Inhomogeneous dynamic nuclear polarization of protons in a lamella-forming diblock copolymer investigated by a small-angle neutron scattering method

By combining two methods of selective doping of paramagnetic species into a microdomain and small-angle neutron scattering (SANS), the spatially inhomo­geneous proton polarization created by dynamic nuclear polarization (DNP) has been precisely evaluated. A lamella-forming diblock copolymer composed of polystyrene (PS) and polyisoprene (PI) block chains (PS-b-PI) was employed, the SANS profile of which clearly shows scattering peaks up to the third order due to interlamellar interference. As a source of electron spin for DNP, 2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPO) was doped into one or other of the microdomains; samples with PS or PI microdomains selectively doped with TEMPO are designated PS^.-b-PI and PS-b-PI^., respectively. The SANS intensity at the first- and third-order peaks is well reproduced by assuming that the proton polarization is homogeneous throughout the sample, but that at the second-order peak cannot be explained by this assumption. This anomaly regarding the second-order peak was successfully explained by a model postulating that proton polarization in a doped microdomain decreases with increasing distance from the interface with a neighbouring doped microdomain. The decrease in proton polarization at the centre of a doped microdomain was estimated to be 0.07 (2) for PS-b-PI^. and 0.05 (1) for PS^.-b-PI, relative to constant proton polarization in a doped microdomain. The inhomogeneous proton polarization results from two competing dynamic processes, i.e. spin diffusion from doped to undoped microdomains, and spin lattice relaxation occurring on the pathway of proton spin diffusion.