supplementaryinformationforsinglemoleculedetection.docVIP

Supplementary Information for “Single molecule detection from a large-scale SERS-active Au79Ag21 substrate” Hongwen Liu,1,? Ling Zhang,1,? Xingyou Lang,1 Yoshinori Yamaguchi,2,3 Hiroshi Iwasaki,2,3 Yasushi Inouye,2 Qikun Xue,1,4,* and Mingwei Chen1, 5,* 1WPI-Advanced Institute for Materials Research, Tohoku University, Sendai 980-8577, Japan 2Department of Applied Physics, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan 3PARC, Graduate School of Engineering, Osaka University, Osaka 565-0871, Japan 4Department of Physics, Tsinghua University, Beijing 100084, China 5School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200030, China ?These authors contributed equally to this work. *Correspondence and requests for materials should be addressed to Q.K.X. or M.W.C. (qkxue@mail.tsinghua.edu.ac; or mwchen@wpi-aimr.tohoku.ac.jp) Supplementary Methods Nanoporous films were prepared by dealloying. The chemical composition of the nanoporous films was controlled by the dealloying time. In this study, the optimal dealloying time of 20 seconds was adopted to give rise to a small pore size of ~15 nm and high residual silver of ~21 at. %. The as-prepared wrinkled substrate was put in aqueous solution of the probe molecules for 4 hours, until the substrate surrounding environment is stabilized and the probe molecules uniformly diffused and adsorbed on the wrinkled nanoporous film surface. The sample, which was covered by a film (about 0.2 mm thick) of aqueous solution of molecules1, was dried in air for 1 hour to immobilize the probe molecules on the substrate surface. Molecular distribution uniformity was proved by repeatable Raman mappings in several different regions. Taking the surface fluctuation of wrinkled films (~2.5 μm in depth) into account, we estimate the average surface density of the probe molecules to be ~0.25 per μm2 of the geometric area of the surface for 1×10-12 M solutions. RAMAN-11 features a sing