Thiocyanate-capped nanocrystal colloids: vibrational reporter of surface chemistry and solution-based route to enhanced coupling in nanocrystal solids.

Autor: Fafarman AT; Department of Electrical and Systems Engineering, University of Pennsylvania, Philadelphia, Pennsylvania 19104, United States., Koh WK, Diroll BT, Kim DK, Ko DK, Oh SJ, Ye X, Doan-Nguyen V, Crump MR, Reifsnyder DC, Murray CB, Kagan CR
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2011 Oct 05; Vol. 133 (39), pp. 15753-61. Date of Electronic Publication: 2011 Sep 09.
DOI: 10.1021/ja206303g
Abstrakt: Ammonium thiocyanate (NH(4)SCN) is introduced to exchange the long, insulating ligands used in colloidal nanocrystal (NC) synthesis. The short, air-stable, environmentally benign thiocyanate ligand electrostatically stabilizes a variety of semiconductor and metallic NCs in polar solvents, allowing solution-based deposition of NCs into thin-film NC solids. NH(4)SCN is also effective in replacing ligands on NCs after their assembly into the solid state. The spectroscopic properties of this ligand provide unprecedented insight into the chemical and electronic nature of the surface of the NCs. Spectra indicate that the thiocyanate binds to metal sites on the NC surface and is sensitive to atom type and NC surface charge. The short, thiocyanate ligand gives rise to significantly enhanced electronic coupling between NCs as evidenced by large bathochromic shifts in the absorption spectra of CdSe and CdTe NC thin films and by conductivities as high as (2 ± 0.7) × 10(3) Ω(-1) cm(-1) for Au NC thin films deposited from solution. NH(4)SCN treatment of PbTe NC films increases the conductivity by 10(13), allowing the first Hall measurements of nonsintered NC solids, with Hall effect mobilities of 2.8 ± 0.7 cm(2)/(V·s). Thiocyanate-capped CdSe NC thin films form photodetectors exhibiting sensitive photoconductivity of 10(-5) Ω(-1) cm(-1) under 30 mW/cm(2) of 488 nm illumination with I(photo)/I(dark) > 10(3) and form n-channel thin-film transistors with electron mobilities of 1.5 ± 0.7 cm(2)/(V·s), a current modulation of >10(6), and a subthreshold swing of 0.73 V/decade.
Databáze: MEDLINE