An addition-crosslinked PDMS sheet (KE541U + C25A/B, HATADA, hardness 40°) was cut into 35 mm × 50 mm pieces, which was used as a silicone rubber specimen. A PDMS sheet with a thickness of 2 mm was mainly used, but a PDMS sheet with a thickness of 0.5 mm was also used for realization at high optical transparency. Commercially available PTFE sheet (NITOFLON®No. 900UL, Nitto Denko; thickness: 0.2 mm) was cut into 45 mm × 70 mm pieces, which was used as a fluoropolymer specimen. The color of PTFE sheet is white and PTFE has no optical transparency due to its high crystallinity. Conversely, the PFA sheet originally has optical transparency as well as PDMS sheet. Therefore, the PFA sheet (AF-0100, DAIKIN INDUSTRIES; thickness: 0.1 mm) was used only when high transparency was required. Copper foil (Cu, 99.9%, CU-113263, Nilaco Corporation; thickness: 0.050 mm) was cut into 30 mm × 25 mm pieces, which was used as a metal foil specimen. A pure copper plate (Cu, 99.96%, CU-113381, Nilaco Corporation; thickness: 0.20 mm) was also cut into 30 mm × 25 mm pieces, which was used as a Cu plate specimen. Stainless steel foil (SUS304, TS200-200-005, IWATA MFG; thickness: 0.05 mm) was cut into 30 mm × 25 mm pieces, which was used as a SUS foil specimen. A stainless steel plate (SUS430, HSO531, Hikari; thickness: 0.5 mm) was also cut into 30 mm × 25 mm pieces, which was used as a SUS plate specimen. A glass slide (S7213, Matsunami Glass Ind.) with 76 mm × 26 mm × 1 mm was used without cutting.
Sample preparation by plasma treatment
Prior to PJ treatment, the PDMS sheets were washed sequentially with acetone (99.5%, Kishida Chemical) and pure water for 1 min each in an ultrasonic bath (US-4R, AS- ONE). The washed PDMS sheets were then dried using an air gun containing N2 gas (99.99%, Iwatani Fine Gas). The washed and dried PDMS sheets were then plasma-treated using open-air-type PJ treatment equipment (Tough Plasma FPE-20, FUJI CORPORATION), but not HAP-treated. The gap between the irradiation hole and the surface of the PDMS sheet was 10 mm; a mixture of N2 gas (99.99%, Iwatani Fine Gas) and air gas (N2/O2 = 79%/21%, Iwatani Fine Gas) was used as a process gas for plasma generation, and the flow rates of N2 and air gases were 29.7 and 0.3 L/min, respectively. The PDMS sheet was placed on a movable stage and fixed using double-sided polyimide tape (10-mm width, No. 4390, 3 M Japan), then the stage was moved at 8 mm/s during PJ treatment. The number of scan operations was only one in this study. To confirm whether the PJ treatment conditions were suitable, two PJ-treated PDMS sheets were prepared under the same PJ treatment conditions; the adhesion strength of the PDMS/PDMS assembly was then measured using a T-peel test. Cohesion failure of the PDMS occurred during the T-peel test, as shown in Supplementary Information Fig. S2(d). It was confirmed that these PJ conditions were suitable for PDMS.
It was previously reported that low-temperature plasma treatment barely improved the adhesion properties of PTFE, whereas HAP treatment significant improved them12,13. On the basis of these reports, the surface of the PTFE sheet was modified via HAP treatment in the present study. The detailed surface treatment procedure for a PTFE sheet using HAP has been previously reported13; hence, it is described only briefly here. Prior to HAP treatment, PTFE sheets as well as PDMS sheets were washed with acetone and pure water using an ultrasonic bath (US-4R, AS- ONE) then dried using an air gun containing N2 gas (99.99%, Iwatani Fine Gas). The washed and dried PTFE sheets were then HAP-treated at 19.1 W/cm2 for 600 s using He gas (99.99%, Iwatani Fine Gas) at atmospheric pressure in a custom-made chamber system (Meisyo Kiko)12,13,14. During HAP treatment, the surface temperature of the PTFE samples was measured with a digital radiation thermometer system (FT-H40K and FT-50A, Keyence); it was confirmed that the maximum surface temperature exceeded 200 °C during HAP treatment at 19.1 W/cm2 for 600 s. To confirm whether the HAP treatment conditions were suitable, an HAP-treated PTFE sheet and unvulcanized NR containing hydrophilic SiO2 powder were prepared; the adhesion strength of the PTFE/NR assembly was then measured using a T-peel test. Cohesion failure of the NR occurred during the T-peel test, as shown in Supplementary Information Fig. S2(e). It was thus confirmed that these HAP conditions were suitable for PTFE14.
A glass slide was used without washing or PJ treatment. Cu foils, Cu plate, SUS foils, and SUS plates as well as PDMS sheets were washed in an ultrasonic bath (US-4R, AS- ONE) then dried using an air gun containing N2 gas (99.99%, Iwatani Fine Gas). The washed and dried Cu foils, Cu plate, SUS foils, and SUS plates were also PJ-treated to clean their surfaces. The gap between the irradiation hole and the surface of the Cu foils, Cu plate, SUS foils, or SUS plates was 10 mm. The stage was moved at 0.8 mm/s during PJ treatment for Cu foils, Cu plate, SUS foils, or SUS plates. The number of scan operations was five for Cu foils, Cu plate, SUS foils, and SUS plates.
Surface chemical composition analysis
XPS measurements were performed using a scanning XPS spectrometer (Quantum-2000, Ulvac-Phi) with a monochromated Al-Kα source. All the XPS spectra were obtained below 5 × 10−6 Pa. The photoelectron take-off angle was 45°, and the X-ray irradiation area was Ø100 μm. Narrow scan XPS spectra of Si2p, C1s, O1s, and F1s were collected at 95–115 eV, 275–300 eV, 525–545 eV, and 680–700 eV, respectively, with a pass energy of 23.50 eV and a step size of 0.05 eV. The cumulative number of measurements was three. During an XPS measurement, the samples were irradiated with a low-speed electron beam and an Ar ion beam to achieve charge neutralization. The obtained XPS spectra of the PDMS samples were referenced to the peak indexed to C–Si–O–Si and/or C–H at 284.6 eV36,37, and the obtained XPS spectra of as-received and HAP-treated PTFE samples were referenced to peaks indexed to –CF2– at 292.5 eV34,35 and 291.8 eV13,38, respectively. The main peak of –CF2– in the C1s-XPS spectra shifted toward lower binding energy for plasma-treated PTFE due to surface charging13,40.
Adhesion strength test for a two-layer assembly
Firstly, the HAP-treated PTFE sample was placed on the PJ-treated PDMS sheets in a mold such that the plasma-treated surfaces faced each other. Secondly, the PTFE/PDMS assembly was compressed without adhesive at 180 °C and 10 MPa for 10 min using a hot-pressing machine (AH-2003, AS-ONE). Thirdly, the PTFE/PDMS assembly was restored to room temperature. Fourthly, the adhesion strength of the PTFE/PDMS assembly was measured using a T-peel test by combining of a digital force gauge (ZP-200N, Imada) and an electric-driven stand (MX-500N, Imada). The T-peel test was conducted at room temperature of 25 ± 5 °C, and the humidity was not controlled. The sweep rate was 60 mm/min. Finally, the average adhesion strength was calculated by dividing the average tensile strength by the width of the PTFE (ca. 10 mm). To verify the reproducibility, three samples were prepared under the same conditions. A PFA/PDMS assembly was also prepared, and its adhesion strength was measured as for the PTFE/PDMS assembly.
Adhesion strength test for a three-layer assembly
The first to third steps for a three-layer assembly were the same as those for a two-layer assembly. Fourthly, a PJ-treated PDMS/PTFE sample was placed on a PJ-treated Cu plate in a mold so that the plasma-treated surfaces faced each other. Fifthly, the PTFE/PDMS/Cu assembly was compressed without adhesive at 180 °C and 5 MPa for 10 min using a hot-pressing machine (AH-2003, AS-ONE). Sixthly, the PTFE/PDMS/Cu assembly was restored to room temperature. Seventhly, the PTFE and PDMS sheet on the Cu plate was cut to a width of 10 mm. Eighthly, the Cu plate was fixed on the electric-driven stand (MX-500N, Imada) using two stainless steel bars, then both the PTFE and PDMS sheets were simultaneously grasped and pulled up when measuring the adhesion strength of the PDMS/Cu interface with a 90° peel test. The 90° peel test was conducted under the same conditions of temperature and humidity as T-peel test. The sweep rate was also 60 mm/min. When the adhesion strength of the PTFE/PDMS interface was measured using a 90° peel test, the Cu plate was fixed on the electric-driven stand using two stainless steel bars, and then only the PTFE sheet was pulled up. The PTFE/PDMS/SUS430 assembly was prepared as for the PTFE/PDMS/Cu assembly. The PFA/PDMS/glass and PTFE/PDMS/glass assemblies were prepared as for the PTFE/PDMS/Cu assembly except for the fifth step, in which the pressure was decreased from 5 to almost 0 MPa (the empty weight of the PFA/PDMS or PTFE/PDMS assembly) because the glass slide was easily broken. The adhesion strengths of PFA/PDMS/glass, PTFE/PDMS/glass, and PTFE/PDMS/SUS430 were measured as for the PTFE/PDMS/Cu assembly. Peeling tests were conducted at least two times for each three-layer assembly to verify the reproducibility.