Piotr Matyba

The dynamic organic p-n junction

Static p-n junctions in inorganic semiconductors are exploited in a wide range of todays electronic appliances. Here, we demonstrate the in situ formation of a dynamic p-n junction structure within an organic semiconductor through electrochemistry. Specifically, we use scanning kelvin probe microscopy and optical probing on planar light-emitting electrochemical cells (LECs) with a mixture of a conjugated polymer and an electrolyte connecting two electrodes separated by 120 microm. We find that a significant portion of the potential drop between the electrodes coincides with the location of a thin and distinct light-emission zone positioned >30 microm away from the negative electrode. These results are relevant in the context of a long-standing scientific debate, as they prove that electrochemical doping can take place in LECs. Moreover, a study on the doping formation and dissipation kinetics provides interesting detail regarding the electronic structure and stability of the dynamic organic p-n junction, which may be useful in future dynamic p-n junction-based devices.

A Unifying Model for the Operation of Light-Emitting Electrochemical Cells

The application of doping in semiconductors plays a major role in the high performances achieved to date in inorganic devices. In contrast, doping has yet to make such an impact in organic electronics. One organic device that does make extensive use of doping is the light-emitting electrochemical cell (LEC), where the presence of mobile ions enables dynamic doping, which enhances carrier injection and facilitates relatively large current densities. The mechanism and effects of doping in LECs are, however, still far from being fully understood, as evidenced by the existence of two competing models that seem physically distinct: the electrochemical doping model and the electrodynamic model. Both models are supported by experimental data and numerical modeling. Here, we show that these models are essentially limits of one master model, separated by different rates of carrier injection. For ohmic nonlimited injection, a dynamic p-n junction is formed, which is absent in injection-limited devices. This unification is demonstrated by both numerical calculations and measured surface potentials as well as light emission and doping profiles in operational devices. An analytical analysis yields an upper limit for the ratio of drift and diffusion currents, having major consequences on the maximum current density through this type of device.

Flexible and Metal-Free Light-Emitting Electrochemical Cells Based on Graphene and PEDOT-PSS as the Electrode Materials

We report flexible and metal-free light-emitting electrochemical cells (LECs) using exclusively solution-processed organic materials and illustrate interesting design opportunities offered by such conformable devices with transparent electrodes. Flexible LEC devices based on chemically derived graphene (CDG) as the cathode and poly(3,4-ethylenedioxythiophene) mixed with poly(styrenesulfonate) as the anode exhibit a low turn-on voltage for yellow light emission (V = 2.8 V) and a good efficiency 2.4 (4.0) cd/A at a brightness of 100 (50) cd/m(2). We also find that CDG is electrochemically inert over a wide potential range (+1.2 to -2.8 V vs ferrocene/ferrocenium) and exploit this property to demonstrate planar LEC devices with CDG as both the anode and the cathode.

Separating Ion and Electron Transport: The Bilayer Light-Emitting Electrochemical Cell

The current generation of polymer light-emitting electrochemical cells (LECs) suffers from insufficient stability during operation. One identified culprit is the active material, which comprises an intimate blend between an ion-conducting electrolyte and an electron-transporting conjugated polymer, as it tends to undergo phase separation during long-term operation and the intimate contact between the ion- and electron-transporting components provokes side reactions. To address these stability issues, we present here a bilayer LEC structure in which the electrolyte is spatially separated from the conjugated polymer. We demonstrate that employing this novel device structure, with its clearly separated ion- and electron-transport paths, leads to distinctly improved LEC performance in the form of decreased turn-on time and improved light emission. We also point out that it will allow for the utilization of combinations of active materials having mutually incompatible solubilities.

Speedup of doping fronts in organic semiconductors through plasma instability

The electrochemical doping transformation in organic semiconductor devices is studied in application to light-emitting cells. It is shown that the device performance can be significantly improved by utilizing new fundamental properties of the doping process. We obtain an instability, which distorts the doping fronts and increases the doping rate considerably. We explain the physical mechanism of the instability, develop theory, provide experimental evidence, and perform numerical simulations. We further show how improved device design can amplify the instability thus leading to a much faster doping process and device kinetics.

Facile fabrication of efficient organic CMOS circuits

Organic electronic circuits based on a combination of n- and p-type transistors (so-called CMOS circuits) are attractive, since they promise the realization of a manifold of versatile and low-cost electronic devices. Here, we report a novel photoinduced transformation method, which allows for a particularly straightforward fabrication of highly functional organic CMOS circuits. A solution-deposited single-layer film, comprising a mixture of the n-type semiconductor [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) and the p-type semiconductor poly-3-hexylthiophene (P3HT) in a 3:1 mass ratio, was utilized as the common active material in an array of transistors. Selected film areas were exposed to laser light, with the result that the irradiated PCBM monomers were photochemically transformed into a low-solubility and high-mobility dimeric state. Thereafter, the entire film was developed via immersion into a developer solution, which selectively removed the nonexposed, and monomeric, PCBM component. The end result was that the transistors in the exposed film areas are n-type, as dimeric PCBM is the majority component in the active material, while the transistors in the nonexposed film areas are p-type, as P3HT is the sole remaining material. We demonstrate the merit of the method by utilizing the resulting combination of n-type and p-type transistors for the realization of CMOS inverters with a high gain of approximately 35.

Distinguishing attosecond electron–electron scattering and screening in transition metals

Significance Electron–electron interactions are among the fastest processes in materials that determine their fascinating properties, occurring on attosecond timescales on up (1 as = 10−18 s). The recent development of attosecond angle-resolved photoemission spectroscopy (atto-ARPES) using high harmonic generation has opened up the possibility of probing electron–electron interactions in real time. In this paper, we distinguish electron–electron screening and charge scattering in the time domain in individual energy bands within a solid. These results open up new possibilities for probing fundamental electron–electron interactions in a host of materials including magnetic, superconducting, and advanced quantum materials. Electron–electron interactions are the fastest processes in materials, occurring on femtosecond to attosecond timescales, depending on the electronic band structure of the material and the excitation energy. Such interactions can play a dominant role in light-induced processes such as nano-enhanced plasmonics and catalysis, light harvesting, or phase transitions. However, to date it has not been possible to experimentally distinguish fundamental electron interactions such as scattering and screening. Here, we use sequences of attosecond pulses to directly measure electron–electron interactions in different bands of different materials with both simple and complex Fermi surfaces. By extracting the time delays associated with photoemission we show that the lifetime of photoelectrons from the d band of Cu are longer by ∼100 as compared with those from the same band of Ni. We attribute this to the enhanced electron–electron scattering in the unfilled d band of Ni. Using theoretical modeling, we can extract the contributions of electron–electron scattering and screening in different bands of different materials with both simple and complex Fermi surfaces. Our results also show that screening influences high-energy photoelectrons (≈20 eV) significantly less than low-energy photoelectrons. As a result, high-energy photoelectrons can serve as a direct probe of spin-dependent electron–electron scattering by neglecting screening. This can then be applied to quantifying the contribution of electron interactions and screening to low-energy excitations near the Fermi level. The information derived here provides valuable and unique information for a host of quantum materials.

Model of the electrochemical conversion of an undoped organic semiconductor film to a doped conductor film

We develop a model describing the electrochemical conversion of an organic semiconductor (specifically, the active material in a light-emitting electrochemical cell) from the undoped nonconducting ...

3D Characterization of Attosecond Pulse Trains with Circular Polarization

Using laser-dressed photoelectron spectroscopy from solids, we fully characterize circularly polarized harmonics for the first time to reconstruct the complex 3D waveform of a circularly polarized attosecond pulse train.