Three silane derivatives including dodecyltrichlorosilane (DDTS), phenyltriethoxysilane (PTES) and 3-aminopropyl-methyl-diethoxysilane (APMDS) were used to modify the indium tin oxide (ITO) surfaces. The effects of various terminal groups of the self-assembled monolayers (SAMs) on the growth behavior and interfacial morphologies of N,N'-di(naphthalene-1-yl)-N.N'-diphenylbenzidine (NPB) film deposited on the SAM-modified ITO were studied, as well as their effects on the performance of organic light-emitting diodes (OLED) devices. The results show that the growth behavior of NPB film over-deposited on the SAM-modified ITO is mainly determined by the wettability of the surface. The covering ability and thermal stability of NPB film on the SAM-modified ITO decrease in the order: bare ITO > ITO/PTES > ITO/APMDS > ITO/ DDTS. However, the covering characteristic of NPB films on these substrates did not show direct relation to the transport of carriers across the anode/NPB interface as evaluated from the cyclic voltammogram and OLED performance. The turn-on voltages for these SMA-modified OLED devices increase in the order: ITO/PTES < ITO/DDTS: bare ITO < ITO/APMDS. The enhancing effect of PTES on the hole injection is ascribed to the similar structure of PTES to NPB. On the contrary, the inhibition effect of APMDS is caused from the interaction of the lone-pair electrons of amine group to the transport carriers. Since these devices are known to be hole dominant, the luminance efficiency increase in a similar order as that for the turn-on voltage: ITO/PTES < ITO/DDTS < bare ITO < ITO/APMDS. (c) 2006 Elsevier B.V. All rights reserved.