Green-and-red photoluminescence from Si-Si and Ge-Ge bonded network homopolymers and copolymers

Recently, we found pure green photoluminescence (PL) at 540 nm (2.34 eV) in a vacuum, which is characteristic of a Si-Si bonded network polymer bearing n-butyl groups (organopolysilyne, SNP). SNP was carefully isolated as an orange-yellow solid by avoidance of contact with air and water in the polymer synthesis and PL measurement. This was in contrast with previous reports that SNPs carrying alkyl groups have a blue PL band around 450-480 nm. By applying the modified technique to a soluble Ge-Ge bonded network polymer carrying n-butyl groups (organopolygermyne, GNP), with much care in synthesising the polymer and measuring the PL, we found that GNP reveals a very brilliant red-coloured PL band at 690 nm (1.80 eV) in a vacuum at 77 K. This was in contrast with a previous report that GNP carrying n-hexyl groups has a green PL band at 560 nm (2.21 eV). On the other hand, soluble Si-Ge network copolymers (SGNPs) prepared in a similar way to SNP and GNP syntheses showed green-and-red dual PL bands at 540 nm and 690 nm. Based on analyses with IR, Raman, HR-TEM, XPS, EELS, UV-Vis and PL data, the dual emission was assumed to originate from the coexistence of Si and Ge domains (1-2 nm in diameter), possibly, in the same skeleton of SGNP.