Fabrication of Nanogroove Arrays on Acrylic Film Using Micro-Embossing Technique
Abstract
:1. Introduction
2. Materials and Methods
2.1. Polymethyl Methacrylate (PMMA) Film
2.2. Fabrication of a Master Mold with Nanostructure Patterns
- (i)
- Silicon wafer was cleaned to remove the surface contamination. Silicon wafer was cleaned with 150 mL of boiled sulfuric acid at 100 °C, 150 mL of hydrogen peroxide as a catalyst. Then, silicon wafer was washed with reverse osmosis water (RO water) to remove sulfuric acid and hydrogen peroxide. However, silicon wafer was immersed in nitric acid to treat the surface of the oxide layer. Then, wafer was dried with nitrogen gas and dehydrated in an oven at 150 °C for about 4 h. Furthermore, silicon wafer was cleaned using plasma with oxygen gas at 300 watts for 20 min, resulting in the growth of a thin layer of silicon dioxide (SiO2) on the surface. Furthermore, organic compound on silicon wafer was removed;
- (ii)
- The polymethyl methacrylate, PMMA 950K-A2 (2% PMMA molecular weight of 950,000 g·mol−1) was diluted in anisole. Anisole was used as a solvent for PMMA due to its ability to dissolve the polymer effectively. The dilution ratio was 1:1. Then, PMMA–anisole solution was coated on silicon wafer via spinning process. On the first layer, PMMA was spin-coated onto the surface of silicon wafer at 500 rpm for 10 s. Then, the second layer was operated at 1500 rpm for 40 s to increase the thickness of PMMA. The spun wafer was heated at 180 °C with heating time around 5 min to achieve the 80 nm thickness of photoresist film;
- (iii)
- In order to be exposed to the electron beam lithography process, the TESCAN MIRA3 machine was utilized. The silicon wafer was put inside the chamber and the pressure was reduced zero. The beam current was about 0.216 nA, and the exposure dose at 400 μC/cm3. The micro-grooves pattern was fabricated onto the surface of PMMA on silicon wafer. The distance between peak to peak of nanogroove arrays was about 500 nm, around 2.5 × 2.5 cm2. The exposed photoresistance experienced chemical changes by the electron beam, achieving polymer scission and breaking the polymer chain;
- (iv)
- The specimen was developed in methyl isobutyl ketone:isopropyl alcohol solution (MIBK:IPA, 3:1) for 50 s. An exposed polymer chain was washed up. A masking layer was prepared on the specimen for etching in the following process;
- (v)
- Buffered oxide etch (BOE) process was used to remove SiO2. BOE is a very selective etch that stops at the silicon and does not etch further. In this process, 400 g of ammonium fluoride (NH3F) with 600 mL of DI water (DIH2O) was mixed. Then, ammonium fluoride solution was mixed with hydrofluoric acid (HF) in a 6:1 ratio. The solution was utilized to remove an oxide layer on a master mold. Silicon wafer master mold was immersed in the solution for 140 s. A result shows that the unmasked oxide layer is exposed as nanogroove arrays are apparent on silicon wafer master mold.
- (vi)
- The wet chemical etching process by potassium hydroxide (KOH) etching was used to create cavities as nanogroove arrays on silicon wafer. A solution of potassium hydroxide at 40% concentration was prepared and heated to 60 °C. Silicon wafer was immersed into a solution for 10 min to remove a resistant out-of-surface silicon wafer. Finally, a master mold was washed up with hydrochloric acid to adjust the pH value.
2.3. Micro-Embossing Process
- (i)
- The set-up for experiment testing was prepared. The size of the upper and lower square quartz glass substrates was 1.2 mm × 20 mm × 20 mm. The lower quartz glass substrate was inserted below a master mold. An acrylic film was placed upon a master mold. The size of the acrylic film was 20 × 20 mm2, and the thickness was 100 and 188 µm. Another quartz glass substrate was placed upon an acrylic film to prevent stress concentration at the upper cylinder that caused the breakage of the master mold;
- (ii)
- In the heating stage, the set-up of an acrylic film and master mold was placed in the micro-embossing machine. They were heated from room temperature (RT) to 100 °C and 150 °C. The heating time was about 4 min;
- (iii)
- In the embossing stage, a pressing load was applied by pressing the upper cylinder down on the quartz glass substrate. The weight of the upper heating plate and the mobile plate was about 10 kg. The embossing pressure was 0.1569 MPa onto the set-up of an acrylic film and master mold. The glass transition temperature (Tg) of the Acryplen film was 90 °C. The micro-embossing process was carried out above an Acryplen’s glass transition temperature at 100 °C and 150 °C, as shown in Figure 4. Then, the embossing time was kept for 2 min. The flow behavior of acrylic film can be enhanced by changing temperature and pressure. The upper cylinder was manually hiked, and the specimen was taken out of the micro-embossing machine;
- (iv)
- In the demolding stage, the specimen was turned out of the micro-embossing machine and cooled down at room temperature for 4 min. The unwinding process for an acrylic film at room temperature allows easy film removal and prevents master mold breakage. Then, an embossed acrylic film was peeled by using tweezers. Thus, an acrylic film with nanostructure was successfully fabricated. In addition, the total cycle time of the micro-embossing process was about 10 min. Finally, the protuberances of micropattern arrays on a stamped acrylic film were analyzed by atomic force microscope.
3. Results
3.1. Nanostructure on a Master Mold
3.2. Fabrication Quality of the Micro-Embossing Process of the Acrylic Film with Nanostructures
4. Discussion
5. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Properties | Methods | Unit |
---|---|---|
Total transmittance | JIS K7361-1 [38] | 92.6% |
haze | JIS K7136 [39] | 0.9% |
Heat shrinkage | MCC Internal (100 °C, 10 min) | MD = 11.4% TD = −1.1% |
Tg (DSC) | MCC Internal | 90 °C |
Tensile strength | JIS K7127 [40] | MD = 34 MPa TD = 33 MPa |
Elongation | JIS K7127 [40] | MD = 138% TD = 136% |
Chemical resistance | Acid (0.1 N H2SO4) | Stable |
Chemical resistance | Alkali (0.1 N NaOH) | Stable |
Chemical resistance | Petroleum chemical (acetone, ethyl acetate) | Dissolved |
Chemical resistance | Petroleum chemicals (methanol) | Liquid mark |
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Raksiri, C.; Potejanasak, P.; Dokyor, T. Fabrication of Nanogroove Arrays on Acrylic Film Using Micro-Embossing Technique. Polymers 2023, 15, 3804. https://doi.org/10.3390/polym15183804
Raksiri C, Potejanasak P, Dokyor T. Fabrication of Nanogroove Arrays on Acrylic Film Using Micro-Embossing Technique. Polymers. 2023; 15(18):3804. https://doi.org/10.3390/polym15183804
Chicago/Turabian StyleRaksiri, Chana, Potejana Potejanasak, and Thitipoom Dokyor. 2023. "Fabrication of Nanogroove Arrays on Acrylic Film Using Micro-Embossing Technique" Polymers 15, no. 18: 3804. https://doi.org/10.3390/polym15183804
APA StyleRaksiri, C., Potejanasak, P., & Dokyor, T. (2023). Fabrication of Nanogroove Arrays on Acrylic Film Using Micro-Embossing Technique. Polymers, 15(18), 3804. https://doi.org/10.3390/polym15183804