To observe bidirectional negative differential resistance at room temperature by narrowing transport channels for charge carriers in vertical organic light-emitting transistor

Bidirectional negative differential resistance (NDR) at room temperature with high peak-to-valley current ratio (PVCR) of ～10 are observed from vertical organic light-emitting transistor indium-tin oxide (ITO)/N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine) (α-NPD)(60 nm)/Al(30 nm)/α-NPD(60 nm)/tris-(8-hydroxyquinoline) aluminium (Alq₃)(50 nm)/Al by narrowing the transport channels for charge carriers with a thick-enough middle Al gate electrode layer to block charge carriers transporting from source electrode to drain electrode. When the transport channel for charge carriers gets large enough, the controllability of gate bias on the drain–source current gets weaker and the device almost works as an organic light-emitting diode only. Therefore, it provides a very simple way to produce NDR device with dominant bidirectional NDR and high PVCR (～10) at room temperature by narrowing transport channels for charge carriers in optoelectronics.     

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.     

P-type doping of organic wide band gap materials by transition metal oxides: A case-study on Molybdenum trioxide

A study on p-doping of organic wide band gap materials with Molybdenum trioxide using current transport measurements, ultraviolet photoelectron spectroscopy and inverse photoelectron spectroscopy is presented. When MoO₃ is co-evaporated with 4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP), a significant increase in conductivity is observed, compared to intrinsic CBP thin films. This increase in conductivity is due to electron transfer from the highest occupied molecular orbital of the host molecules to very low lying unfilled states of embedded Mo₃O₉ clusters. The energy levels of these clusters are estimated by the energy levels of a neat MoO₃ thin film with a work function of 6.86 eV, an electron affinity of 6.7 eV and an ionization energy of 9.68 eV. The Fermi level of MoO₃-doped CBP and N,N′-bis(1-naphtyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (α-NPD) thin films rapidly shifts with increasing doping concentration towards the occupied states. Pinning of the Fermi level several 100 meV above the HOMO edge is observed for doping concentrations higher than 2 mol% and is explained in terms of a Gaussian density of HOMO states. We determine a relatively low dopant activation of ～0.5%, which is due to Coulomb-trapping of hole carriers at the ionized dopant sites.     

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.     

Hybrid intermediate connector for tandem OLEDs with the combination of MoO3-based interlayer and p-type doping

We report on a high-quality hybrid intermediate connector (IC) used in tandem organic light-emitting diodes (OLEDs), which is composed of an ultrathin MoO₃ interlayer sandwiched between a n-type Cs₂CO₃-doped 4,7-diphenyl-1,10-phenanthroline (BPhen) layer and a p-type MoO₃-doped N,N′-diphenyl-N,N′-bis(1-naphthyl)-(1,1′-biphenyl)-4,4′-diamine (NPB) layer. The charge generation characteristics for light emission in tandem OLEDs have been identified by studying the interfaces and the corresponding devices. The hybrid IC structure exhibits superior charge generation capability, and its interfacial electronic structures are beneficial to the generation and injection of electrons and holes into bottom and top emission units, respectively. Compared to the organic-TMO bilayer and doped p–n junction structures, the hybrid IC structure combining MoO₃-based interlayer and p-type doping can effectively decrease the driving voltage and improve the current efficiency of tandem devices due to the increased bulk heterojunction-like charge generation interfaces. Our results indicate that the TMO-based hybrid IC structure can be a good structure in the fabrication of high-efficiency tandem OLEDs.     

Molecular order,charge injection efficiency and the role of intramolecular polar bonds at organic/organic heterointerfaces

The effect of orientational changes in thin films of the non-crystalline hole transport material α-N-N′-diphenyl N-N″-bis(1 naphthayl)-1,1′-biphenyl-4,4′-diamine (α-NPD) on the energy level alignment and the film electronic structure has been investigated by angle-resolved ultraviolet photoelectron spectroscopy and related to the transport characteristics of hole-only devices. Changes in the anisotropic α-sexithiophene (α-6T) substrate from a “standing” to a “flat” molecular orientation induced by mechanical rubbing lead to molecular order and a preferential orientation in subsequently deposited thin α-NPD films and cause a reduction of the charge injection barrier at the organic/organic interface. The results show that the height of this barrier is determined by the surface dipoles of the individual organic films that relate to the orientation of intramolecular polar bonds at the interface.     

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.     

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.     

Efficient electron transport in 4,4′-bis[N-(1-napthyl)-N-phenyl-amino] biphenyl and the applications in white organic light emitting devices

The electron transport capability of 4,4′-bis[N-(1-napthyl)-N-phenyl-amino] biphenyl (α-NPD) was investigated by fundamental physical measurements named as current–voltage (I–V) electrical property evaluation and displacement current measurement (DCM). In electron-dominated devices, the I–V characteristics of α-NPD were similar as that of (8-hydroxyquinolino) aluminum (Alq₃) owing to their same order of electron mobilities. The interface of Al/LiF and α-NPD was proven to be an Ohmic contact through the evaluation of I–V characteristics at low bias regime (<3 V). And an electron injection barrier, 0.21 eV, at Al/LiF/α-NPD was obtained by extrapolating the temperature dependent I–V curves. The electron transport behavior in α-NPD film was further confirmed by DCM evaluations. Furthermore, an efficient white organic light emission device was successfully fabricated by using α-NPD as hole transport layer and electron transport layer, respectively.     

Synthesis, Characterization, and Electroluminescent Characteristics of Mixed-Ligand Zinc(II) Complexes

Mixed-ligand zinc complexes, i.e., 2-(2-hydroxyphenyl)benzothiazolato-5,7- dichloro-8-hydroxyquinolinato zinc(II) [ZnBTZ(Cl₂q)], 2-(2-hydroxyphenyl) benzothiazolato-5,7-dimethyl-8-hydroxyquinolinato zinc(II) [ZnBTZ(Me₂q)], and 2-(2-hydroxyphenyl)benzothiazolato-2-carbonitril-8-hydroxyquinolinato zinc(II) [ZnBTZ(CNq)], were synthesized and characterized. The metal complexes have high thermal stability (>300°C) and high glass-transition temperature (>150°C) and are suitable for optoelectronic applications. Optical properties of the synthesized complexes were characterized by using ultraviolet–visible (UV–Vis) and photoluminescence spectroscopy. Color tuning by changing the ligand was observed in synthesized complexes. Multilayered organic electroluminescent devices were fabricated having structure indium–tin oxide (ITO)/N,N′-diphenyl-N,N′-bis(1-naphthyl)-1,1′-biphenyl-4,4′-diamine (α-NPD)/zinc complex/2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP)/tris(quinolinolate)Al^III (Alq₃)/LiF/Al using the synthesized complexes as emissive material. The electroluminescence spectra show peak emission centered at 532 nm, 572 nm, and 541 nm, respectively, for these materials. The emitted light has chromaticity with Commission Internationale d’Éclairage coordinates x = 0.35 and y = 0.56 for ZnBTZ(Cl₂q), x = 0.49 and y = 0.47 for ZnBTZ(Me₂q), and x = 0.48 and y = 0.40 for ZnBTZ(CNq) complex.     

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.     

Lower hole-injection barrier between pentacene and a 1-hexadecanethiol-modified gold substrate with a lowered work function

We used ultraviolet photoemission spectroscopy (UPS) to study the hole injection barrier at the interface between pentacene and a gold surface treated with 1-hexadecanethiol (HDT). Through these UPS in-situ experiments, we found that the energy barrier between HDT-modified gold and pentacene was 0.74 eV. This energy barrier was 0.11 eV smaller than that between bare gold and pentacene, despite the work function of HDT-modified gold being 1.08 eV lower than that of bare gold. This result does not follow the typical trend, whereby decreasing the work function of a metal increases the energy barrier. The observed behavior can be explained by two factors. First, the bare gold substrate exhibited a large interface dipole, whereas the HDT-modified gold did not. And second, pentacene on the HDT-modified gold substrate had a lower ionization energy than pentacene on bare gold. This finding can be explained in terms of the polarization energy related to the more crystalline structure of pentacene on the HDT-modified gold substrate, which was established by X-ray diffraction analysis. For comparison, we also measured the injection barrier between the amorphous organic semiconductor, N,N′-diphenyl-N,N′bis(1-naphthyl-1,1′-biphenyl-4,4′-diamine (α-NPD)), and HDT-modified gold.     

Effect of lithium and silver diffusion in single-stack and tandem OLED devices

A study of metal (Li, Ag) diffusion has been carried out in an archetypal OLED device based on N,N′-di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine|tris(8-hydroxyquinolinato) aluminum|4,7-diphenyl-1,10-phenanthroline (NPB|Alq₃|Bphen). Using single-stack and two-stack tandem OLED structures with variations of layer thicknesses and metal layer placements, we have found that Ag vapor-deposited on Alq₃ layer can diffuse or penetrate deep into Alq₃, up to ∼2,000 Å, causing luminescence quenching. This diffusion can be substantially prevented by a thin layer of Li or Bphen deposited on Alq₃ prior to the deposition of Ag. In contrast, Li diffusion in either Alq₃ or Bphen is limited to about 50–100 Å. Li appears to be able to diffuse into Bphen irrespective of the order of Li and Bphen depositions.     

Metal/Metal‐Oxide Interfaces: How Metal Contacts Affect the Work Function and Band Structure of MoO3

When transition metal oxides are used in practical applications, such as organic electronics or heterogeneous catalysis, they often must be in contact with a metal. Metal contacts can affect an oxide's chemical and electronic properties within the first few nanometers of the contact, resulting in changes to an oxide's chemical reactivity, conductivity, and energy‐level alignment properties. These effects can alter an oxide's ability to perform its intended function. Thus, the choice of contacting metal becomes an important design consideration when tailoring the properties of transition‐metal oxide thin films or nanoparticles. Here, metal/metal‐oxide interfaces involving a widely used oxide in organic electronics, MoO₃, are examined. It is demonstrated that metal contacts tend to reduce the Mo⁶⁺ cation to lower oxidation states and, consequently, alter MoO₃’s valence electronic structure and work function when the oxide layer is very thin (less than 10 nm). MoO₃ becomes semimetallic and has a lower work function near metal contacts. The observed behavior is attributed to two causes: 1) charge transfer from the metal Fermi level into MoO₃’s low‐lying conduction band and 2) an oxidation‐reduction reaction between the metal and MoO₃ that results in oxidation of the metal and reduction of MoO₃. These results illustrate how interfaces are important to an oxide's ability to provide energy‐level alignment.     

The role of gap states on energy level alignment at an α-NPD/HAT(CN)6 charge generation interface

We report the effect of gap states on energy level alignment in a typical organic charge generation interface of N,N-bis(1-naphthyl)-N,N-diphenyl-1,1-biphenyl-4,4-diamine (α-NPD)/hexaazatriphenylene−hexacarbonitrile [HAT(CN)₆] by using ultraviolet and X-ray photoemission spectroscopy. The gap states tailed from the highest occupied molecular orbital (HOMO) onset of α-NPD dominate the Fermi level pinning at the α-NPD(<1.6 nm)/HAT(CN)₆ interface, which is favorable for charges generation upon bias operation and facilitates the electron injection from the HOMO-tail region of α-NPD to the lowest unoccupied molecular orbital (LUMO) region of HAT(CN)₆.     

Effect of type-II quantum well of m-MTDATA/α-NPD on the performance of green organic light-emitting diodes

The type-II multiple quantum well (MQW) structure is prepared and introduced into green organic green light-emitting diodes consisting of 4,4′-bis-[N-(naphthyl)-N-phenyl-amino]biphenyl (α-NPD) and tris-(8-hydroxyquinolinato)-aluminum (Alq₃). The quantum well (QW) and wall are fabricated by 4,4′,4″-tris-(3-methylphenylphenylamino)triphenylamine (m-MTDATA) and α-NPD, respectively. The device performance of MQW organic light-emitting diodes (OLEDs) has been improved; the luminous efficiency by 25% and power efficiency by 17% compared with the reference device. The performance improvement can be explained by the increased electron-hole balance in the device due to the hole confinement in the QW structure.     

Infrared study of the MoO3 doping efficiency in 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP)

Electrochemical doping produces clear changes in the vibrational spectra of organic semiconductors as we show here for the system molybdenum oxide (MoO₃) doped into the charge transport material 4,4′-bis(N-carbazolyl)-1,1′-biphenyl (CBP). Based on density-functional theory (DFT) calculations of vibrational spectra, the new spectral features can be attributed to the CBP cation that forms as a result of electron transfer from CBP to MoO₃. The intensity of the new vibrational lines is a direct measure for the probability of charge transfer. MoO₃ agglomerating within the CBP matrix limits the active interface area between the two species. The appearance of a broad electronic transition in the infrared range indicates a new electronic structure at the interface compared to the individual components. The intensity of this electronic excitation serves as a measure for the interface area indicating a linear increase with MoO₃ concentration. Deposition onto cooled substrates results in smaller agglomerates, and thus yields a higher efficiency.     

Reducing the driving voltage of organic light-emitting diodes by inserting a transparent ultrathin layer of oxidized silver as a hole-injecting layer

Organic light-emitting diodes (OLEDs) containing a transparent ultrathin layer of oxidized silver as a hole-injecting layer, placed between a indium–tin-oxide (ITO) electrode and the hole-transporting layer, were fabricated, and their electrical and luminescent properties were investigated. The OLEDs had a structure that consisted of an ITO layer; followed by an ultrathin Ag layer oxidized by a ultraviolet (UV)–ozone surface treatment; a N,N′-di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl)-4,4′-diamine (α-NPD) layer; a 5,6,11,12-tetraphenylnaphthacene (rubrene)-doped 9,10-diphenylanthracene (DPA) layer; a tris-(8-hydroxyquinoline) aluminum (Alq₃) layer; a lithium fluoride (LiF) layer; and a Al layer. The operating voltages of the OLEDs with the oxidized Ag (i.e., AgO_x) layer were drastically lower than those of the layer-free OLEDs, because the AgO_x layer, which had high oxidizability, contributed to hole injection as it oxidized the surface of the α-NPD layer. However, the external quantum efficiency of the OLEDs with the AgO_x layer was lower than that of the AgO_x layer-free OLEDs, suggesting that the carrier balance (i.e., the balance between the holes and electrons) became uneven in the emission layer, owing to the insertion of the AgO_x layer. It was assumed that this imbalance resulted from the number of holes in the emission layer being higher because of the increase in hole injection in the AgO_x layer.     

Comparison of Charge‐Carrier Transport in Thin Films of Spiro‐Linked Compounds and Their Corresponding Parent Compounds

The charge‐transport properties of the spiro‐linked compounds 2,2′,7,7′‐tetrakis(diphenylamino)‐9,9′‐spirobifluorene, 2,2′,7,7′‐tetrakis(N,N′‐di‐p‐methylphenylamino)‐9,9′‐spirobifluorene, 2,2′,7,7′‐tetra(m‐tolyl‐phenylamino)‐9,9′‐spirobifluorene, and 2,2′,7,7′‐tetra(N‐phenyl‐1‐naphthylamine)‐9,9′‐spirobifluorene, and their corresponding parent compounds, N,N,N′,N′‐tetraphenylbenzidine, N,N,N′,N′‐tetrakis(4‐methylphenyl)benzidine, and N,N′‐bis(3‐methylphenyl)‐(1,1′‐biphenyl)‐4,4′‐diamine, N,N′‐diphenyl‐N,N′‐bis(1‐naphthyl)‐1,1′‐biphenyl‐4,4′‐diamine, are investigated. The field‐effect mobilities of charge carriers in thin films of the parent compounds are slightly higher than those of the spiro‐linked compounds. However, the transistor action of the parent‐compound thin films vanishes because the films crystallize after being stored in ambient atmosphere for a few days. In contrast, the hole mobilities in thin films of the spiro‐linked compounds do not change significantly after the samples are stored in ambient atmosphere for up to nine months. Also discussed is the temperature dependency of the mobilities of charge carriers, which is presented using two models, namely the Arrhenius and the Gaussian disorder models.     

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.