Injection Barrier Research Articles

Study on the influence of chain extension and substituent position on charge transport properties and optoelectronic properties based on 2,5-di(pyrazine-2-yl)furan derivatives

In this paper, the basic structure of 2,5-di(pyrazine-2-yl)furan (DPF) was initially designed to tune the charge transport properties and photoelectric properties of organic materials by chain extension. Through the calculation of recombination energy, the structure with the introduction of anthracene group (DPF-A) is a stable P-type material with the smallest recombination energy in terms of adiabatic ionization potential, so the chain extended molecule DPF-A was selected as the base for the study of substituent positions. While thiophene, trifluorinated acyl, and methoxy groups were introduced to design DPF-A series derivatives. Density functional theory with high computational accuracy was applied to investigate geometric structure, orbital energy levels, ionization energy, electron affinity energy, and recombination energy. The results show that the increase (decrease) of the HOMO (LUMO) energy level leads to the red (blue)-shift of absorption wavelength and fluorescence emission wavelength; the vertical ionization potential decreases and the vertical electron affinity potential increases, thus the hole and electron injection barrier decreases; the decrease of the hole/electron recombination energy improves the charge transport ability of the molecule. Moreover, the adjustment of thiophene orientation and the position of the introduced group has the potential to transform the p-type material into an n-type material, resulting in the enhanced electron injection ability.

Revisiting Hole Injection in Quantum Dot Light‐Emitting Diodes

AbstractInjecting holes from the hole transport layer (HTL) into the quantum dot (QD) emitting layer in quantum dot light‐emitting diodes (QLEDs) is considered challenging due to the presence of a relatively high hole injection barrier at the HTL/QD interface. However, QLEDs with exceptional brightness and efficiency are achieved, prompting a reevaluation of the traditional hole injection mechanisms. This study examines the hole injection mechanism in QLEDs using a combination of experiments and simulations. The results demonstrate that the applied bias significantly reduces the barrier height between the highest occupied molecular orbital level of the HTL and the valence band (VB) of the QDs, facilitating hole injection. The bending of the lowest unoccupied molecular orbital energy level of the HTL at the HTL/QD interface confines electrons within the QD, effectively minimizing leakage current. Additionally, the triangle‐shaped potential barrier arising from the bending of the VB energy level of the QDs creates favorable conditions for hole–tunneling injection. Moreover, both simulations and experiments consistently demonstrate that the predominant pathway for hole injection from the HTL to the QDs in the QLED device involved thermally assisted tunneling. This study is important to understand the hole injection mechanism in QLEDs.

Electron and hole injection barriers between silicon substrate and RF magnetron sputtered In2O3 : Er films

In2O3 : Er films have been synthesized on silicon substrates by RF magnetron sputter deposition. The currents through the synthesized metal/oxide/semiconductor (MOS) structures (Si/In2O3 : Er/In-contact) have been measured for n and p type conductivity silicon substrates and described within the model of majority carrier thermoemission through the barrier, with bias voltage correction to the silicon potential drop. The electron and hole injection barriers between the silicon substrate and the film have been found to be 0.14 and 0.3 eV, respectively, by measuring the temperature dependence of the forward current at a low sub-barrier bias. The resulting low hole injection barrier is accounted for by the presence of defect state density spreading from the valence band edge into the In2O3 : Er band gap to form a hole conduction channel. The presence of defect state density in the In2O3 : Er band gap is confirmed by photoluminescence data in the respective energy range 1.55–3.0 eV. The band structure of the Si/In2O3 : Er heterojunction has been analyzed. The energy gap between the In2O3 : Er conduction band electrons and the band gap conduction channel holes has been estimated to be 1.56 eV.

Ultrastable and High-Efficiency Deep Red QLEDs through Giant Continuously Graded Colloidal Quantum Dots with Shell Engineering.

Quantum dot (QD) based light-emitting diodes (QLEDs) hold great promise for next-generation lighting and displays. In order to reach a wide color gamut, deep red QLEDs emitting at wavelengths beyond 630 nm are highly desirable but have rarely been reported. Here, we synthesized deep red emitting ZnCdSe/ZnSeS QDs (diameter ∼16 nm) with a continuous gradient bialloyed core-shell structure. These QDs exhibit high quantum yield, excellent stability, and a reduced hole injection barrier. The QLEDs based on ZnCdSe/ZnSeS QDs have an external quantum efficiency above 20% in the luminance range of 200-90000 cd m-2 and a record T95 operation lifetime (time for the luminance to decrease to 95% of its initial value) of more than 20000 h at a luminance of 1000 cd m-2. Furthermore, the ZnCdSe/ZnSeS QLEDs have outstanding shelf stability (>100 days) and cycle stability (>10 cycles). The reported QLEDs with excellent stability and durability can accelerate the pace of QLED applications.

Electron and hole injection barriers between silicon substrate and RF magnetron sputtered In2O3 : Er films

In2O3 : Er films have been synthesized on silicon substrates by RF magnetron sputter deposition. The currents through the synthesized metal/oxide/semiconductor (MOS) structures (Si/In2O3 : Er/In-contact) have been measured for n and p type conductivity silicon substrates and described within the model of majority carrier thermoemission through the barrier, with bias voltage correction to the silicon potential drop. The electron and hole injection barriers between the silicon substrate and the film have been found to be 0.14 and 0.3 eV, respectively, by measuring the temperature dependence of the forward current at a low sub-barrier bias. The resulting low hole injection barrier is accounted for by the presence of defect state density spreading from the valence band edge into the In2O3 : Er band gap to form a hole conduction channel. The presence of defect state density in the In2O3 : Er band gap is confirmed by photoluminescence data in the respective energy range 1.55–3.0 eV. The band structure of the Si/In2O3 : Er heterojunction has been analyzed. The energy gap between the In2O3 : Er conduction band electrons and the band gap conduction channel holes has been estimated to be 1.56 eV.

Tunable charge injection from graphene to halide perovskite induced by reversible ion segregation

Migration of point defects can result in various performance instabilities in organometal halide perovskite devices. In particular, the segregation of charged defects can influence the electron transport, but the correlation between ionic and electronic transports remains elusive. In this work, we use a graphene/methylammonium lead iodide capacitor to probe the effect of ion segregation on the charge injection behavior at the graphene/perovskite junction. In our samples, the ion segregation in the perovskite film is induced by a controllable electric field applied through an electrostatic gate. At the same time, the charge injection from graphene to the perovskite is probed by monitoring changes in the graphene conductivity. It is found that a positive (negative) defect accumulation layer near the graphene/perovskite interface can facilitate electron (hole) injection from the graphene electrode to the perovskite. Because the polarity of the defect accumulation layer is switchable by changing the direction of the applied electric field, the graphene/perovskite interface behaves like a Schottky junction with a tunable charge injection barrier height. This behavior should be generally found in other metal/halide perovskite interfaces as well.

Utilizing VO2 as a Hole Injection Layer for Efficient Charge Injection in Quantum Dot Light-Emitting Diodes Enables High Device Performance.

Quantum dot light-emitting diodes (QLEDs) are promising devices for display applications. Polyethylenedioxythiophene:polystyrene sulfonate (PEDOT:PSS) is a common hole injection layer (HIL) material in optoelectronic devices because of its high conductivity and high work function. Nevertheless, PEDOT:PSS-based QLEDs have a high energy barrier for hole injection, which results in low device efficiency. Therefore, a new strategy is needed to improve the device efficiency. Herein, we have demonstrated a bilayer-HIL using VO2 and a PEDOT:PSS-based QLED that exhibits an 18% external quantum efficiency (EQE), 78 cd/A current efficiency (CE), and 25,771 cd/m2 maximum luminance. In contrast, the PEDOT:PSS-based QLED exhibits an EQE of 13%, CE of 54 cd/A, and maximum luminance of 14,817 cd/m2. An increase in EQE was attributed to a reduction in the energy barrier between indium tin oxide (ITO) and PEDOT:PSS, caused by the insertion of a VO2 HIL. Therefore, our results could demonstrate that using a bilayer-HIL is effective in increasing the EQE in QLEDs.

Modulating J-V hysteresis of planar perovskite solar cells and mini-modules via work function engineering

Commercialization of perovskite solar cells (PSCs) requires the development of high-efficiency devices with none current density-voltage (J-V) hysteresis. Here, electron transport layers (ETLs) with gradual change in work function (WF) are successfully fabricated and employed as an ideal model to investigate the energy barriers, charge transfer and recombination kinetics at ETL/perovskite interface. The energy barrier for electron injection existing at ETL/perovskite is directly assessed by surface photovoltage microscopy, and the results demonstrate the tunable barriers have significant impact on the J-V hysteresis and performance of PSCs. By work function engineering of ETL, PSCs exhibit PCEs over 21% with negligible hysteresis. These results provide a critical understanding of the origin reason for hysteresis effect in planar PSCs, and clear reveal that the J-V hysteresis can be effectively suppressed by carefully tuning the interface features in PSCs. By extending this strategy to a modified formamidinium-cesium-rubidium (FA-Cs-Rb) perovskite system, the PCEs are further boosted to 24.18%. Moreover, 5 cm × 5 cm perovskite mini-modules are also fabricated with an impressive efficiency of 20.07%, demonstrating compatibility and effectiveness of our strategy on upscaled devices.

Unraveling the injection barrier between electrode and organic layer in OLED device: A theoretical prediction model

This study developed a new prediction model for hole injection barriers. Based on the electronegativity equalized model (EEM), the vacuum level shift in the adjacent layers was further considered in this model. In addition, the variation in ΦITO, which is dependent on the doping concentration of Sn, was considered as one of the determinants for predicting the hole injection barrier (HIB) between ITO and the organic layer. Further, the effect of p-dopants on the HTL energy level was also introduced in this model. The predicted HIBs of various anode/organic junctions were quantitatively and qualitatively consistent with UPS experiments. We believe that the developed EEM model can aid in determining the appropriate HTL/HIL organic materials without tremendous effort and time costs.

Reduction of solution-processed copper-oxide-based transistors’ contact resistance using aluminium electrodes

MOSs have drawn great attention in recent years for their potential for low-cost applications. In particular, solution-processed copper oxide transistors have been envisioned; however, research on these has struggled because of their low effective mobility and the high cost of metals used for injection electrodes. Here we report the application of gold and aluminium in source/drain electrodes of the device using cupric oxide as an active layer. Detailed analysis of the contact resistance illustrates a lower injection barrier for aluminium electrodes, making them a suitable replacement for high-cost gold electrodes.

Highly Efficient ITO-Free Quantum-Dot Light Emitting Diodes via Solution-Processed PEDOT:PSS Semitransparent Electrode.

We present a study on the potential use of sulfuric acid-treated poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a viable alternative to indium tin oxide (ITO) electrodes in quantum dot light-emitting diodes (QLEDs). ITO, despite its high conductivity and transparency, is known for its disadvantages of being brittle, fragile, and expensive. Furthermore, due to the high hole injection barrier of quantum dots, the need for electrodes with a higher work function is becoming more significant. In this report, we present solution-processed, sulfuric acid-treated PEDOT:PSS electrodes for highly efficient QLEDs. The high work function of the PEDOT:PSS electrodes improved the performance of the QLEDs by facilitating hole injection. We demonstrated the recrystallization and conductivity enhancement of PEDOT:PSS upon sulfuric acid treatment using X-ray photoelectron spectroscopy and Hall measurement. Ultraviolet photoelectron spectroscopy (UPS) analysis of QLEDs showed that sulfuric acid-treated PEDOT:PSS exhibited a higher work function than ITO. The maximum current efficiency and external quantum efficiency based on the PEDOT:PSS electrode QLEDs were measured as 46.53 cd/A and 11.01%, which were three times greater than ITO electrode QLEDs. These findings suggest that PEDOT:PSS can serve as a promising replacement for ITO electrodes in the development of ITO-free QLED devices.

Improving Charge Injection for Organic Field‐Effect Transistor Array via Chemical Functionalized Van der Waals Top‐Contacts

AbstractEfficient charge injection at metal/semiconductor interface is of great importance for high‐performance organic field‐effect transistors (OFETs). In OFETs, top‐contact configuration generally exhibits better injection efficiency but may induces thermal damage to organic layer and is intrinsically difficult to modified with chemisorbs at metal/semiconductor interface. Herein, a versatile, large‐scale and damage‐free metal integration strategy is reported to achieve efficient charge injection in OFETs by applying self‐assembly monolayers (SAMs) functionalized van der Waals (vdW) top‐contact electrodes. Centimeter scale metal electrodes are transferred onto organic single crystal to form OFETs array without residual left. vdW contact provides a clear and atomic sharp interface, and thus the inherent electronic structure and physical properties of the pristine heterostructure interface can be retained. Modifying fluorinated SAMs at metal/semiconductor interface alters the work function of Au by 350 meV, and thus reduces the energy barrier for charge injection. As a result, OFETs array exhibits excellent performance characteristics with an average mobility of 3.6 cm2 V−1 s−1, negligible hysteresis and a high on/off ratio above 106 on high‐k AlOx dielectric. Organic unipolar inverters based on all vdW contact are also demonstrated. This strategy paves the way for both fundamental study and practical applications of organic electronics.

Self‐Assembled Molecule Doping Enables High‐Efficiency Hole‐Transport‐Layer‐Free Perovskite Light‐Emitting Diodes

AbstractHole‐transport‐layer‐free (HTL‐free) perovskite light‐emitting diodes (PeLEDs) are attracting increasing research attention because of their simplified device structure, fast preparation process, and high cost effectiveness. However, their much lower external quantum efficiency (EQE) as compared with the conventional p‐i‐n type ones has considerably limited their application prospects. Here, a self‐assembled molecule (SAM) doping strategy is proposed by introducing [4‐(3,6‐dimethyl‐9H‐carbazol‐9‐yl) butyl] phosphonic acid (Me‐4PACz) containing PO functional groups into the perovskite precursor solution and preparing the HTL‐free quasi‐2D perovskite films through the one‐step spin‐coating process. The doped Me‐4PACz molecules can not only accumulate at the ITO/perovskite interface to lower the hole injection barrier, but also extend deep into the perovskite layer to suppress the trap density in perovskite films and regulate the crystallization process for monodispersed phase composition. With the further addition of ethoxylated trimethylolpropane triacrylate small molecule containing CO groups to passivate the defects synergistically with Me‐4PACz, the EQE of the corresponding device is boosted from 1.5% to 16.7% together with a 3.5‐fold increase in operational stability, which is the highest efficiency reported so far for HTL‐free PeLEDs. The results demonstrate that the SAM doping strategy can be a viable and facile way to prepare high‐performance HTL‐free PeLEDs for practical applications.

Bright Blue Light‐Emitting Diodes Based on Well‐Modified Carbon Dots by Designing Co‐Host Systems to Balance Carriers’ Injection

AbstractLeveraging bright and stable carbon dots (CDs) for blue light‐emitting diodes (LEDs) is a prospective but challenging topic. Aggregation‐caused quenching (ACQ) of CDs and device engineering of CDs‐LEDs are two issues. Here, blue CDs with quantum yield of 59.75% are synthesized. Hydrogen bonds increase rigidity and facilitate luminescence, while polymer chains increase spatial resistance and resist ACQ. Then, solution‐processed blue CDs‐LEDs are assembled by blending CDs into poly(N‐vinylcarbazole) (PVK) as light‐emitting layer (EML). Furthermore, several other materials are also employed as the second host to reduce injection barrier, facilitate carriers’ transport, and balance carriers’ distribution. In particular, the blue CDs‐LED based on the co‐host system of PVK and 4‐[1‐[4‐[bis(4‐methylphenyl)amino]phenyl]cyclohexyl]‐N‐(3‐methylphenyl)‐N‐(4‐methylphenyl)benzenamine (TAPC) achieves a maximum brightness up to 827.60 cd m−2. This work is a step forward for applying CDs in LEDs.

Suppression of Ionic and Electronic Conductivity by Multilayer Heterojunctions Passivation Toward Sensitive and Stable Perovskite X‐Ray Detectors

AbstractOrganic‐inorganic hybrid perovskites are promising candidates for direct X‐ray detection and imaging. The relatively high dark current in perovskite single crystals (SCs) is a major limiting factor hindering the pursuit of performance and stability enhancement. In this study, the contribution of dark current is disentangled from electronic (σe) and ionic conductivity (σi) and shows that the high σi dominates the dark current of MAPbBr3 SCs. A multilayer heterojunctions passivation strategy is developed that suppresses not only the σi by two orders of magnitude but also σe by a factor of 1.6. The multilayer heterojunctions passivate the halide vacancy defects and increase the electron and hole injection barrier by inducing surface p‐type doping of MAPbBr3. This enables the MAPbBr3 SC X‐ray detectors to obtain a high sensitivity of 19 370 µC Gyair−1 cm−2 under a high electric field of 100 V cm−1, a record high sensitivity for bromine self‐powered devices, and a low detection limit of 42.3 nGyair s−1. The unencapsulated detectors demonstrate a stable baseline after storage for 210 days and outstanding operational stability upon irradiation with an accumulated dose of up to 1944 mGyair.

High‐Efficiency and Narrow‐Band Near‐Ultraviolet Emitters with Low CIEy of 0.03 by Incorporating Extra Weak Charge Transfer Channel into Multi‐Resonance Skeleton

AbstractHybridized local and charge‐transfer (HLCT) excited‐state emitters can effectively utilize non‐radiative triplet excitons through high‐lying reverse intersystem crossing (hRISC), but they are mostly limited to the donor‐π‐acceptor type molecules. It is a great challenge to develop high‐performance near‐ultraviolet (NUV) emitters with narrow‐band emission by HLCT due to the large carrier injection barriers and high triplet energy. In this work, by incorporating planar multi‐resonance (MR) skeleton of oxygen‐bridged triphenylborane (BO) and weak electron‐donating unit of tetraphenyl‐silane (TPS), two NUV emitters of tBOSi and tBOSiCz are developed, where an extra weak charge transfer (CT) channel between BO skeleton and peripheral phenyl in TPS is observed to increase CT component and activate hot exciton channel of hRISC. As a result, tBOSi and tBOSiCz show an outstanding narrow‐band NUV emission at 414 nm with a FWHM of about 32 nm in solution‐processed organic light‐emitting diodes (OLEDs), even at a heavy doping ratio. The best NUV electroluminescent properties are further achieved in the optimal tBOSi‐doped OLEDs with a record efficiency of 9.15% and a low CIEy of 0.034. This work provides a profound guidance for developing high‐performance narrow‐band NUV emitters by an extra weak CT channel into MR skeleton to activate HLCT emission.

Effect of trap position on the electrical properties of unipolar organic semiconductor devices

We investigated the electrical properties of a unipolar organic device by intentionally inserting traps at specific positions within the device. Our findings demonstrate that the trap position has a considerable impact on the charge distribution, electric field, and charge transport behavior of the device. In particular, when the traps are positioned closer to a charge-injection electrode, the organic layer containing the traps experiences more significant band bending, resulting in a higher charge injection barrier. We propose an electrical model that fully explains the observed changes in the electrical properties of the device as a function of trap position.

Work function and energy level alignment tuning at Ti3C2Tx MXene surfaces and interfaces using (metal-)organic donor/acceptor molecules

Two-dimensional MXenes, with ${\mathrm{Ti}}_{3}{\mathrm{C}}_{2}{\mathrm{T}}_{x}$ being the most prominent member, show properties that make them promising for a manifold of applications, including electrodes in light-emitting diodes, solar cells, and field-effect transistors based on organic semiconductors. In these cases, the work function of MXenes plays an important role in the energy level alignment to the subsequently deposited organic layer, as it determines the electron and hole injection barriers. Therefore, methods for controlling the ${\mathrm{Ti}}_{3}{\mathrm{C}}_{2}{\mathrm{T}}_{x}$ work function should be developed. We demonstrate that, by using thin layers of (metal-)organic donor/acceptor molecules, the work function of ${\mathrm{Ti}}_{3}{\mathrm{C}}_{2}{\mathrm{T}}_{x}$ can be tuned over a range of $>3$ eV. This enables tuning the energy level alignment to a subsequently deposited organic semiconductor, all the way from intrinsic Fermi level pinning at the highest occupied molecular energy level (minimal hole injection barrier) to pinning at the lowest unoccupied level (minimal electron injection barrier). Furthermore, it is shown that a predominantly oxygen-terminated surface does not lead to an extraordinary high work function, in contrast to theoretical predictions. The proposed strategy may greatly expand the use of MXenes in conjunction with organic hole and electron transport layers in optoelectronic devices.

Effect of titanium-dioxide nanoparticle on Richardson constant and barrier height of tartrazine dye based Schottky device

Recently Fruit Dyes have achieved a significant interest as organic devices because of they are widely available, customizable and biodegradable. But low conductivity is one of the major limitations. Low conductivity is due to low charge injection from the electrodes to the organic layer and the charge injection process is strongly dependent on the injection barrier height at the metal-dye interface. Higher barrier height causes low charge injection. A detailed analysis is needed to reduce the interfacial barrier to get better conductivity. In this work, we have estimated the interfacial barrier height of Indium tin oxide coated glass/Tartrazine dye/Copper based device with and without titanium dioxide nanoparticles. The devices have been prepared with dye and dye-nanoparticles blends by using the spin coating technique. We have measured the steady state dark current–voltage–temperature characteristics in the range of 288 K to 333 K to estimate the Richardson constant and interfacial barrier height. The Richardson constant was found to be modified from 44.35 × 10–3 to 07.34 × 10–3 Am−2 K−2. We also have found that interfacial barrier height is reduced from 0.71 eV to 0.64 eV in the presence of nanoparticles at room temperature. As the temperature increased, the interfacial barrier height increased to 0.72 eV from 0.71 eV and to 0.68 eV from 0.62 eV for dye based device with and without nanoparticles, respectively. Reduction of the interfacial barrier height indicates an increase in the charge injection through the interface. This work will be informative to improve the charge flow at the metal–fruit dye interface.

Experimental and Theoretical Evidence of Charge Injection Barrier Control by Small-Molecular Charge Injection Layer and Its Effects on Organic–Inorganic Complementary Inverters

Introducing a contact charge injection layer at the interface between the contact electrode and active materials is considered crucial to obtain efficient charge injection behaviors in thin-film transistors (TFTs). Here, we investigate the effect of a small molecule contact charge injection layer through experimental results and theoretical calculations. We found limited electrical characteristics derived from contact resistance in C8-BTBT TFTs with C8-BTBT as the channel and Au as the electrode. We experimentally demonstrated that the limited electrical characteristics of C8-BTBT TFT can be improved by inserting dinaphtho[2,3-b: <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$2^{\prime} $ </tex-math></inline-formula> , <inline-formula xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink"> <tex-math notation="LaTeX">$3^{\prime} $ </tex-math></inline-formula> -f]thieno [3,2-b] thiophene (DNTT), which has a low contact resistance at the junction with Au, as a charge injection layer. The results of improved contact properties through the DNTT charge injection layer were also consistent with the results of energy structural simulations. Furthermore, we verified the effect of the DNTT charge injection layer at the circuit level through improved noise margin characteristics in the complementary inverter composed of asymmetric charge injection layer TFT (ACIL-TFT) and a-indium gallium zinc oxide (IGZO) TFT.