Exploring effects of plasma surface engineering on cellulose nanofilms via broadband THz spectroscopy

• Soft-chemistry plasma approach for surface tuning of cellulose nanofilms. • Cellulose nanofilms preserved bulk microcrystalline properties after plasma thinning. • Broadband THz-TDS reveals many spectral features in the 1.5–14.5 THz range. • Evaluated the CNF thickness requirements for desired THz attenuation. For the extended ultra-wideband THz band up to 10 THz and beyond, materials with different functional properties are required. In addition, the THz shielding devices require the desired thickness for different shielding effects, which can be tailored by the surface functionalities. Here, a plasma-assisted soft chemistry approach was used to tailor the cellulose nanofibrils (CNFs), and the effects of plasma surface treatment were investigated using non-destructive terahertz time-domain spectroscopy (THz-TDS). CNFs with three different thicknesses were investigated as a function of mild and strong plasma treatment. The ultra-broadband THz-TDS evaluation of CNF films overcomes the challenge by surpassing the conventional low-frequency THz-TDS measurements and reveals many characteristic THz features of CNF at 2.1, 3.1, 5.1, 7.0, 10.3 and 10.9 THz. THz-TDS analysis indicates thinning of CNF after plasma treatment due to the plasma etching effect. At the same time, the microcrystalline properties of the CNF samples remain intact even after significant surface modification under plasma carbonisation conditions. Apart from this, the studies proposed the required minimum thickness for THz shielding applications based on the optical parameters and THz properties derived from the plasma-treated CNF structures, which could be used to define the thickness of sustainable shielding materials for THz devices.