Block copolymer self-assembly for nanophotonics

The ability to control and modulate the interaction of light with matter is crucial to achieve desired optical properties including reflection, transmission, and selective polarization. Photonic materials rely upon precise control over the composition and morphology to establish periodic interactions with light on the wavelength and sub-wavelength length scales. Supramolecular assembly provides a natural solution allowing the encoding of a desired 3D architecture into the chemical building blocks and assembly conditions. The compatibility with solution processing and low-overhead manufacturing is a significant advantage over more complex approaches such as lithography or colloidal assembly. Here we review recent advances on photonic architectures derived from block copolymers and highlight the influence and complexity of processing pathways. Notable examples that have emerged from this unique synthesis platform include Bragg reflectors, antireflective coatings, and chiral metamaterials. We further predict expanded photonic capabilities and limits of these approaches in light of future developments of the field

Microfluidics of binary liquid mixtures with temperature-dependent miscibility

Liquid–liquid microfluidic systems rely on the intricate control over the fluid properties of either miscible or immiscible mixtures. Herein, we report on the use of partially miscible binary liquid mixtures that lend their microfluidic properties from a highly temperature-sensitive mixing and phase separation behaviour. For a blend composed of the thermotropic liquid crystal 4-cyano-4′-pentylbiphenyl (5CB) and methanol, mixing at temperatures above the upper critical solution temperature (UCST; 24.4 °C) leads to a uniform single phase while partial mixing can be achieved at temperatures below the UCST. Thermally-driven phase separation inside the microfluidic channels results in the spontaneous formation of very regular phase arrangements, namely in droplets, plug, slug and annular flow. We map different flow regimes and relate findings to the role of interfacial tension and viscosity and their temperature dependence. Importantly, different flow regimes can be achieved at constant channel architecture and flow rate by varying the temperature of the blend. A consistent behaviour is observed for a binary liquid mixture with lower critical solution temperature, namely 2,6-lutidine and water. This temperature-responsive approach to microfluidics is an interesting candidate for multi-stage processes, selective extraction and sensing applications

Ordered Mesoporous to Macroporous Oxides with Tunable Isomorphic Architectures: Solution Criteria for Persistent Micelle Templates

Porous and nanoscale architectures of inorganic materials have become crucial for a range of energy and catalysis applications, where the ability to control the morphology largely determines the transport characteristics and device performance. Despite the availability of a range of block copolymer self-assembly methods, the conditions for tuning the key architectural features such as the inorganic wall-thickness have remained elusive. Toward this end, we have developed solution processing guidelines that enable isomorphic nanostructures with tunable wall-thickness. A new poly(ethylene oxide-b-hexyl acrylate) (PEO-b-PHA) structure-directing agent (SDA) was used to demonstrate the key solution design criteria. Specifically, the use of a polymer with a high Flory-Huggins effective interaction parameter, χ, and appropriate solution conditions leads to the kinetic entrapment of persistent micelle templates (PMT) for tunable isomorphic architectures. Solubility parameters are used to predict conditions for maintaining persistent micelle sizes despite changing equilibrium conditions. Here, the use of different inorganic loadings controls the inorganic wall-thickness with constant pore size. This versatile method enabled a record 55 nm oxide wall-thickness from micelle coassembly as well as the seamless transition from mesoporous materials to macroporous materials by varying the polymer molar mass and solution conditions. The processing guidelines are generalizable and were elaborated with three inorganic systems, including Nb2O5, WO3, and SiO2, that were thermally stable to 600 °C for access to crystalline materials

Acoustic Immunosensing of Exosomes Using a Quartz Crystal Microbalance with Dissipation Monitoring

Exosomes are endocytic lipid-membrane bound bodies with the potential to be used as biomarkers in cancer and neurodegenerative disease. The limitations and scarcity of current exosome characterization approaches have led to a growing demand for translational techniques, capable of determining their molecular composition and physical properties in physiological fluids. Here, we investigate label-free immunosensing, using a quartz crystal microbalance with dissipation monitoring (QCM-D), to detect exosomes by exploiting their surface protein profile. Exosomes expressing the transmembrane protein CD63 were isolated by size-exclusion chromatography from cell culture media. QCM-D sensors functionalized with anti-CD63 antibodies formed a direct immunoassay toward CD63-positive exosomes in 75% v/v serum, exhibiting a limit-of-detection of 2.9 × 108 and 1.4 × 108 exosome sized particles (ESPs)/mL for frequency and dissipation response, respectively, i.e., clinically relevant concentrations. Our proof-of-concept findings support the adoption of dual-mode acoustic analysis of exosomes, leveraging both frequency and dissipation monitoring for use in bioanalytical characterization

Tuning Pore Dimensions of Mesoporous Inorganic Films by Homopolymer Swelling

The functionality and applications of mesoporous inorganic films are closely linked to their mesopore dimensions. For material architectures derived from a block copolymer (BCP) micelle coassembly, the pore size is typically manipulated by changing the molecular weight corresponding to the pore-forming block. However, bespoke BCP synthesis is often a costly and time-consuming process. An alternative method for pore size tuning involves the use of swelling agents, such as homopolymers (HPs), which selectively interact with the core-forming block to increase the micelle size in solution. In this work, poly(isobutylene)-block-poly(ethylene oxide) micelles were swollen with poly(isobutylene) HP in solution and coassembled with aluminosilicate sol with the aim of increasing the resulting pore dimensions. An analytical approach implementing spectroscopic ellipsometry (SE) and ellipsometric porosimetry (EP) alongside atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) in transmission and grazing-incidence (GISAXS) modes enabled us to study the material evolution from solution processing through the manifestation of the mesoporous inorganic film after BCP removal. The in-depth SE/EP analysis evidenced an increase of more than 45% in mesopore diameter with HP swelling and a consistent scaling of the overall void volume and number of pores. Importantly, our analytical toolbox enabled us to study the effect of swelling on the connecting necks between adjacent pores, with observed increases as high as ≈35%, offering novel pathways to sensing, electrochemical, and other mass-transfer-dependent applications

Robust Operation of Mesoporous Antireflective Coatings under Variable Ambient Conditions

Generating mesoporous films with adequate film thickness and refractive index is a common method to achieve amplitude and phase matching in low-cost interference-based antireflective coatings (ARCs). For high-surface-energy materials, pores on the 2-50 nm (i.e., on the subwavelength scale) are subject to capillary condensation by surrounding gas phase water molecules, which hampers their functioning. In this work, we examine the effect of relative humidity on mesoporous ARCs and present a simple method for the preparation of ARCs with robust operation under variable conditions. The materials route is based on the generation of well-defined porous aluminosilicate networks by block copolymer co-assembly with poly(isobutylene)- block-poly(ethylene oxide) and postsynthesis grafting of trichloro(octyl)silane molecules to the pore walls. The functionalized films exhibited a maximum transmittance value of 99.8%, with an average transmittance of 99.1% in the visible wavelength range from 400 to 700 nm. Crucially, the antireflection performance was maintained at high humidity values, with an average transmittance decrease of only 0.2% and maximum values maintained at 99.7%. This compared to maximum and average losses of 3.6 and 2.7%, respectively, for nonfunctionalized reference samples. The ARCs were shown to retain their optical properties within 50 humidity cycles, indicating long-term stability against fluctuating environmental conditions

Synthetic guidelines for the precision engineering of gold nanoparticles

Gold nanoparticles (AuNPs) are one of the most studied nanomaterials with applications spanning from catalysis to biomedicine. While numerous chemical protocols exist that allow bespoke tailoring of chemical, physical and biological properties, their translation towards industrial-scale production remains a challenge. Batch synthesis often suffers from poor reproducibility and scalability, while emerging approaches, such as continuous flow synthesis, are not widely implemented in research labs. Herein, we provide a critical review of recent developments in the field of AuNP synthesis and identify synthetic guidelines for precision engineering of nanoparticle properties

Interparticle Forces of a Native and Encapsulated Metal-Organic Framework and Their Effects on Colloidal Dispersion

The colloidal properties of suspended metal-organic frameworks (MOFs) are critical for device fabrication and application. Herein, van der Waals attractive, electric double layer repulsive, and steric repulsive forces of a native and encapsulated MOF are quantified for the first time. The van der Waals attractive forces were investigated by conducting environmental ellipsometric porosimetry (EEP) and spectroscopic ellipsometry (SE) on submicron, optical-quality nanoparticle films. The repulsive forces were determined from colloid and material characterization measurements. These data were used to predict suspension properties via extended Derjaguin, Landau, Verwey, and Overbeek theory. The state of dispersion was quantified for comparison with theoretical predictions for nine solvents. The MOF encapsulated with a surface-selective modification showed superior suspension in hydrophobic solvents. These findings should expedite the formulation of MOF colloidal suspensions for future works

Using Nanocavity Plasmons to Improve Solar Cell Efficiency

Although in principle very promising, photovoltaic technology has so far failed to deliver robust high efficiency modules at affordable prices. Despite considerable research, high efficiency silicon based cells remain expensive, while the more recent organic photovoltaics are still struggling with low efficiencies and short lifetimes. Meanwhile, over the last few years, the study of localized plasmons [1,2] has also received great attention due to the high field enhancements associated with confined fields , with a wide range of applications possible, from optical switches to substrates for surface enhanced Raman spectroscopy (SERS). Here we discuss how combining the structures normally used in photovoltaic devices with metallic cavities supporting localized plasmons can lead to considerable improvements in the performance of solar cells. In particular we show how by changing the shape and size of spherical voids on a metallic surface, one can tune the plasmon modes to obtain significant absorptions across the solar spectrum [3]. By coating one such nanocavity surface with a sub 100 nm-layer of semiconductor, we can create a nanostructured solar cell, where the localised Mie modes efficiently couple light into the semiconductor layer. As the plasmons electric field enhancement is largest very close to the surface, significant absorption can be maintained even when the semiconductor thickness is reduced to below the typical exciton diffusion length. In addition minority carrier transport is improved. That means we can beat the usual balance between light absorption and exciton recombination loses, and so significantly increase the overall efficiency of the photovoltaic devices. Keywords: plasmons, solar cells, nanostructured surfaces

A Combined Experimental and Theoretical Study into the Performance of Multilayer Vanadium Dioxide Nanocomposites for Energy Saving Applications

In the built environment there is a increasing issue of heat management, with buildings expending significant energy resources to maintain comfortable living temperatures. In many parts of the world, this entails the use of both heating and cooling during daylight hours depending on ambient temperatures. Due to the variation in the desired temperature control classical solutions can become counter productive in their aim of maintaining comfortable temperatures, therefore it is important to employ adaptive solutions that vary their functionality based on circumstance. In recent years vanadium dioxide (VO2) has generated a broad range of interest due to its heat-mediated structural phase transition from a semiconductor to a metal, which occurs at a critical temperature that may be tuned via doping. The phase transition of VO2 significantly modulates its optical properties, with the high temperature metallic state absorbing and reflecting considerably more infrared radiation than the lower temperature monoclinic state due to the presence of free electrons; a window coated with a VO2 film may passively vary its transmission of infrared radiation based on the ambient temperature, in doing so reducing the temperature management energy-load. Here, we present a theoretically optimised design for a thermochromic smart window film based on a multilayer stack of silica, titania and vanadium dioxide (VO2) on a glass substrate and use the simulations to guide the fabrication process. The design makes use of coherent interference within the multi-layered structure to suppress reflection of visible light and improve the reflective component of solar modulation. In doing so, we are able simultaneously improve the visible transmission and solar modulation of the film above what would be possible with a single layer film. Additionally, the use of thin film VO2 also acts to reduce the detrimental transition hysteresis typically seen in small domain sized nanoparticulate VO2 films. The multilayer structure is fabricated via spin coating of sol-gel based precursors and subsequent annealing. After which the structure is optically characterised and results are compared with simulation along with standard single layer VO2 films and other nanoparticulate based VO2 films