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Virtually Bare Nanocrystal Surfaces - Significantly Enhanced Electrical Transport in CuInSe2 and CuIn(1-x)Ga(x)Se2 Thin Films upon Ligand Exchange with Thermally Degradable 1-Ethyl-5-thiotetrazole

We present a facile and safe ligand exchange method for readily synthesized CuInSe2 (CIS) and CuIn(1-x)Ga(x)Se2 (CIGS) nanocrystals (NCs) from oleylamine to 1-ethyl-5-thiotetrazole which preserves the colloidal stability of the chalcopyrite structure. 1-ethyl-5-thiotetrazole as thermally degradable ligand is adapted for the first time for trigonal pyramidal CIS NCs (18 nm), elongated CIS NCs (9 nm) and CIGS NCs (6 nm). The exchanged NC solutions are spin-coated onto Si/SiO2 substrates with predefined gold electrodes to yield ordered NC thin films. These films are thermally annealed at 260 C to completely remove 1-ethyl-5-thiotetrazol leaving virtually bare NC surfaces. We measure the current-voltage characteristics of the NC solids prior to ligand thermolysis in the dark and under illumination and after thermolysis of the ligand in the same manner. The conductivity of trigonal pyramidal CIS NCs increases by four orders of magnitude from 1.4*10E-9 S/cm in the dark to 1.4*10E-5 S/cm for ligand-free illuminated NC films. Elongated CIS NC films show an increase by three orders of magnitude and CIGS NC films exhibit improved conductivity by two orders of magnitude. The degree of conductivity enhancement thereby depends on the NC size accentuating the role of trap-states and internal grain boundaries in ligand-free NC solids for electrical transport. Our approach offers for the first time the possibility to address chalcopyrite materials' electrical properties in a virtually ligand-free state.