Session L12: From Nano to Meso: Assembly Structure and Dynamics of Polymers and Polymer Nanocomposite Thin Films II - Industry Day

Nanoparticles in Polymers: Assembly, Rheology and Properties

Inorganic nanoparticles have the potential of providing functionalities that are difficult to realize using organic materials; and nanocomposites is an effective mean to impart processibility and construct bulk materials with breakthrough properties. The dispersion and assembly of nanoparticles are critical to both processibility and properties of the resulting product. In this talk, we will discuss several methods to control the hierarchical structure of nanoparticles in polymers and resulting rheological, mechanical and optical properties. In one example, polymer-particle interaction and secondary microstructure were designed to provide a low viscosity composition comprising exfoliated high aspect ratio clay nanoparticles; in another example, the microstructure control through templates was shown to enable unique thermal mechanical and optical properties.   

Pressure-Directed Assembly: Nanostructures Made Easy

Precise control of structural parameters through nanoscale engineering to improve optical and electronic properties of functional nanomaterials continuously remains an outstanding challenge. Previous work has been conducted largely at ambient pressure and relies on specific chemical or physical interactions such as van der Waals interactions, dipole-dipole interactions, chemical reactions, ligand-receptor interactions, etc. In this presentation, I will introduce a new pressure-directed assembly method that uses mechanical compressive force applied to nanoparticle arrays to induce structural phase transition and to consolidate new nanomaterials with precisely controlled structures and tunable properties. By manipulating nanoparticle coupling through external pressure, instead of through chemistry, a reversible change in their assemblies and properties can be achieved and demonstrated. In addition, over a certain threshold, the external pressure will force these nanoparticles into contact, thereby allowing the formation and consolidation of one- to three-dimensional nanostructures. Through pressure induced nanoparticle assembly, materials engineering and synthesis become remarkably flexible without relying on traditional crystallization process where atoms/ions are locked in a specific crystal structure. Therefore, morphology or architecture can be readily tuned to produce desirable properties for practical applications. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.   

X-ray Studies of Nano Composites

Nano composite materials are an exciting and fast expanding field. X-ray scattering has been used in order to study the structure properties relation. During the last few years the field has expanded more towards the field of thin films where there’s been a dramatic increase in the use of grazing incidence small angle X-ray scattering (GISAXS). The main issue of GISAXS has been the complex analysis framework necessary for simulating and fitting. In addition, existing software has restricted the scientist in systems that can be simulated and the speed to analyze large amounts of data. Over the last few years we have worked closely with our computational research and supercomputer division to enable the use of supercomputers to simulate at scattering data. We have developed a comprehensive analysis framework to simulate and fit a wide variety of materials and morphologies. The framework is designed to supply scientists with close to real-time feedback during beam times. Therefore, HipGISAXS (High Performance GISAXS) has been developed to run simulations on massively parallel platforms such as the Oak Ridge Supercomputer Titan (OLCF). Further, with inverse modeling algorithms for fitting available in HipGISAXS, such as particle swarm optimization, it can handle a large number of parameters during the structure fitting process. In September of 2014, HipGISAXS was used in a real time demonstration that married the SAXS/WAXS beamline at the ALS with the data handling and processing capabilities at NERSC, and simulation capabilities of running at-scale simulations on Titan at OLCF.   

Swelling and viscoelasticity in photoresist thin films

For a wide range of electronic applications, polymers are processed in the thin film state with the film thickness lower than 100 nm. Understanding the polymer structure property relationship at those characteristic length scales is important to enable the material design for various applications. Extreme ultraviolet lithography (EUVL) is the next generation lithographic technique using low wavelength (13.5 nm) ultraviolet radiation. Quality of the final pattern in the lithographic process depends on the performance of the photoresist polymer during multiple processing steps. Photoresist material development for the EUV lithography presents several challenges for controlling the thin film swelling, density and outgassing. In particular, it has been proposed in the literature that pattern collapse, a lithographic defect where the desired features become deformed, can be caused by the swelling of the photoresist material. In this presentation, the effect of photoresist formulation and architecture on the thin film swelling and viscoelasticity will be discussed. We find that the quencher base could have a significant effect on the swelling characteristics of the photoresist. Additionally, swelling characteristics of the photoresists with covalently bound vs. blended photoacid generator (PAG) were found to be significantly different.   

Patterning Multicomponent Polymer Thin Films via Dynamic Thermal Processing

Bottom-up patterning is gaining increased importance owing to the physical limitations and rising costs of top-down patterning. One example of bottom-up patterning is self-assembling polymer thin films. Although there are several pathways to facilitate polymer thin film self-assembly, this presentation will focus on dynamic thermal field based processes for patterning multicomponent polymer thin films. Dynamic thermal field processing is an attractive roll­to­roll (R2R) amenable directed self­assembly (DSA) method for molecular level organization of multicomponent polymer systems such as block copolymer thin films over large areas without requiring guiding templates. The talk will first outline how parameters such as magnitude of the temperature gradient, velocity of annealing, thermal expansion, and molecular weight of the polymer can be optimized to finely tune the morphology of the block copolymer thin films and also elucidate their associated physical mechanisms. The second part of the talk will outline application of dynamic thermal field processes for fabricating functional nanomaterials and discuss the recent advancements achieved using these processes.