pH-induced changes in the fabrication of multilayers of poly(acrylic acid) and chitosan: fabrication, properties, and tests as a drug storage and delivery system

Multilayers of poly(acrylic acid), PAA, and chitosan, CHI, have been built by the layer-by-layer (LbL) method from aqueous solutions at different pH values and analyzed by the dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The results showed that under all of the assembly conditions considered the growth of the films is nonlinear. The thickness of the PAA layers increases as the pH of the assembling solutions decreases, whereas the adsorption of CHI is almost unaffected by the pH conditions. The comparison of the thickness obtained by D-QCM and by ellipsometry has allowed us to calculate the water content of the films, showing that the multilayers are highly hydrated, with an average water content higher than 20%. The analysis of D-QCM data has provided high-frequency values of the complex shear modulus that are in the megapascal range and shows a transition from mainly viscous to mainly elastic behavior for the added PAA layers, depending on the pH. The monomer surface density in each layer (obtained from the combination of ellipsometry and differential refractive index measurements) indicated that the monomer density depends on the assembly conditions. It was found that the adsorption kinetics is a bimodal process, with characteristic times that depend on the number and nature of the layers. Finally, the possibility of using of these multilayers as a drug storage and delivery system has been evaluated.     

Formation of polyelectrolyte multilayers from polysaccharides at low ionic strength

Layer-by-layer deposition of sodium carboxymethylcellulose (NaCMC) and chitosan (CHI) was used to create polyelectrolyte multilayers on ellipsoidal beta-FeOOH particles at low ionic strength. Using electro-optics, we investigated the formation of films in dependence on the polyelectrolyte charge density by controlling pH of the dipping solutions. We found out a linear growth of the CMC/CHI films when they are constructed from highly charged CHI (at pH 4.0) and weakly charged NaCMC (at pH 4.0 and 5.5). The hydrodynamic thickness of the film constructed at pH 4.0/4.0 is unusually large for a linearly growing film (ca. 220 nm after deposition of 8 bilayers), but it strongly decreases (ca. 4 times) with increasing ionization of NaCMC (at pH 5.5). In both cases, the multilayer buildup proceeded through a series of adsorption-desorption steps. This was explained by a partial loss of CHI from the film surface on exposure to the solution of longer NaCMC molecules. The irregular film growth correlated quite well with the variations in the electrical polarizability of the polymer-coated particles. This correlation enabled us to conclude that the adsorption of both polymers occurs only on the film surface, with no diffusion in and out of the film bulk during deposition of each CMC/CHI bilayer.     

Influence of the molecular architecture on the adsorption onto solid surfaces: comb-like polymers

The processes of adsorption of grafted copolymers onto negatively charged surfaces were studied using a dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The control parameters in the study of the adsorption are the existence or absence on the molecular architecture of grafted polyethyleneglycol (PEG) chains with different lengths and the chemical nature of the main chain, poly(allylamine) (PAH) or poly(L-lysine) (PLL). It was found out that the adsorption kinetics of the polymers showed a complex behavior. The total adsorbed amount depends on the architecture of the polymer chains (length of the PEG chains), on the polymer concentration and on the chemical nature of the main chain. The comparison of the thicknesses of the adsorbed layers obtained from D-QCM and from ellipsometry allowed calculation of the water content of the layers that is intimately related to the grafting length. The analysis of D-QCM results also provides information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. It is shown that the adsorption of polymers with a charged backbone is not driven exclusively by the electrostatic interactions, but the entropic contributions as a result of the trapping of water in the layer structure are of fundamental importance.     

Layer-by-layer electrostatic self-assembly of single-wall carbon nanotube polyelectrolytes

We have used anionic and cationic single-wall carbon nanotube polyelectrolytes (SWNT-PEs), prepared by the noncovalent adsorption of ionic naphthalene or pyrene derivatives on nanotube sidewalls, for the layer-by-layer self-assembly to prepare multilayers from carbon nanotubes with polycations, such as poly(diallyldimethylammonium) or poly(allylamine hydrochloride) (PDADMA or PAH, respectively), and polyanions (poly(styrenesulfonate), PSS). This is a general and powerful technique for the fabrication of thin carbon nanotube films of arbitrary composition and architecture and allows also an easy preparation of all-SWNT (SWNT/SWNT) multilayers. The multilayers were characterized with vis-near-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), surface plasmon resonance (SPR) measurements, atomic force microscopy (AFM), and imaging ellipsometry. The charge compensation in multilayers is mainly intrinsic, which shows the electrostatic nature of the self-assembly process. The multilayer growth is linear after the initial layers, and in SWNT/polyelectrolyte films it can be greatly accelerated by increasing the ionic strength in the SWNT solution. However, SWNT/SWNT multilayers are much more inert to the effect of added electrolyte. In SWNT/SWNT multilayers, the adsorption results in the deposition of 1-3 theoretical nanotube monolayers per adsorbed layer, whereas the nominal SWNT layer thickness is 2-3 times higher in SWNT/polyelectrolyte films prepared with added electrolyte. AFM images show that the multilayers contain a random network of nanotube bundles lying on the surface. Flexible polyelectrolytes (e.g., PDADMA, PSS) probably surround the nanotubes and bind them together. On macroscopic scale, the surface roughness of the multilayers depends on the components and increases with the film thickness.     

Characteristics of polyelectrolyte multilayers: effect of PEI anchoring layer and posttreatment after deposition

The influence of a first (anchoring) layer and film treatment on the structure and properties of polyelectrolyte multilayer (PEM) films obtained from polyallylamine hydrochloride (PAH) and polysodium 4-styrenesulfonate (PSS) was studied. Branched polyethyleneimine (PEI) was used as an anchoring layer. The film thickness was measured by ellipsometry. Complementary X-ray reflectometry and AFM experiments were performed to study the change in the interfacial roughness. We found that the thickness of the PEM films increased linearly with the number of layers and depended on the presence of an anchoring PEI layer. Thicker films were obtained for multilayers having PEI as the first layer comparing to films having the same number of layers but consisting of PAH/PSS only. We investigated the wettability of PEM surfaces using direct image analysis of the shape of sessile water drops. Periodic oscillations in contact angle were observed. PAH-terminated films were more hydrophobic than films with PSS as the outermost layer. The effect of long time conditioning of PEM films in solutions of various pH's or salt (NaCl) concentrations was also examined. Salt or base solutions induced modification in wetting properties of the polyelectrolyte multilayers but had a negligible effect on the film thickness.     

Polyelectrolyte multilayer films of different charge density copolymers with synergistic nonelectrostatic interactions prepared by the layer-by-layer technique

Random copolymers composed of diallyldimethylammonium chloride (DADMAC) and acrylamide with varying contents (8-100 mol %) of the cationic DADMAC component were alternated with polyanionic, fully charged poly(styrenesulfonate) to form multilayer thin films. UV-vis spectrophotometry, FTIR spectroscopy, and quartz-crystal microgravimetry (QCM) were employed to follow multilayer buildup. Atomic force microscopy was used to obtain structural information. Layer thicknesses have been determined with small-angle X-ray scattering and ellipsometry, in addition to values calculated from QCM. While in previous work, a critical charge density limit could be observed, below which no layer growth is possible; in this system, multilayer formation takes place with copolymers with charge densities as low as 8 mol %. Instead of a continuous increase of adsorbed amounts with decreasing charge density above the critical charge density, as found in previous work, similar layer thicknesses for films with 100 and 8 mol % charged polyelectrolytes and maximally adsorbed amounts for copolymers in an intermediate charge density region have been found. This adsorption behavior is explained in terms of synergistic nonelectrostatic interactions between the polyelectrolytes used.     

Controlling structure from the bottom-up: structural and optical properties of layer-by-layer assembled palladium coordination-based multilayers

Layer-by-layer assembly of two palladium coordination-based multilayers on silicon and glass substrates is presented. The new assemblies consist of rigid-rod chromophores connected by terminal pyridine moieties to palladium centers. Both colloidal palladium and PdCl2(PhCN)2 were used in order to determine the effect of the metal complex precursor on multilayer structure and optical properties. The multilayers were formed by an iterative wet-chemical deposition process at room temperature in air on a siloxane-based template layer. Twelve consecutive deposition steps have been demonstrated resulting in structurally regular assemblies with an equal amount of chromophore and palladium added in each molecular bilayer. The optical intensity characteristics of the metal-organic films are clearly a function of the palladium precursor employed. The colloid-based system has a UV-vis absorption maximum an order of magnitude stronger than that of the PdCl2-based multilayer. The absorption maximum of the PdCl2-based film exhibits a significant red shift of 23 nm with the addition of 12 layers. Remarkably, the structure and physiochemical properties of the submicron scale PdCl2-based structures are determined by the configuration of the approximately 15 angstroms thick template layer. The refractive index of the PdCl2-based film was determined by spectroscopic ellipsometry. Well-defined three-dimensional structures, with a dimension of 5 microm, were obtained using photopatterned template monolayers. The properties and microstructure of the films were studied by UV-vis spectroscopy, spectroscopic ellipsometry, atomic force microscopy (AFM), X-ray reflectivity (XRR), scanning electron microscopy (SEM), and aqueous contact angle measurements (CA).     

Adsorption of novel thermosensitive graft-copolymers: Core-shell particles prepared by polyelectrolyte multilayer self-assembly

The adsorption properties of thermosensitive graft-copolymers are investigated with the aim of developing self-assembled multilayers from these copolymers. The copolymers consist of a thermoreversible main chain of poly(N-isopropylacrylamid) and a weak polyelectrolyte, poly(2-vinylpyridine), as grafted side chains. Zeta-potential, single particle light scattering and adsorption isotherms monitor the adsorption of the thermoreversible copolymers to precoated colloidal particles. The results show a smaller surface coverage for a larger density of grafted chains. The surface coverage is discussed in terms of surface charge density in the adsorbed monolayer. Taking into account the monolayer adsorption properties, conditions are developed for the multilayer formation from these copolymers. A low pH provides a sufficient charge density of the grafted chains to achieve a surface charge reversal of the colloids upon adsorption. The charge reversal after each adsorbed layer is monitored by zeta-potential and the increase of the thickness is determined by light scattering. Stable and reproducible multilayers are obtained. The results imply that the conformation of the thermosensitive component in multilayers depends strongly on the grafting density, where the polymer with a higher grafting density adsorbs in a flat conformation while that with a lower grafting density adsorbs with more loops.     

Photocurrent generation in multilayer organic-inorganic thin films with cascade energy architectures

Zirconium organobisphosphonate multilayer thin films of viologen derivatives were grown on copper dithiolate multilayers of 5,15-di(p-thiolphenyl)-10,20-di(p-tolyl)porphyrin (POR) and 5,15-di(p-thiolphenyl)-10,20-di(p-tolyl)porphyrinzinc (ZOR) on a variety of substrates (e.g. Au, SiO(2)), using solution depositions methods. The multilayer structures were studied by atomic force microscopy, UV-vis spectroscopy, and ellipsometry. In the case of copper dithiolate thin films, layer-by-layer lamellar growth with low surface roughness resulted, while higher surface roughness was observed in the growth of Zr viologen bisphosphonate films. Gold electrodes modified with zirconium bisphosphonate multilayers of viologen on top of copper dithiolate multilayers of porphyrin derivatives (ZOR or POR) were photoelectroactive and produced efficient and stable photocurrents using visible light. By arranging the zinc-porphyrin (ZOR) and the free base porphyrin (POR) donors in an energetically favorable fashion, according to their redox potentials and optical energy gaps, the photoinduced charge separation was improved, and higher photocurrent quantum yields ( approximately 4%) and fill factor ( approximately 50%) of the photoelectrode were achieved.     

Layer-by-layer deposited multilayer films of oligo(pyrenebutyric acid) and a perylene diimide derivative: structure and photovoltaic properties

Multilayer films of oligo(pyrenebutyric acid) (OPB) and N,N'-bis(N,N-dimethylaminopropylaminopropyl)-3,4,9,10-perylenediimide (BDMAPAP-PDI) were successfully fabricated by layer-by-layer deposition. Multilayer growth was monitored by ultraviolet-visible (UV-vis) spectroscopy, fluorescence spectroscopy, ellipsometry, and atomic force microscopy (AFM). It was found that extraction was scarcely observed although both components (OPB and BDMAPAP-PDI) have low molecular weights and both electrostatic interactions and pi-pi stacking contributed to the multilayer deposition. The multilayers exhibit a rapid photocurrent response, and excitations of both OPB and BDMAPAP-PDI can lead to the effective charge dissociation. The incident photon to current conversion efficiency (IPCE) of the composite film with 5 bilayers was measured to be 1.29% at the absorption peak of BDMAPAP-PDI. Fluorescence quenching and photovoltaic conversion studies indicated that strong photoinduced charge transfer interactions occurred at the area of OPB/BDMAPAP-PDI heterojunction in the films, which strongly enhanced the photoresponse of the multilayer films.     

聚甲基丙烯酸甲酯Langmuir-Blodgett复合膜及其在光电导体中的应用

制备了聚甲基丙烯酸甲酯(PMMA)LB复合膜,将其作为阻挡层首次应用于机能分离型光电导体领域。从π-A曲线发现PMMA单分子膜具有表面压力的各向异性和松弛特性。TEM照片显示,PMMA分子链在复合膜中有序排列。转移比、UV和XPS研究表明,复合膜沉积均匀。以PMMA-LB复合膜作为阻挡层的光电导体表面充电电位V₀=1518V,光照1s后的光衰百分率△V_1a=50.16%,半衰期t_1/2=0.93s.     

Layer-by-layer deposition of polyelectrolyte macroinitiators for enhanced initiator density in surface-initiated ATRP

The layer-by-layer (L-b-L) deposition of oppositely charged polyelectrolytic macroinitiators has been demonstrated on planar silica substrates. The build-up of the macroinitiator multilayers was monitored by ellipsometry (up to 21 layers) and dual polarization interferometry (up to 17 layers) and good agreement was found between these techniques. The increase in L-b-L thickness was approximately linear, with an average thickness of 2.3 A per layer of deposited macroinitiator. Surface-initiated ATRP of a model nonionic methacrylic monomer, 2-hydroxyethyl methacrylate (HEMA) in a 1:1 methanol/water mixture was conducted at ambient temperature. Increasing the number of macroinitiator layers led to a significant increase in PHEMA brush thickness up to 110 nm, which is attributed to the greater surface grafting density. PHEMA brush thicknesses obtained after 22 h showed a linear dependence on the number of layers of deposited macro-initiator, with all layers exhibiting near-identical growth kinetics. X-ray photoelectron spectroscopy was used to monitor L-b-L assembly and also to confirm PHEMA growth. This technique indicated the loss of small counterions from the multilayers during L-b-L deposition and confirmed an increase in the surface density of bromoester initiator groups as the number of deposited macroinitiator layers was increased. For 17 macroinitiator layers, the bromoester initiator density is estimated to be approximately 4.9 +/- 0.2 nm (-2) from the DPI data. This is comparable to that calculated for ATRP initiator monolayers obtained by either thiol or silane chemistry. Ellipsometry suggested that the macroinitiator multilayers were weakly hydrated prior to the in situ HEMA polymerization. AFM studies indicated that the PHEMA brushes had appreciable surface roughness, but this roughness became negligible compared to the brush thickness with increasing macroinitiator layers.     

聚苯乙炔LB多层膜及其光电导性能的研究

制备了聚苯乙炔（ＰＰＡ）ＬＢ多层膜，将其作为电荷产生层首次应用于机能分离型光电导体领域．从π Ａ曲线发现，ＰＰＡ单分子膜具有表面压力的各向异性和松弛特性．ＴＥＭ照片显示，ＰＰＡ分子链在ＬＢ膜中有序排列．转移比和ＸＰＳ的研究表明，复合膜沉积均匀．与ＰＰＡ涂膜相比，以ＰＰＡ ＬＢ多层膜作为电荷产生层的光电导体表面充电电位Ｖ０＝１３４５Ｖ，光照１ｓ后的光衰百分比ΔＶ１ｓ＝６５０５％，半衰时间ｔ１／２＝０５８ｓ，具有更优异的光电导性能．     

Perfecting imperfect "monolayers": removal of siloxane multilayers by CO2 snow treatment

Self-assembled monolayers (SAMs) of N-(3-triethoxysilylpropyl)-4-hydroxybutyramide were prepared on silicon oxide on silicon (Si/SiO(2)). Initial silane adsorption and high-temperature annealing led to a stable base monolayer with many large over-lying islands of disordered multilayers as a result of the non-self-limited growth process. The disordered multilayers were hydrolyzed and subsequently removed by CO(2) snow treatment. The resulting films were one monolayer thick as measured by ellipsometry. Atomic force microscopy, attenuated total reflection Fourier transform infrared spectroscopy, and contact angle analysis showed that the films were composed of monolayers with full and uniform surface coverage rather than nonuniform coverage by islands or patches of multilayers. Monolayers of octadecyltrichlorosilane were also prepared by multilayer removal via CO(2) treatment, showing the general applicability of the technique toward siloxane SAMs. We believe that CO(2) is an excellent solvent for weakly bound and hydrolyzed molecules that compose multilayers, and this ability to prepare near-perfect monolayer films from imperfect ones allows for less stringent formation conditions.     

Structure of self-assembled multilayers prepared from water-soluble polythiophenes

We have studied the structure and morphology of self-assembled polyelectrolyte multilayers prepared using poly(styrenesulfonate) (PSS) and four different cationic poly(alkoxythiophene) derivatives bearing methylimidazolium-terminated ionic side chain at the 3-position of the thiophene ring: poly(1-methyl-3-[3-[3-thienyloxy]-propyl]-1H-imidazolium) (P3TOPIM), poly(1-methyl-3-[6-[3-thienyloxy]-hexyl]-1H-imidazolium) (P3TOHIM), poly(1-methyl-3-[2-[(4-methyl-3-thienyl)oxy]-ethyl]-1H-imidazolium ) (P4Me-3TOEIM), and poly(1-methyl-3-[6-[(4-methyl-3-thienyl)oxy]-hexyl]-1H-imidazolium ) (P4Me-3TOHIM). All the multilayers exhibited regular growth. The thickness of the multilayers was measured with ellipsometry, their layer-by-layer growth was followed by polarization modulation infrared reflection-absorption spectroscopy (PM-IRRAS) and ellipsometry, and the morphology of the films was studied by atomic force microscopy (AFM). The length of the methylimidazolium-terminated side chain (C(n), n = 2, 3, 6) and the substituent (H or Me) at the 4-position of the thiophene ring were varied. All multilayers were inhomogeneous in the sub-micrometer scale and contained aggregates of two kinds. The large ones with a low and constant surface number density were attributed to PSS, whereas the small aggregates were polythiophene-based. The surface density of these organic semiconducting nanoparticles greatly depended on the structure of polythiophene, being favored by polymer regioregularity and the length of the side chain. The side chains remained disordered in all the multilayers, but with polythiophenes having hexyl chains both the imidazolium and thiophene rings tended to orient themselves more perpendicular to the surface than in films containing shorter chains (C2 or C3). The relative water content of the multilayers (at 7.1% relative humidity) did not depend on the film thickness and was the lowest for P4Me-3TOHIM. As the number of bilayers increased the methylimidazolium-sulfonate ion pairs gradually weakened and became more individually hydrated.     

Assembly of poly(N-isopropylacrylamide)-co-acrylic acid microgel thin films on polyelectrolyte multilayers: Effects of polyelectrolyte layer thickness, surface charge, and microgel solution pH

Temperature- and pH-sensitive poly(N-isopropylacrylamide)?Cco-acrylic acid (pNIPAm-co-AAc) microgels were deposited on glass substrates coated with polyelectrolyte multilayers composed of the polycation poly(allylamine hydrochloride) (PAH) and the polyanion poly(sodium 4-styrenesulfonate) (PSS). The microgel density and structure of the resultant films were investigated as a function of: (1) the number of PAH/PSS layers (layer thickness); (2) the charge on the outer layer of the polyelectrolyte multilayer film; and (3) the pH of microgel deposition solution. The resultant films were studied by differential interference contrast optical microscopy, atomic force microscopy, and scanning electron microscopy. It was found that the coverage of the microgels on the surface was a complex function of the pH of the deposition solution, the charge on the outer layer of the polyelectrolyte thin film and the PAH/PSS layer thickness; although it appears that microgel charge plays the biggest role in determining the resultant surface coverage.     

Multilayers of oppositely charged SiO2 nanoparticles: effect of surface charge on multilayer assembly

The growth behavior of all-silica nanoparticle multilayer thin films assembled via layer-by-layer deposition of oppositely charged SiO2 nanoparticles was studied as a function of assembly conditions. Amine-functionalized SiO2 nanoparticles were assembled into multilayers through the use of three different sizes of negatively charged SiO2 nanoparticles. The assembly pH of the nanoparticle suspensions needed to achieve maximum growth for each system was found to be different. However, the surface charge /z/ of the negatively charged silica nanoparticles at the optimal assembly pH was approximately the same, indicating the importance of this parameter in determining the growth behavior of all-nanoparticle multilayers. When /z/ of the negatively charged nanoparticles lies between 0.6z(0) and 1.2z(0) (where z(0) is the pH-independent value of the zeta-potential of the positively charged nanoparticles used in this study), the multilayers show maximum growth for each system. The effect of particle size on the film structure was also investigated. Although nanoparticle size significantly influenced the average bilayer thickness of the multilayers, the porosity and refractive index of multilayers made from nanoparticles of different sizes varied by a small amount. For example, the porosity of the different multilayer systems ranged from 42 to 49%. This study further demonstrates that one-component all-nanoparticle multilayers can be assembled successfully by depositing nanoparticles of the same material but with opposite surface charge.     

Release of a dye from hydrogen-bonded and electrostatically assembled polymer films triggered by adsorption of a polyelectrolyte

The absorption of dyes within hydrogen-bonded and electrostatically assembled multilayers and subsequent release of the dyes from the films were studied in situ using FTIR-ATR. Multilayers were composed of poly(methacrylic acid), PMAA, and poly(ethylene oxide), PEO (hydrogen-bonded multilayers), or of PMAA and 22% quarternized copolymer of N-ethyl-4-vinylpyridium bromide and 4-vinylpyridine, Q22 (electrostatically stabilized multilayers). After multilayer deposition, the solution pH was changed to produce excess charge within the films. Dyes with charge opposite to the excess charge of the film (Rhodamine 6G for hydrogen-bonded films or Bromophenol Blue for electrostatically assembled multilayers) were then allowed to absorb within multilayers. In both systems, the dyes were uniformly included within the films. The top layers largely affected the loading capacity of the multilayers, suggesting weaker binding of the dyes with the top layers. Dye release into a 0.01 M phosphate buffer was significantly smaller as compared to release in the presence of 0.05-0.5 mg/mL solutions of adsorbing polymers whose charge was the same as the excess charge within the films. We found that with the PMAA/PEO films, dye release did not depend on the concentration of polymer in solution, but was largely controlled by the amount of charge accumulated within the adsorbing polymer layer on the top of the film. For electrostatically stabilized PMAA/Q22 systems, dye release increased with increasing concentration of Q22 in solution, suggesting a significant contribution of the competition of solution species in the release mechanism. Our findings contribute to the understanding of interactions of small molecules with polymer multilayers and might have ramifications for novel applications of multilayer films as new materials for the controlled delivery of chemicals.     

Thickness, surface morphology, and optical properties of porphyrin multilayer thin films assembled on Si(100) using copper(I)-catalyzed azide-alkyne cycloaddition

We report the structure, optical properties and surface morphology of Si(100) supported molecular multilayers resulting from a layer-by-layer (LbL) fabrication method utilizing copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC), also known as "click" chemistry. Molecular based multilayer films comprised of 5,10,15,20-tetra(4-ethynylphenyl)porphyrinzinc(II) (1) and either 1,3,5-tris(azidomethyl)benzene (2) or 4,4'-diazido-2,2'-stilbenedisulfonic acid disodium salt (3) as a linker layer, displayed linear growth properties up to 19 bilayers. With a high degree of linearity, specular X-ray reflectivity (XRR) measurements yield an average thickness of 1.87 nm/bilayer for multilayers of 1 and 2 and 2.41 nm/bilayer for multilayers of 1 and 3. Surface roughnesses as determined by XRR data fitting were found to increase with the number of layers and generally were around 12% of the film thickness. Tapping mode AFM measurements confirm the continuous nature of the thin films with roughness values slightly larger than those determined from XRR. Spectroscopic ellipsometry measurements utilizing a Cauchy model mirror the XRR data for multilayer growth but with a slightly higher thickness per bilayer. Modeling of the ellipsometric data over the full visible region using an oscillator model produces an absorption profile closely resembling that of a multilayer grown on silica glass. Comparing intramolecular distances from DFT modeling with experimental film thicknesses, the average molecular growth angles were estimated between 40° and 70° with respect to the substrate surface depending on the bonding configuration.     

Coordination-based gold nanoparticle layers

Gold nanoparticle (NP) mono- and multilayers were constructed on gold surfaces using coordination chemistry. Hydrophilic Au NPs (6.4 nm average core diameter), capped with a monolayer of 6-mercaptohexanol, were modified by partial substitution of bishydroxamic acid disulfide ligand molecules into their capping layer. A monolayer of the ligand-modified Au NPs was assembled via coordination with Zr4+ ions onto a semitransparent Au substrate (15 nm Au, evaporated on silanized glass and annealed) precoated with a self-assembled monolayer of the bishydroxamate disulfide ligand. Layer-by-layer construction of NP multilayers was achieved by alternate binding of Zr4+ ions and ligand-modified NPs onto the first NP layer. Characterization by atomic force microscopy (AFM), ellipsometry, wettability, transmission UV-vis spectroscopy, and cross-sectional transmission electron microscopy showed regular growth of NP layers, with a similar NP density in successive layers and gradually increased roughness. The use of coordination chemistry enables convenient step-by-step assembly of different ligand-possessing components to obtain elaborate structures. This is demonstrated by introducing nanometer-scale vertical spacing between a NP layer and the gold surface, using a coordination-based organic multilayer. Electrical characterization of the NP films was carried out using conductive AFM, emphasizing the barrier properties of the organic spacer multilayer. The results exhibit the potential of coordination self-assembly in achieving highly controlled composite nanostructures comprising molecules, NPs, and other ligand-derivatized components.