` This readme.txt file was generated on <2023-09-01> by Recommended citation for the data: Yang, Szu-Ming; Oh, Jinwoo; Magruder, Benjamin R; Kim, HeeJoong; Dorfman, Kevin D; Mahanthappa, Mahesh K; Ellison, Christopher J (2023). Data for Surface Relief Terraces in Double Gyroid-Forming Polystyrene-block-Polylactide Thin Films. Retrieved from the Data Repository for the University of Minnesota, https://doi.org/10.13020/qc9e-qc68. ------------------- GENERAL INFORMATION ------------------- 1. Title of Dataset: Data for "Surface Relief Terraces in Double Gyroid-Forming Polystyrene-block-Polylactide Thin Films" 2. Author Information Principal Investigator Contact Information Name: Christopher J. Ellison Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: cellison@umn.edu Associate or Co-investigator Contact Information Name: Szu-Ming Yang Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: yang5421@umn.edu Associate or Co-investigator Contact Information Name: Jinwoo Oh Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: joh@umn.edu Associate or Co-investigator Contact Information Name: Benjamin R. Magruder Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: magru018@umn.edu Associate or Co-investigator Contact Information Name: HeeJoong Kim Institution: University of Minnesota Address: Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: kim00244@umn.edu Associate or Co-investigator Contact Information Name: Kevin D. Dorfman Institution: University of Minnesota Address:Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: dorfman@umn.edu Associate or Co-investigator Contact Information Name: Mahesh K. Mahanthappa Institution: University of Minnesota Address:Department of Chemical Engineering and Materials Science, 421 Washington Ave SE, Minneapolis, Minnesota 55455 Email: maheshkm@umn.edu 3. Date published or finalized for release: 4. Date of data collection (single date, range, approximate date) : 20200801-20230530 5. Geographic location of data collection (where was data collected?): University of Minnesota 6. Information about funding sources that supported the collection of the data: Funding for this work was from the National Science Foundation (NSF) through the Materials Research Science and Engineering Center (MRSEC) under Award Number DMR-2011401. Parts of this work were carried out in the Characterization Facility, University of Minnesota, which receives partial support from the NSF through the MRSEC (Award Number DMR-2011401) and the NNCI (Award Number ECCS-2025124) programs. 7. Overview of the data (abstract): This study describes the thin film self-assembly behavior of a polystyrene-block-polylactide (SL-G) diblock copolymer, which undergoes melt self-assembly in bulk into a double gyroid (DG) network phase with a cubic unit cell parameter a = 52.7 nm. Scanning electron microscopy (SEM) and grazing-incidence small-angle X-ray scattering (GISAXS) reveal that thermally annealing 140–198 nm thick copolymer films on SiO2 substrates below the morphological order-to-disorder transition temperature yields polydomain DG structures, in which the (422) planes are oriented parallel to the surface. Bright-field optical microscopy (OM) and atomic force microscopy (AFM) analyses further reveal the film thickness-dependent formation of topographical terraces, including islands, holes, and bicontinuous features. The occurrence of these features sensitively depends on the incommensurability of the as-prepared film thickness and the (211)-interplanar spacing (d211) of the DG unit cell. While the steps heights between adjacent terraces exhibiting characteristic “double wave” patterns of the DG (422) planes coincide with d211, previously unreported transition zones between adjacent terraces are observed wherein “boomerang” and “droplet” patterns are observed. These intermediate patterns follow the expected sequence of adjacent termination planes of the bulk DG unit cell along the [211] direction, as confirmed by comparisons with self-consistent mean-field theory calculations. -------------------------- SHARING/ACCESS INFORMATION -------------------------- Licenses/restrictions placed on the data: CC0 1.0 Universal Links to publications that cite or use the data: https://doi.org/???? Was data derived from another source? N/A If yes, list source(s): Terms of Use: Data Repository for the U of Minnesota (DRUM) By using these files, users agree to the Terms of Use. https://conservancy.umn.edu/pages/drum/policies/#terms-of-use Links to other publicly accessible locations of the data:N/A Links/relationships to ancillary data sets:N/A --------------------- DATA & FILE OVERVIEW --------------------- Purpose Statement: This document describes all data in figures associated with Yang et al. "Suface Relief Terraces in Double Gyroid-Forming Polystyrene-block-Polylactide Thin Films". File List 1. Filename: Fig. 1 Schematic depiction of SL-G self-assembly into an cubic DG structure. Short description: Cubic DG unit cell structure and representative termination planes based on SCFT calculation. 2. Filename: Fig. 2 AFM, SEM, and GISAXS pattern of SL-G thin film with tavg = 165 nm = 7.7d211. Short description: AFM, SEM, and GISAXS pattern of SL-G thin film before and after thermal annealing. 2. Filename: Fig. 3 Surface Relief terraces of SL-G thin films with different thicknesses. Short description: AFM images of SL-G thin films with average thickness ranging from 168 nm (7.8d211) to 193 nm (9.0d211). 3. Filename: Fig. 4 Terraces and transition zone formed in an SL-G thin film with tavg = 198 nm (9.2d211) after thermal annealing. Short description: Top-view schematic of poly-grain SL-G thin film after thermal annealing. AFM images of terraces and transition zone formed in an SL-G thin film with tavg = 198 nm (9.2d211) after thermal annealing. SCFT solutions of representative crystallographic planes along the [211] direction. 4. Filename: Fig. 5 Analysis of terraces and transition zone formed in an SL-G thin film with tavg = 198 nm (9.2d211) after thermal annealing. Short description: AFM images of terraces and transition zone, Height profile of of terraces and transition zone, and SCFT simulation results of the termination planes along [211] direction in DG unit cell and the corresponding height of the transition zone and surface relief island. 5. Filename: Fig. S1 Synthesis of PS-OH and hydroxyl-terminated PS-PLA (PS-PLA-OH). Short description: Chemdraw file for styrene, PS-OH, and PS-PLA-OH. 6. Filename: Fig. S2 1H NMR spectrum of PS-OH. Short description: NMR Data for PS-OH. 7. Filename: Fig. S3 Endcapping reaction of PS-PLA-OH to produce acetylated PS-PLA (SL-G). Short description: Chemdraw file for SL-G 8. Filename: Fig. S4 1H NMR spectra of PS-PLA-OH and SL-G. Short description: NMR Data for PS-PLA-OH and SL-G. 9. Filename: Fig. S5 SEC-LS chromatograms for PS-OH, PS-PLA-OH, and SL-G. Short description: SEC-LS Data for PS-OH, PS-PLA-OH, and SL-G. 10. Filename: Fig. S6 DSC data for PS-PLA-OH and SL-G. Short description: DSC data for PS-PLA-OH and SL-G. 11. Filename: Fig. S7 TGA analyses for PS-PLA-OH and SL-G. Short description: TGA data for PS-PLA-OH and SL-G. 12. Filename: Fig. S8 DG-forming bulk SL-G. Short description: SEM image and SAXS data for bulk SL-G. 13. Filename: Fig. S9 SL-G thin film sample preparation Short description: SL-G thin film sample preparation 14. Filename: Fig. S10 SL-G thin film thickness measurement Short description: Ellipsometer Data and AFM image of SL-G thin film 15. Filename: Fig. S11 Etched SL-G thin films annealed at different temperature Short description: AFM images of etched SL-G thin films annealed at different temperature 16. Filename: Fig. S12 2D-GISAXS patterns of SL-G thin films thermally annealed for 1 min at 180 °C (unetched) with different film thickness Short description: 2D-GISAXS data for annealed SL-G thin films with different thickness 17. Filename: Fig. S13 Top-view SEM images of etched SL-G thin films with the indicated thicknesses Short description: SEM images of etched SL-G thin films with the indicated thicknesses 18. Filename: Fig. S14 Optical microscopy (OM) images of thermally annealed SL-G thin films with different thickness Short description: OM images of thermally annealed SL-G thin films with different thickness 19. Filename: Fig. S15 Visualizations of different termination planes along the [211] direction in an ideal DG unit cell Short description: SCFT calculation for visualizations of different termination planes along the [211] direction in an ideal DG unit cell 20. Filename: Fig. Fig. S16 AFM image and and height profiles of transition zone along different routes in SL-G thin films Short description: AFM image and height profiles of transition zone along different routes in SL-G thin films Additional related data collected that was not included in the current data package: None. Are there multiple versions of the dataset? N -------------------------- METHODOLOGICAL INFORMATION -------------------------- Description of methods used for collection/generation of data: Details of polymer synthesis were provided in paper "Suface Relief Terraces in Double Gyroid-Forming Polystyrene-block-Polylactide Thin Films". Chemical Characterization: Proton nuclear magnetic resonance (1H NMR) spectroscopy in CDCl3 at 22 °C was performed on a Bruker Avance III HD spectrometer operating at 400 MHz, with 1H chemical shifts reported in parts per million (ppm) relative to the residual protiated solvent signal (δ 7.26 ppm). Molecular weight characterization: Absolute molecular weights and molecular weight dispersities (Ð = Mw/Mn) of the PS-OH macroinitiator and PS-PLA-OH were determined by size-exclusion chromatography (SEC). These analyses employed an Agilent Infinity 1260 HPLC running with HPLC grade tetrahydrofuran (THF) at a elution rate of 1 mL/min, which was equipped with three Waters Styragel HR columns (300 mm length, 7.8 mm diameter), a Wyatt DAWN HELEOS-II 18-angle static light scattering (LS) detector, and a Wyatt Optilab T-rEX differential refractive index detector. Absolute molecular weight determination assumed 100% mass recovery in the chromatographic separation. Since LS typically underestimates the value of Ð, we use SEC with a conventional calibration curve constructed using narrow dispersity polystyrene standards (Agilent EasiCal PS Standards). The latter analyses were conducted using a Viscotek GPCMax VE 2001 system running in HPLC grade THF with an eluent flow rate of 1 mL/min, which was equipped with two Agilent Technologies PLGel Mixed-B columns (350 mm x 7.5 mm), a Viscotek VE 3580 refractive index (RI) detector. Both analyses relied on samples prepared with concentrations of 2-4 mg polymer/mL THF. Thermal Analysis: The thermal properties of PS-PLA-OH were characterized by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC measurements were conducted using a Mettler Toledo DSC1 instrument under a nitrogen atmosphere. The temperature ramp rate was set to 10 °C/min, and both the 1st and 2nd heating cycles scanned the temperature from 30 °C to 200 °C. Dynamic TGA measurements were performed on a TA Instruments Q500 under operating with a nitrogen gas flow rate of 100 mL/min and a ramp rate of 10 °C/min. Ellipsometer: DG Thin films thicknesses were measured using an M-2000V ellipsometer (J.A. Woollam Co.) with 370 to 1000 nm (390 wavelengths) at three different incident angles (55°, 65°, 75°). Scanning electron microscopy (SEM): To enhance contrast between the microdomains, the PLA block was in some cases selectively removed by chemical etching of the sample by immersion in 0.1 M NaOH in 50:50 v/v CH3OH/H2O for 10 min. SEM was performed on a Hitachi SU8230 with a detection mode of secondary electron imaging. The working distance was about 4 mm, and the accelerating voltage and beam current were 1.5 kV and 10 mA, respectively. Atomic Force Microscopy (AFM): To enhance contrast between the microdomains, the PLA block was in some cases selectively removed by chemical etching of the sample by immersion in 0.1 M NaOH in 50:50 v/v CH3OH/H2O for 10 min. AFM imaging was conducted using a Bruker Nanoscope V in tapping mode, stabilized in the repulsive regime. AFM Tips (HQ:NSC36/AL BS, force constant = 2 N/m, resonance frequency = 130 kHz) were purchased from MikroMasch USA, and AFM images were analyzed using freely available Gwyddion software for scanning probe microscopy data visualization. Transmission small-angle X-ray scattering (T-SAXS): T-SAXS measurements were performed on a SAXSLAB Ganesha instrument at ambient temperature under vacuum. The instrument was equipped with a Cu K X-ray microsource, two scatterless collimating apertures, and Eiger 1M (Dectris) detector (79.9 mm x 77.2 mm active area) that was calibrated using a silver behenate standard (d = 58.38 Å). Grazing-incidence small-angle X-ray scattering (GISAXS) GISAXS measurements were performed at the 8-ID-E beamline of the Advanced Photon Source (Argonne National Laboratory, IL, USA). GISAXS patterns of unetched SL-G thin films were measured at an incident angle of 0.14°, using a 3600 mm sample-to-detector distance. The 2D GISAXS data were analyzed using GIXSGUI 1.7.3. People involved with sample collection, processing, analysis and/or submission: S.M.Y., J.O., B.R.M., and H.K. collect involved with sample collection, data processing; S.M.Y., J.O., B.R.M., H.K., K.D.D., M.K.M., and C.J.E. involved with data analysis and submission. ---------------------------- Directory Structure ---------------------------- +---Fig. 1 Schematic depiction of SL-G self-assembly. | DG unit cell with different termination planes.PNG | Representative Termination Planes.PNG | Termination planes along the [110] Direction_0.PNG | Termination planes along the [110] Direction_1.PNG | Termination planes along the [110] Direction_2.PNG | Termination planes along the [110] Direction_3.PNG | Termination planes along the [110] Direction_4.PNG | Termination planes along the [110] Direction_5.PNG | Termination planes along the [110] Direction_6.PNG | Termination planes along the [110] Direction_7.PNG | Termination planes along the [110] Direction_8.PNG | Termination planes along the [110] Direction_9.PNG | Termination planes along the [110] Direction_10.PNG | Termination planes along the [211] Direction.PNG | Termination planes along the [211] Direction_0.PNG | Termination planes along the [211] Direction_1.PNG | Termination planes along the [211] Direction_2.PNG | Termination planes along the [211] Direction_3.PNG | Termination planes along the [211] Direction_4.PNG | Termination planes along the [211] Direction_5.PNG | Termination planes along the [211] Direction_6.PNG | Termination planes along the [211] Direction_7.PNG | Termination planes along the [211] Direction_8.PNG | Termination planes along the [211] Direction_9.PNG | Termination planes along the [211] Direction_10.PNG | +---Fig. 2 AFM, SEM, and GISAXS pattern of SL-G thin film with tavg = 165 nm = 7.7d211. | AFM images of an SL-G thin film after thermal annealing with tavg = 165 nm = 7.7d211.GWY | AFM images of an SL-G thin film before thermal annealing with tavg = 165 nm = 7.7d211.GWY | 2D-GISAXS data for terraced polygrain SL-G thin film_matlab.FIG | AFM images of an SL-G thin film after thermal annealing with tavg = 165 nm = 7.7d211.PNG | AFM images of an SL-G thin film before thermal annealing with tavg = 165 nm = 7.7d211.PNG | 2D-GISAXS pattern for terraced polygrain SL-G thin film, wherein the calculated reflected and transmitted peaks are respectively marked with white squares and red circles.TIF | Birds-eye view SEM image (60° tilted) of the etched polygrain SL-G thin film.TIF | Calculated reflected and transmitted peaks based on the lattice constants a = 49.0 nm, b = c = 52.0 nm, α = 93°, β = γ = 94.TIF | Top-view SEM image of a polygrain SL-G thin film after PLA removal by chemical etching.TIF | +---Fig. 3 Surface Relief terraces of SL-G thin films with different thicknesses. | AFM images of SL-G thin films with average thickness tavg = 7.8d211.GWY | AFM images of SL-G thin films with average thickness tavg = 8.3d211.GWY | AFM images of SL-G thin films with average thickness tavg = 8.5d211.GWY | AFM images of SL-G thin films with average thickness tavg = 8.7d211.GWY | AFM images of SL-G thin films with average thickness tavg = 7.8d211.TIF | AFM images of SL-G thin films with average thickness tavg = 8.3d211.TIF | AFM images of SL-G thin films with average thickness tavg = 8.5d211.TIF | AFM images of SL-G thin films with average thickness tavg = 8.7d211.TIF | Height profile of bicontinuous feature.TIF | Height profile of holes.TIF | Height profile of islands.TIF | +---Fig. 4 Terraces and transition zone formed in an SL-G thin film with tavg = 198 nm (9.2d211) after thermal annealing. | Top-view schematic of poly-grain SL-G thin film after thermal annealing identifying the transition zone.PNG | AFM images of terraces and transition zone formed in an SL-G thin film.PNG | SCFT solutions of representative crystallographic planes along the [211] direction.PNG | AFM images of terraces and transition zone formed in an SL-G thin film.GWY | +---Fig. 5 Analysis of terraces and transition zone formed in an SL-G thin film with tavg = 198 nm (9.2d211) after thermal annealing. | AFM image of higher terraces formed in an SL-G thin film.PNG | AFM image enlargement of the area bounded by the blue box.PNG | AFM images of the transition zone bounded by the yellow box.PNG | Height profile of the island and transition zone along the line scan.PNG | Simulation results of the termination planes along [211] direction in DG unit cell.PNG | AFM image of higher terraces formed in an SL-G thin film.GWY | +---Fig. S1 Synthesis of PS-OH and hydroxyl-terminated PS-PLA. | Styrene.cdxml | PS-OH.cdxml | Hydroxyl terminated PS-PLA.cdxml | +---Fig. S2 1H NMR spectrum of PS-OH. | NMR PSOH.xlsx | +---Fig. S3 Endcapping reaction of PS-PLA-OH to produce acetylated PS-PLA (SL-G). | SL-G.cdxml | +---Fig. S4 1H NMR spectra of PS-PLA-OH and SL-G. | NMR_PS-PLA-OH&SL-G.xlsx | +---Fig. S5 SEC-LS chromatograms for PS-OH, PS-PLA-OH, and SL-G. | SEC-LS_PSOH&PS-PLA-OH&SL-G.xlsx | +---Fig. S6 DSC data for PS-PLA-OH and SL-G. | DSC_PS-PLA-OH&SL-G.xlsx | +---Fig. S7 TGA analyses for PS-PLA-OH and SL-G. | TGA_PS-PLA-OH&SL-G.xlsx | +---Fig. S8 DG-forming bulk SL-G. | SEM of bulk SL-G.PNG | TSAXS_unetched bulk SL-G.xlsx | +---Fig. S9 SL-G thin film sample preparation | SL-G thin film sample preparation.PNG | +---Fig. S10 SL-G thin film thickness measurement | SL-G thin film thickness check.spm | Thickness check.xlsx | +---Fig. S11 Etched SL-G thin films annealed at different temperature | Etched SL-G thin films annealed at 150 °C.GWY | Etched SL-G thin films annealed at 160 °C.GWY | Etched SL-G thin films annealed at 170 °C.GWY | Etched SL-G thin films annealed at 180 °C.GWY | +---Fig. S12 2D-GISAXS patterns of SL-G thin films thermally annealed for 1 min at 180 °C (unetched) with different film thickness | GISAXS_SL-G_6.5d211.FIG | GISAXS_SL-G_7.1d211.FIG | GISAXS_SL-G_7.8d211.FIG | GISAXS_SL-G_8.0d211.FIG | GISAXS_SL-G_8.3d211.FIG | GISAXS_SL-G_8.5d211.FIG | GISAXS_SL-G_8.7d211.FIG | GISAXS_SL-G_9.0d211.FIG | +---Fig. S13 Top-view SEM images of etched SL-G thin films with the indicated thicknesses | no terraces_8.0d211.TIF | no terraces_8.0d211_2.TIF | Islands_8.1d211.TIF | Bicontinuous_8.5d211.TIF | Bicontinuous_8.5d211_2.TIF | Bicontinuous_8.5d211_3.TIF | Holes_8.7d211.TIF | Holes_8.7d211_2.TIF | Holes_8.7d211_3.TIF | no terraces_9.0d211.TIF | +---Fig. S14 Optical microscopy (OM) images of thermally annealed SL-G thin films with different thickness | OM_SL-G_7.6d211.TIF | OM_SL-G_7.8d211.TIF | OM_SL-G_8.0d211.TIF | OM_SL-G_8.3d211.TIF | OM_SL-G_8.5d211.TIF | OM_SL-G_8.6d211.TIF | OM_SL-G_8.8d211.TIF | OM_SL-G_9.0d211.TIF | +---Fig. S15 Visualizations of different termination planes along the [211] direction in an ideal DG unit cell | Different termination planes along the [211] direction.TIF | +---Fig. S16 AFM image and and height profiles of transition zone along different routes in SL-G thin films | Gentle and steep slope.xlsx | Etched SL-G thin films annealed at 180 °C.GWY |