1：Experimental Design and Method Selection:

The study combines sol–gel chemistry with a diblock copolymer template (PS-b-PEO) to direct nanostructure formation. Slot-die printing is used for large-scale film deposition. The ternary morphology phase diagram is probed by varying weight fractions of 1,4-dioxane, HCl, and TTIP.

2：Sample Selection and Data Sources:

Films are deposited on precleaned silicon (Si) or fluorine-doped tin oxide (FTO)-coated glass substrates. A total of 21 composition points are studied.

3：List of Experimental Equipment and Materials:

Chemicals include PS-b-PEO (Polymer Source Inc.), TTIP (Sigma-Aldrich), 1,4-dioxane, and HCl (Carl Roth). Equipment includes a slot-die coater, microfluidic device (PHD 2000 infuse/withdraw, Harvard Apparatus), field-emission SEM (Zeiss NVision 40), optical microscope (Axiolab A, Carl Zeiss), GISAXS setup at PETRA III (DESY), XRD (Bruker D8 ADVANCE), and TEM (PHILIPS CM200-FEG).

4：Experimental Procedures and Operational Workflow:

PS-b-PEO is dissolved in 1,4-dioxane, filtered, and mixed with TTIP and HCl using a microfluidic device. The solution is printed on substrates at 5 mm/s, dried for 10 min, and calcined at 450–550°C to remove the template and crystallize TiO

5：Film thickness is controlled by optimizing printing parameters. Data Analysis Methods:

Surface morphology is analyzed with SEM and OM. Inner morphology is probed with GISAXS, with data fitted using DWBA, EIA, and LMA models. Crystal phase and crystallinity are characterized with XRD and TEM.