Self-Assembly and Post-Fabrication Functionalization of Microphase Separated Thin Films of a Reactive Azlactone-Containing Block Copolymer
Bibliographic record
Abstract
We report on the thin film self-assembly and post-fabrication functionalization of cylinder-forming poly(styrene- block -2-vinyl-4,4-dimethylazlactone) (PS- b -PVDMA) block copolymers (BCPs). Thermal annealing of an asymmetric BCP composition, to drive microphase separation in thin films, results in high defect densities and poor long-range order. Using FTIR spectroscopy and ellipsometry, we demonstrate that thermal annealing results in reactions between the azlactone groups and the underlying substrate leading to BCP “pinning”. We demonstrate that solvent annealing circumvents these issues and drives high fidelity microphase separation of the BCP in thin films. The solvent annealing approach also enables control over domain orientation; we show that parallel and perpendicularly oriented cylinders with diameters of 11.7 ± 1.2 nm and a center-to-center distance of 25.2 ± 2.6 nm can be obtained using a BCP with M n = 29.5 kDa and f S = 0.75. The PVDMA segments in these self-assembled thin films remain available for reaction with primary amine-functionalized nucleophiles. X-ray photoelectron spectroscopy (XPS) depth-profiling reveals that reactions between azlactone groups and incoming amines occur primarily in the top few nanometers of the reactive domains. Finally, we demonstrate that the azlactone groups in both parallel and perpendicularly oriented cylindrical thin films can selectively incorporate trimethylaluminum vapor, which can be subsequently converted into Al 2 O 3 nanowires and nanodots with dimensions of 16 and 12 nm, respectively.
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How this classification was reachedexpand
Full frame distilled prediction
Teacher imitationNot calibrated prevalence, not ground truth. Human validation pending. Learned from the 10,348 direct Codex labels and 10,348 direct Gemma labels. Candidate is the union of thresholded teacher heads; consensus is their intersection. These outputs are machine_predicted_unvalidated and are not human labels or direct frontier model labels.
Codex and Gemma teacher scores by category
| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
| Meta-epidemiology (narrow) | 0.000 | 0.000 |
| Meta-epidemiology (broad) | 0.000 | 0.000 |
| Bibliometrics | 0.000 | 0.000 |
| Science and technology studies | 0.000 | 0.000 |
| Scholarly communication | 0.000 | 0.000 |
| Open science | 0.000 | 0.000 |
| Research integrity | 0.000 | 0.000 |
| Insufficient payload (model declined to judge) | 0.000 | 0.000 |
Machine scores (provisional)
The two teacher heads of the student model, read on this work. A score orders the frame for review; it never asserts a category, and the validation status ships verbatim with every row.
Baseline scores from an immature model (maturity gate not passed, 7 training rounds). Scores rank; they never assert a category.
score_only:v0-immature-baseline · verbatim from the scoring run: score_only means the number may rank works, and no category label ships from itClassification
machine, unvalidatedMachine predicted; a candidate call from one teacher head, not a consensus.
How this classification was reached, model by model and score by score, is at the end of the page under "How this classification was reached".