. No evidence of direct crystallization is observed under TEM. Nanocrystals are formed as a consequence of series of multistage phase transitions. This provides evidence that the energy dissipation occurs too quickly for direct crystallization, as crystals are found in regions having undergone substantial compositional changes. A host of conventional electron microscopy methods were employed to characterize the structural changes induced by 1 MeV Ni ion irradiation in Ni52.5Nb10Zr15Ti15Pt7.5 and identify the phases that form, Ni3Nb, Ni3Ti and Ni3Zr. Scanning TEM analysis revealed Pt segregation near crystal regions due to irradiation. Due to a lack of Pt crystal phases observed and high concentrations of Pt in crystal regions it is postulated that Pt is substituting for Ni to form (Ni,Pt)3Nb and (Ni,Pt)3Ti.

None

Nanocrystalline £\-Zr condensates deposited by ion beam sputtering on the NaCl (100) surfaces and then annealed at 100 ¢J to 750 ¢J in air. The phases present were identified by transmission electron microscopy to be nanometer-size £\-Zr+ZrO¡B£\-Zr+ZrO+c-ZrO2¡Bc-ZrO2¡Bc-+t-ZrO2¡Bt-ZrO2¡Band t-+m-ZrO2 phase assemblages with increasing annealing temperature. The zirconia showed strong {100} preferred orientation due to parallel epitaxy with NaCl (100) when annealed between 150 ¢J and 500 ¢J in air. The c- and t-zirconia condensates also showed (111)-specific coalescence among themselves. The c- and/or t-ZrO2 formation can be accounted for by the small grain size, the presence of low-valence Zr cation and the lateral constraint of the neighboring grains. (Part 1) Nanocrystalline £\-Zr condensates were deposited on the NaCl (100) plane at 25 to 450 ¢J by radio frequency ion beam sputtering from a pure 99.9¢H Zr disk. The nano condensates were identified by transmission electron microscopy to be quasiamorphous, £\-Zr, £\-Zr+ZrO and £\-Zr+ZrO+c-ZrO2 phase assemblages with increasing substrate temperature. At 400 ¢J and under 1-20 sccm oxygen, c- and t-ZrO2 nanocondensates were assembled on NaCl (100) as monolayer nanocrystalline material and showed strong preferred orientation. The c- and/or t-ZrO2 were retained by small grain size, low-valence Zr cation and 2-D matrix constraint of the film. (Part 2) Nanosized c- and t-ZrO2 were formed as monolayer nanocrystalline film on NaCl (100) plane by radio frequency ion beam sputtering. The microstructure and the epitaxy relationship with the NaCl (100) plane were studied by a high resolution transmission electron microscope. The epitaxy orientation was found to be [001]Z//[001]N, [100]Z//[1 0]N (group A), and [011]Z//[001]N, [100]Z//[100]N (group B) between zirconia (Z) and NaCl (N). Group B has two variants and is the dominant type. The possible causes for the epitaxy relationship are discussed. Crystallites within the same group can merge by rotation and coalesce into a single crystal, whereas crystallites in different groups can form high-angle grain boundaries. (Part 3) Special interfaces were formed for the c- and/or t-ZrO2 (Z) nano-crystals when deposited on the NaCl (N) (100) cleavage plane by ion beam sputtering to follow the epitaxy relationships of [001]Z//[001]N, (100)Z//(1 0)N (group A); and [011]Z//[001]N, (100)Z//(100)N (group B1) or (100)Z//(010)N (group B2). The nanoparticles in group A and B were impinged and coalesced to form {220}A/{200}B and {200}A/{111}B interfaces; with anchored dislocation whereas those in group B1 and B2 form {220}B1/{200}B2 interface. The {220}A/{200}B interface is found to be of especially low energy due to good match O2¡V lattice sites, and smoothly joints {200} and {220} planes across the interfaces without mismatch strain and dislocations. The special interfaces may shed light on the epitaxial mechanism of nanocrystalline materials in general. (Part 4)

Aim of this work was, to investigate the preparation of Si NC memories by sputter deposition. The milestones are as follows: - Review of relevant literature. - Development of processes for an ultrathin tunnel-oxide and high quality sputtered SiO2 for use as control-oxide. - Evaluation of methods for the preparation of an oxygen-deficient silicon oxide inter-layer (the precursor of the Si NC layer). - Characterization of deposited films. - Establishment of techniques capable of probing the phase separation of SiOx and the formation of Si NC. - Establishment of annealing conditions compatible with the requirements of current CMOS technology based on experimental results and simulations of Si NC formation. - Preparation Si NC memory capacitors using the developed processes. - Characterization of these devices by suitable techniques. Demonstration of their memory functionality.

Colloidal nanocrystal assemblies offer an attractive opportunity for designer metamaterials. The ability to permute chemical composition, size, shape, and arrangement of nanocrystals leads to an astounding number of unique materials properties that find use in an extensive array of applications---ranging from solar cells to medicine. However, to take full advantage of these materials in useful applications, the nature of their assembly and their behavior under external stimuli must be well understood. Additionally, the assembly of colloidal nanocrystals into thin films provides a promising pathway to the solution-processing of inorganic materials that are prohibitively too expensive and/or difficult to deposit by conventional methods. Nanocrystal superlattices (NCSLs) of sterically stabilized nanocrystals were assembled by slow evaporation of colloidal dispersions on various substrates. Detailed analysis of the NCSL structures was carried out using transmission and scanning electron microscopy (TEM and SEM) and small-angle x-ray scattering (SAXS). Body-centered cubic (bcc) NCSLs, in particular, were studied in detail and ligand packing frustration was proposed as a significant driving force for their assembly. The behavior of NCSLs was also studied by SAXS under mild heating and solvent vapor exposure revealing several remarkable order-order, order-disorder, and amorphous-crystalline structural transitions. Colloidal Cu(In [subscript 1-x] Ga [subscript x])Se₂ (CIGS) nanocrystals were synthesized by arrested precipitation and formulated into inks. These inks were spray deposited into thin films under ambient conditions to serve as the active light absorbing material in printed low-cost photovoltaic (PV) devices. These devices, which were fabricated without the need for high temperature processes, have achieved power conversion efficiencies above 3 % under AM1.5 illumination. While the efficiencies of these devices are still too low for commercial viability, this work does provide a proof of concept that reasonable efficient solar cells can be created with a low-cost printable process using nanocrystal inks. Since high temperatures are not used to form the light-absorbing layer, nanocrystal-based solar cells were built on flexible light weight plastic substrates. The main obstacle to achieving high power conversation efficiencies was found to be the ability to extract the photo induced charge carriers. Nanocrystal films suffer from poor transport that leads to high recombination rates in thicker films. To date, the best efficiencies have been achieved with thin light absorber layers that only absorb a fraction of the incident light. / text

Recent advancements in nanotechnology create a need for a better understanding of the underlying physical processes that lead to the different behavior of nanoscale structures in comparison to bulk materials. The influence of the surrounding environment on the physical and optical properties of nanoscale objects embedded inside them is of particular interest. This research is focused on the optical properties of semiconductor quantum dots which are zero-dimensional nanostructures. There are many investigation techniques for measuring the local parameters and structural characteristics of Quantum Dot structures. They include X-ray diffraction, Transmission Electron Microscopy, Wavelength Dispersive Spectroscopy, etc. However, none of these is suitable for the study of large areas of quantum dots matrices and substrates. The existence of spatial inhomogeneity in the quantum dots allows for a deeper and better understanding of underlying physical processes responsible in part icular for the observed changes in photoluminescence (PL) characteristics. Spectroscopic PL mapping can reveal areas of improved laser performance of InAs/InGaAs quantum dots structures. Establishing physical mechanisms responsible for two different types of spatial PL inhomogeneity in InAs/InGaAs quantum dots structures for laser applications was the first objective of this research. Most of the bio-applications of semiconductor quantum dots utilize their superior optical properties over organic fluorophores. Therefore, optimization of QD labeling performance with biomolecule attachment was another focus of this research. Semiconductor quantum dots suspended in liquids were investigated, especially the influence of surrounding molecules that may be attached or bio-conjugated to the quantum dots for specific use in biological reactions on the photoluminescence spectrum. Provision of underlying physical mechanisms of optical property instability of CdSe/ZnS quantum dots used for biologi cal applications was in the scope of this research. Bioconjugationand functionalization are the fundamental issues for bio-marker tagging application of semiconductor quantum dots. It was discovered that spatially resolved photoluminescence spectroscopy and PL photo-degradation kinetics can confirm the bioconjugation. Development of a methodology that will allow the spectroscopic confirmation of bio-conjugation of quantum dot fluorescent tags and optimization of their performance was the final goal for this research project.

This dissertation presents novel applications of ligand-capped II-VI semiconductor nanocrystals (i.e. CdSe and CdTe).Hybrid polymer-nanocrystal thin films were prepared using a bottom-up electrochemical crosslinking method, where thiophene-functionalized CdSe NCs were wired to electron-rich 3,4-dioxy-substituded thiophene polymers. Both nanocomposite and effective monolayer (EML) films were achieved by controlling monomer feed ratios during the crosslinking steps. These hybrid thin films showed enhanced photoelectrochemical current efficiencies with a variety of solution acceptor molecules compared to polymer control films, which was due to sensitization by the CdSe NCs. The electronic structure of the polymer played a critical role in the potential (doping) dependent hole capture efficiency from photoexcited CdSe NCs. Furthermore, photocurrent efficiencies were correlated with nanocrystal size, which was a direct product of frontier orbital energy shifting due to quantum confinement effects.All-inorganic CdTe-CdSe nanocrystal solar cells were fabricated by a facile layer-by-layer procedure. A low-temperature sintering strategy was utilized to electronically couple the nanocrystal thin films, which maintained the individual electronic properties of the nanocrystals. The electrical characteristics of these solar cells displayed predictable trends in open circuit voltage with varying CdSe NC diameter.Novel CdSe NC diffraction gratings were prepared by a facile microcontact molding procedure. These transmission gratings showed exceptionally high diffraction efficiencies that were dependent on optimum grating morphologies and the refractive index contrast provided by the nanocrystals, which was size-dependent. These films also showed promise as coupling gratings for internal reflection elements.