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Interplay between vacuum-grown monolayers of alkyl phosphonic acids and the performance of organic transistors based on dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene

Hannah, Stuart and Cardona, Javier and Lamprou, Dimitrios A. and Sutta, Pavol and Baran, Peter and Al Ruzaiqi, Afra and Johnston, Karen and Gleskova, Helena (2016) Interplay between vacuum-grown monolayers of alkyl phosphonic acids and the performance of organic transistors based on dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene. ACS Applied Materials and Interfaces, 8 (38). pp. 25405-25414. ISSN 1944-8244

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Monolayers of six alkyl phosphonic acids ranging from C8 to C18 were prepared by vacuum evaporation and incorporated into low-voltage organic field-effect transistors based on dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT). Similar to solution-assembled monolayers, the molecular order for vacuum deposited monolayers improved with increasing length of the aliphatic tail. At the same time, FTIR measurements suggested lower molecular coverage for longer phosphonic acids. The comparison of FTIR and vibration frequencies calculated by Density Functional Theory indicated that monodentate bonding does not occur for any phosphonic acid. All monolayers exhibited low surface energy of ~17.5 mJ/m2 with a dominating Lifshitz-van der Waals component. Their surface roughness was comparable, while the nanomechanical properties were varied but not correlated to the length of the molecule. However, large improvement in the transistor performance was observed with increasing length of the aliphatic tail. Going from C8 to C18 the mean threshold voltage decreased from ‒1.37 to ‒1.24 V, the field-effect mobility increased from 0.03 to 0.33 cm2/Vs, the off-current decreased from ~ 8×10-13 to ~ 3×10-13 A, and for transistors with L = 30 um the on-current increased from ~ 3×10-8 to ~ 2×10-6 A, and the on/off current ratio increased from ~ 3×104 to ~ 4×106. Similarly, transistors with longer phosphonic acids exhibited much better air and bias-stress stability. The achieved transistor performance opens up a completely ‘dry’ fabrication route for ultra-thin dielectrics and low-voltage organic transistors.