Toward Nonepitaxial Laser Diodes.

Thin-film organic, colloidal quantum dot, and metal halide perovskite semiconductors are all being pursued in the quest for a wavelength-tunable diode laser technology that does not require epitaxial growth on a traditional semiconductor substrate. Despite promising demonstrations of efficient light-emitting diodes and low-threshold optically pumped lasing in each case, there are still fundamental and practical barriers that must be overcome to reliably achieve injection lasing. This review outlines the historical development and recent advances of each material system on the path to a diode laser. Common challenges in resonator design, electrical injection, and heat dissipation are highlighted, as well as the different optical gain physics that make each system unique. The evidence to date suggests that continued progress for organic and colloidal quantum dot laser diodes will likely hinge on the development of new materials or indirect pumping schemes, while improvements in device architecture and film processing are most critical for perovskite lasers. In all cases, systematic progress will require methods that can quantify how close new devices get with respect to their electrical lasing thresholds. We conclude by discussing the current status of nonepitaxial laser diodes in the historical context of their epitaxial counterparts, which suggests that there is reason to be optimistic for the future.

Thermal Properties of Polymer Hole-Transport Layers Influence the Efficiency Roll-off and Stability of Perovskite Light-Emitting Diodes.

While the performance of metal halide perovskite light-emitting diodes (PeLEDs) has rapidly improved in recent years, their stability remains a bottleneck to commercial realization. Here, we show that the thermal stability of polymer hole-transport layers (HTLs) used in PeLEDs represents an important factor influencing the external quantum efficiency (EQE) roll-off and device lifetime. We demonstrate a reduced EQE roll-off, a higher breakdown current density of approximately 6 A cm-2, a maximum radiance of 760 W sr-1 m-2, and a longer device lifetime for PeLEDs using polymer HTLs with high glass-transition temperatures. Furthermore, for devices driven by nanosecond electrical pulses, a record high radiance of 1.23 MW sr-1 m-2 and an EQE of approximately 1.92% at 14.6 kA cm-2 are achieved. Thermally stable polymer HTLs enable stable operation of PeLEDs that can sustain more than 11.7 million electrical pulses at 1 kA cm-2 before device failure.

Origins of Photoluminescence Instabilities at Halide Perovskite/Organic Hole Transport Layer Interfaces.

Metal halide perovskites are promising for optoelectronic device applications; however, their poor stability under solar illumination remains a primary concern. While the intrinsic photostability of isolated neat perovskite samples has been widely discussed, it is important to explore how charge transport layers─employed in most devices─impact photostability. Herein, we study the effect of organic hole transport layers (HTLs) on light-induced halide segregation and photoluminescence (PL) quenching at perovskite/organic HTL interfaces. By employing a series of organic HTLs, we demonstrate that the HTL's highest occupied molecular orbital energy dictates behavior; furthermore, we reveal the key role of halogen loss from the perovskite and subsequent permeation into organic HTLs, where it acts as a PL quencher at the interface and introduces additional mass transport pathways to facilitate halide phase separation. In doing so, we both reveal the microscopic mechanism of non-radiative recombination at perovskite/organic HTL interfaces and detail the chemical rationale for closely matching the perovskite/organic HTL energetics to maximize solar cell efficiency and stability.

Substrate-embedded metal meshes for ITO-free organic light emitting diodes.

Organic light-emitting diodes (OLEDs) have great potential for use in large-area display and lighting applications, but their widespread adoption for large areas is hindered by the high cost and insufficient performance of indium tin oxide (ITO) anodes. In this study, we introduce an alternative anode material - a silver mesh embedded in glass - to facilitate production of large-area OLEDs. We present a facile, scalable manufacturing technique to create high aspect ratio micromeshes embedded in glass to provide the planar geometry needed for OLED layers. Our phosphorescent green OLEDs achieve a current efficiency of 51.4 cd/A at 1000 cd/m2 and reach a slightly higher external quantum efficiency compared to a standard ITO/glass reference sample. Notably, these advancements are achieved without any impact on the viewing angle of the OLEDs. These findings represent a promising advancement towards ITO-free, high-efficiency OLEDs for various high performance, large-area applications, such as lighting and displays.

Perovskites for Next-Generation Optical Sources.

Next-generation displays and lighting technologies require efficient optical sources that combine brightness, color purity, stability, substrate flexibility. Metal halide perovskites have potential use in a wide range of applications, for they possess excellent charge transport, bandgap tunability and, in the most promising recent optical source materials, intense and efficient luminescence. This review links metal halide perovskites' performance as efficient light emitters with their underlying materials electronic and photophysical attributes.

Reduced Recombination and Capacitor-like Charge Buildup in an Organic Heterojunction.

Organic photovoltaic (OPV) efficiencies continue to rise, raising their prospects for solar energy conversion. However, researchers have long considered how to suppress the loss of free carriers by recombination-poor diffusion and significant Coulombic attraction can cause electrons and holes to encounter each other at interfaces close to where they were photogenerated. Using femtosecond transient spectroscopies, we report the nanosecond grow-in of a large transient Stark effect, caused by nanoscale electric fields of ∼487 kV/cm between photogenerated free carriers in the device active layer. We find that particular morphologies of the active layer lead to an energetic cascade for charge carriers, suppressing pathways to recombination, which is ∼2000 times less than predicted by Langevin theory. This in turn leads to the buildup of electric charge in donor and acceptor domains-away from the interface-resistant to bimolecular recombination. Interestingly, this signal is only experimentally obvious in thick films due to the different scaling of electroabsorption and photoinduced absorption signals in transient absorption spectroscopy. Rather than inhibiting device performance, we show that devices up to 600 nm thick maintain efficiencies of >8% because domains can afford much higher carrier densities. These observations suggest that with particular nanoscale morphologies the bulk heterojunction can go beyond its established role in charge photogeneration and can act as a capacitor, where adjacent free charges are held away from the interface and can be protected from bimolecular recombination.

Perovskite Light-Emitting Diodes with Improved Outcoupling Using a High-Index Contrast Nanoarray.

Organic-inorganic hybrid perovskite light-emitting diodes (PeLEDs) are promising for next-generation optoelectronic devices due to their potential to achieve high color purity, efficiency, and brightness. Although the external quantum efficiency (EQE) of PeLEDs has recently surpassed 20%, various strategies are being pursued to increase EQE further and reduce the EQE gap compared to other LED technologies. A key point to further boost EQE of PeLEDs is linked to the high refractive index of the perovskite emissive layer, leading to optical losses of more than 70% of emitted photons. Here, it is demonstrated that a randomly distributed nanohole array with high-index contrast can effectively enhance outcoupling efficiency in PeLEDs. Based on a comprehensive optical analysis on the perovskite thin film and outcoupling structure, it is confirmed that the nanohole array effectively distributes light into the substrate for improved outcoupling, allowing for 1.64 times higher light extraction. As a result, highly efficient red/near-infrared PeLEDs with a peak EQE of 14.6% are demonstrated.

Erratum: Corrigendum: Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors.

Nature Materials 16, 1209-1215 (2017); published online 13 November 2017; corrected after print 15 December 2017. In the version of this Article originally published, the source of 'ZADN' stated in the Methods should have read 'obtained as free research samples from Guangzhou ChinaRay OptoelectronicMaterials' instead of 'China-Ray'.

Corrigendum: Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors.

This corrects the article DOI: 10.1038/nmat5027.

Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors.

Chemical doping of organic semiconductors using molecular dopants plays a key role in the fabrication of efficient organic electronic devices. Although a variety of stable molecular p-dopants have been developed and successfully deployed in devices in the past decade, air-stable molecular n-dopants suitable for materials with low electron affinity are still elusive. Here we demonstrate that photo-activation of a cleavable air-stable dimeric dopant can result in kinetically stable and efficient n-doping of host semiconductors, whose reduction potentials are beyond the thermodynamic reach of the dimer's effective reducing strength. Electron-transport layers doped in this manner are used to fabricate high-efficiency organic light-emitting diodes. Our strategy thus enables a new paradigm for using air-stable molecular dopants to improve conductivity in, and provide ohmic contacts to, organic semiconductors with very low electron affinity.

Methods for Conducting Electron Backscattered Diffraction (EBSD) on Polycrystalline Organic Molecular Thin Films.

Electron backscattered diffraction (EBSD) is a technique regularly used to obtain crystallographic information from inorganic samples. When EBSD is acquired simultaneously with emitting diodes data, a sample can be thoroughly characterized both structurally and compositionally. For organic materials, coherent Kikuchi patterns do form when the electron beam interacts with crystalline material. However, such patterns tend to be weak due to the low average atomic number of organic materials. This is compounded by the fact that the patterns fade quickly and disappear completely once a critical electron dose is exceeded, inhibiting successful collection of EBSD maps from them. In this study, a new approach is presented that allows successful collection of EBSD maps from organic materials, here the extreme example of a hydrocarbon organic molecular thin film, and opens new avenues of characterization for crystalline organic materials.

Homoepitaxy of Crystalline Rubrene Thin Films.

The smooth surface of crystalline rubrene films formed through an abrupt heating process provides a valuable platform to study organic homoepitaxy. By varying growth rate and substrate temperature, we are able to manipulate the onset of a transition from layer-by-layer to island growth modes, while the crystalline thin films maintain a remarkably smooth surface (less than 2.3 nm root-mean-square roughness) even with thick (80 nm) adlayers. We also uncover evidence of point and line defect formation in these films, indicating that homoepitaxy under our conditions is not at equilibrium or strain-free. Point defects that are resolved as screw dislocations can be eliminated under closer-to-equilibrium conditions, whereas we are not able to eliminate the formation of line defects within our experimental constraints at adlayer thicknesses above ∼25 nm. We are, however, able to eliminate these line defects by growing on a bulk single crystal of rubrene, indicating that the line defects are a result of strain built into the thin film template. We utilize electron backscatter diffraction, which is a first for organics, to investigate the origin of these line defects and find that they preferentially occur parallel to the (002) plane, which is in agreement with expectations based on calculated surface energies of various rubrene crystal facets. By combining the benefits of crystallinity, low surface roughness, and thickness-tunability, this system provides an important study of attributes valuable to high-performance organic electronic devices.

Mixed-Halide Perovskites with Stabilized Bandgaps.

One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (VOC) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned VOC from 1.05 to 1.45 V in solar cells.

Diode-Pumped Organo-Lead Halide Perovskite Lasing in a Metal-Clad Distributed Feedback Resonator.

Organic-inorganic lead halide perovskite semiconductors have recently reignited the prospect of a tunable, solution-processed diode laser, which has the potential to impact a wide range of optoelectronic applications. Here, we demonstrate a metal-clad, second-order distributed feedback methylammonium lead iodide perovskite laser that marks a significant step toward this goal. Optically pumping this device with an InGaN diode laser at low temperature, we achieve lasing above a threshold pump intensity of 5 kW/cm(2) for durations up to ∼25 ns at repetition rates exceeding 2 MHz. We show that the lasing duration is not limited by thermal runaway and propose instead that lasing ceases under continuous pumping due to a photoinduced structural change in the perovskite that reduces the gain on a submicrosecond time scale. Our results indicate that the architecture demonstrated here could provide the foundation for electrically pumped lasing with a threshold current density Jth < 5 kA/cm(2) under sub-20 ns pulsed drive.

Real-Time Tracking of Singlet Exciton Diffusion in Organic Semiconductors.

Exciton diffusion in organic materials provides the operational basis for functioning of such devices as organic solar cells and light-emitting diodes. Here we track the exciton diffusion process in organic semiconductors in real time with a novel technique based on femtosecond photoinduced absorption spectroscopy. Using vacuum-deposited C_{70} layers as a model system, we demonstrate an extremely high diffusion coefficient of D≈3.5×10^{-3} cm^{2}/s that originates from a surprisingly low energetic disorder of <5 meV. The experimental results are well described by the analytical model and supported by extensive Monte Carlo simulations. The proposed noninvasive time-of-flight technique is deemed as a powerful tool for further development of organic optoelectronic components, such as simple layered solar cells, light-emitting diodes, and electrically pumped lasers.

3D printed quantum dot light-emitting diodes.

Developing the ability to 3D print various classes of materials possessing distinct properties could enable the freeform generation of active electronics in unique functional, interwoven architectures. Achieving seamless integration of diverse materials with 3D printing is a significant challenge that requires overcoming discrepancies in material properties in addition to ensuring that all the materials are compatible with the 3D printing process. To date, 3D printing has been limited to specific plastics, passive conductors, and a few biological materials. Here, we show that diverse classes of materials can be 3D printed and fully integrated into device components with active properties. Specifically, we demonstrate the seamless interweaving of five different materials, including (1) emissive semiconducting inorganic nanoparticles, (2) an elastomeric matrix, (3) organic polymers as charge transport layers, (4) solid and liquid metal leads, and (5) a UV-adhesive transparent substrate layer. As a proof of concept for demonstrating the integrated functionality of these materials, we 3D printed quantum dot-based light-emitting diodes (QD-LEDs) that exhibit pure and tunable color emission properties. By further incorporating the 3D scanning of surface topologies, we demonstrate the ability to conformally print devices onto curvilinear surfaces, such as contact lenses. Finally, we show that novel architectures that are not easily accessed using standard microfabrication techniques can be constructed, by 3D printing a 2 × 2 × 2 cube of encapsulated LEDs, in which every component of the cube and electronics are 3D printed. Overall, these results suggest that 3D printing is more versatile than has been demonstrated to date and is capable of integrating many distinct classes of materials.

Sublimed C60 for efficient and repeatable perovskite-based solar cells.

Thermally evaporated C60 is a near-ubiquitous electron transport layer in state-of-the-art p-i-n perovskite-based solar cells. As perovskite photovoltaic technologies are moving toward industrialization, batch-to-batch reproducibility of device performances becomes crucial. Here, we show that commercial as-received (99.75% pure) C60 source materials may coalesce during repeated thermal evaporation processes, jeopardizing such reproducibility. We find that the coalescence is due to oxygen present in the initial source powder and leads to the formation of deep states within the perovskite bandgap, resulting in a systematic decrease in solar cell performance. However, further purification (through sublimation) of the C60 to 99.95% before evaporation is found to hinder coalescence, with the associated solar cell performances being fully reproducible after repeated processing. We verify the universality of this behavior on perovskite/silicon tandem solar cells by demonstrating their open-circuit voltages and fill factors to remain at 1950 mV and 81% respectively, over eight repeated processes using the same sublimed C60 source material. Notably, one of these cells achieved a certified power conversion efficiency of 30.9%. These findings provide insights crucial for the advancement of perovskite photovoltaic technologies towards scaled production with high process yield.

Resonant cavity enhanced light harvesting in flexible thin-film organic solar cells.

Dielectric/metal/dielectric (DMD) electrodes have the potential to significantly increase the absorption efficiency and photocurrent in flexible organic solar cells. We demonstrate that this enhancement is attributed to a broadband cavity resonance. Silver-based semitransparent DMD electrodes with sheet resistances below 10 ohm/sq. are fabricated on flexible polyethylene terephthalate (PET) substrates in a high-throughput roll-to-roll sputtering tool. We carefully study the effect of the semitransparent DMD electrode (here composed of Zn(x)Sn(y)O(z)/Ag/In(x)Sn(y)O(z)) on the optical device performance of a copper phthalocyanine (CuPc)/fullerene (C60) bilayer cell and illustrate that a resonant cavity enhanced light trapping effect dominates the optical behavior of the device.