Abstract The field of organic electronics thrives on the hope of enabling low‐cost, solution‐processed electronic devices with mechanical, optoelectronic, and chemical properties not available from inorganic semiconductors. A key to the success of these aspirations is the ability to controllably dope organic semiconductors with high spatial resolution. Here, recent progress in molecular doping of organic semiconductors is summarized, with an emphasis on solution‐processed p‐type doped polymeric semiconductors. Highlighted topics include how solution‐processing techniques can control the distribution, diffusion, and density of dopants within the organic semiconductor, and, in turn, affect the electronic properties of the material. Research in these areas has recently intensified, thanks to advances in chemical synthesis, improved understanding of charged states in organic materials, and a focus on relating fabrication techniques to morphology. Significant disorder in these systems, along with complex interactions between doping and film morphology, is often responsible for charge trapping and low doping efficiency. However, the strong coupling between doping, solubility, and morphology can be harnessed to control crystallinity, create doping gradients, and pattern polymers. These breakthroughs suggest a role for molecular doping not only in device function but also in fabrication—applications beyond those directly analogous to inorganic doping.
more »
« less
The Interlayer Method: A Universal Tool for Energy Level Alignment Tuning at Inorganic/Organic Semiconductor Heterojunctions
Abstract The combination of inorganic and organic semiconductors in a heterojunction is considered a promising approach to overcome limitations of each individual material class. However, to date only few examples of improved (opto‐)electronic functionality have been realized with such hybrid heterojunctions. The key to unraveling the full potential offered by inorganic/organic semiconductor heterojunctions is the ability to deliberately control the interfacial electronic energy levels. Here, a universal approach to adjust the offset between the energy levels at inorganic/organic semiconductor interfaces is demonstrated: the interlayer method. A monolayer‐thick interlayer comprising strong electron donor or acceptor molecules is inserted between the two semiconductors and alters the energy level alignment due to charge transfer with the inorganic semiconductor. The general applicability of this method by tuning the energy levels of hydrogenated silicon relative to those of vacuum‐processed films of a molecular semiconductor as well as solution‐processed films of a polymer semiconductor is exemplified, and is shown that the energy level offset can be changed by up to 1.8 eV. This approach can be used to adjust the energy levels at the junction of a desired material pair at will, and thus paves the way for novel functionalities of optoelectronic devices.
more »
« less
- Award ID(s):
- 1807797
- PAR ID:
- 10453689
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 31
- Issue:
- 10
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Efficient electrical doping of organic semiconductors relies on identifying appropriate molecular dopants that are capable of ionizing semiconductor molecules with a high yield, thereby creating mobile charges. We explore the suitability of two different material parameters to predict ion pair formation for different sets of semiconductor–dopant combinations: (i) redox-potentials measured by cyclic voltammetry in solution and (ii) ionization energy (IE)/electron affinity (EA) measured on thin films by ultraviolet/inverse photoelectron spectroscopy. Our study suggests, at least for molecular semiconductors and dopants, that redox-potentials are better suited to identify matching material pairs and their ion pair formation yield than IE/EA values. This is ascribed to the dependence of IE/EA values on molecular orientation and film structure on and above the meso-scale. In contrast, cyclic voltammetry measurements, although performed on solutions rather than on thin films, capture dopant–semiconductor energy levels on the molecular scale, which is more relevant for doping even in the case of solid thin films.more » « less
-
Complex oxides and semiconductors exhibit distinct yet complementary properties owing to their respective ionic and covalent natures. By electrically coupling complex oxides to traditional semiconductors within epitaxial heterostructures, enhanced or novel functionalities beyond those of the constituent materials can potentially be realized. Essential to electrically coupling complex oxides to semiconductors is control of the physical structure of the epitaxially grown oxide, as well as the electronic structure of the interface. Here we discuss how composition of the perovskite A- and B- site cations can be manipulated to control the physical and electronic structure of semiconductor – complex oxide heterostructures. Two prototypical heterostructures, Ba1-xSrxTiO3/Ge and SrZrxTi1-xO3/Ge, will be discussed. In the case of Ba1-xSrxTiO3/Ge, we discuss how strain can be engineered through A-site composition to enable the re-orientable ferroelectric polarization of the former to be coupled to carriers in the semiconductor. In the case of SrZrxTi1-xO3/Ge we discuss how B-site composition can be exploited to control the band offset at the interface. Analogous to heterojunctions between compound semiconducting materials, control of band offsets, i.e. band-gap engineering, provide a pathway to electrically couple complex oxides to semiconductors to realize a host of functionalities.more » « less
-
Abstract Semiconductor heterojunctions are ubiquitous components of modern electronics. Their properties depend crucially on the band alignment at the interface, which may exhibit straddling gap (type-I), staggered gap (type-II) or broken gap (type-III). The distinct characteristics and applications associated with each alignment make it highly desirable to switch between them within a single material. Here we demonstrate an electrically tunable transition between type-I and type-II band alignments in MoSe2/WS2heterobilayers by investigating their luminescence and photocurrent characteristics. In their intrinsic state, these heterobilayers exhibit a type-I band alignment, resulting in the dominant intralayer exciton luminescence from MoSe2. However, the application of a strong interlayer electric field induces a transition to a type-II band alignment, leading to pronounced interlayer exciton luminescence. Furthermore, the formation of the interlayer exciton state traps free carriers at the interface, leading to the suppression of interlayer photocurrent and highly nonlinear photocurrent-voltage characteristics. This breakthrough in electrical band alignment control, interlayer exciton manipulation, and carrier trapping heralds a new era of versatile optical and (opto)electronic devices composed of van der Waals heterostructures.more » « less
-
Abstract Organic doping is widely used for defining the majority charge carriers of organic thin films, tuning the Fermi level, and improving and stabilizing the performance of organic light‐emitting diodes and organic solar cells. However, in contrast to inorganic semiconductors, the doping concentrations commonly used are quite high (in the wt% range). Such high concentrations not only limit the scope of doping in organic field‐effect transistors (OFETs), but also limit the doping process itself resulting in a low doping efficiency. Here, the mechanism of doping at ultralow doping concentrations is studied. Doped C60metal‐oxide‐semiconductor (MOS) junctions are used to study doping at the 100 ppm level. With the help of a small‐signal drift‐diffusion model, it is possible to disentangle effects of traps at the gate dielectric/organic semiconductor interface from effects of doping and to determine the doping efficiency and activation energy of the doping process. Doped C60OFETs with an ultralow operation voltage of 800 mV and an excellent on/off ratio of up to 107are realized. The devices have low subthreshold swing in the range of 80 mV dec−1and a large transconductance of up to 8 mS mm−1.more » « less