Exciton and Excited-State Charge Transfer at 2D van der Waals Interfaces

Combining materials with diverse properties into two‐dimensional (2D) van der Waals heterostructures lies at the heart of electronic, optoelectronic, and photonic applications. Prerequisite is a significant degree of electronic or photonic coupling of the constituents across the heterointerface. Understanding and controlling these interactions is mandatory to achieve the desired functionality. This review focuses on the charge and energy transfer processes and their dynamics in a specific class of van der Waals heterostructures, namely such composed of semiconducting transition metal dichalcogenides and conjugated organic molecules. With the help of prototypical material combinations, the importance of a precise knowledge of the interfacial electronic structure is demonstrated as it governs the excited‐state dynamics. This review aims at providing basic design guidelines to achieve functional 2D organic/inorganic van der Waals heterostructures with final properties that can be designed by careful selection of the organic component.Peer Reviewe

Resonance Energy Transfer from Monolayer WS2 to Organic Dye Molecules: Conversion of Faint Visible-Red into Bright Near-Infrared Luminescence

The synergetic combination of transition metal dichalcogenides (TMDCs) with organic dye molecules in functional heterostructures is promising for various optoelectronic applications. Here resonance energy transfer (RET) from a red‐emitting WS2 monolayer (1L‐WS2) to a layer of near‐infrared (NIR) emitting organic dye molecules is demonstrated. It is found that the total photoluminescence (PL) yield of the heterostructures is up to a factor of eight higher as compared to the PL yield of pristine 1L‐WS2. This is attributed to the efficient conversion of the mostly non‐radiative excitons in 1L‐WS2 into radiative excitons in the dye layer. A type‐I energy level alignment of the 1L‐WS2/dye interface assures the emission of bright PL. From excitation density‐dependent PL experiments, it is concluded that RET prevails against defect‐assisted non‐radiative recombination as well as Auger‐type exciton‐exciton annihilation in 1L‐WS2. The work paves the way for employing organic dye molecules in heterostructures with TMDCs in nanoscale light‐emitting devices with improved efficiency and tunable color.Peer Reviewe

Strong coupling of monolayer WS2 excitons and surface plasmon polaritons in a planar Ag/WS2 hybrid structure

Monolayer (1L) transition metal dichalcogenides (TMDC) are of strong interest in nanophotonics due to their narrow-band intense excitonic transitions persisting up to room temperature. When brought into resonance with surface plasmon polariton (SPP) excitations of a conductive medium opportunities for studying and engineering strong light-matter coupling arise. Here, we consider a most simple geometry, namely a planar stack composed of a thin silver film, an Al2O3 spacer and a monolayer of WS2. We perform total internal reflection ellipsometry which combines spectroscopic ellipsometry with the Kretschmann-Raether-type surface plasmon resonance configuration. The combined amplitude and phase response of the reflected light at varied angle of incidence proves that despite the atomic thinness of 1L-WS2, the strong coupling (SC) regime between A excitons and SPPs propagating in the thin Ag film is reached. The phasor representation of rho corroborates SC as rho undergoes a topology change indicated by the occurrence of a double point at the cross over from the weak to the strong coupling regime. Our findings are validated by both analytical transfer matrix method calculations and numerical Maxwell simulations. The findings open up new perspectives for applications in plasmonic modulators and sensors benefitting from the tunability of the optical properties of 1L-TMDCs by electric fields, electrostatic doping, light and the chemical environment.Comment: 15 pages, 3 figure

Space Charge Transfer in Hybrid Inorganic/Organic Systems

We discuss density functional theory calculations of hybrid inorganic/organic systems (HIOS) that explicitly include the global effects of doping (i.e. position of the Fermi level) and the formation of a space-charge layer. For the example of tetrafluoro-tetracyanoquinodimethane (F4TCNQ) on the ZnO(000$\bar{1}$) surface we show that the adsorption energy and electron transfer depend strongly on the ZnO doping. The associated work function changes are large, for which the formation of space-charge layers is the main driving force. The prominent doping effects are expected to be quite general for charge-transfer interfaces in HIOS and important for device design

Fast Photoresponse from Hybrid Monolayer MoS2/Organic Photodetector

As a direct-bandgap transition semiconductor with high carrier mobility, monolayer (ML) transition metal dichalcogenides (TMDCs) have attracted significant attention as a promising class of material for photodetection. It is reported that these layers exhibit a persistent photoconductance (PPC) effect, which is assigned to long-lasting hole capture by deep traps. Therefore, TMDCs-based photodetectors show a high photoresponse but also a slow response. Herein, intensity-modulated photocurrent spectroscopy (IMPS) with steady-state background illumination is performed to investigate the photoresponse dynamics in a hybrid photodetector based on ML MoS2 covered with an ultrathin layer of phthalocyanine (H2Pc) molecules. The results demonstrate that adding the H2Pc layer speeds up the photoresponse of the neat ML-MoS2 photodetector by almost two orders of magnitude without deteriorating its responsivity. The origin of these improvements is revealed by applying the Hornbeck–Haynes model to the photocarrier dynamics in the IMPS experiment. It is shown that the improved response speed of the hybrid device arises mostly from a faster detrapping of holes in the presence of the H2Pc layer, while the trap densities remain rather unchanged. Meanwhile, the additional absorption of photons in the H2Pc layer contributes to photocarrier generation, resulting in an enlarged responsivity of the hybrid device.Collaborative Research in Engineering, Science and Technology CentrePeer Reviewe

Uncovering the (un-)occupied electronic structure of a buried hybrid interface

The energy level alignment at organic/inorganic (o/i) semiconductor interfaces is crucial for any light-emitting or -harvesting functionality. Essential is the access to both occupied and unoccupied electronic states directly at the interface, which is often deeply buried underneath thick organic films and challenging to characterize. We use several complementary experimental techniques to determine the electronic structure of p -quinquephenyl pyridine (5P-Py) adsorbed on ZnO(1 0   −1 0). The parent anchoring group, pyridine, significantly lowers the work function by up to 2.9 eV and causes an occupied in-gap state (IGS) directly below the Fermi level EF. Adsorption of upright-standing 5P-Py also leads to a strong work function reduction of up to 2.1 eV and to a similar IGS. The latter is then used as an initial state for the transient population of three normally unoccupied molecular levels through optical excitation and, due to its localization right at the o/i interface, provides interfacial sensitivity, even for thick 5P-Py films. We observe two final states above the vacuum level and one bound state at around 2 eV above EF, which we attribute to the 5P-Py LUMO. By the separate study of anchoring group and organic dye combined with the exploitation of the occupied IGS for selective interfacial photoexcitation, this work provides a new pathway for characterizing the electronic structure at buried o/i interfaces.Deutsche Forschungsgemeinschafthttps://doi.org/10.13039/501100001659Peer Reviewe