Controlling the morphology of spin coated polymer blend films.

Thin films of polymer mixtures made by spin-coating can phase separate in two ways - by forming lateral domains, or by separating into two distinct layers. The latter situation - self-stratification or vertical phase separation - could be advantageous in a number of practical applications, such as polymer photovoltaics. In our experiments, we have used time-resolved small-angle light scattering and light reflectivity during spin coating to study the structure development in PS/PMMA and PFB/F8BT blends, solution cast in toluene. A sample cell was designed, made and mounted on the apparatus to manipulate the evaporation rate. Having solved the Meyerhofer equation for thinning rate and by fitting the model to the experimental data, we are able to extract the evaporation rate of toluene during spin coating. We demonstrate that, by controlling the evaporation rate during the spin-coating process, we can obtain either selfstratification or lateral phase separation in the same system. We relate this to a previously hypothesised mechanism for phase separation during spin coating in thin films, according to which a transient wetting layer breaks up due to a Marangoni-type instability driven by a concentration gradient of solvent within the drying film. Our results show that a high evaporation rate leads to a laterally phase separated structure, while reducing the evaporation rate suppresses the interfacial instability and leads to a self-stratified final film. Using the set up we developed to control the morphology through evaporation rate, we made preliminary photovoltaic devices. It is possible to control the efficiency of the polymer photovoltaics by means of process parameters such as evaporation rate

Cyclical 'flipping' of morphology in block copolymer films

We studied the kinetics of nanopattern evolution in (polystyrene-b-polyethylene oxide) diblock copolymer thin films. Using scanning force microscopy, a highly unexpected cylindrical flipping of morphology from normal to parallel to the film plane was detected during solvent annealing of the film (with average thickness of 30 nm) at high vapor pressure. Using an in situ time-resolved light scattering device combined with an environmental cell enabled us to obtain kinetic information at different vapor pressures. The data indicated that there is a threshold value for the vapor pressure necessary for the structural transition. We propose a swelling and deswelling mechanism for the orientation flipping of the morphology. The cyclic transition occurs faster in thick films (177 nm) where the mass uptake and solvent volume fraction is smaller and therefore the driving force for phase separation is higher. We induced a stronger segregation by confining the chains in graphoepitaxially patterned substrates. As expected, the cyclic transition occurred at higher rate. Our work is another step forward to understanding the structure evolution and also controlling the alignment of block copolymer nanocylinders independently of thickness and external fields

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high- lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during "solvo-microwave" annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 degrees C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during "solvo-microwave" annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O-2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film

Highly Ordered Titanium Dioxide Nanostructures via a Simple One Step Vapor Inclusion Method in Block Copolymer Films

Nanostructured crystalline titanium dioxide (TiO2) finds applications in numerous fields such as photocatalysis or photovoltaics where its physical and chemical properties depend on its shape and crystallinity. We report a simple method of fabricating TiO2 nanowires by selective area deposition of titanium tetraisopropoxide (TTIP) and water in a CVD-based approach at low temperature by utilizing PS-b-PEO self-assembled block copolymer thin film as a template. Parameters such as exposure time to TTIP (minutes to hours), working temperature (~18 to 40 °C) and relative humidity (20 to 70 RH%) were systemically investigated through GISAXS, SEM and XPS and optimized for fabrication of TiO2 nanostructures. The resulting processing conditions yielded titanium dioxide nanowires with a diameter of 24 nm. An extra calcination step (400 – 700 °C) was introduced to burn off the remaining organic matrix and introduce phase change from amorphous to anatase in TiO2 nanowires without any loss in order

Large block copolymer self-assembly for fabrication of subwavelength nanostructures for applications in optics

Nanostructured surfaces are common in nature and exhibit properties such as antireflectivity (moth eyes), self-cleaning (lotus leaf), iridescent colors (butterfly wings), and water harvesting (desert beetles). We now understand such properties and can mimic some of these natural structures in the laboratory. However, these synthetic structures are limited since they are not easily mass produced over large areas due to the limited scalability of current technologies such as UV-lithography, the high cost of infrastructure, and the difficulty in nonplanar surfaces. Here, we report a solution process based on block copolymer (BCP) self-assembly to fabricate subwavelength structures on large areas of optical and curved surfaces with feature sizes and spacings designed to efficiently scatter visible light. Si nanopillars (SiNPs) with diameters of ∼115 ± 19 nm, periodicity of 180 ± 18 nm, and aspect ratio of 2–15 show a reduction in reflectivity by a factor of 100, <0.16% between 400 and 900 nm at an angle of incidence of 30°. Significantly, the reflectivity remains below 1.75% up to incident angles of 75°. Modeling the efficiency of a SiNP PV suggests a 24.6% increase in efficiency, representing a 3.52% (absolute) or 16.7% (relative) increase in electrical energy output from the PV system compared to AR-coated device

Selective molecular annealing:in situ small angle X-ray scattering study of microwave-assisted annealing of block copolymers

Microwave annealing has emerged as an alternative to traditional thermal annealing approaches for optimising block copolymer self-assembly. A novel sample environment enabling small angle X-ray scattering to be performed in situ during microwave annealing is demonstrated, which has enabled, for the first time, the direct study of the effects of microwave annealing upon the self-assembly behavior of a model, commercial triblock copolymer system [polystyrene-block-poly(ethylene-co-butylene)-block-polystyrene]. Results show that the block copolymer is a poor microwave absorber, resulting in no change in the block copolymer morphology upon application of microwave energy. The block copolymer species may only indirectly interact with the microwave energy when a small molecule microwave-interactive species [diethylene glycol dibenzoate (DEGDB)] is incorporated directly into the polymer matrix. Then significant morphological development is observed at DEGDB loadings ≥6 wt%. Through spatial localisation of the microwave-interactive species, we demonstrate targeted annealing of specific regions of a multi-component system, opening routes for the development of "smart" manufacturing methodologies

Cyclical \u27flipping\u27 of morphology in block copolymer films

We studied the kinetics of nanopattern evolution in (polystyrene-b-polyethylene oxide) diblock copolymer thin films. Using scanning force microscopy, a highly unexpected cylindrical flipping of morphology from normal to parallel to the film plane was detected during solvent annealing of the film (with average thickness of 30 nm) at high vapor pressure. Using an in situ time-resolved light scattering device combined with an environmental cell enabled us to obtain kinetic information at different vapor pressures. The data indicated that there is a threshold value for the vapor pressure necessary for the structural transition. We propose a swelling and deswelling mechanism for the orientation flipping of the morphology. The cyclic transition occurs faster in thick films (177 nm) where the mass uptake and solvent volume fraction is smaller and therefore the driving force for phase separation is higher. We induced a stronger segregation by confining the chains in graphoepitaxially patterned substrates. As expected, the cyclic transition occurred at higher rate. Our work is another step forward to understanding the structure evolution and also controlling the alignment of block copolymer nanocylinders independently of thickness and external fields

Solvothermal Vapor Annealing of Lamellar Poly(styrene)- block -poly( d , l -lactide) Block Copolymer Thin Films for Directed Self-Assembly Application

International audienceSolvo-thermal vapor annealing (STVA) was employed to induce microphase separation in a lamellar forming semicrystalline block copolymer (BCP) thin film containing a rapidly degradable block. Directed self-assembly of poly(styrene)-block-poly(D,L-lactide) (PS-b-PLA) BCP films via topographically patterned silicon nitride was demonstrated with alignment over macroscopic areas. Interestingly, we observed lamellar patterns aligned parallel as well as perpendicular to graphoepitaxial guiding patterns . PS-b-PLA BCP microphase separated with high a degree of order in an atmosphere of tetrahydrofuran (THF) with an elevated vapor pressure (at ca. 40-60°C). Grazing incidence small angle X-ray scattering (GISAXS) measurements of PS-b-PLA films reveals the through-film uniformity of perpendicular domains after STVA. Perpendicular lamellar orientation was observed on both hydrophilic and relatively hydrophobic surfaces with a periodicity (L0) of ~ 32.5 nm. The rapid removal of the PLA domains is demonstrated using a mild basic solution for the development of a well-defined PS mask template. GISAXS data reveals the through-film uniformity is retained following wet etching. The experimental results in this article demonstrate highly oriented PS-b-PLA microdomains after a short annealing period and facile PLA removal forming porous on-chip etch masks for nanolithography application

Study of the kinetics and mechanism of rapid self-assembly in block copolymer thin films during solvo-microwave annealing

Microwave annealing is an emerging technique for achieving ordered patterns of block copolymer films on substrates. Little is understood about the mechanisms of microphase separation during the microwave annealing process and how it promotes the microphase separation of the blocks. Here, we use controlled power microwave irradiation in the presence of tetrahydrofuran (THF) solvent, to achieve lateral microphase separation in high-χ lamellar-forming poly(styrene-b-lactic acid) PS-b-PLA. A highly ordered line pattern was formed within seconds on silicon, germanium and silicon on insulator (SOI) substrates. In-situ temperature measurement of the silicon substrate coupled to condition changes during “solvo-microwave” annealing allowed understanding of the processes to be attained. Our results suggest that the substrate has little effect on the ordering process and is essentially microwave transparent but rather, it is direct heating of the polar THF molecules that causes microphase separation. It is postulated that the rapid interaction of THF with microwaves and the resultant temperature increase to 55 °C within seconds causes an increase of the vapor pressure of the solvent from 19.8 to 70 kPa. This enriched vapor environment increases the plasticity of both PS and PLA chains and leads to the fast self-assembly kinetics. Comparing the patterns formed on silicon, germanium and silicon on insulator (SOI) and also an in situ temperature measurement of silicon in the oven confirms the significance of the solvent over the role of substrate heating during “solvo-microwave” annealing. Besides the short annealing time which has technological importance, the coherence length is on a micron scale and dewetting is not observed after annealing. The etched pattern (PLA was removed by an Ar/O2 reactive ion etch) was transferred to the underlying silicon substrate fabricating sub-20 nm silicon nanowires over large areas demonstrating that the morphology is consistent both across and through the film.We gratefully acknowledge Science Foundation Ireland (SFI) CSET/CRANN and a LAMAND NMP FP7 grant for funding this project.Peer Reviewe

Local Thermomechanical Analysis of a Microphase-Separated Thin Lamellar PS‑<i>b</i>‑PEO Film

We use atomic force microscopy (AFM) and hot tip AFM (HT-AFM) to thermophysically characterize a 30 nm thick film of poly­(styrene-<i>block</i>-ethylene oxide), PS-<i>b</i>-PEO, and to modify its lamellar patterns having spacing of 39 ± 3 nm. AFM tip scans of the polymer film induce either abrasive surface patterns or nanoscale ripples, which depend upon the tip force, temperature, and number of scans. The evolution of the lamellar patterns is explained by the polymer film molecular structure and mode I crack propagation in the polymer combined with the stick-and-slip behavior of the AFM tip. The HT-AFM measurements at various tip–sample temperatures and scanning speeds yield several thermophysical quantities: the PEO melting temperature of 54 ± 12 °C, the PS glass transition temperature of 54 ± 12 °C, the PS-<i>b</i>-PEO specific heat of 3.6 ± 2.7 J g^–1 K^–1, the PEO melting enthalpy of 111 ± 88 J g^–1, and the free energy of Helmholtz for PEO unfolding (and melting) of 10^–20 J nm^–2. These quantities are obtained for PS-<i>b</i>-PEO volumes of 30 000 nm³, which correspond to 30 ag of the polymer