Molecular weight dependence of the morphology in P3HT:PCBM solar cells.

In polymer-based photovoltaic devices, optimizing and controlling the active layer morphology is important to enhancing the device efficiency. Using poly(3-hexylthiophene) (P3HT) with well-defined molecular weights (MWs), synthesized by the Grignard metathesis (GRIM) method, we show that the morphology of the photovoltaic active layer and the absorption and crystal structure of P3HT are dependent on the MW. Differential scanning calorimetry showed that the crystallinity of P3HT reached a maximum for intermediate MWs. Grazing-incidence wide-angle X-ray diffraction showed that the spacing of the (100) planes of P3HT increased with increasing MW, while the crystal size decreased. Nonlinear crystal lattice expansions were found for both the (100) and (020) lattice planes, with an unusual π-π-stacking enhancement observed between 50 and 100 °C. The melting point depression for P3HT, when mixed with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), and, hence, the Flory-Huggins interaction parameter depended on the MW. PCBM was found to perturb the ordering of P3HT chains. In photovoltaic devices, P3HT with a MW of ∼20K showed the best device performance. The morphologies of these blends were studied by grazing-incidence small-angle X-ray scattering (GISAXS) and resonant soft X-ray scattering. In GISAXS, we observed that the low-molecular-weight P3HT more readily crystallizes, promoting a phase-separated morphology.

An in situ grazing incidence X-ray scattering study of block copolymer thin films during solvent vapor annealing.

In situ grazing-incidence small-angle X-ray scattering experiments on thin films of block copolymers during annealing in neutral solvent vapors are reported. By removing the solvent in a controlled manner, the period of the microphase separated morphology is found to increase with increasing block copolymer concentration in a power law manner with an exponent ∼ 2/3. By venting the systems at different rates during the solvent removal process, kinetically arresting the system, the period of the microphase separated morphology in the dried film can be varied.

On the self-assembly of brush block copolymers in thin films.

We describe a simple route to fabricate two dimensionally well-ordered, periodic nanopatterns using the self-assembly of brush block copolymers (brush BCPs). Well-developed lamellar microdomains oriented perpendicular to the substrate are achieved, without modification of the underlying substrates, and structures with feature sizes greater than 200 nm are generated due to the reduced degree of chain entanglements of brush BCPs. A near-perfect linear scaling law was found for the period, L, as a function of backbone degree of polymerization (DP) for two series of brush BCPs. The exponent increases slightly from 0.99 to 1.03 as the side chain molecular weight increases from ∼2.4 to ∼4.5 kg/mol(-1) and saturated with further increase in the side chain molecular weight due to the entropic penalty associated with the packing of the side chains. Porous templates and scaffolds from brush BCP thin films are also obtained by selective etching of one component.

Line patterns from cylinder-forming photocleavable block copolymers.

A robust route for the preparation of nanoscopic line patterns from polystyrene-block-poly(ethylene oxide) featuring a photocleavable o-nitrobenzyl ester junction is demonstrated. After mild UV (λ = 365 nm) exposure and selective removal of the PEO microdomains, the polymer trench patterns are used as scaffold to fabricate highly ordered arrays of silica or Au line patterns.

Solvent-assisted directed self-assembly of spherical microdomain block copolymers to high areal density arrays.

The fabrication process for 5 Tb/in(2) bit patterns using solvent-assisted directed self-assembly is investigated. The N-methyl-2-pyrrolidone solvent vapor-annealing method was used to achieve good long-range lateral ordering of low-molecular-weight polystyrene-block-polydimethylsiloxane with a lattice spacing of 11 nm on flat Si substrates, PS modified substrates and lithographically patterned substrates, respectively.

Self-assembly of symmetric brush diblock copolymers.

Self-assembled structures of brush block copolymers (BrBCPs) with polylactide (PLA) and polystyrene (PS) side chains were studied. The polynorbornene-backbone-based BrBCPs containing approximately equal volume fractions of each block self-assembled into highly ordered lamellae with domain spacing ranging from 20 to 240 nm by varying molecular weight of the backbone in the bulk state, as revealed by small-angle X-ray scattering (SAXS). The domain size increased approximately linearly with backbone length, which indicated an extended conformation of the backbone in the ordered state. In situ SAXS measurements suggested that the BrBCPs self-assemble with an extremely fast manner which could be attributed to a reduced number of entanglements between chains. The strong segregation theory and Monte Carlo simulation also confirmed this near-linear dependence of the domain spacing on backbone length, rationalizing experimental results.

Photocleavable Triblock Copolymers Featuring an Activated Ester Middle Block: "One-Step" Synthesis and Application as Locally Reactive Nanoporous Thin Films.

Polystyrene-block-poly(maleimide pentafluorophenyl ester-co-styrene)-block-poly(ethylene oxide) with an o-nitrobenzyl ester junction was synthesized by "one-step" RAFT polymerization. Highly ordered and locally reactive nanoporous thin films were obtained from the photocleavable triblock copolymer after spin coating, solvent annealing, UV exposure, and washing with methanol/water to remove the minor block PEO. The local reactivity in the thin films was demonstrated by fabrication of iron oxide nanotori after post-modification with an amino-functionalized ferrocene and treatment with oxygen plasma.

Orienting block copolymer microdomains with block copolymer brushes.

A simple, rapid, and robust technique for controlling the self-assembly of block copolymers (BCPs) with a large segmental interaction parameter, χ, is described using a surface modified with anchored BCP brushes. End-functionalized poly(styrene-b-ethylene oxide)s (PS-b-PEOs), where the fraction of PS (f(PS)) was varied, end-functionalized neat PS, and end-functionalized neat PEO were end-grafted onto Si substrates modifying the surface with polymer brushes. Thin films of cylinder-forming PS-b-PEO were prepared on modified Si substrates and thermally annealed. When neat PS and PEO were used as the anchored brushes, the microdomains of the PS-b-PEO oriented parallel to the substrate upon thermal annealing due to the preferential interactions of one block to the anchored brushes. However, when end-functionalized PS-b-PEOs were used to modify the substrate, hexagonally packed cylindrical PEO microdomains oriented normal to the substrate, having long-range lateral ordering, were obtained over a very wide range of f(PS) (0.32 to 0.77).

Fabrication of silicon oxide nanodots with an areal density beyond 1 teradots inch(-2).

The combination of solvent annealing, surface reconstruction, and a tone-reversal etching procedure provides an attractive approach to utilize block copolymer (BCP) lithography to fabricate highly ordered and densely packed silicon oxide nano-dots on a surface. The obtained silicon oxide nano-dots feature an areal density of 1.3 teradots inch(-2) .

Highly ordered nanoporous template from triblock copolymer.

Silica nanoporous templates from poly(1,4-isoprene)-block-polystyrene-block-poly(2-vinyl pyridine) (IS2VP) were prepared. The films of IS2VP spin-coated from toluene showed a dimple-type structure with short-range lateral order. When the films were exposed to a mixed solvent vapor of toluene/hexane, a highly ordered and oriented core-shell structure, consisting of an outer shell of PI, a middle shell of PS, and a core of P2VP, was obtained. The PI was degraded by UV-ozone treatment and removed. A film of polydimethylsiloxane (PDMS) was spin coated onto the remaining film with dimple-type structures and, upon heating, was drawn into the interstitial regions by capillary action. Exposure to oxygen plasma converted the PDMS into silica and degraded all other remaining polymers. This led to highly ordered and oriented nanoporous silica that could be used as an etching mask for transfer of the pattern or templates for metal loading.