We investigate α-(AlxGa1-x)2O3 layers deposited by PLD for 0≤x≤1 on a- and m-plane sapphire. RSM measurements reveal a fundamental difference for these planes. Pseudomorphic α-(AlxGa1-x)2O3 on m-plane sapphire shows a shear strain e'5 along the c-axis vanishing on a-plane sapphire. Similarly, only relaxed m-plane α-(AlxGa1-x)2O3 exhibits a global lattice tilt in c-axis direction. Modeling of lattice constants and e'5 as function of x prove the shear strain to be due to the non-vanishing C14 component of the stress-strain tensor for α-(AlxGa1-x)2O3 contributing only for the m-plane. We further explain the occurrence of the lattice tilt and identify possible relaxation mechanisms.
Combination of monolayer (ML) transition metal dichalcogenides (TMDC) with molecular layers with strong light matter coupling can enhance, control, and spectrally tune the absorption and emission of such heterostructures. Essential is hereby the energy level alignment at the heterointerface that governs the transfer of electronic excitations. At interfaces with a staggered type-II energy level alignment fast excited-state charge transfer has been utilized to enhance and spectrally expand the photoresponse of MoS2-based hybrid photodetectors. At interfaces with a straddling type-I energy level alignment, transfer of excitons on a sub-picosecond time scale results in an enhanced PL yield from ML-MoS2 in the heterostructure and an according overall modulation of the photo-response.
Polyethylenimine (PEI) layers are used as cathode interlayer to reduce the work function of electrode materials and are frequently applied to organic or perovskite opto-electronic devices. PEI was applied from solution on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate mixture, zinc oxide and graphite. Choice of solvent and residual solvent removal ensure the superior functionality. [1] Furthermore, a single-step formation of a low work function cathode interlayer and n‑type bulk doping from semiconducting polymer/PEI blend solution was observed. [2]
[1] S. Bontapalle et al., Adv. Mater. Interface 7 (2020) 2000291.
[2] K. Seidel et al., ACS Appl. Mater. Interfaces 12 (2020) 28801.
Molecular electrical doping is of central technological relevance for organic (opto-) electronics since it allows control of charge carrier density and Fermi level position in organic semiconductors (OSCs). Here, we chose to investigate the doping capability of the n-dopant 1,2,3,4,1′,2′,3′,4′-octaphenylrhodocene (OPR). Using the bulky, strongly reducing metallocene to dope the electron-transport polymer poly{[N,N-bis(2-octyldodecyl)naphthalene-1,4,5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5’-(2,2’-bithiophene)} [P(NDI2OD-T2)] leads to an increased bulk conductivity and decreased contact resistance. While the former is due to low-level n-doping of the polymer, trap filling and concomitant charge carrier mobility increase, the latter is caused by an accumulation of OPR at an indium tin oxide (ITO) substrate.
Stephen Barlow, Michael Fusella, Samik Jhulki, Antoine Kahn, Norbert Koch, Elena Longhi, Kyung Min Lee, Xin Lin, Seth Marder, Karttikay Moudgil, Barry Rand, Chad Risko, Berthold Wegner, Fengyu Zhang
Electrical doping of organic semiconductors increases conductivity and reduces injection barriers from electrode materials, both of which effects can improve the performance of organic light-emitting diodes (OLEDs). However, the low electron affinities of typical OLED electron-transport materials make the identification of suitable n-dopants particularly challenging; electropositive metals such as the alkali metals are not easily handled and form monoatomic ions that are rather mobile in host materials, whereas molecular dopants that operate as simple one-electron reductants must have low ionization energies, which leads to severe air sensitivity. This presentation will discuss approaches to circumventing this issue by coupling electron transfer to other chemical reactivity. In particular, dimers formed by certain highly reducing organometallic sandwich compounds and organic radicals can be handled in air, yet have effective reducing potentials, corresponding to formation of the corresponding monomeric cations and contribution of two electrons to the semiconductor, of ca. –2.0 V vs. ferrocene. These values fall a little short of what is required for typical OLED materials; approaches to further extending the doping reach of these dimers will be described. One such approach involving photoirradiation of a dimer:semiconductor blend leads to metastable doping of a material with a redox potential of –2.24 V, which allows the fabrication of efficient OLEDs in which even high-workfunction electrodes, such as indium tin oxide, can be used as electron-injection contacts.
The electronic structure of interfaces comprising electronic materials governs fundamental charge and energy transfer processes, and thus the functionality and efficiency of electronic and optoelectronic devices featuring these interfaces. Mixed cation and halide perovskites are considered prime materials for photovoltaics. Yet, the fundamental understanding of their electronic structure and the energy level alignment with charge transport layers is limited. As is discussed in this contribution, perovskite surface states and concomitant surface photovoltage effects can mask the ground state electronic properties in photoemission experiments, and only low photon dose procedures allow unraveling reliable interface energetics of relevance for devices. Two-dimensional (2D) transition metal dichalcogenides (TMD) semiconductors also emerge as highly interesting electronic materials. They feature direct energy gaps in monolayer form, and their pronounced excitonic nature offers the possibility of fine-tuning electronic and optical properties by engineering the dielectric environment. As exemplified here, the exciton binding energy of MoS2 and WSe2 can vary by a factor of two, depending on the substrate’s dielectric constant. Furthermore, charge transfer interactions with molecular electron donors and acceptors facilitate doping of TMDs. The mechanism of this type of interface doping is contrasted with that of conventional semiconductor (GaN, Si) surfaces. For the latter case, it is demonstrated how molecular donors and acceptors can be employed to tune the level alignment at inorganic/organic semiconductor heterojunctions over extreme intervals.
ZnO is attracting significant interest as a candidate for hybrid photovoltaic and light-emitting devices. We studied electronic coupling at interfaces of ZnO with conjugated organic molecules like ladder-type oligo(phenylenes) (LOP) and NTCDA whose fundamental optical excitations are resonant to the ZnO band gap as well as with polymers employing a combination of time-resolved techniques as well as in situ differential reflectance and photoemission spectroscopy.
Our studies provide evidence for the formation of hybrid charge transfer excitations (HCTE) across (Zn,Mg)O/organic interfaces. We show that by interfacial design the properties of these HCTE can be tuned and by that the charge separation process. The impact of the HCTE on photovoltaic parameters like the open circuit voltage and short circuit current is exemplarily demonstrated in (Zn,Mg)O/P3HT diodes.
Furthermore, we show that by proper alignment of the frontier molecular orbitals with the semiconductor valence and conduction band edges, exciton dissociation at the interface can be switched off while exciton transfer efficiencies of up to 80 % are maintained. Thus, efficient conversion of ZnO excitons into highly emissive excitons of the organic (LOP) layer is achieved which is essential for the realization of hybrid light-emitting diodes.
In this work we investigate the mechanisms responsible for the energy level alignment at inorganic and organic semiconductors interfaces with photoelectron spectroscopy. We focus on the different contributions that lead to a substantial work function increase (up to 2.5 eV) when depositing thin layers of organic acceptor molecules [1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile (HATCN) and 2,2'-(perfluoronaphthalene-2,6- diylidene)dimalononitrile (F6-TCNNQ)] on two different inorganic semiconductors (ZnO and GaN). We discuss models to describe this work function increase, which take into account the role of bulk donor concentration of the inorganic semiconductors, their surface state density, and the distance between the inorganic semiconductor and the adsorbed molecules, and we emphasize the importance of surface states on the inorganic semiconductor. The absence of any adsorption-induced core level features for F6-TCNNQ indicates fractional charge transfer, in contrast to HATCN, where additional core level features indicate integer charge transfer. Finally, we demonstrate the utility of this interlayer approach by changing the energy level alignment between the showcase hybrid system ZnO/Sp6
Controlling the energy level alignment at the ubiquitous interfaces in modern organic light emitting diodes, i.e., organic/electrode and organic/organic, is mandatory for achieving highest performance. While for some interfaces the understanding has matured over the past years – often with the help of photoelectron spectroscopy investigations, a lack of material-overarching and general models seems to persist. In this context, it is interesting to note that photoelectron experiments reported by different groups often returned a different level alignment for a given interface, which certainly should be unsettling for device engineers. It turns out that Fermi-level pinning and its consequences for charge density re-distribution across a device stack is an overarching mechanism that should always be considered. For intrinsic organic heterojunctions of materials with moderate acceptor/donor character the electrostatic potential across the interface changes only marginally – if at all. This situation, however, can be significantly altered when at least one of the two semiconductors is Fermi-level pinned by the "effective work function" of the other one, which is established by the contact to the electrode. Consequently, device engineering has to fully take into account the effect of adding the electrodes to a device stack, otherwise correlations between assumed electronic structure and device performance remain uncertain.
Innovative hybrid inorganic/organic structures (HIOS) should implement exciton creation by electrical injection in inorganic semiconductors followed by resonant energy transfer and light emission from the organic semiconductor. An inherent obstacle of such designs is the typically unfavorable energy level alignment at HIOS interfaces, which assists in exciton separation thus quenching light emission. Here, we introduce a technologically relevant method to optimize the hybrid structure's energy levels: ZnO and a tailored ladder-type oligophenylene. Using an organometallic donor interlayer the ZnO work function is substantially lowered eliminating the ZnO - L4P-sp3 interfacial energy level offsets enhancing the hybrid structure's radiative emission yield sevenfold.
The increasing interest in non-volatile memory devices has extended the exploration towards new materials, such as organic-inorganic hybrids. Devices based on organic semiconductors and embedded metal nanoparticles (MNPs) were found to display resistive bistability, suitable for programmable electronic applications. Different models were developed to explain the resistive switching mechanism occurring in the devices. Charging/ de-charging of MNPs and concomitant resistivity changes was mainly proposed as mechanism, despite the lack of solid experimental evidence.[ ] In this contribution we report on the role of the space-charge field due to charged MNPs in two-terminal devices, via electrical characterization. Devices comprise 4,4-bis[N-(1-naphthyl)-N-phenyl-amino]diphenyl (α-NPD) with embedded gold nanoparticles (AuNPs). The electrical characterization (current vs bias) of the devices was conducted with and without illumination during operation. Due to the energy level alignment of the chosen materials, the AuNPs behave as deep charge carrier traps. The induced space-charge spontaneously sets the device to the low conductivity state. The de-charging of the AuNPs can then be dynamically induced through illumination, setting the device to a high conductivity state.
Despite the ability to optically control the charging state of the AuNPs, the devices do not display any bistability. This finding provides evidence that the commonly proposed MNPs charging/de-charging mechanism can be excluded as the cause for electrical bistability in two-terminal devices, and that other mechanisms, such as filament formation, should be evoked.
Herein we report on the fabrication and the properties of two highly efficient blue light emitting multilayer polymer light emitting diodes (PLEDs). The first device structure combines a thermally stabilized polymer with a material processed from an orthogonal solvent, allowing for the fabrication of a triple layer structure from solution. The well known poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine) (TFB), which can be stabilized in a bake-out procedure, was used as a hole transporting layer. A novel pyrene – triphenylamine (PPyrTPA) copolymer was used as emissive layer. The stack was finalized by a poly(fluorene) - derivative with polar side-chains, therefore being soluble in a polar solvent which allows for the deposition onto PPyrTPA without redissolving. The resulting PLED showed bright-blue electroluminescence (CIE1931 coordinates x=0.163; y=0.216) with a high efficiency of 1.42 cd/A and a peak luminescence of 16500 cd/m². The second presented device configuration comprises a thermally stabilized indenofluorene – triphenylamine copolymer acting as hole transporter, and an emissive copolymer with building blocks specifically designed for blue light emission, effective charge carrier injection and transport as well as for exciton generation. This multilayer PLED led to deep-blue emission (CIE1931 x=0.144; y=0.129) with a remarkably high device efficiency of 9.7 cd/A. Additionally, atomic force microscopy was carried out to investigate the film morphology of the components of the stack and x-ray photoemission spectroscopy was performed to ensure a full coverage of the materials on top of each other. Ultraviolet photoemission spectroscopy confirmed the desired type-II band level offsets on the individual interfaces.
G. Schwabegger, F. Quochi, G. Hernandez-Sosa, T. Djuric, G. Bongiovanni, A. Vollmer, M. Oehzelt, I. Salzmann, R. Resel, N. Koch, H. Sitter, C. Simbrunner
To preserve the morphological properties of para-hexaphenyl (p-6P) based nano- bers and simultaneously tune their emission wavelength, periodic organic-organic hetero-epitaxy was utilized. Multilayer structures of p-6P and -sexithiophene (6T) have been prepared by hot wall epitaxy and analyzed by scanning force microscopy, uorescence microscopy, X-ray di raction and time resolved spectroscopy. We demonstrate that organic heteroepitaxy can be applied to produce multilayered nano- bers with high crystallinity, well de ned epitaxial relationships along di erent material phases, molecular azimuthal order, and long-range morphological homogeneity. It is shown, that it is possible to precisely control and tune the highly polarized photoluminescence emission of the nano- bers from the blue to the green and orange spectral regime by a variation of the 6T concentration. Remarkably, it is possible to prepare nano- bers emitting white polarized light.
One approach to increase the overall performance of organic light emitting devices is to separate the light-emitting volume from the ones which are assigned to charge injection or transport. We realized such polymer hetero-layer structures by combination of hole transporting materials like polyparaphenylenevinylene (PPV) with new electron transporting materials, i.e. heterocyclic polymers and heterocyclic low molecular compounds, especially phenyl quinoxalines (PQs). The electronic properties of these heterocyclic compounds have been investigated by various methods including ultraviolet photoelectron spectroscopy. PQs show electron affinities near 3.5 eV and ionization potentials below 6 eV. Measurements of thermally stimulated depolarization currents (TSDC) were carried out in order to study both dipolar relaxation and charge transport processes in single layer devices. The TSDC spectra revealed the prominence of both dipolar relaxation and of charge transport processes. The dipolar processes show activation energies between 0.4 eV and 1 eV which are typical values for small relaxing entities like polymer side groups. Current-voltage and current-luminance characteristics were used to study the prepared heterolayer devices. Double layers made of PPV and polyphenylquinoxaline (PPQ) are characterized by low onset voltages near 2 V and high luminous efficiency of more than 0.8 cd/A. The experimental findings show that PPQs are promising materials in the field of organic electroluminescence.
Efficiency of organic light emitting devices can be increased by separating the zones of exciton recombination from the electrodes by the insertion of additional organic layers which act as protecting - and as hole or electron blocking layers. We realized such polymer hetero-layer structures by combination of hole transporting and emitting materials like polyparaphenylenevinylene (PPV) or its derivatives with new electron transporting materials, i.e. heterocyclic polymers and heterocyclic low molecular compounds, especially phenyl quinoxalines. Current-voltage molecular compounds, especially phenyl quinoxalines. Current-voltage and current-luminance characteristics were used to study the prepared heterolayer devices. Optical spectroscopy as well as UV photoelectron spectroscopy were used to characterize the electronic structure of the individual materials. Quantum chemical calculations completed the spectroscopic studies and supported the interpretation of experimental findings. Double layers made of PPV and polyphenylquinoxaline (PPQ) are characterized by low onset voltages of about 2.2 V, high efficiency, and high brightness reaching values of more than 2000 cd/m2 at a driving voltage of 10 V. The experimental findings show that PPQs are promising materials for organic electroluminescence applications.
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