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Mask Free OLED Fabrication Process for Non-Tunable and Tunable White OLED Panels
In this program we demonstrated a method for mask free fabrication of OLEDs. Conventional OLEDs use at least 2 shadowmasks during the fabrication process to define the deposition pattern for the organic layers and for the cathode layer. Although effective, the use of masks requires mask handling and mask change equipment which increases the cost of the OLED deposition system. New sets of masks are required for every new product design, and the mask sets require frequent cleaning as organic material builds up on the masks over time and can be a source of particle defects resulting in yield loss. The method investigated in this program uses laser removal of organic material to pattern the organic layers and define a moisture impermeable seal region. This method is digital and can be applied to any new panel design, avoiding the costs of new masks sets and associated yield loss. In addition, we developed a platform technology for producing white color tunable or dim-to-warm white OLEDs and demonstrated patterning of tunable white OLEDs using the low-cost mask free fabrication process.
Highly Efficient Blue OLEDs Based on Metal‐Assisted Delayed Fluorescence Pd(II) Complexes
Abstract A series of metal‐assisted delayed fluorescence (MADF) palladium(II) complexes, PdN1N, PdN1N‐dm, and PdN6N, are studied. Their 77 K photoluminescence emission spectra show a narrow primary emission peak at 464, 466, and 470 nm, respectively, with small vibronic peaks characteristic of many phosphorescent emitters. At room temperature (300 K), the dominant emission peaks for PdN1N, PdN1N‐dm, and PdN6N are slightly redshifted to 472, 470, and 476 nm, respectively. In the meantime, a broad sideband is also shown between 410 and 450 nm due to the MADF process. A blue device employing PdN1N‐dm demonstrates an electroluminescence emission peak at 476 nm and the maximum external quantum efficiency (EQE) of 25.1%. The high maximum EQE of the blue organic light‐emitting diode (OLED) device indicates that both the phosphorescence and the delayed fluorescence are very efficient. In addition, a stable OLED device of PdN1N‐dm gives a maximum EQE of 9.8% and the estimated operational lifetime LT 70 of 350 h at the practical luminance of 100 cd m −2 .
Efficient Blue Phosphorescent OLEDs with Improved Stability and Color Purity through Judicious Triplet Exciton Management
Abstract Highly efficient and stable blue phosphorescent organic light‐emitting diodes are achieved by employing a step‐wise graded doping of platinum(II) 9‐(pyridin‐2‐yl)‐2‐(9‐(pyridin‐2‐yl)‐9 H ‐carbazol‐2‐yloxy)‐9 H ‐carbazole (PtNON) in a device setting. A device employing PtNON demonstrates a high peak external quantum efficiency (EQE) of 17.4% with an estimated LT 70 lifetime of over 1330 h at a brightness of 1000 cd m −2 . PtNON is then investigated as a “triplet sensitizer” in an alternating donor–acceptor doped emissive layer to further improve the device emission color purity by carefully managing an efficient Förster resonant energy transfer from PtNON to 2,5,8,11‐tetra‐ tert ‐butylperylene as a selected acceptor material. Thus, such OLED devices demonstrate an EQE of 16.9% with color coordinates of (0.16, 0.25) and an estimated luminance (LT 70 ) lifetime of 628 h at a high brightness of 1000 cd m −2 .
OLED Display Driver (oled) v1.0
This is a simple C-language driver for an OLED display board which includes a few fonts and provides a simple API to the application layer.
Enhanced Light Outcoupling from OLEDs Fabricated on Novel Low-Cost Patterned Plastic Substrates of Varying Periodicity
OLEDs continue to make strides in display applications, but their commercial utilization in solid-state lighting (SSL) is lagging. An ongoing challenge, in particular for manufacturing, is the need for enhanced efficiency and hence the necessity to increase in an inexpensive approach the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass, the external quantum efficiency (EQE) is only ~20%. About 50% of the light is lost to internal waveguiding in the high refractive index (RI) organic + ITO anode layers and to surface plasmon polaritons (SPPs) at the organic/metal cathode interface. Another ~30% of the light is externally waveguided in the substrate to its edges. While extraction of the externally waveguided light is commonly addressed by adding a microlens array (MLA) or a scattering layer at the substrate’s air-side, light outcoupling increases by only ~1.6-1.7x (vs up to 2.5x in improving from ~20% to ~50%). The use of a hemispherical lens or an index matching fluid (IMF) at the substrate/photodetector (PD) interface increases the outcoupling by at least 2x; these approaches however, are not viable industrially, and even a MLA is sometimes undesirable due to its non-planar, scattering structure. In multi-stack tandem OLEDs, where the metal cathode is far from the emitting zone(s), the impact of photons loss to SPPs decreases. Our project addressed the ~50% loss to the internally waveguided light and SPPs. We evaluated OLEDs fabricated on patterned or planarized plastic substrates manufactured in a cost-effective approach compatible with a roll-to-roll (R2R) process. The OLEDs were either (i) patterned to various degrees depending on the pitch a and height or depth h of the pattern features or (ii) planar, with a pattern buried under a flat high RI planarization layer. We demonstrated that the outcoupling from green patterned OLEDs reaches ~50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a MLA, a hemispherical lens, or IMF. Simulations conducted in parallel with the experimental effort demonstrated how diffraction by conformally corrugated OLEDs increases the outcoupling to >60%. Structures with varying pitch values were also simulated indicating that combining domains of varying pitch could increase outcoupling to 55-60%. Experimentally, we additionally assessed the role a and h in determining not only the OLED efficiencies, but also their structural properties, i.e., the uniformity and conformality throughout the OLED stack. As planar OLEDs are preferred over corrugated devices, we studied different patterns in plastic substrates that were planarized by a high RI formulation. Planar green OLEDs on such structures showed enhanced efficiencies with EQEs larger than 60% with the addition of an IMF (to extract the substrate mode) at the substrate/Si PD interface. White OLEDs showed EQEs of 45.5%. Plastic substrates are currently less attractive than glass substrates due to drawbacks such as permeability to water vapor and oxygen, and in some cases thermal instability. Plastic substrates however, are flexible and easy to handle unlike thin flexible glass, and once transparent thin barrier films are available, they will become more attractive; they are already of interest in medical applications. Importantly, as it is easy to generate various patterns in different plastic materials, they provide excellent means for assessing and optimizing enhancing extracting structures. Such structures can also be transferred to glass substrates with some process modifications. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to R2R manufacturing. R2R processes are of drastically lower-cost than batch or single-unit fabrication. The patterned plastic can be a part of an integrated substrate either plastic or glass, which includes also a MLA or a planar layer with embedded scattering particles, as well as a conductive metal mesh/electrode design. SSL is environmentally-friendly and as OLED SSL becomes more efficient it will reduce electricity consumption, and hence lighting cost, as well as produce less expensive attractive lighting fixtures. Our university-industry collaboration is hence of major benefit to the public as it demonstrates the feasibility of manufacturing optimized extracting substrates for highly efficient OLEDs for SSL in a future R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. Moreover, newly developed methods by our team allow low-cost roll manufactured substrates to be transferred to flexible or rigid glass substrates, which solves the plastic substrate barrier issues, and when combined with device encapsulation will increase the OLEDs’ environmental stability.
Roll-to-Roll Integrated Substrates for OLED Lighting (Final Report)
OLED lighting has immense potential as aesthetically pleasing, energy-efficient general illumination. Unlike other light sources, such as incandescents, fluorescents, and inorganic LEDs, OLEDs naturally emit over a large-area surface. They are glare free, do not need to be shaded, and are cool to the touch, requiring no heatsink. The best efficiencies and lifetimes reported are on par with or better than current forms of illumination. However, the cost for OLED lighting remains high – so much so that these products are not market competitive and there is very low consumer demand. We believe that flexible, plastic-based devices will highlight the advantages of aesthetically-pleasing OLED lighting systems while paving the way for lowering both materials and manufacturing costs. These flexible devices require new development in substrate and support technology, which was the focus of the work reported here. Sinovia Technologies, as part of a collaborative team, has developed integrated plastic substrates to serve as supports for flexible OLED lighting. These substrates include a barrier to protect the OLED from moisture and oxygen-related degradation, a smooth, highly conductive transparent anode to define the OLED area, and a light scattering layer to improve emission efficiency. To ensure low cost, the anode pattern must be defined using high throughput, continuous processing, and any pattern shape should be possible. No current patterning technique meets all of these requirements. This SBIR work demonstrated the use of flexographic printing as an effective method of patterning for integrated substrates. Flexography is a letterpress process commonly used for many types of everyday items including boxes, retail bags, milk cartons, food packaging, disposable cups, adhesive tapes, envelopes, wallpaper, and newspaper. The printing process can go as fast as 600 meters per minute with feature resolution around 10 microns, showing promise for low-cost with high throughput. In this case, Sinovia has successfully used this technique to print transparent anode patterns roll-to-roll as part of our integrated substrate for OLED lighting. We have characterized the printed films and tailored the edges of the printed areas for OLED compatibility. We followed this by making white OLEDs using these anodes. To ensure that our anodes were compatible with different OLED stack structures, we fabricated solution-processed polymer white OLEDs, as well as collaborated with OLEDWorks to fabricate evaporated small-molecule devices. Comparing to results from our previous studies, we find that the flexography process does not have any detrimental effects to our overall substrate. We were able to show that our flexographically printed integrated substrate improves OLED efficiency by 24 – 35%, similar to previous results demonstrated using batch-patterning techniques. The success of this work represents two substantial opportunities for OLED lighting manufacturers. The first to first facilitate flexible lighting panels at scale, and the second to lower costs for by enabling roll-to-roll manufacture of the entire device stack. When realized, both of these will help OLED to become market competitive with other forms of general illumination.
Patterned OLEDs: effect of substrate corrugation pitch and height
Abstract An ongoing OLED challenge is cost-effective enhancement of light extraction, i.e., increasing the external quantum efficiency ( EQE ∼20% in conventional devices). OLEDs on corrugated substrates often show enhanced EQE s providing insight into light emission processes. In particular, patterned plastic substrates directly imprinted easily at room temperature and amenable to low-cost R2R production are ideal for studying/optimizing various structures, further elucidating the extraction process. We show new semi-quantitative data of the effect of the pitch ( a ) and height/depth ( h ) of plastic substrate patterns on the OLEDs’ stack and EQE , focusing on new designs, interestingly, some showing surprisingly enhanced EQE s that were neither reported nor discussed before. These includ e : ( i ) shallow ( h < 200 nm) convex polycarbonate with a ∼ 750 versus ∼400 nm, where the h gradually decreases as the OLED stack is built and ( ii ) concave PET/CAB with large a (∼2.8 and ∼7.8 μ m), where the EQE enhancement of conformal OLEDs may be due largely to scattering. EQE s of green, blue, and white phosphorescent OLEDs were measured. OLEDs on substrates with narrow a ∼ 400 nm and low h < 200 nm s h owed no enhancement, resembling flat devices. In contrast, OLEDs on substrates with comparable or smaller h , but larger a ∼ 750 nm show signific a nt EQE enhancement despite h reduction across the stack. Green OLEDs with a ∼ 750 nm and h ∼ 160 to ∼180 nm, showed EQE s ∼30%, reaching ∼58% with substrate mode extraction. Surprisingly, fully conformal OLEDs on a PET/CAB substrate with a ∼ 7.8 μ m showed blue a nd white EQE s reaching ∼33%, without substrate mode extraction. The enhancing patterns increase the OLEDs’ EQE by reducing surface plasmon excitation and internal waveguiding. The experimental results for OLEDs on substrates with a < 2 μ m are supported by scattering matrix simulations that assume conformal stacks, incorporating diffraction for internal losses reduction. EQE enhancement not predicted by simulations may be due additionally to scattering mostly for substrates with a signific a ntly larger than the emitting wavelength.
High Aspect Ratio OLEDs
Long-term reliability is especially challenging for organic light emitting diodes (OLEDs) used in solid-state lighting applications because OLED lifetime is inversely proportional to luminance, and most lighting applications demand high luminance. This project explored a new strategy to overcome this tradeoff by constructing OLEDs on a substrate with sub-mm, high aspect ratio surface texture. By creating more active OLED area per unit lighting panel area, the device current density required to generate a given panel luminance decreases. We validated this approach for both fluorescent and phosphorescent OLEDs, demonstrating good thickness uniformity on corrugated substrates with area enhancement factors up to 1.4x using a standard thermal evaporator. Relative to planar controls at the same panel current density, the high aspect ratio devices achieve a 2.7-fold increase in operating lifetime and up to a 40% increase in external light extraction efficiency. Experiments carried out on a pilot-line OLED manufacturing system demonstrated good coating uniformity, indicating that this approach has the potential to be implemented at scale and therefore offers a powerful pathway to improve the efficiency and lifetime of OLED lighting.
Enhanced Light Extraction from Low Cost White OLEDs Fabricated on Novel Patterned Substrates” (Final Report)
Organic LEDs (OLEDs) are a very attractive emerging solid state lighting (SSL) technology. Currently, one of the main challenges is to increase the extraction of the light generated inside the OLED into the forward (viewing) hemisphere. In conventional OLEDs fabricated on a transparent flat anode coated on glass the outcoupling factor is only about 20%. About 50% of the light is lost at the metal cathode (surface plasmon excitation), and waveguided internally in the organic layers and the transparent anode. Another ~30% is waveguided in the substrate to its edges. The research addressed this issue of outcoupling by evaluating OLEDs fabricated on corrugated plastic substrates manufactured in a cost-effective approach. It demonstrated that the outcoupling from such OLEDs can exceed 50% by mitigating plasmon–related loss and internal waveguiding, even without the addition of a microlens array or a hemispherical lens, either of which extracts the light trapped in the substrate. Simulations conducted in parallel with the experimental effort demonstrated how the corrugation assists in the outcoupling. The project also evaluated the role of the corrugation pitch and height in determining the outcoupling factor and other properties of the OLEDs. The technical effectiveness and economic feasibility of the project lie in the patterning of the extracting plastic substrates in an approach that is scalable to roll-to-roll (R2R) manufacturing. R2R processes are drastically lower-cost than batch or single-unit fabrication. The corrugated plastic substrates studied are part of an integrated substrate that includes also a microlens array at the air-side of the substrate and a conductive electrode. The project that was a university-industry collaboration is of major benefit to the public as it demonstrates the feasibility of manufacturing highly efficient OLEDs for SSL in a R2R process, which would drastically reduce the manufacturing cost and increase production in the USA. SSL is efficient and environmentally-friendly. It reduces electricity consumption, and hence lighting cost.
Printed Anodes and Internal Light Extraction Layers on Flexible Glass to Create Cost Effective and High Efficacy Bendable OLED Lighting Panels
In this project, OLEDWorks developed a high efficacy and cost-effective flexible OLED lighting system which could reduce the cost of OLED light by introducing a combination of printable and scalable scattering type internal light extraction (ILE) and transparent conductive silver nanowire technologies that are compatible with roll-to-roll (R2R) processing methods. High efficacy was achieved by co-optimization of the internal light extraction, silver nanowire and ITO anodes, and stacked white OLED structure to reduce unwanted absorption, increase the outcoupling efficiency, and lower the OLED voltage. At the end of Phase I of this project a power efficacy of 90 lm/W was demonstrated in a flexible OLED lighting device based on ultrathin bendable glass. Without much additional work, the milestone of 100 lm/W is certainly within reach, and with further work on light extraction and white OLED materials, we believe 120 lm/W or higher is achievable within the next few years.
Low refractive index OLEDs for practical high-efficiency outcoupling. Final report
Improving OLED light extraction is a significant on-going challenge for the OLED lighting industry. The goal of this program was to explore the potential to improve internal light extraction in a manufacturable way by lowering the refractive index of the OLED stack through dilution with an electrically-inert, low refractive index molecule. We accomplished this goal, identifying a small molecule that can be co-evaporated in the hole transport layer of OLEDs at high loading to reduce the refractive index by 0.2-0.3 refractive index units without degrading charge transport. Implementing this dilution molecule in the hole transport layer of a range of single and multi-stack OLEDs, we demonstrated the ability to improve their internal light extraction by up to ~35% without increasing their drive voltage or reducing their operational lifetime. Importantly, these findings extend to state-of-the-art device architectures with proprietary OLED materials.
Low Cost Corrugated Substrates for High Efficiency OLEDs (Final Report)
The external quantum efficiency (EQE) of a planar OLED is limited to 25%. Around 75% of the light is trapped in the substrate, waveguided and SPP modes. In this project, we demonstrated that nano-structures can significantly improve the EQE of OLEDs. The objective is to improve the EQE to 70% using corrugated substrate, low index layer incorporation and micro lens arrays. We conducted optical study of the operating devices using ARES measurement, and used the result to guide the design of corrugated substrates as well as the OLED stack for better performance. During the first year of the program, we have demonstrated over 60% EQE in a corrugated green OLED with half-ball lens for light extraction. By comparing, the optical characteristics of OLEDs fabricated on single and poly crystal corrugated structures, we confirm that the enhancement using corrugated substrates comes from waveguided and SPP modes extraction. To push the device EQE to 70%, further optimization of the corrugated substrate is needed. The extraction of waveguided and SPP modes are influenced by the corrugation pitch, depth and profile. Therefore, we developed a series of processes to precisely control the corrugation morphology. Through comparison of different corrugated substrates, we observed that while an abrupt surface profile results in stronger mode extraction, it also introduces strong leakage current; while a smooth profile are less efficient in mode extraction, it preserves the quality of an OLED. Based on these observations, we conclude that a single crystal hole corrugation results in optimum EQE % and low leakage current when planarized with PEDOT. To improve the extraction of waveguided mode, we also introduce a low index contrast layer (ICL) to increase the index contrast between corrugated ITO and glass interface. We optimized our recipe for the index contrast layer processing and reduced its refractive index from 1.50 to 1.38. As a result, the optimized device shows 47.6% EQE, which is 1.64 times higher than the reference planar device. By extracting the substrate mode with a hemispherical lens, we obtained an EQE of 71.6%, which is a 2.46 times enhancement. The cross-section SEM image reveals the high EQE is due to the formation of an air gap at the interface of the ICL, resulting in an increase of the index contrast to Δn ~ 1. We use angle-resolved electroluminescence spectroscopy (ARES) to demonstrate that the ICL improves the diffraction efficiency at the ITO/glass interface, extracts TM, TE waveguide and SPP mode more efficiently, and leads to the observed high efficiency. We also address the directional emission issue with the single crystalline microlens arrays (MLAs) by fabricating polycrystalline MLAs. The process uses colloidal assembly method to create a mono-layer of silica spheres, then uses PDMS stamps to replicate the pattern for multi-use imprinting. The MLAs are close-packed in short range but have random orientations in the long range. This avoids stronger extraction along the optical axes of single crystal MLAs and prevents the directional emission issue. We also demonstrate that the color shift induced by the corrugation can be minimized using MLAs. In this scenario, the MLAs work as diffuser to randomize the directional emission from extracted waveguide and SPP modes.
OLEDs on planarized light outcoupling-enhancing structures in plastic
Light extraction from OLEDs remains a challenge. While consumer demand for OLEDs in display technology continues to grow as prices decline, commercial use of OLEDs in solid state lighting (SSL) applications is lagging due to low light extraction, which results in low efficiency. Previous studies have been directed toward increasing the light extraction factor η out , but cost effective approaches that will enable high throughput and potential upscaling, as well as elucidation of the extraction process, are still lagging. One promising approach is the use of buried light extraction enhancing patterns that are planarized with a high refractive index (RI) layer. When adding substrate mode extracting means, the highest external quantum efficiencies (EQEs) were achieved using a complex approach of planarized vacuum nano holes. Here we present η out -enhancing planarized extraction structures (PES) in plastic. While plastic substrates currently present long-term stability issues and other drawbacks, as we show, they provide a tool for simple, inexpensive, and rapid generation of various enhancing structures that importantly can be transferred to the preferred rigid and flexible glass substrates. Moreover, plastic substrates are attractive for biomedical applications. The successful structures we present are easily scalable periodic corrugations, e.g., with pitch a ~ 4.25 µm and pitch/depth ratio a/h ~2.4 planarized by a layer of RI ~1.9, resulting in maximal EQEs exceeding 60% for a green OLED and 48.5% for a white OLED. Comparable increased EQEs were achieved for structures with a ~ 15 and 16 µm, and a/h ~ 2.1 and 4, respectively. Enhanced extraction was also observed with a very simply fabricated quasiperiodic nanohole array, and surprisingly, with a random shallow design. The latter is at variance with simulations based on diffraction only. Results are discussed in terms of a, h, and structural parameters together with scattering matrix simulations to assess the effect of various PES parameters and the nanoparticle-embedded planarizing layer on η out . The experiments and simulations indicate contributions of diffraction, reflection, and scattering to EQE enhancement.
Increasing the Stability of Deep Blue Phosphor‐Sensitized OLEDs Using the Polariton‐Enhanced Purcell Effect
Abstract The stability of efficient, deep blue organic light‐emitting diodes (OLEDs) remains a major challenge in the field of organic electronics. Poor device stability originates from the high probability for destructive non‐radiative triplet exciton annihilation events. Phosphor‐sensitized fluorescence (PSF) is proposed to achieve an efficient, deep blue color by energy transfer from phosphors to fluorophores. Recently, the polariton‐enhanced Purcell (PEP) effect is introduced to decrease the triplet radiative lifetime and density, resulting in an increase in blue phosphorescent OLED lifetime. Here, the PEP effect is introduced to enhance the stability of the PSF‐OLEDs. It is shown that the PEP effect increases all radiative decay rates of the phosphors and fluorophores, leading to a reduction in the triplet annihilation events. Using a Pt‐complex phosphor sensitizer and a so‐called multi‐resonance fluorescent emitter in a PEP cavity, a 3.1‐fold lifetime increase is observed at a current density ofJ= 10 mA cm −2 , reduced EQE roll‐off and deep blue color with Commission Internationale de l'Eclairage coordinates of (0.13, 0.09). The PEP effect maximally extends PSF‐OLED lifetimes in devices with the highest triplet‐to‐singlet energy transfer rates. Moreover, this work suggests that the benefits of PEPs apply to all triplet‐based OLEDs.
Understanding, Predicting, and Mitigating Catastrophic Shorts for Improved OLED Lighting Panel Reliability (Final Report)
Catastrophic OLED lighting panel failure due to electrical shorting was a significant reliability challenge facing the industry. The goal of this program was to develop a basic scientific understanding of how incipient shorts in an OLED originate and grow to a catastrophic level, and to develop mitigation strategies that enable the industry to reach the DOE target of 0.01% failure rate. We accomplished this goal, identifying the origin of shorts, understanding how the evolve over time, and ultimately identifying a mitigation strategy that was implemented by our industry partner and demonstrated to completely eliminate catastrophic shorts in production OLED panels. We identified two general classes of panel defect, termed bright spots and hot spots, that respectively originate from indium-tin-oxide agglomerations and microscale organic semiconductor dust particles on the substrate. The former are largely benign whereas the latter can lead to local shunts that grow over time and cause catastrophic failure. We understand the growth process as a self-reinforcing cycle, where shunt-induced heating volatilizes the surrounding organic semiconductor, which in turn expands the shunt and leads to even more heating. Based on these results, we identified several practical strategies to arrest the growth of early-stage shorts or prevent them entirely. These results will reduce the cost and improve the reliability of OLED lighting.
High Efficacy, Long Lifetime Flexible White OLED Lighting Panels
In this project, OLEDWorks and partners made significant progress in advancing OLED light extraction technology. Improving light extraction efficiency remains one of the most important research topics for OLEDs. Current state-of-the-art white OLED products extract only about 50% of the photons that are generated within the device. Promising new light extraction concepts, such as those based on sub electrode micro lens arrays (SEMLAs), were explored in this project with the potential to achieve extraction efficiency of 60% or higher. Flexible thin glass substrates with integrated SEMLAs were successfully fabricated and scaled to large area. When combined with optimized high efficiency stacked white OLED structures, we achieved the program goals of 120 LPW efficacy and long lifetime more than 100,000 hours.