polycrystalline and defects/variations in the local order of OSC fi lm create a distribution of ionization energies. [ 1 ] Every molecule/polymer in a fi lm will thus have its own individual ionization potential (IP) and electron affi nity (EA), with the fi lm IP and EA then represented by the smallest/ largest individual IP/EA. The frontier parts of the resulting occupied and unoccupied state distributions forming the energy gap are often modeled as being either Gaussian or exponential, [ 2 ] and the most easily oxidized/reduced states in an OSC fi lm are typically referred to as tail states or gap states. [ 3 ] Due to processing conditions relevant to printed electronics, the fi lms typically are physisorbed on substrates, forming weakly interacting interfaces. The energy level alignment at interfaces [3][4][5][6][7] and over heterolayer stacks [ 8 ] featuring OSC is an intensively studied topic and the integer charge transfer (ICT) model [ 4,5,9 ] was developed to describe the energy level alignment for the particular case of weakly-interacting metal/OSC and OSC/OSC interfaces obtained from physisorbed fi lms. Figure 1 a shows the typical energy level alignment behavior for OSC weakly interacting interfaces that follow the ICT model, where the resulting work function (WF) is either substrate independent (i, iii) or linearly dependent with a slope of ≈1 (ii). The Fermi level pinning is a result of spontaneous charge transfer across the interface when the substrate work function is larger (smaller) than the energy required to oxidize (gained from reducing) a molecule/polymer at an interface forming an integer charge transfer state (due to interaction with the transferred charge/image charge on the substrate). The most easily oxidized (or reduced) molecules/polymers adjacent to the interface are "used up" in this process until enough charge has been transferred across the interface to create a potential step that equilibrates the Fermi level, with the resulting pinning energies being referred to as the E ICT+,− (Figure 1 a). The integer charge transfer state (ICT+,−) energies depend on the inter and intramolecular order, [ 5 ] so that at a given interface, there hence will be a distribution of ICT+ and ICT− energies, see Figure 1 b. The ICT model enables energy level offsets at heterojunctions to be predicted, but the extent of the resulting energy level bending (ELB) region is fi ercely debated with a variety of results ranging from abrupt space charge regions with no ELB extending beyond the fi rst monolayer at an interface, to virtually no potential drop at the interface and ELB regions extending several tens
Energy Level Bending in Ultrathin Polymer Layers Obtained through Langmuir-Shäfer DepositionQinye Bao , Simone Fabiano , Mattias Andersson , Slawomir Braun , Zhengyi Sun , Xavier Crispin , Magnus Berggren , Xianjie Liu , and Mats Fahlman * The semiconductor-electrode interface impacts the function and the performance of (opto)electronic devices. For printed organic electronics the electrode surface...