The results of studying the electronic states of the conduction band and interface potential barrier during the formation of ultrathin films of thiophene-phenylene co-oligomer CH3-phenylene-thiophene-thiophene-phenylene-CH3 (CH3-PTTP-CH3) on the surface of ZnO and films of biphenyl tetracarboxylic dianhydride (BPDA) on the ZnO surface are presented. A 100 nm thick ZnO layer was prepared by atomic layer deposition (ALD). Organic CH3-PTTP-CH3 films and BPDA films up to 8 nm thick were formed by thermal vacuum deposition. During film deposition, the electronic characteristics of the surface were studied using total current spectroscopy (TCS) in the energy range from 5 eV to 20 eV above EF. In this energy range, the structure of the maxima of the unoccupied electronic states of CH3-PTTP-CH3 and BPDA films was determined. As a result of the CH3-PTTP-CH3 film deposition, a decrease in the work function to 4.0 eV was found, compared with the value of the work function of 4.2 eV measured from the ALD ZnO substrate. This corresponds to the transfer of a negative charge from the СH3-PTTP-CH3 film to the substrate. The charge transfer at the interface between the BPDA film and the ALD ZnO substrate occurs in the opposite direction, since a 4.7 eV increase of the work function was registered during the formation of this interface. The СH3-PTTP-СH3 and BPDA films studied and the layer-by-layer grown ZnO film represent a continuous coating on sufficiently large surface areas of the order of 10 micrometers x 10 micrometers. The roughness of the ZnO surface does not exceed 4 nm, and the surface roughness of CH3-PTTP-CH3 and BPDA films was 10–15 nm.
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