Organic Vapor Phase Deposition Research Articles

Optical Properties and Growth Characteristics of 8-Quinolinolato Lithium (Liq) Nano-Layers Deposited by Gas Transport Deposition.

Organometallic complexes containing reactive alkali metals, such as lithium (Li), represent a promising material approach for electron injection layers and electron transport layers (EILs and ETLs) to enhance the performance of Organic Light-Emitting Diodes (OLEDs). 8-Quinolinolato Lithium (Liq) has shown remarkable potential as an EIL and ETL when conveyed in very thin films. Nevertheless, the deposition of nano-layers requires precise control over both thickness and morphology. In this work, we investigate the optical properties and morphological characteristics of Liq thin films deposited via Organic Vapor Phase Deposition (OVPD). Specifically, we present our methodology for analyzing the measured pseudodielectric function <ε(ω)> using Spectroscopic Ellipsometry (SE), alongside the nano-topography of evaporated Liq nano-layers using Atomic Force Microscopy (AFM). This information can contribute to the understanding of the functionality of this material, since ultra-thin Liq interlayers can significantly increase the operational stability of OLED architectures.

Numerical modeling and investigation of material mixing and utilization during organic vapor phase deposition

Numerical modeling and investigation of material mixing and utilization during organic vapor phase deposition

Ferroelectric-like behavior in HfO2/Al2O3/AlN metal-insulator-semiconductor capacitor through AlN thermal stress

By modulating the thermal stress during film growth, the strained aluminum nitride (AlN) thin films with ferroelectric-like behavior were successfully grown by metal organic chemical vapor phase deposition (MOCVD) on silicon (Si) (111) substrate. The capacitors with strained AlN were fabricated and experimentally demonstrated, the linear to ferroelectric-like behavior on the fabricated AlN capacitors was observed, and the behavior was explained in terms of residual strains in the film. This work reports the ferroelectric-like properties of AlN film grown under specific deposition conditions for the first time.

Luminance enhancement of top-emitting blue organic light emitting diodes encapsulated with silicon nitride thin films by a double-layer nano-structure

Even though it is in high demand to introduce a nano-structure (NS) light extraction technology on a silicon nitride to be used as a thin film encapsulation material for an organic light-emitting diode (OLED), only an industry-incompatible wet method has been reported. This work demonstrates a double-layer NS fabrication on the silicon nitride using a two-step organic vapor phase deposition (OVPD) of an industry-compatible dry process. The NS showed a wrinkle-like shape caused by coalescence of the nano-lenses. The NS integrated top-emitting OLED revealed 40 percent enhancement of current efficiency and improvement of the luminance distribution and color change according to viewing angle.

Simulation study on the diversity and characteristics of twin structures in GaN

Gallium nitride (GaN) is a promising material for high-frequency and high-power electronics owing to its high thermal stability, wide bandgap, and high breakdown voltage. Monocrystalline GaN films are usually produced by metal organic chemical vapor phase deposition using Si, SiC, or Al 2 O 3 as the substrate. However, the difference in lattice constants and thermal expansion coefficients causes many defects in GaN epilayers . In particular, the formation of twins will strongly influence the electronic properties of GaN-based devices. In this study, the solidification process of GaN was simulated by molecular dynamics at a cooling rate of 10 12 K/s, and the twin structures in GaN were discussed. The results of this simulation showed two types of twins, including coherent twin and rotating twin, which were analyzed by visualization technology. The formation of twins was related to the coexistence of zinc blende and wurtzite phases. Furthermore, the types of twins were closely associated to the stacking ways of zinc blende and wurtzite structures. In general, it is essential to study the microstructure and the structural evolution of twin GaN, in order to give references to experiments about the growth and characteristics of twins. • Zinc blende and wurtzite nucleated randomly and formed lots of complex structures at the beginning of crystallization. • Coherent and rotating twins were formed according to different stacking methods of zinc blende and wurtzite structures. • The rules for the combination of twin structures in GaN crystals have been summarized and it can be generalized. • An error in the stacking sequence can cause the metastable phase c-GaN to start seeding the h-GaN phase.

Identification of Star Defects in Gallium Nitride with HREBSD and ECCI.

This paper characterizes novel “star” defects in GaN films grown with metal–organic vapor phase deposition (MOVPE) on GaN substrates with electron channeling contrast imaging (ECCI) and high-resolution electron backscatter diffraction (HREBSD). These defects are hundreds of microns in size and tend to aggregate threading dislocations at their centers. They are the intersection of six nearly ideal low-angle tilt boundaries composed of $\langle a\rangle$-type pyramidal edge dislocations, each on a unique slip system.

Heat Dissipation in Flexible Nitride Nanowire Light-Emitting Diodes.

We analyze the thermal behavior of a flexible nanowire (NW) light-emitting diode (LED) operated under different injection conditions. The LED is based on metal–organic vapor-phase deposition (MOCVD)-grown self-assembled InGaN/GaN NWs in a polydimethylsiloxane (PDMS) matrix. Despite the poor thermal conductivity of the polymer, active nitride NWs effectively dissipate heat to the substrate. Therefore, the flexible LED mounted on a copper heat sink can operate under high injection without significant overheating, while the device mounted on a plastic holder showed a 25% higher temperature for the same injected current. The efficiency of the heat dissipation by nitride NWs was further confirmed with finite-element modeling of the temperature distribution in a NW/polymer composite membrane.

Fast Organic Vapor Phase Deposition of Thin Films in Light-Emitting Diodes.

Fast deposition of thin films is essential for achieving low-cost, high-throughput phosphorescent organic light-emitting diode (PHOLED) production. In this work, we demonstrate rapid and uniform growth of semiconductor thin films by organic vapor phase deposition (OVPD). A green PHOLED comprising an emission layer (EML) grown at 50 Å/s with bis[2-(2-pyridinyl-N)phenyl-C](acetylacetonato)iridium(III) (Ir(ppy)2(acac)) doped into 4,4'-bis(N-carbazolyl)-1,1'-biphenyl (CBP) exhibits a maximum external quantum efficiency of 20 ± 1%. The morphology, charge transport properties, and radiative efficiency under optical and electrical excitation of the PHOLED EML are investigated as functions of the deposition rate via both experimental and theoretical approaches. The EML shows no evidence for gas phase nucleation of the organic molecules at deposition rates as high as 50 Å/s. However, the roll-off in quantum efficiency at high current progressively increases with deposition rate due to enhanced triplet-polaron annihilation. The roll-off results from accumulation of stress within the PHOLED EML that generates a high density of defect states. The defects, in turn, act as recombination sites for triplets and hole polarons, leading to enhanced triplet-polaron annihilation at high current. We introduce a void nucleation model to describe the film morphology evolution that is observed using electron microscopy.

The formation of an optically functional nano-lens array by substrate surface treatment

Recently, a nano-lens array (NLA) technology has been developed to greatly enhance light extraction efficiencies and color stabilities of red, green and blue organic light-emitting diodes. The fabrications of N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (C44H32N2, NPB) NLAs on oxide layers were accomplished by an organic vapor phase deposition during which surface tensions of NPB were increased by its crystallization. To emphasize the importance of the fabrication technology, the kinds of substrate materials on which NLAs are formed should be extended to high surface energy nitrides. Herein, to understand the role of the surface condition of a silicon nitride substrate in the formation of NLA, three types of nitride substrates are prepared by using surface treatment, while one NPB deposition recipe is used. Very interestingly, even though nano-lens is not observed in an untreated substrate with high surface energy, nano-lens is formed by surface treatment and the resulting decrease in surface energy. This indicates that NLA formation is not limited to an oxide substrate, but is determined by the difference in surface energy values between a substrate and a deposited material on the substrate. Furthermore, the morphological change of NPB by surface treatment is extensively discussed using contact angle experiments.

Optimization of Transparent Organic Light-Emitting Diodes by Simulation-Based Design of Organic Capping Layers.

In this work, we use the transfer matrix method to optimize TPBi capping layers deposited on organic light emitting diodes with respect to light extraction and transmittance. The green transparent organic light emitting diodes comprise three organic semiconductors (CBP, Ir(ppy)₃ and TPBi) forming an efficient simplified phosphorescent organic light emitting diode stack. A transparent cathode of 2 nm Cs₂CO₃, 2 nm Al and 16 nm Au is deposited by thermal evaporation. The diode stack as well as the capping layer are deposited by organic vapor phase deposition. The refractive indices and extinction coefficients of all materials in the transparent organic light emitting diodes (glass, indium tin oxide, organic semiconductors and cathode) are determined using spectroscopic ellipsometry combined with optical transmittance and reflectance measurements. With these spectrally resolved data, we calculate the transmittance of transparent organic light emitting diodes with TPBi capping layers of different thicknesses. The results were validated with high accuracy in the visible spectral range and beyond (360 nm-1000 nm) by a series of experiments. By choosing a TPBi capping layer of optimized thickness (here 50 nm), we fabricated transparent organic light emitting diodes with an optical transmittance which was strongly enhanced from 47% (reference without capping layer) to 65%, measured at 555 nm.

Surface passivation of InP using an organic thin film

We demonstrate the surface passivation of InP using thin layers of a perylenetetracarboxylic diimide derivative (PTCDI-C9) applied via organic vapor phase deposition (OVPD). The organic layer forms a conformal crystalline film on the InP surface, which is confirmed by atomic force microscopy and X-ray diffraction. Area-dependent photoluminescence measurements indicate that the coating reduces surface recombination. The organic thin film deposited by OVPD exhibits improved photoconductivity compared to an unpassivated InP sample, and to a layer deposited via vacuum thermal evaporation. Our results suggest that semiconductor surface passivation using organic thin films deposited by OVPD has applications to a variety of optoelectronic devices, particularly with structures requiring sidewall or conformal coatings.

Continuous roll-to-roll fabrication of organic photovoltaic cells via interconnected high-vacuum and low-pressure organic vapor phase deposition systems

We demonstrate continuous roll-to-roll (R2R) fabrication of single junction and tandem organic photovoltaic (OPV) cells on flexible plastic substrates employing a system that integrates organic deposition by high vacuum thermal evaporation (VTE) and low pressure organic vapor phase deposition (OVPD). By moving the substrate from chamber to chamber and then depositing films on stationary substrates, we achieve power conversion efficiencies of PCE = 8.6 ± 0.3% and 8.9 ± 0.2% for the single junction and tandem cells, respectively. Single junction OPVs are also fabricated on a continuously translating substrate at 0.3 cm/s, to achieve PCE = 8.5 ± 0.2%. Thin films grown on translating substrates by OVPD show &amp;lt;3% thickness non-uniformity and 0.66 nm root mean square surface roughness, similar to that obtained by VTE. Our results suggest that R2R film deposition comprising multiple vapor deposition technologies is a promising method for rapid speed and continuous manufacturing of high quality, small molecular weight organic electronic materials.

Zirconium Tetrakis(8-hydroxyquinolinolate) and Lithium Schiff-Base Cluster Complex for Efficient Charge Injection and Transfer in Green PHOLED processed by OVPD

ABSTRACTTypical electron transport (2,2′,2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi)) and injection (Cs2CO3) materials are successfully replaced by zirconium tetrakis(8-hydroxyquinolinolate) (Zrq4) and lithium 2-((o-tolylimino)methyl)-phenolate (EI-111) in simplified OLED (organic light-emitting diodes) processed by organic vapor phase deposition (OVPD). The performance of combining Zrq4 and EI-111 is analyzed in unipolar devices and compared to devices with configurations of Zrq4/Cs2CO3, TPBi/EI-111 and TPBi/Cs2CO3. Current density-voltage (J-V) measurements are performed and correlated to different carrier injection and transport properties. The investigated material combinations are implemented in the simplified OLED structures and compared to each other. To account for the high HOMO level of Zrq4, 5 nm of TPBi are added to confine holes and excitons in the emissive layer (EML) and to improve device performance. After tailoring the organic stack for OLED with Zrq4, a remarkable boost in device efficiency is observed. The luminous efficacy increased from 3.0 to 21.9 lm/W and the EQE from 2.1 to 11.0 % for a device with Zrq4/EI-111. Furthermore, OLED having Zrq4/Cs2CO3 show an even greater enhancement to 26.3 lm/W and 11.7 %.

Wafer‐Scale Epitaxial 1T′, 1T′–2H Mixed, and 2H Phases MoTe2 Thin Films Grown by Metal–Organic Chemical Vapor Deposition

Abstract2D materials beyond molybdenum disulfide such as molybdenum ditelluride (MoTe2) have attracted increasing attention because of their distinctive properties, such as phase‐engineered, relatively narrow direct bandgap of 1.0–1.1 eV and superior carrier transport. However, a wafer‐scale synthesis process is required for achieving practical applications in next‐generation electronic devices using MoTe2 thin films. Herein, the direct growth of atomically thin 1T′, 1T′–2H mixed, and 2H phases MoTe2 films on a 4 in. SiO2/Si wafer with high spatial uniformity (≈96%) via metal–organic vapor phase deposition is reported. Furthermore, the wafer‐scale phase engineering of few‐layer MoTe2 film is investigated by controlling the H2 molar flow rate. While the use of a low H2 molar flow rate results in 1T′ and 1T′–2H mixed phase MoTe2 films, 2H phase MoTe2 films are obtained at a high H2 molar flow rate. Field‐effect transistors fabricated with the prepared 2H and 1T′ phases MoTe2 channels reveal p‐type semiconductor and semimetal properties, respectively. This work demonstrates the potential for reliable wafer‐scale production of 1T′ and 2H phases MoTe2 thin films employing the H2 molar flow rate‐controlled phase tunable method for practical applications in next‐generation electronic devices as a p‐type semiconductor and Wyle semimetal.

Defect formation and optical activation of Tb implanted AlxGa1−xN films using channeled implantation at different temperatures

AlxGa1−xN (x = 0.20, 0.50, 0.63) films grown on (0001) sapphire substrates by metal organic chemical vapor phase deposition were implanted with Tb ions at 150 keV and a fluence of 7 × 1014 Tb cm−2. The implantation was carried out with the beam aligned with the c-axis and the implantation temperature was varied from room temperature (RT) to 550 °C. Additionally, post-implantation rapid thermal annealing was performed at 1200 °C during 120 s. The impact of implantation temperature on the damage accumulation is investigated. Rutherford backscattering spectrometry/channeling (RBS/C) measurements show that two damage regions are forming and the damage is not decreasing monotonically with the increase of implantation temperature. Bulk damage follows the same trend for all AlxGa1−xN compositions, increasing when the temperature is raised up to ~100 °C, and then decreasing for higher temperatures. A good agreement is observed between the damage accumulation obtained from RBS/C and the strain profile derived from symmetric (0002) 2θ-ω X-ray diffraction scans. Transmission electron microscopy results show the suppression of basal stacking faults after implantation at 550 °C. Tb lattice site location studies revealed two preferential sites: the substitutional cation site and a site displaced from that by 0.2 Å along the c-axis. A higher substitutional fraction of Tb ions is obtained for implantation temperature of 550 °C. The optical activity investigated by photoluminescence showed that after thermal annealing, the 5D4 → 7FJ intra-4f8 transition is detected in all the samples.

Correction to Nanoscale Control of Morphology in Fullerene-Based Electron-Conducting Buffers via Organic Vapor Phase Deposition.

Correction to Nanoscale Control of Morphology in Fullerene-Based Electron-Conducting Buffers via Organic Vapor Phase Deposition.

Simplified efficient phosphorescent organic light-emitting diodes by organic vapor phase deposition

The most efficient phosphorescent organic light-emitting diodes (OLEDs) are comprised of complex stacks with numerous organic layers. State-of-the-art phosphorescent OLEDs make use of blocking layers to confine charge carriers and excitons. On the other hand, simplified OLEDs consisting of only three organic materials have shown unexpectedly high efficiency when first introduced. This was attributed to superior energy level matching and suppressed external quantum efficiency (EQE) roll-off. In this work, we study simplified OLED stacks, manufactured by organic vapor phase deposition, with a focus on charge balance, turn-on voltage (Von), and efficiency. To prevent electrons from leaking through the device, we implemented a compositionally graded emission layer. By grading the emitter with the hole transport material, charge confinement is enabled without additional blocking layers. Our best performing organic stack is composed of only three organic materials in two layers including the emitter Ir(ppy)3 and yields a Von of 2.5 V (&amp;gt;1 cd/m2) and an EQE of 13% at 3000 cd/m2 without the use of any additional light extraction techniques. Changes in the charge balance, due to barrier tuning or adjustments in the grading parameters and layer thicknesses, are clearly visible in the current density-voltage-luminance (J-V-L) measurements. As charge injection at the electrodes and organic interfaces is of great interest but difficult to investigate in complex device structures, we believe that our simplified organic stack is not only a potent alternative to complex state-of-the-art OLEDs but also a well suited test vehicle for experimental studies focusing on the modification of the electrode-organic semiconductor interface.

Backside Contacting for Uniform Luminance in Large-Area OLED

ABSTRACTWe have investigated organic light emitting diode (OLED) backside contacting for the enhancement of luminance uniformity as a superior alternative to gridlines. In this approach, the low-conductivity OLED anode is supported by a high-conductivity auxiliary electrode and vertically contacted through via holes. Electrical simulations of large-area OLEDs have predicted that this method allows comparable luminance uniformity while sacrificing significantly less active area compared to the common gridline approach.The method for fabricating backside contacts is comprised of five steps: (1) Thin-film encapsulation of the OLED, (2) Patterning of the OLED surface with lithography (resist mask defining via hole positions), (3) Via hole formation to the bottom anode by a plasma etching process, (4) Organic residues removal and sidewall insulation. (5) Contacting of the anode with a high-conductivity auxiliary electrode.Backside-contacted OLEDs processed by organic vapor phase deposition show high luminance uniformity. Scanning electron microscopy pictures and electrical breakthrough measurements confirm efficient sidewall insulation.

Multilayer porous structures of HVPE and MOCVD grown GaN for photonic applications

In this paper we report on a comparative study of electrochemical processes for the preparation of multilayer porous structures in hydride vapor phase epitaxy (HVPE) and metal organic chemical vapor phase deposition (MOCVD) grown GaN. It was found that in HVPE-grown GaN, multilayer porous structures are obtained due to self-organization processes leading to a fine modulation of doping during the crystal growth. However, these processes are not totally under control. Multilayer porous structures with a controlled design have been produced by optimizing the technological process of electrochemical etching in MOCVD-grown samples, consisting of five pairs of thin layers with alternating-doping profiles. The samples have been characterized by SEM imaging, photoluminescence spectroscopy, and micro-reflectivity measurements, accompanied by transfer matrix analysis and simulations by a method developed for the calculation of optical reflection spectra. We demonstrate the applicability of the produced structures for the design of Bragg reflectors.

Experimental and theoretical studies of the structure and optical properties of nickel phthalocyanine nanowires

By using organic vapor phase deposition method, nickel phthalocyanines (NiPc) nanowires were successfully prepared, and the effects of heating temperature on the structural and optical properties of NiPc nanowires were investigated. Both the crystal structures of NiPc powders and nanowires are studied by x-ray diffraction patterns (XRD) and Fourier transform infrared spectra (FTIR). The lattice constants of NiPc nanowires from the fitting of XRD patterns are a = 13.04 Å, b = 3.75 Å, c = 24.32 Å, β = 94.10°, belonging to the space group of monoclinic (P21/c). X-ray photo-electron spectroscopy (XPS) suggests main peaks at 284.82 eV and 286.18 eV for C-C and C-N bonds and two peaks at 397.8 eV and 398.8 eV for N-C and the N–Ni bonds, respectively, in NiPc nanowires. FTIR spectra show a structural transition from powder to nanowire. The optical properties of NiPc nanowires have been investigated via a comparison between theoretical and experimental approaches. The most significant absorption peaks of NiPc nanowires in the visible region are located at 626 nm and 672 nm, showing a blue shift comparing with the β-NiPc. We have also theoretically revealed the excitation energies in NiPc single molecule and dimer in the form of α and β phases using time-dependent density-functional theory. These theoretical results are in qualitative agreement with the measurements of optical properties. Moreover, no noticeable change in crystalline form is shown when tuning the heating temperature from 420 °C to 450 °C, suggesting a wide synthesis temperature window. The reduced Ni-Ni distance indicated a clear advantage over powder in terms of potential applications in organic electronics.