Interest in organic semiconductors has grown enormously in the last few years, indeed their use in microelectronics is continuously rising up in a large range of fields, spanning from academic to industrial new applications [1]. They provide a large number of interesting properties that have pushed a gradual replacement of classical amorphous silicon-based devices with organic ones [2], as they promise to be the best candidates as drivers of the necessary green and digital transition and become the building blocks in a huge number of future applications.In most devices, particularly in OTFTs, the quality and properties of the interface between semiconductor and dielectric are of fundamental importance for the device electrical characteristics [3-4]. Dinaphtho [2,3-b:2′,3′-f] thieno [3,2-b] thiophene (DNTT)-based OTFTs are among the best-known devices as they provide good performances in terms of charge mobility, good stability as well as easy processing and they are particularly suitable to study deeper the role of insulator/semiconductor interface [5-6]. It has been widely reported that the best performances of the small molecule organic based transistors, in terms of charge mobility as well as stability, are obtained when the molecules align with their long axis almost perpendicular to the growth surface. The DNTT molecules deposited on SiO2, align to form a homogeneous film, which results to be highly crystalline and provides good transport properties. However, in DNTT-based OTFTs different insulator surfaces, above which the active layer is grown, can provide different properties in terms of morphology and surface energy so that the electrical performances of the resulted devices can span in a wide range [7].In this work, we have studied the growth of DNTT semiconductor thin films on two different dielectric materials relating the ordered DNTT thin film structure to the OTFTs' electrical characteristics. OTFTs have been fabricated with Bottom Gate Top Contact (BGTC) configuration using thermal SiO2 or a double layer of SiO2/CytopTM as gate dielectrics. Semiconductor thin films, with thicknesses ranging from 3 nm to 50 nm, were detailed analyzed with high resolution AFM and XRD measurements (Fig. 1a, b, c, d) for different growth conditions to understand the morphologies of the films starting by the very first ordered layers of DNTT semiconductors. Our measurements show that DNTT molecules on SiO2 and Cytop pack into ordered structures placing themselves with their long axis perpendicular to the plane of the substrate (edge-on). However, in the case of DNTT on SiO2, a portion of ordered molecules can lie horizontally on the substrate (face-on). This causes an increase of defective states for the majority carriers in the conductive channel of the transistor, with a consequent reduction of the field-effect mobility (Fig. 1a, b). Numerical simulations were performed to analyze the effects of different semiconductor film morphologies on the electrical characteristics of the OTFTs. We also show that the morphological semiconductor differences lead to better performances for organic phototransistors based on DNTT/Cytop interface [8].[1] C. Wang et al., Chemical reviews 2012, 112 (4), 2208-2267.[2] Y. Bonnassieux et al., Flexible and Printed Electronics 2021, 6 (2), 023001.[3] H. I. Un et al., Advanced Science 2019, 6 (20), 1900375.[4] H. Sirringhaus et al., Advanced materials 2014, 26 (9), 1319-1335.[5] H. Chang et al., Org. Electron., 2015, 22, 86-91.[6] Q. Wang et al., ACS applied materials & interfaces 2018, 10 (26), 22513-22519.[7] M. Geiger et al., Advanced Materials Interfaces 2020, 7 (10), 1902145.[8] S. Calvi, et al., Org. Electron., 2022, 102, 106452. Figure 1
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