The rapid development of the science and technology of organic semiconductors has already led to mass application of organic light‐emitting diodes (OLEDs) in television monitors of outstanding quality as well as in a large variety of smaller displays found in smartphones, tablets, and other gadgets, while introduction of the technology to the illumination sector is imminent. Notably, the requirements of all such applications for emission in the visible range of the electromagnetic spectrum are well tuned to the optical and electronic properties of typical organic semiconductors, thereby representing relatively “low‐hanging fruits,” in terms of material development and exploitation. However, the question arises as to whether developing materials suited for efficient near‐infrared (NIR, 700–1000 nm) emission is possible, and, crucially, desirable to enable new classes of applications spanning from through‐space, short‐range communications to biomedical sensors, night vision, and more generally security applications to name but a few. Here, the major fundamental hurdles to be overcome to achieve efficient NIR emission from organic π‐conjugated systems are discussed, recent progress is reviewed, and an outlook for further development of both materials and applications is provided.
We take advantage of a recent breakthrough in the synthesis of α,β-unfunctionalised 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) moieties, which we symmetrically conjugate with oligothienyls in an unexpectedly stable form, and produce a “metal-free” A-D-A (acceptor-donor-acceptor) oligomer emitting in the near-infrared (NIR) thanks to delocalisation of the BODIPY low-lying lowest unoccupied molecular orbital (LUMO) over the oligothienyl moieties, as confirmed by density functional theory (DFT). We are able to retain a PL efficiency of 20% in the solid state (vs. 30% in dilute solutions) by incorporating such a dye in a wider gap polyfluorene matrix and demonstrate organic light-emitting diodes (OLEDs) emitting at 720 nm. We achieve external quantum efficiencies (EQEs) up to 1.1%, the highest value achieved so far by a “metal-free” NIR-OLED not intentionally benefitting from triplet-triplet annihilation. Our work demonstrates for the first time the promise of A-D-A type dyes for NIR OLEDs applications thereby paving the way for further optimisation.
The structural nature of heterointerfaces in core-shell semiconductor quantum dots (QDs) plays a crucial role in tailoring their optical properties. In this work we have focused on using surface-enhanced Raman spectroscopy as a nondestructive tool to investigate the structural evolution of such interfaces in CdSe/CdS and CdSe/Cd0.5Zn0.5S colloidal QDs. A comparison between the two systems shows significant structural variation across the core-shell interfaces for the two different materials: a smooth interface for the former and an abrupt interface for the latter. This structural difference modifies the electronic structure within the QDs, which directly dictates the confinement behavior of the electrons and holes. The implications of this translate to a better understanding of why graded CdSe/CdS/Cd0.5Zn0.5S/ZnS QDs are so lucrative for linear and nonlinear fluorescence-based applications.
Visible light communication (VLC) is a wireless technology that relies on optical intensity modulation and is potentially a game changer for internet-of-things (IoT) connectivity. However, VLC is hindered by the low penetration depth of visible light in non-transparent media. One solution is to extend operation into the "nearly (in)visible" near-infrared (NIR, 700-1000 nm) region, thus also enabling VLC in photonic bio-applications, considering the biological tissue NIR semitransparency, while conveniently retaining vestigial red emission to help check the link operativity by simple eye inspection. Here, we report new far-red/NIR organic light-emitting diodes (OLEDs) with a 650-800 nm emission range and external quantum efficiencies among the highest reported in this spectral range (>2.7%, with maximum radiance and luminance of 3.5 mW/cm 2 and 260 cd/m 2 , respectively). With these OLEDs, we then demonstrate a "real-time" VLC setup achieving a data rate of 2.2 Mb/s, which satisfies the requirements for IoT and biosensing applications. These are the highest rates ever reported for an online unequalised VLC link based on solution-processed OLEDs.
The development of efficient and biocompatible organic near-infrared emitters is attractive for many applications, spanning from photodynamic therapy [1] to light fidelity (Li-Fi) all-optical networking systems. [2][3][4] In particular, the range 700-1000 nm is interesting for medical applications, given the semitransparency of biological tissue in this spectral interval, [5] and we will specifically refer to this range as near-infrared (NIR) in the following text. Compared to conventional inorganic materials, organic NIR emitters are interesting also for their mechanical conformability, which makes them appealing for the integration in flexible and stretchable devices. [6] Furthermore, the metal-free organic light-emitting materials can be a cheap and biocompatible alternative to inorganic ones for application in wearable, implantable, or in vivo medical applications, such as for sensing of body temperature, heart and respiration rates, blood pressure, glucose level, and oxygenation. [7] In the search for ever-higher efficiencies, several classes of materials have been investigated, such as perovskite-structured methylammonium lead halides, [8][9][10] quantum dots, [11] and organometallic phosphorescent complexes. [12][13][14][15][16][17][18][19] However, although such hybrid materials afford substantial electroluminescence (EL) external quantum efficiency (EQE) in the NIR, in some cases exceeding 10% [8,10] or even 20% or so, [13] their use of heavy, toxic, and/or costly metals is not ideal for manufacturing, sustainability, environmental impact, and, in perspective, biocompatibility. Furthermore, in such hybrid systems, and in general in materials that leverage triplet excitons to boost the EQE, [20,21] exciton recombination dynamics typically fall in the hundreds of nanoseconds or even in the microsecond (or longer) range, which intrinsically limits the bandwidth when integrated in devices for telecommunications. For Li-Fi applications, [2][3][4] fluorescent molecular and polymeric materials are preferred, given that the typical fluorescence lifetime of these materials is of the order of few nanoseconds or less, thereby ideally allowing data transmission rates up to the Gb s −1 regime.In the last decade, scientists have attempted different strategies to develop heavy-metal-free NIR fluorescent organic light-emitting diodes (OLEDs), with chemical design essentially revolving around the careful combination of donor and acceptor groups to both tune the spectral range (up to 1000 nm) and maximize the EQE. [22][23][24][25][26][27][28][29][30][31][32][33] Very recently, we have, for Due to the so-called energy-gap law and aggregation quenching, the efficiency of organic light-emitting diodes (OLEDs) emitting above 800 nm is significantly lower than that of visible ones. Successful exploitation of triplet emission in phosphorescent materials containing heavy metals has been reported, with OLEDs achieving remarkable external quantum efficiencies (EQEs) up to 3.8% (peak wavelength > 800 nm). For OLEDs incorporating f...
The energy gap law (EG-law) and aggregation quenching are the main limitations to overcome in the design of near-infrared (NIR) organic emitters. Here, we achieve unprecedented results by synergistically addressing both of these limitations. First, we propose porphyrin oligomers with increasing length to attenuate the effects of the EG -law by suppressing the non-radiative rate growth, and to increase the radiative rate via enhancement of the oscillator strength. Second, we design side chains to suppress aggregation quenching. We find that the logarithmic rate of variation in the non-radiative rate vs. EG is suppressed by an order of magnitude with respect to previous studies, and we complement this breakthrough by demonstrating organic light-emitting diodes with an average external quantum efficiency of ~1.1%, which is very promising for a heavy-metal-free 850 nm emitter. We also present a novel quantitative model of the internal quantum efficiency for active layers supporting triplet-to-singlet conversion. These results provide a general strategy for designing high-luminance NIR emitters.
The shell thickness and composition of CdSe–Cd x Zn1–x S core–shell quantum dots (QDs) are defining parameters for the efficiency of such materials as light emitters. In this work we present a detailed study into the optical absorption and fluorescence properties of CdSe–CdS, CdSe–Cd0.5Zn0.5S, and CdSe–ZnS QDs as a function of shell thickness. Moreover, the single-exciton recombination dynamics of these systems are analyzed by means of a time-correlated single-photon counting technique and directly related to the specific core–shell interfaces of the various QDs studied using a phenomenological kinetic model. The findings from this model highlight the strong role of the core–shell interface on both steady state photoluminescence and exciton recombination dynamics in these systems.
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