The influence of donor material on achieving high photovoltaic response for organic bulk heterojunction cells with small ratio donor component

Authors demonstrated impact of series small ratio donors in C₆₀ matrix on photovoltaic (PV) performance. A series of donor materials such as N′,N′-Di-1-naphthyl-N′,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB), 4,-4′-Bis(carbazol-9-yl) (CBP), 4,4′,4″-tris(N-3-methylphenyl-N-phenyl-amine)triphenyl-amine (m-MTDATA), copper phthalocyanine (CuPc) and 4,4,4-tris(n-carbazolyl-triphenyl-amine) (TCTA) were blended with fullerene (C₆₀) by different ratio. It was found that although donor–acceptor (DA) interface in planar heterojunction (PHJ) structure increased charge separation probability at the near interface section, the PV response was stronger for bulk heterojunction (BHJ) with low-ratio donor doping into C₆₀ matrix in which exciton dissociation can take place immediately after photon absorption without a diffusion progress. The power conversion efficiency (PCE) of BHJ-PV cell based on NPB donor reaches 2.25%, which is double of that of the PHJ cell. In terms of our series results we obtained that ΔE_HOMO (HOMO_C60–HOMO_donor) between C₆₀ acceptor and donors would provide a maximal influence on achievement of a maximal PCE and an optimal ΔE_HOMO locates around 0.8 eV, which implies that dissociation of photo-exciton at C₆₀ matrix needs feasible driving force. More detail mechanism was also argued.     

Light emitting field-effect transistors with vertical heterojunctions based on pentacene and tris-(8-hydroxyquinolinato) aluminum

We report a top-contact light emitting field-effect transistor based on an asymmetric vertical heterojunction using pentacene as a field-effect layer and tris-(8-hydroxyquinolinato) aluminum (Alq₃) as an electron transport and luminescent material, which is fabricated on an indium tin oxide (ITO)-coated glass substrate with poly (methyl methacrylate) (PMMA) as a gate dielectric. The Alq₃ layer underneath the drain electrode roughly occupies one half of the pentacene surface forming an asymmetric heterojunction with pentacene. A hole transport layer N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) is introduced to occupy the other half of the pentacene surface underneath the source electrode to allow vertical hole transport in the device. We have realized the electrical switching functionality of a field-effect transistor (FET) and the control of electroluminescence (EL) simultaneously under ambient atmosphere. The device exhibits typical p-channel characteristics and green emission from Alq₃ is observed adjacent to the drain electrode. A working principle of the device is discussed in detail. Furthermore, this device configuration enables high-spatial-resolution fluorescence imaging of device operation, which is a simple and powerful tool for studying organic luminescent materials.     

Thermal stability of devices with molybdenum oxide doped organic semiconductors

We demonstrate the thermal stability of transition-metal-oxide (molybdenum oxide; MoO₃)-doped organic semiconductors. Impedance spectroscopy analysis indicated that thermal deformation of the intrinsic 1,4-bis[N-(1-naphthyl)-N′-phenylamino]-4,4′-diamine (NPB) layer is facilitated when the MoO₃-doped NPB layer is deposited on the intrinsic NPB layer. The resistance of the intrinsic NPB layer is reduced from 300 kΩ to 3 kΩ after thermal annealing at 100 °C for 30 min. Temperature-dependent conductance/angular frequency–frequency (G/w-f-T) analysis revealed that the doping efficiency of MoO₃, which is represented by the activation energy (E_a), is reduced after the annealing process.     

Low and small resistance hole-injection barrier for NPB realized by wide-gap p-type degenerate semiconductor,LaCuOSe:Mg

LaCuOSe:Mg is a wide-gap p-type semiconductor with a high conductivity and a large work function. Potential of LaCuOSe:Mg as a transparent hole-injection electrode of organic light-emitting diodes (OLEDs) was examined by employing N,N′-diphenyl-N,N′-bis (1,1′-biphenyl)-4,4′-diamine (NPB) for a hole transport layer. Photoemission spectroscopy revealed that an oxygen plasma treated surface of LaCuOSe:Mg formed a hole-injection barrier as low as 0.3 eV, which is approximately a half of a conventional ITO/NPB interface. Hole-only devices composed of a LaCuOSe:Mg/NPB/Al structure showed a low threshold voltage ∼0.2 V and high-density current drivability of 250 mA cm⁻² at 2 V, which is larger by two orders of magnitude than that of ITO/NPB/Al devices. These results demonstrate that LaCuOSe:Mg has great potential as an efficient transparent anode for OLEDs and other organic electronic devices.     

Interface electronic structures of organic light-emitting diodes with WO3 interlayer: A study by photoelectron spectroscopy

The energy level alignment and chemical reaction at the interface between the hole injection and transport layers in an organic light-emitting diode (OLED) structure has been studied using in-situ X-ray and ultraviolet photoelectron spectroscopy. The hole injection barrier measured by the positions of the highest occupied molecular orbital (HOMO) for N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB)/indium tin oxide (ITO) was estimated 1.32 eV, while that with a thin WO₃ layer inserted between the NPB and ITO was significantly lowered to 0.46 eV. This barrier height reduction is followed by a large work function change which is likely due to the formation of new interface dipole. Upon annealing the WO₃ interlayer at 350 °C, the reduction of hole injection barrier height largely disappears. This is attributed to a chemical modification occurring in the WO₃ such as oxygen vacancy formation.     

Dark current and photovoltage models on the formation of depletion region in C60/NPB organic heterojunctions

We establish quantitative models on the formation of depletion regions in organic photodiodes (OPD) based on fullerene/N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (C₆₀/NPB) heterojunctions. The models describe the relation of dark current and open-circuit voltage to the deposited thickness of C₆₀ or NPB. Interfacial electronic structures, such as built-in potential, the charge density, the minimized thicknesses of completely developed depletion regions and the energy level bending on each side of the heterojunction were derived from the fitting model. Also, we observed a shift of depletion region from NPB to C₆₀ due to the relative change of charge density under illumination. The device performance proved the reasonability of the models. This paper provides a universally applicable method to probe the interfacial information of organic semiconductors.     

Versatile hole injection of VO2: Energy level alignment at N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine/VO2/fluorine-doped tin oxide

Energy level alignments at the interface of N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB)/VO₂/fluorine-doped tin oxide (FTO) were studied by photoemission spectroscopy. The overall hole injection barrier between FTO and NPB was reduced from 1.38 to 0.59 eV with the insertion of a VO₂ hole injection layer. This could allow direct hole injection from FTO to NPB through a shallow valence band of VO₂. Surprisingly, VO₂ can also act as a charge generation layer due to its small band gap of 0.80 eV. That is, its conduction band is quite close to the Fermi level, and thus electrons can be extracted from the highest occupied molecular orbital (HOMO) of NPB, which is equivalent to hole injection into the NPB HOMO.     

The role of molybdenum oxide as anode interfacial modification in the improvement of efficiency and stability in organic light-emitting diodes

It has been experimentally found that molybdenum oxide (MoO₃) as the interfacial modification layer on indium-tin-oxide (ITO) in organic light-emitting diodes (OLEDs) significantly improves the efficiency and lifetime. In this paper, the role of MoO₃ and MoO₃ doped N,N′-di(naphthalene-1-yl)–N,N′-diphenyl-benzidine (NPB) as the interface modification layer on ITO in improvement of the efficiency and stability of OLEDs is investigated in detail by atomic force microscopy (AFM), polarized optical microscopy, transmission spectra, ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). The studies on the energy level and the morphology of the films treated at different temperatures clearly show that the MoO₃ and MoO₃:NPB on ITO can reduce the hole injection barrier, improve the interfacial stability and suppress the crystallization of hole-transporting NPB, leading to a higher efficiency and longer lifetime of OLEDs.     

High performance top-emitting organic light-emitting diodes with copper iodide-doped hole injection layer

Efficient top-emitting organic light-emitting diodes were fabricated using copper iodide (CuI) doped 1,4-bis[N-(1-naphthyl)-N′-phenylamino]-4,4′-diamine (NPB) as a hole injection layer and Ir(ppy)₃ doped CBP as the emitting layer. CuI doped NPB layer functions as an efficient p-doped hole injection layer and significantly improves hole injection from a silver bottom electrode. The top-emitting device shows high current efficiency of 69 cd/A with Lambertian emission pattern. The enhanced hole injection is originated from the formation of the charge transfer complex between CuI and NPB.     

Bulk and interface properties of molybdenum trioxide-doped hole transporting layer in organic light-emitting diodes

Effects of doping molybdenum trioxide (MoO₃) in N,N′-diphenyl-N,N′-bis(1,1′-biphenyl)-4,4′-diamine (NPB) are studied at various thicknesses of doped layer (25–500 Å) by measuring the current–voltage characteristics, the capacitance–voltage characteristics and the operating lifetime. We formed charge transfer complex of NPB and MoO₃ by co-evaporation of both materials to achieve higher charge density, lower operating voltage, and better reliability of devices. These improved performances may be attributed to both bulk and interface properties of the doped layer. The authors demonstrated that the interface effects play more important role in lowering the operating voltage and increasing the lifetime.     

Electrical characterization of cobalt phthalocyanine/p-silicon heterojunction

We report the fabrication of organic/inorganic heterojunction of cobalt phthalocyanine (CoPc) with p-type silicon (p-Si) using vacuum thermal evaporation. At ambient conditions, the electrical characteristics of the heterojunction are investigated. The optical band gap of CoPc is calculated from absorption spectrum using Tauc׳s law. The electrical characterization of the heterojunction shows rectifying behavior with a rectification ratio (RR) of 316. Different diode parameters are extracted from the current–voltage (I–V) curves, such as ideality factor n, barrier height ϕ, series resistance R_s and shunt resistance R_sh. These parameters are in good agreement with those calculated from the functions of Cheungs and Norde . The conduction of charge carriers through the interface of p-Si/CoPc is also studied. The fabricated heterojunction could be a promising candidate for its potential use in electronic applications.     

A simple organic diode structure with strong rectifying characteristics

A simple organic diode structure has been made based on N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB)/Fullerene (C₆₀) heterojunction. Ultraviolet photoelectron spectroscopy measurements show an energy level alignment at the heterojunction as such that no potential barrier near this heterojunction to hinder the formation of charge transfer excitons, which recombines at a very fast rate. This fast exciton recombination at this heterojunction makes NPB/C₆₀ behave like an ideal Ohmic contact and thus leads to an extremely high 7.8 × 10⁴ rectifying ratio from the electrode/organic contacts.     

Ambipolar permeable metal-base transistor based on NPB/C60 heterojunction

In this paper, we report the fabrication of permeable metal-base organic transistors based on N,N′-diphenyl-N,N′-bis(1-naphthylphenyl)-1,1′-biphenyl-4,4′-diamine (NPB)/C₆₀ heterojunction as both emitter and collector. By applying different polarities of voltage bias to the collector and the base, and input current to the emitter, the ambipolar behavior can be observed. The device demonstrates excellent common-base characteristics both in P-type and N-type modes with common-base current gains of 0.998 and 0.999, respectively.     

Hybrid Solar Cells Based on Nanoparticles of CuInS2 in Organic Matrices

We report on solution‐processed hybrid solar cells consisting of a nanocrystalline inorganic semiconductor, CuInS₂, and organic materials. Synthesis of quantized CuInS₂ nanoparticles was performed using a colloidal route, where the particle surface was shielded by an organic surfactant. First attempts were made to use nanocrystalline CuInS₂ with fullerene derivatives to form flat‐interface donor–acceptor heterojunction solar cells. We investigated also bulk heterojunctions by replacing the CuInS₂ single layer by a blend of CuInS₂ and p‐type polymer (PEDOT:PSS; poly(3,4‐ethylenedioxythiophene:poly(styrene sulfonic acid) in the same cell configuration. Bulk heterojunction solar cells show better photovoltaic response with external quantum efficiencies up to 20 %.     

Origin of Enhanced Hole Injection in Inverted Organic Devices with Electron Accepting Interlayer

Conventional organic light emitting devices have a bottom buffer interlayer placed underneath the hole transporting layer (HTL) to improve hole injection from the indium tin oxide (ITO) electrode. In this work, a substantial enhancement in hole injection efficiency is demonstrated when an electron accepting interlayer is evaporated on top of the HTL in an inverted device along with a top hole injection anode compared with the conventional device with a bottom hole injection anode. Current–voltage and space‐charge‐limited dark injection (DI‐SCLC) measurements were used to characterize the conventional and inverted N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)(1,1′biphenyl)‐4,4′diamine (NPB) hole‐only devices with either molybdenum trioxide (MoO₃) or 1,4,5,8,9,11‐hexaazatriphenylene hexacarbonitrile (HAT‐CN) as the interlayer. Both normal and inverted devices with HAT‐CN showed significantly higher injection efficiencies compared to similar devices with MoO₃, with the inverted device with HAT‐CN as the interlayer showing a hole injection efficiency close to 100%. The results from doping NPB with MoO₃ or HAT‐CN confirmed that the injection efficiency enhancements in the inverted devices were due to the enhanced charge transfer at the electron acceptor/NPB interface.     

Investigation of voltage reduction in nanostructure-embedded organic light-emitting diodes

We investigated the reduction of the operating voltage in organic light-emitting diodes containing WO₃ nanoislands. The thickness of the organic layer and the periodicity of the nanoislands were varied in order to quantitatively analyze the electrical changes. The thickness of the N,N′-bis(naphthalen-1-yl)-N,N′-bis(phenyl)-benzidine (NPB) layer was varied from 150 nm to 600 nm, and various periodic nanoislands of 300 nm, 330 nm, and 370 nm were fabricated. Two geometric factors, which are the effective length and effective area, influence the operating voltage. The effective length is determined by the relative thickness of the nanoislands compared with the organic thickness, and the reduction of the operating voltage is linearly proportional to the relative thickness. The effective area is a nonlinear function of periodicity, and the voltage is reduced as the periodicity decreases.     

High mobility ambipolar organic field-effect transistors with a nonplanar heterojunction structure

Ambipolar organic field-effect transistors (OFETs) based on a bilayer structure of highly crystalline small molecules, n-type α,ω-diperfluorohexylquaterthiophene (DFH-4T) and p-type dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT), are investigated. By employing DFH-4T/DNTT as the bottom/top layers and appropriate high work function (WF) electrodes in a bottom-gate, top-contact configuration, the superior ambipolar characteristics with matched electron and hole mobilities of 1–1.1 cm² V⁻¹ s⁻¹ are achieved. Intriguingly, this high-performance device exhibits a unique feature of an extremely rough, nonplanar heterojunction in the DFH-4T/DNTT combination and a large electron injection barrier from the high WF electrodes to DFH-4T, suggesting some underlying mechanisms for the effective charge transport and injection. The electrical and structural analyses reveal that the crystal packing of the bottom DFH-4T layer supports the growth of a high-quality DNTT crystal network for high-mobility hole transport upon the nonplanar heterojunction, and also enables the formation of an enlarged organic/metal contact surface for efficient electron injection from the high WF electrodes, as the key attributes leading to an overall excellent ambipolar behavior. The effect of intrinsic charge accumulation at the heterojunction interface on the ambipolar conduction is also discussed. Furthermore, a complementary-like inverter constructed with two DFH-4T/DNTT ambipolar OFETs is demonstrated, which shows a gain of 30.     

High performance photomultiplication perovskite photodetectors with PC60BM and NPB as the interlayers

Organic-inorganic hybrid perovskites have attracted more attention as successful light harvesting materials for solution-processed semiconductors and exhibit remarkable optoelectronic properties. Here photomultiplication-type photodetectors based on perovskite CH₃NH₃PbI₃ are demonstrated. By introducing suitable interlayers at the CH₃NH₃PbI₃/electrode interfaces, the performance of the photodetector is significantly improved. The optimized device with a N,N′-di(naphthalene-1-yl)-N,N′-diphenylbenzidine anode interface layer and [6,6]-phenyl-C₆₀-butyric acidmethyl ester cathode interface layer shows a broadband response with a high photocurrent gain of about 177 and a high detectivity of 4.6 × 10¹³ Jones, which are higher than the reference device. Besides, the response speed of the device is also increased. The improvement is attributed to the improved charge carrier collection efficiency and suppressed dark current of the device.