Organic Heterostructures Research Articles

Interface energetics and engineering of organic heterostructures in organic photovoltaic cells

The reliable information about interface energetics of organic materials, especially the energy level alignment at organic heterostructures is of pronounced importance for unraveling the photon harvesting and charge separation process in organic photovoltaic (OPV) cells. This article provides an overview of interface energetics at typical planar and mixed donor-acceptor heterostructures, perovskite/organic hybrid interfaces, and their contact interfaces with charge collection layers. The substrate effect on energy level offsets at organic heterostructures and the processes that control and limit the OPV operation are presented. Recent efforts on interface engineering with electrical doping are also discussed.

Impact of MoO3 interlayer on the energy level alignment of pentacene-C60 heterostructure.

Using in situ ultraviolet photoelectron spectroscopy, the electronic structure evolutions at the interface between pentacene and fullerene (C60), a classical organic donor-acceptor heterostructure in organic electronic devices, on indium-tin oxide (ITO) and MoO3 modified ITO substrates have been investigated. The insertion of a thin layer MoO3 has a significant impact on the interfacial energy level alignment of pentacene-C60 heterostructure. For the deposition of C60 on pentacene, the energy difference between the highest occupied molecular orbital of donor and the lowest unoccupied molecular orbital of acceptor (HOMO(D)-LUMO(A)) offset of C60/pentacene heterostructure increased from 0.86 eV to 1.54 eV after the insertion of a thin layer MoO3 on ITO. In the inverted heterostructrure where pentacene was deposited on C60, the HOMO(D)-LUMO(A) offset of pentacene/C60 heterostructure increased from 1.32 to 2.20 eV after MoO3 modification on ITO. The significant difference of HOMO(D)-LUMO(A) offset shows the feasibility to optimize organic electronic device performance through interfacial engineering approaches, such as the insertion of a thin layer high work function MoO3 films.

Selfassembly of α,ω‐dithiols on surfaces and metal dithiol heterostructures

α,ω‐Dithiols present an interesting case of molecules with two reactive terminal ‐SH groups (HS‐R‐SH) that allow their use as binders between different metallic entities. They have thus been used in molecular electronics conduction measurements, in “nanogap” electrodes of interest in plasmonics, as building blocks of more complex structures such as metal intercalated superlattices and in the formation of metalized organic thin films, including doped graphene type films. There exist however many problems, because the molecules may end up in undesirable configurations with both thiol terminals bound to the same metal particle/substrate or link with other molecules to produce “multi‐molecule” or “multilayer” structures. This report discusses various key questions on dithiol linking with metal surfaces and the quest of protocols of making problem free dithiol metal structures. It then describes the use of dithiols and their SAMs to produce various metal organic heterostructures useful for molecular electronics and formation of doped metalized organic thin films. We discuss the build up of these structures by self assembly and lithography, their chemical composition and functional properties. image

Organic photodiodes constructed from a single radial heterojunction microwire

An organic radial heterostructure microwire constructed by Alq3and P3HT demonstrated high rectification properties and photoresponsivity as a photodiode.

Single-particle to single-particle transformation of an active type organic μ-tubular homo-structure photonic resonator into a passive type hetero-structure resonator.

Self-assembled hexagonal organic submicrotubes, upon electronic excitation with an UV laser, display an active type polarized whispering gallery mode (WGM) resonance in the visible (Vis) range (400-600 nm). Due to the photonic cavity effect the tubes show fluorescence (FL) signal intensity 5× greater than the corresponding powder state. Furthermore, the same tubes, which are passive to a visible laser, produce yellow-orange emitting carbonaceous lumps when burnt with an intense laser beam (42 mW) forming a chemically binary heterogeneous structure. The hetero-structure upon excitation with a visible laser at the passive tubular part showed emission in the Vis-Near infrared (NIR) range (500-800 nm) with WGMs thus producing a passive/active type hetero-structure photonic resonator.

Tunable charge transfer properties in metal-phthalocyanine heterojunctions.

Organic materials such as phthalocyanine-based systems present a great potential for organic device applications due to the possibility of integrating films of different organic materials to create organic heterostructures which combine the electrical capabilities of each material. This opens the possibility to precisely engineer and tune new electrical properties. In particular, similar transition metal phthalocyanines demonstrate hybridization and charge transfer properties which could lead to interesting physical phenomena. Although, when considering device dimensions, a better understanding and control of the tuning of the transport properties still remain in the focus of research. Here, by employing conductive atomic force microscopy techniques, we provide an insight about the nanoscale electrical properties and transport mechanisms of MnPc and fluorinated phthalocyanines such as F16CuPc and F16CoPc. We report a transition from typical diode-like transport mechanisms for pure MnPc thin films to space-charge-limited current transport regime (SCLC) for Pc-based heterostructures. The controlled addition of fluorinated phthalocyanine also provides highly uniform and symmetric-polarized transport characteristics with conductance enhancements up to two orders of magnitude depending on the polarization. We present a method to spatially map the mobility of the MnPc/F16CuPc structures with a nanoscale resolution and provide theoretical calculations to support our experimental findings. This well-controlled nanoscale tuning of the electrical properties for metal transition phthalocyanine junctions stands as key step for future phthalocyanine-based electronic devices, where the low dimension charge transfer, mediated by transition metal atoms could be intrinsically linked to a transfer of magnetic moment or spin.

A pure organic heterostructure of μ-oxo dimeric iron(iii) porphyrin and graphitic-C3N4 for solar H2 roduction from water

A novel pure organic heterostructure was constructed between g-C3N4 and (FeTPP)2O as a photocatalyst for solar H2 production from water splitting.

Flexible heterostructures based on metal phthalocyanines thin films obtained by MAPLE

Heterostructures based on zinc phthalocyanine (ZnPc), magnesium phthalocyanine (MgPc) and 5,10,15,20-tetra(4-pyrydil)21H,23H-porphine (TPyP) were deposited on ITO flexible substrates by Matrix Assisted Pulsed Laser Evaporation (MAPLE) technique. Organic heterostructures containing (TPyP/ZnPc(MgPc)) stacked or (ZnPc(MgPc):TPyP) mixed layers were characterized by X-ray diffraction-XRD, photoluminescence-PL, UV–vis and FTIR spectroscopy. No chemical decomposition of the initial materials was observed. The investigated structures present a large spectral absorption in the visible range making them suitable for organic photovoltaics applications (OPV). Scanning electron microscopy-SEM and atomic force microscopy-AFM revealed morphologies typical for the films prepared by MAPLE. The current–voltage characteristics of the investigated structures, measured in dark and under light, present an improvement in the current value (∼3 order of magnitude larger) for the structure based on the mixed layer (Al/MgPc:TPyP/ITO) in comparison with the stacked layer (Al/MgPc//TPyP/ITO). A photogeneration process was evidenced in the case of structures Al/ZnPc:TPyP/ITO with mixed layers.

Charge transport and recombination in heterostructure organic light emitting transistors

Light-emitting field effect transistors (LEFETs) are a class of organic optoelectronic device capable of simultaneously delivering the electrical switching characteristics of a transistor and the light emission of a diode. We report on the temperature dependence of the charge transport and emissive properties in a model organic heterostructure LEFET system from 300K to 135K. We study parameters such as carrier mobility, brightness, and external quantum efficiency (EQE), and observe clear thermally activated behaviour for transport and injection. Overall, the EQE increases with decreasing temperature and conversely the brightness decreases. These contrary effects can be explained by a higher recombination efficiency occurring at lower temperatures, and this insight delivers new knowledge concerning the optimisation of both the transport and emissive properties in LEFETs.

Current–voltage characteristics of organic heterostructure devices with insulating spacer layers

The dark current density in donor/acceptor organic planar heterostructure devices at a given forward voltage bias can either increase or decrease when an insulating spacer layer is added between the donor and acceptor layers. The dominant current flow process in these systems involves the formation and subsequent recombination of interfacial exciplex states. If the exciplex recombination rate limits current flow, an insulating interface layer decreases the dark current. However, if the exciplex formation rate limits the current, an insulating interface layer may increase the dark current. We present a device model to describe this behavior, and we discuss relevant experimental data.

Thin film properties of tetracyanoquinodimethane (TCNQ) with novel templating effects

Film properties and new templating behaviours in strong electron acceptor TCNQ.

Magnetoelectroluminescence of organic heterostructures: Analytical theory and spectrally resolved measurements

The effect of a magnetic field on the electroluminescence of organic light emitting devices originates from the hyperfine interaction between the electron/hole polarons and the hydrogen nuclei of the host molecules. In this paper, we present an analytical theory of magnetoelectroluminescence for organic semiconductors. To be specific, we focus on bilayer heterostructure devices. In the case we are considering, light generation at the interface of the donor and acceptor layers results from the formation and recombination of exciplexes. The spin physics is described by a stochastic Liouville equation for the electron/hole spin density matrix. By finding the steady-state analytical solution using Bloch-Wangsness-Redfield theory, we explore how the singlet/triplet exciplex ratio is affected by the hyperfine interaction strength and by the external magnetic field. To validate the theory, spectrally resolved electroluminescence experiments on BPhen/m-MTDATA devices are analyzed. With increasing emission wavelength, the width of the magnetic field modulation curve of the electroluminescence increases while its depth decreases. These observations are consistent with the model.

Charge transport across organic heterostructure: Role of interfacial density of states

The mechanism of carrier transport across organic-organic hetero-interfaces is crucial for organic devices. For purposes of this study, we choose two hole transport materials 4, 4′, 4″-tris(N-3-methylphenyl-N-phenyl-amino) triphenyl-amine (m-MTDATA) and N, N′-diphenyl-N, N′-bis(1-naphthyl) (1, 1′-biphenyl)-4, 4′diamine. We demonstrate that transport across such interfaces can be controlled by introducing a thin undoped layer, which is chosen to be 10–30 nm of m-MTDATA layer in this particular case. By correlating the low frequency capacitance-voltage and temperature dependence of current density-voltage (J-V) characteristics, we show that the occupation of local density of states (LDOS) on both sides controls the transport at the hetero-interface and that it can be modified by the introduction of interlayer. The thickness of the undoped interlayer effectively acts as a control on carrier concentration at the interface leading to the modification of the effective energy offset, and overlap of the LDOS. The slope of the J-V characteristics in the exponential regime has a temperature dependent term and a purely voltage dependent term. The temperature dependence of J-V characteristics is explained by including field dependence of mobility and tunneling across LDOS. We trace the origin of the offset at the hetero-interface and estimate its values for the different cases consistent with the proposed model of thermally assisted tunneling at the interface.

Laser prepared organic heterostructures based on star-shaped arylenevinylene compounds

This paper presents some studies about the preparation by matrix-assisted pulsed laser evaporation (MAPLE) technique of organic bulk heterojunctions made from the mixture of a star-shaped arylenevinylene compound, 4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine as donor and fullerene derivative, [6, 6]-phenyl C61 butyric acid butyl ester, as acceptor, in the weight ratio 1:2. The mixed layer has been characterized by spectroscopic (UV–Vis, Fourier transform infrared) and microscopic (AFM) methods, and the effects of the deposition conditions (number of pulses) and of a buffer layer of poly(aniline-co-aniline propane sulfonic acid) or poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) have been analyzed. The study of the electrical properties has revealed a typical solar cell behavior for the heterostructure glass/ITO/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/4,4′,4″-tris[(4′-diphenylamino)styryl] triphenylamine: [6, 6]-phenyl C61 butyric acid butyl ester/Al, confirming that MAPLE could be an adequate method for the preparation of active layer based on bulk heterojunction for solar cells.

Microstructural Characterization of Organic Heterostructures by (Transmission) Electron Microscopy

Transmission electron microscopy can be a powerful tool to characterize organic heterostructures, if suitable methods are applied. Here, we present with the example of codeposited films of pentacene (PEN) and perfluoropentacene (PFP) different techniques, which can also be applied to the radiation-sensitive organic materials. The structure and morphology of codeposited films of PEN and PFP on a KCl(100) substrate have been investigated by different (transmission) electron microscopy techniques. When prepared by stoichiometrically equivalent coevaporation of both compounds, the films exhibit an intermixed phase that consists of a 1:1 mixture of the two molecules. Unavoidable excess of one of the two molecules was shown to lead to a spread-out film consisting of the respective molecule, which was verified for the case of PEN excess and whose growth was shown in detail. Interestingly, the film of segregated PEN exhibits a distinctly distinguishable growth from the pure PEN on the same substrate material, forming a 4-fold symmetry aligned with the KCl⟨001⟩ directions. The adaption of an automated nanocrystal orientation and phase mapping technique for the transmission electron microscope, commercially available as the so-called ASTAR system, to these beam-sensitive materials will be discussed as this method not only offers additional functionality for the nanoscale characterization of the films but is inherently advantageous for materials that are prone to beam-induced structural changes.

Multilevel resistive memory switching in graphene sandwiched organic polymer heterostructure

A novel multilevel resistive switching was observed in trilayer stacked geometry composed of graphene nano flakes sandwiched between polyvinylidene fluoride layers fabricated by spin coating method, which are expected to fulfill the need of high density data storage memories. External parameters such as current compliance and induced voltage pulse imposed on the devices provided an aid to tune the inherent resistance states. As fabricated devices exhibited multi level switching with stable resistance ratios between different resistance states having excellent data retention and endurance. Space charge limited conduction and Fowler–Nordheim (F–N) tunneling were found to be responsible for the switching mechanism. Graphene enriched with trapping sites provides the adequate environment for F–N tunneling process to occur, resulting in multi-bit resistance states.

Alternate Heteroepitaxial Growth of Highly Oriented Organic Multilayer Films

The heterostructure, a basic active unit applied in the device level, plays an important role in traditional inorganic optoelectronics. In the organic field, although the requirement for the heterostructure is crucial, achievement and understanding on the growth and functionality of organic heterostructure are still finite, especially for ordered crystalline organic multilayers with smooth interfaces. Here a series of highly ordered crystalline heterostructures with molecule-level smoothness were obtained from single layer to alternate multilayer with a phthalocyanine molecule and a perylene derivative. Well-defined epitaxy relationship and crystal alignment were evidenced from the atomic force microscopy (AFM), X-ray diffraction (XRD), and transmission electron microscope (TEM) results. The evolution of the films reveals that, for organic-organic alternate multilayer growth, along with the intrinsic properties of organic molecules such as the packing and preferred growth direction, the soft matter properties of organic films contribute to well-defined heteroepitaxy despite that the lattice mismatch between the two materials' bulk phases is large. Thin film phases of the first few layers benefit the grain coalescence and thus the formation of smooth films. Potential application is implied from the heterojunctions' good transport ability.

Laser prepared organic heterostuctures on glass/AZO substrates

This paper presents some studies about the bi-layer organic heterostructures realized with zinc phthalocyanine (ZnPc) as donor layer and 1,4,5,8-naphthalene-tetracarboxylic dianhydride (NTCDA) as acceptor layer, on substrate of glass covered by Al doped ZnO (AZO) layer. These heterostructures have been prepared using laser techniques: pulsed laser deposition (PLD) in an atmosphere of oxygen for AZO films deposition and matrix assisted pulsed laser evaporation (MAPLE) for organic films deposition. The influence of the deposition conditions on the transmission of the organic films has been analysed.The effect of the oxygen plasma treatment, with duration of 5min and 10min, on the surface topography, structural and optical properties of AZO layers deposited by PLD and, as consequence, on the optical and electrical properties of the single layer (ZnPc) and bi-layer (ZnPc/NTCDA) organic heterostructure, deposited by MAPLE, was investigated.

Efficient Bilayer Electrodes for Photosensitive Organic Heterostructure

The possibility of increasing the photosensitivity of organic heterostructures by using the bilayer transparent ITO electrodes with organic conducting polymer polyaniline, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) complex (PEDOT:PSS) and CuI has been verified experimentally. Photosensitive n-type organic semiconductor N,N′-dimethyl-3,4,9,10-perylenetetracarboxylic acid diimide (МРР) and p-type pentacene were chosen as components of these heterostructures. Usage of ITO/PEDOT:PSS bilayer electrodes leads to increasing the photovoltaic sensitivity of these heterostructures by 2–3 orders and by 1–2 orders when using CuI due to decreasing the recombination of excitons and increasing the potential barrier heights on the interface between the organic semiconductor and layers of PEDOT:PSS and CuI.

Heteroepitaxial growth of surface mounted metal–organic framework thin films with hybrid adsorption functionality

Metal–organic framework thin film heterostructures of type [Cu3btc2] on top of [Cu2ndc2dabco] were fabricated on quartz crystal microbalance substrates using a step-by-step growth approach and the resulting hybrid adsorption properties for volatile organic compounds were studied.