Improving the thermal stability of top-emitting organic light-emitting diodes by modification of the anode interface

This research was financially supported by the EPSRC NSF-CBET lead agency agreement (EP/R010595/1, 1706207), the DARPA-NESD program (N66001-17-C-4012) and the Leverhulme Trust (RPG-2017-231). Y.D. acknowledges a stipend from the Chinese Scholarship Council (CSC). C.K. acknowledges support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2017R1A6A3A03012331). M.C.G. acknowledges support from the Alexander von Humboldt Stiftung through the Humboldt-Professorship.Top‐emitting organic light‐emitting diodes (OLEDs) are of interest for numerous applications, in particular for displays with high fill factors. To maximize efficiency and luminance, molecular p‐doping of the hole transport layer (p‐HTL) and a highly reflective anode contact, for example, made from silver, are used. Atomic layer deposition (ALD) is attractive for thin film encapsulation of OLEDs but generally requires a minimum process temperature of 80 °C. Here it is reported that the interface between the p‐HTL and the silver anode of top‐emitting OLEDs degrades during an 80 °C ALD encapsulation process, causing an over fourfold reduction in OLED current and luminance. To understand the underlying mechanism of device degradation, single charge carrier devices are investigated before and after annealing. A spectroscopic study of p‐HTLs indicates that degradation is due to the interaction between diffusing silver ions and the p‐type molecular dopant. To improve the stability of the interface, either an ultrathin MoO3 buffer layer or a bilayer HTL is inserted at the anode/organic interface. Both approaches effectively suppress degradation. This work shows a route to successful encapsulation of top‐emitting OLEDs using ALD without sacrificing device performance.Publisher PDFPeer reviewe

A substrateless, flexible, and water-resistant organic light-emitting diode

This research was financially supported from the Leverhulme Trust (RPG-2017-231), the EPSRC NSF-CBET lead agency agreement (EP/R010595/1, 1706207), the DARPA NESD programme (N66001-17-C-4012) and the RS Macdonald Charitable Trust. C.K. acknowledges support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2017R1A6A3A03012331). C.M. acknowledges funding from the European Commission through a Marie Skłodowska Curie individual fellowship (703387). A.M. acknowledges funding through an individual fellowship of the Deutsche Forschungsgemeinschaft (404587082). M.C.G. acknowledges funding from the Alexander von Humboldt Stiftung (Humboldt-Professorship).Despite widespread interest, ultrathin and highly flexible light-emitting devices that can be seamlessly integrated and used for flexible displays, wearables, and as bioimplants remain elusive. Organic light-emitting diodes (OLEDs) with µm-scale thickness and exceptional flexibility have been demonstrated but show insufficient stability in air and moist environments due to a lack of suitable encapsulation barriers. Here, we demonstrate an efficient and stable OLED with a total thickness of ≈ 12 µm that can be fully immersed in water or cell nutrient media for weeks without suffering substantial degradation. The active layers of the device are embedded between conformal barriers formed by alternating layers of parylene-C and metal oxides that are deposited through a low temperature chemical vapour process. These barriers also confer stability of the OLED to repeated bending and to extensive postprocessing, e.g. via reactive gas plasmas, organic solvents, and photolithography. This unprecedented robustness opens up a wide range of novel possibilities for ultrathin OLEDs.Publisher PDFPeer reviewe

Accurate efficiency measurements of organic light-emitting diodes via angle-resolved spectroscopy

Funding: EPSRC NSF-CBET lead agency agreement (EP/R010595/1, 1706207), the Leverhulme Trust (RPG-2017-231), the Volkswagen Foundation (No. 93404), and the Alexander von Humboldt Stiftung (Humboldt-Professorship to M.C.G.). C.K. acknowledges support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2017R1A6A3A03012331). Diese Arbeit wurde mitfinanziert durch Steuermittel auf der Grundlage des vom Sächsischen Landtag beschlossenen Haushaltes.The accurate characterization of thin-film LEDs – including organic light emitting diodes (OLEDs), perovskites and quantum dot LEDs – is crucial to our understanding of the factors that influence their efficiency and thus to the fabrication of LEDs with improved performance and stability. In addition, detailed information about the angular characteristics of LED emission is useful to assess the suitability of individual architectures, e.g. for display applications. Here, the implementation of a goniometer-based measurement system and corresponding protocol are described that allow to accurately determine the current-voltage-luminance characteristics, external quantum efficiency and luminous efficacy of OLEDs and other emerging thin-film LEDs. The system allows recording of angle-resolved electroluminescence spectra and accurate efficiency measurements for devices with both Lambertian and non-Lambertian emission characteristics. A detailed description of the setup and a protocol for assembling and aligning the required hardware are provided. Drawings of all custom parts and the open-source Python software required to perform the measurement and to analyze the data are included.Publisher PDFPeer reviewe

High brightness, highly directional organic light-emitting diodes as light sources for future light-amplifying prosthetics in the optogenetic management of vision loss

Funding: Engineering and Physical Sciences Research Council (Grant Number(s): EP/R010595/1). National Science Foundation (Grant Number(s): 1706207). Defense Sciences Office, DARPA (Grant Number(s): N66001-17-C-4012). Leverhulme Trust (Grant Number(s): RPG-2017-231). Alexander von Humboldt-Stiftung (Grant Number(s): Humboldt Professur). National Research Foundation of Korea (GrantNumber(s): 2017R1A6A3A03012331). China Sponsorship Council.Optogenetic control of retinal cells transduced with light-sensitive channelrhodopsins can enable restoration of visual perception in patients with vision loss. However, a light intensity orders of magnitude higher than ambient light conditions is required to achieve robust cell activation. Relatively bulky wearable light amplifiers are currently used to deliver sufficient photon flux (>1016 photons/cm2/s in a ±10° emission cone) at a suitable wavelength (e.g., 600 nm for channelrhodopsin ChrimsonR). Here, ultrahigh brightness organic light-emitting diodes (OLEDs) with highly directional emission are developed, with the ultimate aim of providing high-resolution optogenetic control of thousands of retinal cells in parallel from a compact device. The orange-emitting phosphorescent OLEDs use doped charge transport layers, generate narrowband emission peaking at 600 nm, and achieve a luminance of 684 000 cd m–2 at 15 V forward bias. In addition, tandem-stack OLEDs with a luminance of 1 152 000 cd m–2 and doubled quantum efficiency are demonstrated, which greatly reduces electrical and thermal stress in these devices. At the photon flux required to trigger robust neuron firing in genetically modified retinal cells and when using heat sinking and realistic duty cycles (20% at 12.5 Hz), the tandem-stack OLEDs therefore show a greatly improved half-brightness lifetime of 800 h.Publisher PDFPeer reviewe

Distributed feedback lasers based on green fluorescent protein and conformal high refractive index oxide layers

Funding: European Research Council (ERC StG ABLASE, 640012). M.K. and A.M. acknowledge funding from the EPSRC DTG (EP/M506631/1 and EP/M508214/1). L.T. acknowledges studentship funding through the EPSRC CM-CDT (EP/L015110/1). M.S. acknowledges funding from the Royal Society (Dorothy Hodgkin Fellowship, DH160102). I.D.W.S. acknowledges funding from a Royal Society Wolfson research merit award.Fluorescent proteins have emerged as an attractive gain material for lasers, especially for devices requiring biocompatibility. However, due to their optical properties, integration with distributed feedback (DFB) resonators is not readily achievable. Here, a DFB laser with enhanced green fluorescent protein (eGFP) as the gain material is demonstrated by incorporating a thin (65 nm), high refractive index (n = 2.12) ZrO2 interlayer as waveguide core. Deposition of ZrO2 via atomic layer deposition yields a smooth and conformal film as required to minimize optical losses. Lasing emission is obtained from 2D second‐order DFB eGFP lasers at pump power densities above 56.6 kW cm–2 and a wavelength tuning range of Δλ = 51.7 nm is demonstrated. Furthermore, it is shown that in contrast to conventional organic DFB lasers, both transverse electric (TE) and transverse magnetic (TM) modes are accessible. The effective refractive index of these modes can be predicted accurately through optical modelling. Using far‐field imaging, the laser beam profile is studied and TE and TM modes are distinguished.Publisher PDFPeer reviewe

Season\u27s influence on the relationship between mass concentrations of sulphur dioxide and sulphate in the air

Studiran je odnos masenih koncentracija (p) sumpor-dioksida i sulfata u prirodnim uvjetima, tj. u dvije gradske sredine s različitim razinama atmosferskog onečišćenja tijekom zimskog i ljetnog razdoblja. Na svakom mjernom mjestu tijekom sezone sakupljeno je i analizirano pedesetak uzoraka sumpor-dioksida, dima·i lebdećih čestica. U uzorcima lebdećih čestica određivana je ukupna masena koncentracija lebdećih čestica, sulfata, kalcija, olova, željeza, mangana i bakra. Studirana je korelacija po sezonama između masenih koncentracija sulfata i sumpor-dioksida, lebdećih čestica, dima, te pojedinih komponenata lebdećih čestica. Dobivena je dobra korelacija između masenih koncentracija sulfata i lebdećih čestica. Razine masenih koncentracija sumpor-dioksida, dima, sulfata i lebdećih čestica značajno su više tijekom zimskog razdoblja u obim sredinama. Na obim je mjestima dobiven gotovo jednak prosječni maseni udjel (w) sulfata (oko 10) u lebdećim česticama i tijekom zimskog i ljetnog razdoblja. Izračunate jednadžbe regresije za odnos između sulfatnog S i ukupnog S (sulfati i sumpor-dioksid) za ljetno i zimsko razdoblje međusobno se razlikuju. Izgleda da se taj sezonski utjecaj na odnos masenih koncentracija sumpor-dioksida i sulfata može dovesti u vezu s različitim porijeklom i različitim razinama masenih koncentracija lebdećih čestica u zraku.The relationship between sulphur dioxide and sulphate was studied in natural conditions, in two urban areas with different levels of air pollution during the winter and summer periods. About fifty samples of sulphur dioxide, smoke and suspended particulates were collected and analysed on each measuring site during the season. In the sample of suspended particulates the total mass concentration of suspended particulates, sulphate, calcium, lead, iron, manganese and copper was determined. The correlation between sulphate and sulphur dioxide, suspended particulates, smoke and some suspended particulate\u27s components was studied by seasons. A good correlation was found between the concentration of sulphate and suspended particulates. The concentration levels of sulphur dioxide, smoke, sulphate and suspended particulates were significantly higher during the winter period in both areas. On both locations the average mass fraction of sulphate (about 10%) in suspended particulates was nearly the same during the winter and summer periods. The calculated equation regressions for the relationship between sulphate S and total S (sulphate and sulphur dioxide) for the summer and winter period are reciprocally different. It seems that the season\u27s influence on the relationship between sulphur dioxide and sulphate might be due to a different origin and different levels of suspended particulates in the air

Optogenetic stimulation probes with single-neuron resolution based on organic LEDs monolithically integrated on CMOS

Funding: This work was supported in part by the Defense Advanced Research Projects Agency (DARPA) under contract N6600117C4012, by the National Institutes of Health under grant U01NS090596, by the Leverhulme Trust (RPG-2017-231) and by the Alexander von Humboldt Stiftung (Humboldt-Professorship to M.C.G.). This work was performed in part at the Columbia Nano Initiative cleanroom facility, at the CUNY Advanced Science Research Center Nanofabrication Facility, and at the Singh Center for Nanotechnology, part of the National Nanotechnology Coordinated Infrastructure Program, which is supported by the National Science Foundation grant NNCI-2025608. C.-K.M. acknowledges funding from the European Commission through a Marie-Skłodowska Curie Individual Fellowship (101029807).The use of optogenetic stimulation to evoke neuronal activity in targeted neural populations—enabled by opsins with fast kinetics, high sensitivity and cell-type and subcellular specificity—is a powerful tool in neuroscience. However, to interface with the opsins, deep-brain light delivery systems are required that match the scale of the spatial and temporal control offered by the molecular actuators. Here we show that organic light-emitting diodes can be combined with complementary metal–oxide–semiconductor technology to create bright, actively multiplexed emissive elements. We create implantable shanks in which 1,024 individually addressable organic light-emitting diode pixels with a 24.5 µm pitch are integrated with active complementary metal–oxide–semiconductor drive and control circuitry. This integration is enabled by controlled electrode conditioning, monolithic deposition of the organic light-emitting diodes and optimized thin-film encapsulation. The resulting probes can be used to access brain regions as deep as 5 mm and selectively activate individual neurons with millisecond-level precision in mice.Publisher PDFPeer reviewe

1,3,4-oxadiazole-based deep-blue thermally activated delayed fluorescence emitters for organic light emitting diodes

We are grateful to the EPSRC for financial support (grants EP/P010482/1, EP/J01771X, EP/J00916 and EP/R035164/1). We gratefully acknowledge funding through the EPSRC NSF- CBET lead agency agreement (EP/R010595/1, 1706207) and a Leverhulme Trust Research Grant (RPG-2017-231). We thank the EPSRC UK National Mass Spectrometry Facility at Swansea University for analytical services. Z.L. and W. L. thank the China Scholarship Council (grant numbers 201703780004 and 201708060003)A series of four 1,3,4-oxadiazole-based thermally activated delayed fluorescence (TADF) derivatives are reported as emitters for organic light emitting diodes (OLEDs). As a function of the nature of the substituent on the weak 1,3,4-oxadiazole acceptor their emission color could be tuned from green-blue to blue. The highly twisted conformation between carbazoles and oxadiazoles results in effective separation of the HOMO and the LUMO resulting in a small singlet-triplet splitting. The corresponding singlet-triplet energy gaps (∆EST) range from 0.22 to 0.28 eV resulting in an efficient reverse intersystem crossing (RISC) process and moderate to high photoluminescence quantum yields (ΦPL), ranging from 35 to 70% in a DPEPO matrix. Organic light-emitting diodes (OLEDs) based on i-2CzdOXD4CF3Ph achieve maximum external quantum efficiency (EQEmax) of up to 12.3% with a sky-blue emission at CIE of (0.18, 0.28) while the device based on i-2CzdOXDMe shows blue emission at CIE of (0.17, 0.17) with a maximum EQE of 11.8%.PostprintPeer reviewe

Photostimulation for in vitro optogenetics with high power blue organic light-emitting diodes

Funding: Leverhulme Trust (RPG-2017-231), the EPSRC NSF-CBET lead agency agreement (EP/R010595/1, 1706207), the DARPA NESD programme (N66001-17-C-4012) and the RS Macdonald Charitable Trust. C.M. acknowledges funding by the European Commission through a Marie Sklodowska-Curie Individual Fellowship (703387). Y. L. Deng acknowledges support from the Chinese Scholarship Council (CSC).Optogenetics, photostimulation of neural tissues rendered sensitive to light, is widely used in neuroscience to modulate the electrical excitability of neurons. For effective optical excitation of neurons, light wavelength and power density must fit with the expression levels and biophysical properties of the genetically encoded light‐sensitive ion channels used to confer light sensitivity on cells—most commonly, channelrhodopsins (ChRs). As light sources, organic light‐emitting diodes (OLEDs) offer attractive properties for miniaturized implantable devices for in vivo optical stimulation, but they do not yet operate routinely at the optical powers required for optogenetics. Here, OLEDs with doped charge transport layers are demonstrated that deliver blue light with good stability over millions of pulses, at powers sufficient to activate the ChR, CheRiff when expressed in cultured primary neurons, allowing live cell imaging of neural activity with the red genetically encoded calcium indicator, jRCaMP1a. Intracellular calcium responses scale with the radiant flux of OLED emission, when varied through changes in the current density, number of pulses, frequency, and pulse width delivered to the devices. The reported optimization and characterization of high‐power OLEDs are foundational for the development of miniaturized OLEDs with thin‐layer encapsulation on bioimplantable devices to allow single‐cell activation in vivo.Publisher PDFPeer reviewe

Narrowband organic light-emitting diodes for fluorescence microscopy and calcium imaging

Funding: Leverhulme Trust (RPG-2017-231), the EPSRC NSF-CBET lead agency agreement (EP/R010595/1, 1706207), the DARPA NESD program (N66001-17-C-4012) and the RS Macdonald Charitable Trust. C.M. acknowledges funding from the European Commission through a Marie Skłodowska Curie individual fellowship (703387). A.M. acknowledges funding through an individual fellowship of the Deutsche Forschungsgemeinschaft (404587082). Y.D. acknowledges support from the Chinese Scholarship Council (CSC). L.T. acknowledges studentship funding through the EPSRC CM-CDT (EP/L015110/1). M.S. acknowledges funding by the Royal Society (Dorothy Hodgkin Fellowship, DH160102).Fluorescence imaging is an indispensable tool in biology, with applications ranging from single‐cell to whole‐animal studies and with live mapping of neuronal activity currently receiving particular attention. To enable fluorescence imaging at cellular scale in freely moving animals, miniaturized microscopes and lensless imagers are developed that can be implanted in a minimally invasive fashion; but the rigidity, size, and potential toxicity of the involved light sources remain a challenge. Here, narrowband organic light‐emitting diodes (OLEDs) are developed and used for fluorescence imaging of live cells and for mapping of neuronal activity in Drosophila melanogaster via genetically encoded Ca2+ indicators. In order to avoid spectral overlap with fluorescence from the sample, distributed Bragg reflectors are integrated onto the OLEDs to block their long‐wavelength emission tail, which enables an image contrast comparable to conventional, much bulkier mercury light sources. As OLEDs can be fabricated on mechanically flexible substrates and structured into arrays of cell‐sized pixels, this work opens a new pathway for the development of implantable light sources that enable functional imaging and sensing in freely moving animals.PostprintPeer reviewe