Dependence of Photocurrent Enhancements in Quantum Dot (QD)‐Sensitized MoS2 Devices on MoS2 Film Properties

This report demonstrates highly efficient nonradiative energy transfer (NRET) from alloyed CdSeS/ZnS semiconductor nanocrystal quantum dots (QDs) to MoS₂ films of varying layer thicknesses, including pristine monolayers, mixed monolayer/bilayer, polycrystalline bilayers, and bulk‐like thicknesses, with NRET efficiencies of over 90%. Large‐area MoS₂ films are grown on Si/SiO₂ substrates by chemical vapor deposition. Despite the ultrahigh NRET efficiencies there is no distinct increase in the MoS₂ photoluminescence intensity. However, by studying the optoelectronic properties of the MoS₂ devices before and after adding the QD sensitizing layer photocurrent enhancements as large as ≈14‐fold for pristine monolayer devices are observed, with enhancements on the order of ≈2‐fold for MoS₂ devices of mixed monolayer and bilayer thicknesses. For the polycrystalline bilayer and bulk‐like MoS₂ devices there is almost no increase in the photocurrent after adding the QDs. Industrially scalable techniques are specifically utilized to fabricate the samples studied in this report, demonstrating the viability of this hybrid structure for commercial photodetector or light harvesting applications.     

Merocyanine/C60 Planar Heterojunction Solar Cells: Effect of Dye Orientation on Exciton Dissociation and Solar Cell Performance

In this study the charge dissociation at the donor/acceptor heterointerface of thermally evaporated planar heterojunction merocyanine/C₆₀ organic solar cells is investigated. Deposition of the donor material on a heated substrate as well as post‐annealing of the complete devices at temperatures above the glass transition temperature of the donor material results in a twofold increase of the fill factor. An analytical model employing an electric‐field‐dependent exciton dissociation mechanism reveals that geminate recombination is limiting the performance of as‐deposited cells. Fourier‐transform infrared ellipsometry shows that, at temperatures above the glass transition temperature of the donor material, the orientation of the dye molecules in the donor films undergoes changes upon annealing. Based on this finding, the influence of the dye molecules’ orientations on the charge‐transfer state energies is calculated by quantum mechanical/molecular mechanics methods. The results of these detailed studies provide new insight into the exciton dissociation process in organic photovoltaic devices, and thus valuable guidelines for designing new donor materials.     

A Twisting Donor‐Acceptor Molecule with an Intercrossed Excited State for Highly Efficient,Deep‐Blue Electroluminescence

In an organic electroluminescent (EL) device, the recombination of injected holes and electrons produces what appears to be an ion‐pair or charge‐transfer (CT) exciton, and this CT exciton decays to produce one photon directly, or relaxes to a low‐lying local exciton (LE). Thus the full utilization of both the energy of the CT exciton and the LE should be a pathway for obtaining high‐efficiency EL. Here, a twisting donor‐acceptor (D‐A) triphenylamine‐imidazol molecule, TPA‐PPI, is reported: its synthesis, photophysics, and EL performance. Prepared by a manageable, one‐pot cyclizing reaction, TPA‐PPI exhibits deep‐blue emission with high quantum yields (90%) both in solution and in the solid state. Fluorescent solvatochromic experiments for TPA‐PPI solutions show a red‐shift of 57 nm (3032 cm^?1) from low‐polarity hexane (406 nm) to high‐polarity acetonitrile (463 nm), accompanied by the gradual disappearance of the vibrational band in the spectra with increased solvent polarity. The photophysical investigation and DFT analysis suggest an intercrossed CT and LE excited state of the TPA‐PPI, originating from its twisting D‐A configuration. This is a rare instance that a CT‐state material shows highly efficient deep‐blue emission. EL characterization demonstrates that, as a deep‐blue emitter with CIE coordinates of (0.15, 0.11), the performance of a TPA‐PPI‐based device is rather excellent, displaying a maximum current efficiency of >5.0 cd A^?1, and a maximum external quantum efficiency of >5.0%, corresponding to a maximum internal quantum efficiency of >25%. The effective utilization of the excitation energy arising from materials with intercrossed‐excited‐state (LE and CT) characters is thought to be beneficial for the improved efficiency of EL devices.     

Over 17.4% Efficiency of Layer-by-Layer All-Polymer Solar Cells by Improving Exciton Utilization in Acceptor Layer

Layer-by-layer all-polymer solar cells (LbL all-PSCs) are prepared with PM6 and PY-IT by using sequential spin coating method. The exciton dissociation efficiency in acceptor layer near electrode is rather low due to the limited exciton diffuse distance and impossible energy transfer from narrow bandgap acceptor to wide bandgap donor. In this study, less PM6 is incorporated into PY-IT layer to enhance exciton dissociation in PY-IT layer near electrode. A power conversion efficiency (PCE) of 17.45% is achieved in the LbL all-PSCs incorporating 10 wt% PM6 into PY-IT layer, which is much larger than 16.04% PCE of PM6/PY-IT-based LbL all-PSCs. Over 8% PCE enhancement can be realized by incorporating 10 wt% PM6 into PY-IT layer, which is attributed to the enhanced exciton utilization efficiency in PY-IT layers near electrode. The enhanced exciton utilization efficiency in PY-IT layer can be confirmed from the quenched photoluminescence (PL) emission in PY-IT:PM6 films. Meanwhile, charge transport in acceptor layers can be optimized by incorporating less PM6, as confirmed from the optimized molecular arrangement. This study indicates that the strategy of incorporating less donor into acceptor layer has great potential in fabricating efficient LbL all-PSCs by improving exciton utilization efficiency in acceptor layer near electrode.     

Conjugated Block Copolymers as Model Systems to Examine Mechanisms of Charge Generation in Donor–Acceptor Materials

Fully conjugated donor–acceptor block copolymers are established as model systems to elucidate fundamental mechanisms of photocurrent generation in organic photovoltaics. Using analysis of steady‐state photoluminescence quenching, exciton dissociation to a charge transfer state within individual block copolymer chains is quantified. By making a small adjustment to the conjugated backbone, the electronic properties are altered enough to disrupt charge transfer almost entirely. Strong intermolecular coupling of the electron donor is introduced by synthesizing block copolymer nanoparticles. Transient absorption spectroscopy is used to monitor charge generation in block copolymer isolated chains and nanoparticles. While efficient charge transfer is observed in isolated chains, there is no indication of complete charge separation. In the nanoparticles, long‐lived polarons are observed as early as ≈15 ns. Thus, aggregation of electron donors can facilitate efficient charge generation.     

Co‐Interlayer Engineering toward Efficient Green Quasi‐Two‐Dimensional Perovskite Light‐Emitting Diodes

With respect to three‐dimensional (3D) perovskites, quasi‐two‐dimensional (quasi‐2D) perovskites have unique advantages in light‐emitting devices (LEDs), such as strong exciton binding energy and good phase stability. Interlayer ligand engineering is a key issue to endow them with these properties. Rational design principles for interlayer materials and their processing techniques remain open to investigation. A co‐interlayer engineering strategy is developed to give efficient quasi‐2D perovskites by employing phenylbutylammonium bromide (PBABr) and propylammonium bromide (PABr) as the ligand materials. Preparation of these co‐interlayer quasi‐2D perovskite films is simple and highly controllable without using antisolvent treatment. Crystallization and morphology are readily manipulated by tuning the ratio of co‐interlayer components. Various optical techniques, including steady and ultrafast transient absorption and photoluminescence spectroscopies, are used to investigate their excitonic properties. Photoluminescence quantum yield (PLQY) of the perovskite film is dramatically improved to 89% due to the combined optimization of exciton binding energy and suppression of trap state formation. Accordingly, a high current efficiency of 66.1 cd A^?1 and an external quantum efficiency of 15.1% are achieved for green co‐interlayer quasi‐2D perovskite LEDs without using any light out‐coupling techniques, indicating that co‐interlayer engineering is a simple and effective approach to develop high‐performance perovskite electroluminescence devices.     

Highly Efficient Solid‐State Near‐Infrared Emitting Material Based on Triphenylamine and Diphenylfumaronitrile with an EQE of 2.58% in Nondoped Organic Light‐Emitting Diode

The development of efficient near‐infrared (NIR) emitting material is of current focus. Donor–acceptor (D–A) architecture has been proved to be an effective strategy to obtain narrow energy gap. Herein, a D–A‐type NIR fluorescent compound 2,3‐bis(4′‐(diphenylamino)‐[1,1′‐biphenyl]‐4‐yl)fumaronitrile (TPATCN) is synthesized and fully characterized. As revealed by theoretical calculations and photophysical experiments, TPATCN exerts the advantages of the relatively large dipole moment of the charge transfer state and a certain degree of orbital overlap of the local excited state. A highly mixed or hybrid local and charge transfer excited state might occur to simultaneously achieve both a large fraction of singlet formation and a high quantum efficiency in D–A system. TPATCN exhibits strong NIR fluorescence with the corresponding thin film quantum efficiency of 33% and the crystal efficiency of 72%. Remarkably, the external quantum efficiency of nondoped NIR organic light‐emitting diode (OLED) reaches 2.58% and remains fairly constant over a range of 100–300 mA cm^?2, which is among the best results for NIR OLEDs reported so far.     

Magnetic Field Effect in Organic Light‐Emitting Diodes Based on Electron Donor–Acceptor Exciplex Chromophores Doped with Fluorescent Emitters

A new type of organic light‐emitting diode (OLED) has emerged that shows enhanced operational stability and large internal quantum efficiency approaching 100%, which is based on thermally activated delayed fluorescence (TADF) compounds doped with fluorescent emitters. Magneto‐electroluminescence (MEL) in such TADF‐based OLEDs and magneto‐photoluminescence (MPL) in thin films based on donor–acceptor (D–A) exciplexes doped with fluorescent emitters with various concentrations are investigated. It has been found that both MEL and MPL responses are thermally activated with substantially lower activation energy compared to that in the pristine undoped D–A exciplex host blend. In addition, both MPL and MEL steeply decrease with the emitter's concentration. This indicates the existence of a loss mechanism, whereby the triplet charge‐transfer state in the exciplex host blend may directly decay to the lowest, nonemissive triplet state of the fluorescent emitter molecules.     

Near‐Field Energy Transfer Using Nanoemitters For Optoelectronics

Effective utilization of excitation energy in nanoemitters requires control of exciton flow at the nanoscale. This can be readily achieved by exploiting near‐field nonradiative energy transfer mechanisms such as dipole‐dipole coupling (i.e., Förster resonance energy transfer) and simultaneous two‐way electron transfer via exchange interaction (i.e., Dexter energy transfer). In this feature article, we review nonradiative energy transfer processes between emerging nanoemitters and exciton scavengers. To this end, we highlight the potential of colloidal semiconductor nanocrystals, organic semiconductors, and two‐dimensional materials as efficient exciton scavengers for light harvesting and generation in optoelectronic applications. We present and discuss unprecedented exciton transfer in nanoemitter–nanostructured semiconductor composites enabled by strong light–matter interactions. We elucidate remarkably strong nonradiative energy transfer in self‐assembling atomically flat colloidal nanoplatelets. In addition, we underscore the promise of organic semiconductor–nanocrystal hybrids for spin‐triplet exciton harvesting via Dexter energy transfer. These efficient exciton transferring hybrids will empower desired optoelectronic properties such as long‐range exciton diffusion, ultrafast multiexciton harvesting, and efficient photon upconversion, leading to the development of excitonic optoelectronic devices such as exciton‐driven light‐emitting diodes, lasers, and photodetectors.     

Employing ∼100% Excitons in OLEDs by Utilizing a Fluorescent Molecule with Hybridized Local and Charge‐Transfer Excited State

In principle, the ratio (Φ) of the maximum quantum efficiencies for electroluminescence (EL) to photoluminescence (PL) can be expected to approach unity, if the exciton (bound electron–hole pair) generated from the recombination of injected electrons and holes in OLEDs has a sufficiently weak binding energy. However, seldom are examples of Φ > 25% reported in OLEDs because of the strongly bound excitons for most organic semiconductors in nature. Here, a twisting donor–acceptor triphenylamine‐thiadiazol molecule (TPA‐NZP) exhibits fluorescent emission through a hybridized local and charge‐transfer excited state (HLCT), which is demonstrated from both fluorescent solvatochromic experiment and quantum chemical calculations. The HLCT state possesses two combined and compatible characteristics: a large transition moment from a local excited (LE) state and a weakly bound exciton from a charge transfer (CT) state. The former contributes to a high‐efficiency radiation of fluorescence, while the latter is responsible for the generation of a high fraction of singlet excitons. Using TPA‐NZP as the light‐emitting layer in an OLED, high Φ values of 93% (at low brightness) and 50% (at high brightness) are achieved, reflecting sufficient employment of the excitons in the OLED. Characterization of the EL device shows a saturated deep‐red emission with CIE coordinates of (0.67, 0.32), accompanied by a rather excellent performance with a maximum luminance of 4574 cd m^?2 and a maximum external quantum efficiency (η_ext) of ～2.8%. The HLCT state is a new way to realize high‐efficiency of EL devices.     

Photophysical Study of DPPTT‐T/PC70BM Blends and Solar Devices as a Function of Fullerene Loading: An Insight into EQE Limitations of DPP‐Based Polymers

Diketopyrrolopyrrole (DPP)‐based polymers have been consistently used for the fabrication of solar cell devices and transistors due to the existence of intermolecular short contacts, resulting in high electron and hole mobilities. However, they also often show limited external quantum efficiencies (EQEs). In this contribution, the authors analyze the limitations on EQE by a combined study of exciton dissociation efficiency, charge separation, and recombination kinetics in thin films and solar devices of a DPP‐based donor polymer, DPPTT‐T (thieno[3,2‐b]thiophene‐diketopyrrolopyrrole copolymer) blended with varying weight fractions of the fullerene acceptor PC₇₀BM. From the correlations between photoluminescence quenching, transient absorption studies, and EQE measurements, it is concluded that the main limitation of photon‐to‐charge conversion in DPPTT‐T/PC₇₀BM devices is poor exciton dissociation. This exciton quenching limit is related not only to the low affinity/miscibility of the materials, as confirmed by wide angle X‐ray diffraction diffraction and transmission electron microscopy data, but also to the relatively short DPPTT‐T singlet exciton lifetime, possibly associated with high nonradiative losses. A further strategy to improve EQE in this class of polymers without sacrificing the good extraction properties in optimized blends is therefore to limit those nonradiative decay processes.     

Optical,Electrical, and Magnetic Studies of Organic Solar Cells Based on Low Bandgap Copolymer with Spin ½ Radical Additives

The charge photogeneration and recombination processes in organic photovoltaic solar cells based on blend of the low bandgap copolymer, PTB7 (fluorinated poly‐thienothiophene‐benzodithiophene) with C60‐PCBM using optical, electrical, and magnetic measurements in thin films and devices is studied. A variety of steady state optical and magneto‐optical techniques were employed, such as photoinduced absorption (PA), magneto‐PA, doping‐induced absorption, and PA‐detected magnetic resonance (PADMR); as well as picosecond time‐resolved PA. The charge polarons and triplet exciton dynamics in films of pristine PTB7, PTB7/fullerene donor–acceptor (D–A) blend is followed. It is found that a major loss mechanism that limits the power conversion efficiency (PCE) of PTB7‐based solar cell devices is the “back reaction” that leads to triplet exciton formation in the polymer donor from the photogenerated charge‐transfer excitons at the D–A interfaces. A method of suppressing this “back reaction” by adding spin½ radicals Galvinoxyl to the D–A blend is presented; this enhances the cell PCE by ≈30%. The same method is not effective for cells based on PTB7/C70‐PCBM blend, where high PCE is reached even without Galvinoxyl radical additives.     

Efficient and Tunable Thermally Activated Delayed Fluorescence Emitters Having Orientation‐Adjustable CN‐Substituted Pyridine and Pyrimidine Acceptor Units

A series of twisted D–π–A type emitters based on the acridine donor unit and CN‐substituted pyridine, pyrimidine, and benzene acceptor units are studied. They not only allow one to systematically probe the influence of different acceptor strengths, but also permit one to intriguingly probe the influence of tunable conformations (twist angles) within the acceptor moieties through controlling the orientation of asymmetric heteroaromatic ring relative to the donor component. Intramolecular charge‐transfer transitions are observed in all these compounds and emission wavelengths are widely tunable from deep blue to yellow not only by the general acceptor strength due to the characters of heteroarene and CN‐substitution pattern but also by the subtle control of in‐acceptor conformation (twist angles). Small triplet‐to‐singlet energy gaps (ΔE_ST) and significant thermally activated delayed fluorescence (TADF) characteristics are obtained in a series of D–π–A compounds with sufficient acceptor strengths and tunable in‐acceptor conformation, yielding a series of efficient blue‐green to yellow TADF emitters with promisingly high photoluminescence quantum yields of 90%–100%. Highly efficient blue‐green to yellow TADF organic light‐emitting diodes (OLEDs) having external quantum efficiencies of up to 23.1%–31.3% are achieved using these efficient TADF emitters, which are among the most efficient TADF OLEDs ever reported.     

量子阱中Be受主的光致发光

报道了掺杂在GaAs体材料中和δ掺杂在一系列GaAs/AlAs多量子阱中的Be受主带间跃迁的光致发光. 实验所用样品,GaAs体材料中均匀掺杂Be受主的外延单层和一系列量子阱宽度从3到20nm,并在量子阱中央进行了Be受主δ掺杂的GaAs/AlAs多量子阱样品都是通过分子束外延技术制备的. 在4,20,40,80及120K不同温度下,分别对上述样品进行了光致发光谱的测量,清楚地观察到了受主束缚激子从1S3/2(Γ6)基态到同种宇称2S3/2(Γ6)激发态的两空穴跃迁,并从实验上得到了不同量子阱宽度下Be受主从1S3/2(Γ6)到2S3/2(Γ6)态的带间跃迁能量. 理论上利用变分原理,在单带有效质量模型和包络函数近似下,数值计算了Be受主1S3/2(Γ6)→2S3/2(Γ6)的跃迁能量随量子阱宽度的变化关系,比较发现理论计算和实验结果符合较好.     

量子阱中Be受主的光致发光

报道了掺杂在GaAs体材料中和δ掺杂在一系列GaAs/AlAs多量子阱中的Be受主带间跃迁的光致发光.实验所用样品,GaAs体材料中均匀掺杂Be受主的外延单层和一系列量子阱宽度从3到20nm,并在量子阱中央进行了Be受主δ掺杂的GaAs/AlAs多量子阱样品都是通过分子束外延技术制备的.在4,20,40,80及120K不同温度下,分别对上述样品进行了光致发光谱的测量,清楚地观察到了受主束缚激子从1S3/2(Γ6)基态到同种宇称2S3/2(Γ6)激发态的两空穴跃迁,并从实验上得到了不同量子阱宽度下Be受主从1S3/2(Γ6)到2S3/2(Γ6)态的带间跃迁能量.理论上利用变分原理,在单带有效质量模型和包络函数近似下,数值计算了Be受主1S3/2(Γ6)→2S3/2(Γ6)的跃迁能量随量子阱宽度的变化关系,比较发现理论计算和实验结果符合较好.     

A Red Thermally Activated Delayed Fluorescence Emitter Simultaneously Having High Photoluminescence Quantum Efficiency and Preferentially Horizontal Emitting Dipole Orientation

The development of red thermally activated delayed fluorescence (TADF) emitters having excellent optoelectronic properties and satisfactory electroluminescence efficiency is full of challenges due to strict molecular design principles. Two red TADF molecules, 3‐(9,9‐dimethylacridin‐10(9H)‐yl)acenaphtho[1,2‐b]quinoxaline‐9,10‐dicarbonitrile and 3‐(2,7‐dimethyl‐10H‐spiro[acridine‐9,9′‐fluoren]‐10‐yl)acenaphtho[1,2‐b]quinoxaline‐9,10‐dicarbonitrile, are developed by adopting a donor–acceptor molecular architecture bearing an electron‐accepting acenaphtho[1,2‐b]quinoxaline‐9,10‐dicarbonitrile (ANQDC) moiety and a 9,9‐dimethyl‐9,10‐dihydroacridine or 2,7‐dimethyl‐10H‐spiro[acridine‐9,9′‐fluorene] electron donor. The combined effects of rigid and planar D/A moieties and highly steric hindrance between D and A groups endow both molecules with high rigidity to suppress nonradiative decay processes, resulting in high photoluminescence quantum efficiencies (Φ_PLs) of up to 95%. Attributed to the linear and planar acceptor motif and rod‐like molecular configuration, both emitters achieve high horizontal ratios of emitting dipole orientation of ≈80%. The organic light‐emitting diodes (OLEDs) based on both emitters exhibit red emissions peaking at ≈615 nm and successfully afford ultrahigh electroluminescence performance with an external quantum efficiency of nearly 28% and a power efficiency of above 50 lm W^?1, on par with the state‐of‐the‐art device efficiency for red TADF OLEDs. This presents a feasible design strategy for excellent TADF emitters simultaneously possessing high Φ_PLs and horizontally aligned emitting dipoles.     

Ultrathin Highly Luminescent Two‐Monolayer Colloidal CdSe Nanoplatelets

Surface effects in atomically flat colloidal CdSe nanoplatelets (NLPs) are significantly and increasingly important with their thickness being reduced to subnanometer level, generating strong surface related deep trap photoluminescence emission alongside the bandedge emission. Herein, colloidal synthesis of highly luminescent two‐monolayer (2ML) CdSe NPLs and a systematic investigation of carrier dynamics in these NPLs exhibiting broad photoluminescence emission covering the visible region with quantum yields reaching 90% in solution and 85% in a polymer matrix is shown. The astonishingly efficient Stokes‐shifted broadband photoluminescence (PL) emission with a lifetime of ≈100 ns and the extremely short PL lifetime of around 0.16 ns at the bandedge signify the participation of radiative midgap surface centers in the recombination process associated with the underpassivated Se sites. Also, a proof‐of‐concept hybrid LED employing 2ML CdSe NPLs is developed as color converters, which exhibits luminous efficacy reaching 300 lm W_opt^?1. The intrinsic absorption of the 2ML CdSe NPLs (≈2.15 × 10⁶ cm^?1) reported in this study is significantly larger than that of CdSe quantum dots (≈2.8 × 10⁵ cm^?1) at their first exciton signifying the presence of giant oscillator strength and hence making them favorable candidates for next‐generation light‐emitting and light‐harvesting applications.     

Quantum chemical calculations,synthesis and properties of novel organic molecules with photoinduced intramolecular electron transfer and large change in electric dipole moment in the excited state

The topic of this paper is bipolar organic compounds containing both charged electron donor and electron acceptor groups interconnected by various kinds of bridges (–D–X–A⁺). Such betaines are subject to photoinduced intramolecular electron transfer (PIET), large change in dipole moment in the excited state and considerable hyperpolarisability, which causes large non‐linear optical effects in solutions and Longmuir–Blodgett (LB) films. Quantum chemical calculations (CNDO/S, ZINDO/S) of some types of betaines containing a 1,3‐indandione anion or diazole anion electron donor part and an N‐pyridinium cation electron acceptor part show that the HOMO and LUMO are strongly localized and an effective PIET takes place. The calculated change in dipole moment in the excited state, δμ=μ_g−μ_ex , is substantial (8–20 D) and in many cases the direction of μ is reversed. The character of the bridge X in betaines shows the largest effect on μ_g and δμ, especially in the case of X=p‐phenylene. The pyrazole anion is a better electron donor than the 1,3‐indandione anion. The synthesis of betaines containing a 1,3‐indandione anion part of an N‐pyridinium cation part interconnected directly or through a p‐phenylene bridge has been achieved and their electron absorption spectra have been investigated. Preliminary experiments confirm NLO effects in solutions and LB films. The synthesis of novel substituted betaines is unlimited and the synthesis of polymer‐bonded or surface‐bonded betaines is possible. Copyright © 1999 John Wiley & Sons, Ltd.     

量子限制效应对限制在多量子阱中受主束缚能的影响

从实验和理论上,研究了量子限制效应对限制在GaAs/AIAs多量子阱中受主对重窄穴束缚能的影响.实验中所用的样品是通过分子束外延技术生长的一系列GaAs/AIAs多量子阱,量子阱宽度从3nm到20nm,并且在量子阱中央进行了浅受主铍(Be)原子的δ掺杂.在4,20,40,80和120K不同温度下,分别对上述系列样品进行了光致发光谱(PL)的测量,清楚地观察到了受主束缚激子从ls3/2(Г6)基态到同种宇称2s3/2(Г6)激发态的两空穴跃迁,并且从实验上测得了在不同量子阱宽度下受主的束缚能.理论上应用量子力学中的变分原理,数值计算了受主对重空穴束缚能随量子阱宽度的变化关系,比较发现理论计算和实验结果符合较好.     

Exciton Dynamics and Effects of Structural Order in Morphology‐Controlled J‐Aggregate Assemblies

Narrow‐band photoluminescence (PL) together with high quantum efficiency from organic molecules is essential for high‐color‐purity emitters. Supramolecular assemblies like J‐aggregates are promising materials due to their narrow PL signal with full‐width at half maximum <20 nm. However, their microcrystalline nature and coherent exciton migration results in strong nonradiative exciton recombination at the grain boundaries that diminish the photoluminescence quantum yield (PLQY), and possibilities for improving the crystallinity by tuning the growth mechanism are limited. Here, two distinct routes to grow different J‐aggregate morphologies like platelets and lamellar crystals with improved crystallinity by surface‐guided molecular assembly are demonstrated, thereby suppressing nonradiative decay and improving PLQY. Both platelets and lamellar crystals show similar absorbance at room temperature. However, temperature‐dependent PL studies show sevenfold (twofold) higher PLQY for lamellar films compared to platelets at 6 K (300 K). Using time‐resolved PL spectroscopy, different nonradiative decay pathways are identified. The dependence of exciton diffusion on energetic disorder and nonradiative decay is discussed. The results suggest that the difference in domain size and order gives rise to significantly enhanced radiative decay from lamellar films as compared to platelets or films formed by spin‐coating.