Chemically selective soft X‐ray patterning of polymers

The chemically selective modification of polymer mixtures by monochromated soft X‐rays has been explored using the high‐brightness fine‐focused 50 nm beam of a scanning transmission X‐ray microscope. Four different polymer systems were examined: a polymethylmethacrylate (PMMA) polyacrylonitrile (PAN) bilayer film; a PMMA‐ blend ‐PAN microphase‐separated film; a poly(MMA‐ co ‐AN) copolymer film; and a poly(ethyl cyanoacrylate) homopolymer film. A high level of chemically selective modification was achieved for the PMMA/PAN bilayer; in particular, irradiation at 288.45 eV selectively removed the carbonyl group from PMMA while irradiation at 286.80 eV selectively reduced the nitrile group of PAN, even when these irradiations were carried out at the same ( x , y ) position of the sample. In the last two homogenous polymer systems, similar amounts of damage to the nitrile and carbonyl groups occurred during irradiation at either 286.80 or 288.45 eV. This is attributed to damage transfer between the C[triple‐bond]N and C=O groups mediated by primary electrons, secondary electrons or radical/ionic processes, aided by their close spatial proximity. Although the overall thickness of the bilayer sample at 70 nm is smaller than the lateral line spreading of 100 nm, the interface between the layers appears to effectively block the transport of energy, and hence damage, between the two layers. The origins of the line spreading in homogeneous phases and possible origins of the damage blocking effect of the interface are discussed. To demonstrate chemically selective patterning, high‐resolution multi‐wavelength patterns were created in the PMMA/PAN bilayer system.