Low Photoluminescence Quantum Efficiency Research Articles

Antithermal-Quenching Near-Infrared Emitting Lu2SrAl4SiO12:Cr3+ Garnet-Type Phosphor for High-Resolution Nonvisual Imaging.

Near-infrared (NIR) light allows fast and nondestructive detection with deep penetration into biological tissues and is widely used in food inspection, biomedical imaging, night vision security, and other fields. Cr3+-doped NIR first region (NIR-I) phosphors have many interesting features that have attracted a lot of attention recently. However, practical issues, such as low photoluminescence quantum efficiency and poor thermal stability, need to be addressed. We synthesized Cr3+-doped Lu2SrAl4SiO12 garnet-type phosphors using a high-temperature solid-state reaction method. Under blue-light (@ 430 nm) excitation, the phosphors exhibited broadband NIR-I emission in the range of 600-1000 nm, with an emission peak at 710 nm. This system is unique, as the emission had multipeak sharp-line superposition and the Cr3+ ions were situated in a relatively strong crystal field environment, as opposed to a weak crystal field environment for other matrix. The optimal doping content of Cr3+ ions was 2 mol %, and its internal quantum efficiency was ∼76.8%. Surprisingly, this NIR phosphor showed an antithermal quenching effect, and the integrated luminescence intensity of NIR-I emission measured at 573 K was 206.3% of that measured at 303 K. We found that the antithermal quenching of NIR-I luminescence was caused by the extremely low thermal expansion coefficient and rigid structure of the Lu2SrAl4SiO12 matrix in the temperature range, as well as the weakening of electron-phonon coupling with increasing temperature. The optimized phosphor was packaged with a blue chip into a NIR phosphor-converted light-emitting diode device. The light source device showed an output power of 119.02 mW and an electro-optical conversion efficiency of 11.02% under a driving current of 300 mA. The application potential of this NIR phosphor was demonstrated in the field of high-resolution nondestructive imaging.

Enhancing Emission and Stability in Na-Doped Cs3Cu2I5 Nanocrystals.

Lead-free Cs3Cu2I5 metal halides have garnered significant attention recently due to their non-toxic properties and deep-blue emission. However, their relatively low photoluminescence quantum efficiency and poor stability have limited their applications. In this work, sodium iodide (NaI) is used to facilitate the synthesis of Cs3Cu2I5 nanocrystals (NCs), demonstrating improved photoluminescence intensity, photoluminescence quantum yield, and stability. Systematic optoelectronic characterizations confirm that Na+ is successfully incorporated into the Cs3Cu2I5 lattice without altering its crystal structure. The improved Photoluminescence Quantum Yield (PLQY) and stability are attributed to the strengthened chemical bonding, which effectively suppresses vacancy defects in the lattice. Additionally, light-emitting diodes (LEDs) based on 10% NaI-doped Cs3Cu2I5 NCs were assembled, emitting vibrant blue light with a maximum radiant intensity of 82 lux and Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.15, 0.1). This work opens new possibilities for commercial lighting display applications.

Achieving Nearly 100% Photoluminescence Quantum Efficiency in Organic Radical Emitters by Fine‐Tuning the Effective Donor‐Acceptor Distance

AbstractDonor‐acceptor (D–A•) type luminescent organic radicals have received widespread attention as efficient doublet emitters. However, their generally low photoluminescence quantum efficiency (PLQE) and limited photostability restrict their various applications. Since unraveling the relationship between structure and properties of D–A• type luminescent radicals remains a challenge, here, a series of tri(2,4,6‐trichlorophenyl)methyl (TTM) radical derivatives, which differ by the location of their ring fusion sites and nature of their heteroatoms, is synthesized. The PLQE of isomers varies by ten times as a function of ring fusion sites. In particular, the PLQE of a radical undergoing ring fusion at the carbazole 3,4‐position is as high as 98.0%. Quantum‐chemical calculations show that in the case of overlapping holes and electrons, by increasing the effective distance between the D and A moieties, the radiative transition rates of the radicals increase. Also, decreasing the electronic coupling between the charge‐transfer and local‐excited states and avoiding large geometrical distortions between the ground state (D0)_and the first excited state (D1) can significantly reduce the nonradiative transition rates. This work offers a design strategy to obtain efficient and stable luminescent radicals by modifying the sites of ring fusion, which allows control of the radiative and nonradiative transition rates.

Na+-doped lead-free double perovskite Cs2AgInCl6 for broadband solar-blind UV detection

As a new generation of photonic materials, lead-free halide double perovskite materials demonstrate strong UV-light excited broadband emission that are promising for solar-blind ultraviolet (UV) light detectors. However, their practical applications are strongly limited by the low photoluminescence quantum efficiency because of the parity-forbidden nature of electronic transitions. Herein, the idea of cation alloying into lead-free halide double perovskite is proposed to mitigate the weak electronic transition and to improve the luminescence yield. By using the hydrothermal method, a series of Cs2NaxAg1-xInCl6 microcrystals were fabricated and the influences of Na-doping on the structural evolution and optical properties are investigated. Notably, the luminescence properties can be greatly improved by introducing an alloying element. By leveraging the UV-to-visible spectral conversion capability of the developed halide crystals, we fabricated a luminescent composite film by incorporating Cs2NaxAg1-xInCl6 perovskite nanocrystals into a polymethyl methacrylate matrix. Using this composite film as a spectral converter, we successfully demonstrated a solar-blind ultraviolet light detector with broadband and efficient response. Our work provides a novel solution for broadband solar-blind UV detection that could have practical implications for commercialization of metal halide based luminescent materials.

Heptazine-Based π-Conjugated Materials for Light-Emitting.

On the basis of planar and relatively rigid nitrogen-rich heterocyclic system of the heptazine core, heptazine-based π-conjugated materials have aroused widespread attention over the past decade by virtue of the fascinating electronic, optical, thermal, and mechanical properties in the fields of light-emitting, photocatalysis, sensors, environmental remediation, and so forth. However, there are still several obstacles to be solved before practical applications, such as low photoluminescence quantum efficiencies for light-emitting and weak visible absorption for photocatalysis. To further enhance various properties of heptazine-based π-conjugated materials, a series of strategies have been developed, including ingenious molecular design and modification, novel synthetic, and preparation methods. In this review, the significant progress of monomeric and polymeric heptazine-based π-conjugated materials and their applications typically in light-emitting are reviewed, which is beneficial for the acceleration of practical applications of heptazine-based materials and devices.

Enhanced Electroluminescence Based on a π-Conjugated Heptazine Derivative by Exploiting Thermally Activated Delayed Fluorescence.

Heptazine derivatives have attracted much attention over the past decade by virtue of intriguing optical, photocatalytic as well as electronic properties in the fields of hydrogen evolution, organic optoelectronic technologies and so forth. Here, we report a simple π-conjugated heptazine derivative (HAP-3DF) possessing an n→π* transition character which exhibits enhanced electroluminescence by exploiting thermally activated delayed fluorescence (TADF). Green-emitting HAP-3DF shows relatively low photoluminescence quantum efficiencies (Φ p) of 0.08 in toluene and 0.16 in doped film with bis(2-(diphenylphosphino)phenyl) ether oxide (DPEPO) as the matrix. Interestingly, the organic light-emitting diode (OLED) incorporating 8 wt% HAP-3DF:DPEPO as an emitting layer achieved a high external quantum efficiency (EQE) of 3.0% in view of the fairly low Φ p of 0.16, indicating the presence of TADF stemming from n→π* transitions. As the matrix changing from DPEPO to 1,3-di (9H-carbazol-9-yl)benzene (mCP), a much higher Φ p of 0.56 was found in doped film accompanying yellow emission. More importantly, enhanced electroluminescence was observed from the OLED containing 8 wt% HAP-3DF:mCP as an emitting layer, and a rather high EQE of 10.8% along with a low roll-off was realized, which should be ascribed to the TADF process deriving from exciplex formation.

Intermediate-phase-assisted low-temperature formation of \u03b3-CsPbI3 films for high-efficiency deep-red light-emitting devices

Black phase CsPbI3 is attractive for optoelectronic devices, while usually it has a high formation energy and requires an annealing temperature of above 300 °C. The formation energy can be significantly reduced by adding HI in the precursor. However, the resulting films are not suitable for light-emitting applications due to the high trap densities and low photoluminescence quantum efficiencies, and the low temperature formation mechanism is not well understood yet. Here, we demonstrate a general approach for deposition of γ-CsPbI3 films at 100 °C with high photoluminescence quantum efficiencies by adding organic ammonium cations, and the resulting light-emitting diode exhibits an external quantum efficiency of 10.4% with suppressed efficiency roll-off. We reveal that the low-temperature crystallization process is due to the formation of low-dimensional intermediate states, and followed by interionic exchange. This work provides perspectives to tune phase transition pathway at low temperature for CsPbI3 device applications.

High-efficiency red thermally activated delayed fluorescence emitters based on benzothiophene-fused spiro-acridine donor

Red thermally activated delayed fluorescence (TADF) emitters underperform their blue and green counterparts, largely due to their low photoluminescence quantum efficiency and isotropic orientation. Here, we designed two rigid and strong electron-rich donor moieties, 3-methyl-13H-spiro[benzo[4,5]thieno[3,2-c]acridine-5,9′-fluorene] (MSTA) and 3-phenyl-13H-spiro[benzo[4,5]thieno[3,2-c]acridine-5,9′-fluorene] (PSTA), by fusing benzothiophene unit on a spiro-acridine framework. Combined with a rigid, linear, and planar acenaphtho[1,2-b]quinoxaline-9,10-dicarbonitrile (ANQDC) acceptor, two red emitters, ANQDC-MSTA and ANQDC-PSTA, were synthesized and characterized. In virtue of high rigidity and linear donor–acceptor (D-A) molecular skeleton, both emitters showed distinct TADF nature, high photoluminescence quantum efficiencies and high horizontal ratios of emitting dipole orientation of ≈85%. Consequently, the ANQDC-PSTA-based OLEDs realized high external quantum efficiency (EQE) of 24.7% at an electroluminescence peak (ELpeak) of 622 nm, together with Commission Internationale de l’Eclairage 1931 (CIE1931) coordinates of (0.61, 0.38). Furthermore, with the modulation of the microcavity effect on the device architecture, we delivered a 19.1% EQE in a deep-red EL region, with an ELpeak of 646 nm and favorable CIE1931 coordinates of (0.64, 0.36). These efficiencies are on par with the highest EL performance for red TADF OLEDs in the similar color gamut.

Stable Luminescent Radicals and Radical-Based LEDs with Doublet Emission

Radical-based light-emitting diodes are an innovative type of organic light-emitting diodes (OLEDs), which adopt luminescent radicals as emitters, aiming at improving the external quantum efficienc...

34‐1: Invited Paper: Towards Efficient and Stable Printed Single‐layer OLEDs

The efficiency and stability of single‐layer polymer light‐emitting diodes is compromised by unbalanced charge transport, absence of triplet‐exciton harvesting and low photoluminescence quantum efficiencies. We demonstrate that tuning the energy levels of the organic semiconductor can prevent charge trapping, which is the main cause of unbalanced charge transport. By additionally using a novel strategy to enhance charge injection, efficient single‐layer organic light‐emitting diodes are presented based on a trap‐free organic semiconductor exhibiting thermally activated delayed fluorescence.

Tunable Dual‐Emission in Monodispersed Sb3+/Mn2+ Codoped Cs2NaInCl6 Perovskite Nanocrystals through an Energy Transfer Process

Double halide perovskites are a class of promising semiconductors applied in photocatalysis, photovoltaic devices, and emitters to replace lead halide perovskites, owing to their nontoxicity and chemical stability. However, most double perovskites always exhibit low photoluminescence quantum efficiency (PLQE) due to the indirect bandgap structure or parity-forbidden transition problem, limiting their further applications. Herein, the self-trapped excitons emission of Cs2 NaInCl6 by Sb-doping, showing a blue emission with high PLQE of 84%, is improved. Further, Sb/Mn codoped Cs2 NaInCl6 nanocrystals are successfully synthesized by the hot-injection method, showing a tunable dual-emission covering the white-light spectrum. The studies of PL properties and dynamics reveal that an energy transfer process can occur between the self-trapped excitons and dopants (Mn2+ ). The work provides a new perspective to design novel lead-free double perovskites for realizing a unique white-light emission.

Highly efficient luminescence from space-confined charge-transfer emitters.

Charge-transfer (CT) complexes, formed by electron transfer from a donor to an acceptor, play a crucial role in organic semiconductors. Excited-state CT complexes, termed exciplexes, harness both singlet and triplet excitons for light emission, and are thus useful for organic light-emitting diodes (OLEDs). However, present exciplex emitters often suffer from low photoluminescence quantum efficiencies (PLQEs), due to limited control over the relative orientation, electronic coupling and non-radiative recombination channels of the donor and acceptor subunits. Here, we use a rigid linker to control the spacing and relative orientation of the donor and acceptor subunits, as demonstrated with a series of intramolecular exciplex emitters based on 10-phenyl-9,10-dihydroacridine and 2,4,6-triphenyl-1,3,5-triazine. Sky-blue OLEDs employing one of these emitters achieve an external quantum efficiency (EQE) of 27.4% at 67 cd m-2 with only minor efficiency roll-off (EQE = 24.4%) at a higher luminous intensity of 1,000 cd m-2. As a control experiment, devices using chemically and structurally related but less rigid emitters reach substantially lower EQEs. These design rules are transferrable to other donor/acceptor combinations, which will allow further tuning of emission colour and other key optoelectronic properties.

Introductory lecture: origins and applications of efficient visible photoluminescence from silicon-based nanostructures.

A variety of silicon-based nanostructures with dimensions in the 1-5 nm range now emit tunable photoluminescence (PL) spanning the visible range. Achievement of high photoluminescence quantum efficiency (PLQY) relies critically on their surface chemistry passivation and an impressive "tool box" of options have been developed. Two distinct PL bands are dominant. The "S-Band" (red-green emission with Slow microsecond decay) has PLQY that has steadily improved from ∼3% in 1990 to 65 ± 5% by 2017. The "F-Band" (blue-yellow with Fast nanosecond decay) has reported PLQY values that have improved from ∼0.1% in 1994 to as high as ∼90% by 2016. The vast literature on both bands is surveyed and for the S-band, size-structure-PL correlations and selective photo-excitation studies are highlighted. Resonant photoexcitation and single quantum dot studies have revealed the key role of quantum confinement and the excitonic phonon-assisted nature of the radiative transitions. For the F-band, in contrast, specific phenomenological studies are highlighted that demonstrate similar emission without the presence of silicon nanostructures. Low PLQY F-band emission from pure silicon-silica core shell systems is probably associated with oxide-related defects, but ultrahigh PLQY from many lower temperature synthesis routes is likely to be from carbon-based nanostructures or chromophores, not silicon nanostructures. Potential applications for both PL bands include sensing, medical imaging, theranostics, photovoltaics, LED colour converters and nano-thermometry. Emerging "green" synthesis routes are mentioned. If scalability and cost are significantly improved then a number of other proposed uses of ultra-efficient PL from "nano-Si" could become viable in cosmetics, catalysis, security and forensics.

Efficient sky-blue perovskite light-emitting diodes via photoluminescence enhancement

The efficiencies of green and red perovskite light-emitting diodes (PeLEDs) have been increased close to their theoretical upper limit, while the efficiency of blue PeLEDs is lagging far behind. Here we report enhancing the efficiency of sky-blue PeLEDs by overcoming a major hurdle of low photoluminescence quantum efficiency in wide-bandgap perovskites. Blending phenylethylammonium chloride into cesium lead halide perovskites yields a mixture of two-dimensional and three-dimensional perovskites, which enhances photoluminescence quantum efficiency from 1.1% to 19.8%. Adding yttrium (III) chloride into the mixture further enhances photoluminescence quantum efficiency to 49.7%. Yttrium is found to incorporate into the three-dimensional perovskite grain, while it is still rich at grain boundaries and surfaces. The yttrium on grain surface increases the bandgap of grain shell, which confines the charge carriers inside grains for efficient radiative recombination. Record efficiencies of 11.0% and 4.8% were obtained in sky-blue and blue PeLEDs, respectively.

Charge-Carrier Dynamics of Lead-Free Halide Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (NCs) have been widely studied for application in optoelectronic devices due to their excellent optical properties and low-cost synthesis. However, the toxicity of lead and the poor stability of the NCs hindered their practical applications. Sn2+-based perovskite with low toxicity was first developed; however, the Sn2+-based perovskite NCs are unstable in air and oxidize easily. Recently, air-stable lead-free perovskite NCs have been developed and received increasing attention. Unfortunately, the optical and optoelectronic properties of these lead-free halide perovskite NCs are generally far worse than those of lead-perovskite NCs. Understanding the charge-carrier dynamics of semiconductors is crucial to improve their optical properties. In this Account, we mainly review our recent research progress on the study of charge-carrier dynamics in air-stable lead-free perovskite NCs. The exciton trapping followed by nonradiative recombination was the major carrier relaxation pathway and resulted in a low photoluminescence quantum efficiency (PLQE). A feasible route for passivating surface traps and tuning the self-trapped excitons from "dark" (nonradiative) to "bright" (radiative) was proposed. Through this strategy, the PLQE could be increased over 100-fold. In addition, we have compared several photophysical properties of lead-free perovskite NCs with that of lead perovskite NCs, such as charge-carrier relaxation, exciton-phonon coupling, and hot-carrier cooling. In 2017, we reported the synthesis, optical properties, and charge-carrier dynamics of Cs3Bi2X9 (X: Cl, Br, I) NCs. The Cs3Bi2Br9 NCs exhibited clear exciton trapping processes with time scales in the range of 2-20 ps. The fast trapping processes could be passivated via the use of surfactants (such as oleic acid), and the PLQE increased over 20-fold (from 0.2% to 4.5%). The low PLQE may be due to the reduced dimensionality of Cs3Bi2Br9 (2D) compared with the 3D cubic perovskite structure of CsPbBr3. We next reported double perovskite Cs2AgSb1-yBiyX6 (X: Br, Cl; 0 ≤ y ≤ 1) NCs, which exhibited a similar 3D cubic perovskite structure to that of the lead-perovskite NCs. The charge-carrier dynamics indicated that the sub-band-gap exciton trapping processes were dominated by ultrafast (∼1-2 ps) intrinsic self-trapping and trapping at surface defects (∼50-100 ps). While trapping at surface defects can be passivated using surfactants, the self-trapping processes is due to the giant carrier-phonon coupling effect. By designing direct band gap double perovskite NCs to tune the sub-band-gap trapping processes, bright dual-color emission was achieved. Furthermore, the violet PLQE could be improved to 36.6%, which is comparable to that in lead halide perovskite NCs. We hope this Account will deepen the understanding of the charge-carrier dynamics in lead-free perovskite NCs and guide the design of high-performance lead-free perovskites.

Microsecond Carrier Lifetimes, Controlled p-Doping, and Enhanced Air Stability in Low-Bandgap Metal Halide Perovskites.

Mixed lead–tin halide perovskites have sufficiently low bandgaps (∼1.2 eV) to be promising absorbers for perovskite–perovskite tandem solar cells. Previous reports on lead–tin perovskites have typically shown poor optoelectronic properties compared to neat lead counterparts: short photoluminescence lifetimes (<100 ns) and low photoluminescence quantum efficiencies (<1%). Here, we obtain films with carrier lifetimes exceeding 1 μs and, through addition of small quantities of zinc iodide to the precursor solutions, photoluminescence quantum efficiencies under solar illumination intensities of 2.5%. The zinc additives also substantially enhance the film stability in air, and we use cross-sectional chemical mapping to show that this enhanced stability is because of a reduction in tin-rich clusters. By fabricating field-effect transistors, we observe that the introduction of zinc results in controlled p-doping. Finally, we show that zinc additives also enhance power conversion efficiencies and the stability of solar cells. Our results demonstrate substantially improved low-bandgap perovskites for solar cells and versatile electronic applications.

Tailored Synthesis of an Unprecedented Pb-Mn Heterometallic Halide Hybrid with Enhanced Emission.

Organic-inorganic lead halide hybrids have attracted extensive interest in solid-state lighting, due to their superior color tunability and low-cost solution processing. However, the relatively low photoluminescence quantum efficiency (PLQE) is a common issue for most bulk lead halide hybrids. Inspired by the intriguing luminescence properties of heterometallic complexes, we rationally developed an unprecedented two-dimensional (2D)Pb-Mn heterometallic halide hybrid, (C5H14N2)2Pb4MnCl14 (2), through a precisely tailored synthetic approach based on (C5H14N2)2Pb5Cl14 (1). Intriguingly, 2 features a unique 2D heterometallic halide layer configuration, in which the strong quantum confinement facilitates efficient energy transfer from bound excitons to d-states of Mn2+, resulting in highly sensitized Mn2+emission. The PLQE of 2 is up to 32%, considerably higher than that of pristine 1 (less than 1%). Moreover, 2 presents significant environmental and thermal stability, benefiting from its cluster feature. To our best knowledge, this is the first example of construction of a Pb-Mn heterometallic halide hybrid with bulk highly efficient red emission. This work provides a way to enhance the PLQE of lead halide hybrids via sensitization in rationally designed heterometallic halide hybrids.

Ultrasonic synthesis of Mn-doped CsPbCl3 quantum dots (QDs) with enhanced photoluminescence

Mn-doped CsPbCl3 (CsPbCl3:Mn) perovskite colloidal quantum dots (QDs) attract a great deal of interests, and have great potentials for various optoelectronics applications due to their outstanding optical and electrical properties. However, practical applications of CsPbCl3:Mn QDs are severely limited by the cumbersome preparation methods and low photoluminescence quantum efficiency (PLQY). Herein, we propose a single-step ultrasonic synthesis method to successfully synthesize CsPbCl3:Mn QDs with controlled size and morphology by changing the Mn:Pb ratio. Simultaneously, we introduce triethylamine (TETN) to passivate the surface of CsPbCl3:Mn QDs. The phase purity, microstructure, chemical composition and photoluminescence properties of the samples were investigated by means of various analytic techniques. The synthesized QDs exhibit dual emissions of 411 and 601 nm, ascribing to the excitonic emission of QDs and the characteristic Mn2+ emission, respectively. The quantum yield of the CsPbCl3:Mn QDs could therefore be significantly improved from 17.49 to 41.15%. We believe that the facial synthesis method and the surface passivation of TETN can also be applied to other transition metal or lanthanide ions doped lead halide perovskite QDs.

Bright Free Exciton Electroluminescence from Mn-Doped Two-Dimensional Layered Perovskites.

Two-dimensional (2D) perovskites incorporating hydrophobic organic spacer cations show improved film stability and morphology compared to their three-dimensional (3D) counterparts. However, 2D perovskites usually exhibit low photoluminescence quantum efficiency (PLQE) owing to strong exciton-phonon interaction at room temperature, which limits their efficiency in light-emitting diodes (LEDs). Here, we demonstrate that the device performance of 2D perovskite LEDs can be significantly enhanced by doping Mn2+ in (benzimidazolium)2PbI4 2D perovskite films to suppress the exciton-phonon interaction. The distorted [PbI6]4- octahedra by Mn-doping and the rigid benzimidazolium (BIZ) ring without branched chains in the 2D perovskite structure lead to improved crystallinity and rigidity of the perovskites, resulting in suppressed phonon-exciton interaction and enhanced PLQE. On the basis of this strategy, for the first time, we report yellow electroluminescence from free excitons in 2D ( n = 1) perovskites with a maximum brightness of 225 cd m-2 and a peak EQE of 0.045%.

High-efficiency colloidal quantum dot infrared light-emitting diodes via engineering at the supra-nanocrystalline level.

Colloidal quantum dot (CQD) light-emitting diodes (LEDs) deliver a compelling performance in the visible, yet infrared CQD LEDs underperform their visible-emitting counterparts, largely due to their low photoluminescence quantum efficiency. Here we employ a ternary blend of CQD thin film that comprises a binary host matrix that serves to electronically passivate as well as to cater for an efficient and balanced carrier supply to the emitting quantum dot species. In doing so, we report infrared PbS CQD LEDs with an external quantum efficiency of ~7.9% and a power conversion efficiency of ~9.3%, thanks to their very low density of trap states, on the order of 1014 cm-3, and very high photoluminescence quantum efficiency in electrically conductive quantum dot solids of more than 60%. When these blend devices operate as solar cells they deliver an open circuit voltage that approaches their radiative limit thanks to the synergistic effect of the reduced trap-state density and the density of state modification in the nanocomposite.