Reducing proximity effects is a key factor for achieving a higher resolution in electron-beam lithography and realizing the mastering of patterned media. The effect of substrate materials on backscattering electrons was investigated by simulation and experiment, and resolution enhancement was demonstrated. In Monte Carlo simulations with 100 keV incident electrons, the intensity of backscattering electrons decreased with decreasing atomic number of substrates. On the other hand, both the density of substrates and the existence of 10 nm thin films had negligible effects on the intensity of backscattering electrons. The measured exposure distributions from line-scanned electron beams supported the results of simulations. The intensity of backscattering electrons was reduced by using a carbon substrate, and circumferentially aligned high-density patterns of 878 Gbit/in.2 were resolved.