Unity Photoluminescence Quantum Yield Research Articles

12‐1: Invited Paper: Narrowing the Emission Linewidth of I‐III‐VI Quantum Dots

In recent years, I‐III‐VI semiconductor quantum dots (QDs) have shown significant improvements that have unlocked new capabilities and end markets. Some typical examples of I‐III‐VI QDs are CuAlS2 (blue), AgInS2 (green), CuInSe2 (red) CuInSe2 (near‐IR), but other compositions and alloys are possible. These materials exhibit tunable photoluminescence (PL) emissions, and can achieve near unity PL quantum yield. They can have efficient broad emission, but also can have narrow emission, large Stokes shifts, and high optical extinction coefficients. These materials are often more stable, safer, and lower cost than alternatives such as CdSe, InP, and PbS or PbSe QDs. In this work, we discuss industrialization and scale‐up of I‐III‐VI QDs, starting with critical end uses related to spectrum optimization for greenhouses and solar energy. We also update on recent progress narrowing the emission linewidth (full‐width at half maximum) of I‐III‐VI QDs to the point that they are becoming competitive with legacy QDs used in displays and lighting.

Dynamic Reversible Full‐Color Piezochromic Fluorogens Featuring Through‐Space Charge‐Transfer Thermally Activated Delayed Fluorescence and their Application as X‐Ray Imaging Scintillators

AbstractThermally activated delayed fluorescence (TADF) emitters featuring through‐space charge transfer (TSCT) can be excellent candidates for piezochromic luminescent (PCL) materials due to their structural dynamics. Spatial donor‐acceptor (D−A) stacking arrangements enable the modulation of inter‐ and intramolecular D−A interactions, as well as spatial charge transfer states, under varying pressure conditions. Herein, we demonstrate an effective approach toward dynamic reversible full‐color PCL materials with TSCT‐TADF characteristics. Their single crystals exhibit a full‐color‐gamut PCL process spanning a range of 170 nm. Moreover, the TSCT‐TADF‐PCL emitters display a unity photoluminescence quantum yield, and show promising application in X‐ray scintillator imaging.

Dynamic Reversible Full-Color Piezochromic Fluorogens Featuring Through-Space Charge-Transfer Thermally Activated Delayed Fluorescence and their Application as X-Ray Imaging Scintillators.

Thermally activated delayed fluorescence (TADF) emitters featuring through-space charge transfer (TSCT) can be excellent candidates for piezochromic luminescent (PCL) materials due to their structural dynamics. Spatial donor-acceptor (D-A) stacking arrangements enable the modulation of inter- and intramolecular D-A interactions, as well as spatial charge transfer states, under varying pressure conditions. Herein, we demonstrate an effective approach toward dynamic reversible full-color PCL materials with TSCT-TADF characteristics. Their single crystals exhibit a full-color-gamut PCL process spanning a range of 170 nm. Moreover, the TSCT-TADF-PCL emitters display a unity photoluminescence quantum yield, and show promising application in X-ray scintillator imaging.

Transparent and Planar Cs3Cu2Cl5 Crystals for Micrometer-Resolution X-ray Imaging Screen.

Copper-based (I) halide perovskites have emerged as a promising candidate for scintillation screens in X-ray inspection and imaging areas due to their solution processability and high light yield. Here, a centimeter-sized Cs3Cu2Cl5 single crystal was grown by a slow-cooling method. The planar orientation was controlled in a space-confined chamber, generating a planar crystal which is readily used for a scintillation screen without any further shaping. The crystal exhibited a unity photoluminescence quantum yield and superior scintillation performance. The Cs3Cu2Cl5 single crystal exhibited a high light yield up to 95,000 photons/MeV, which enabled an X-ray detector of a detection limit down to 2.7 μGyair/s. The homemade imager demonstrated a spatial resolution of 105 lp/mm, representing an unprecedented micrometer resolution in laboratory. Importantly, the stability of Cs3Cu2Cl5 was significantly improved by a new surface passivation procedure, whereby the passivated crystal reserved its phase after 6 months' storage in a vial. This work introduced a new solution-based synthetic method for two-dimensional scintillating crystals, opening many avenues to high-performance X-ray imaging applications.

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing.

The investigation of organic light-emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple-resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (<30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 μJ cm-2 . Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet-triplet annihilation under long-pulsed excitation ranging from 20 μs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo-stability resulted in improved lasing and electroluminescence stability compared to that of 5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (DABNA)-core. These findings indicate the potential of CzBN-core as a promising framework for achieving long-pulsed wave and electrically-pumped lasing in the future.

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing

AbstractThe investigation of organic light‐emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple‐resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (&lt;30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 μJ cm−2. Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet‐triplet annihilation under long‐pulsed excitation ranging from 20 μs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo‐stability resulted in improved lasing and electroluminescence stability compared to that of 5,9‐diphenyl‐5,9‐diaza‐13b‐boranaphtho[3,2,1‐de]anthracene (DABNA)‐core. These findings indicate the potential of CzBN‐core as a promising framework for achieving long‐pulsed wave and electrically‐pumped lasing in the future.

A Multiple Resonance Emitter Integrating Para‐B‐π‐B′/Meta‐N‐π‐N Pattern via an Unembedded Organoboron Decoration for Both High‐Efficiency Solution‐ and Vacuum‐Processed OLEDs

AbstractMultiple resonance (MR)‐type thermally activated delayed fluorescence (TADF) emitters have promising prospects for high‐color‐purity organic light‐emitting diodes (OLEDs), but they are seldom attempted in the fabrication of solution‐processed devices. In addition, another issue with MR‐TADF emitters is that their heteroatom patterns are very limited, hampering their diversity. Herein, a novel double boron (B)‐containing MR‐TADF paradigm that merges an unembedded organoboron unit and a B‐embedded π‐fused MR framework into one system, furnishing a unique para‐B‐π‐B′/meta‐N (nitrogen)‐π‐N molecular pattern is proposed. Based on this, a proof‐of‐concept molecule, BNB′‐1, is developed, simultaneously achieving a bright sharp emission peaking at 540 nm with a full width at half maximum (FWHM) of only 24.5 nm/98 meV, a nearly unity photoluminescence quantum yield and excellent organic solubility. A solution‐processed OLED using BNB′‐1 emitter delivers an impressive external quantum efficiency (EQE) as high as 36.2% with an emissive FWHM of only 30.0 nm/0.13 eV at ≈540 nm; both parameters set new records among the ever‐reported solution‐processed MR‐OLEDs. Moreover, BNB′‐1 also obtains a superhigh EQE of 40.3% in vacuum‐processed OLEDs, surpassing all MR‐OLEDs in the similar emission region. This work provides an interesting solution to develop high‐performance solution‐processable MR‐TADF emitters with diverse heteroatom patterns.

Light-Induced Wavelength Dependent Self Assembly Process for Targeted Synthesis of Phase Stable 1D Nanobelts and 2D Nanoplatelets of CsPbI3 Perovskites.

Despite black cubic phase α-CsPbI3 nanocrystals having an ideal bandgap of 1.73 eV for optoelectronic applications, the phase transition from α-CsPbI3 to non-perovskite yellow δ-CsPbI3 phase at room temperature remains a major obstacle for commercial applications. Since γ-CsPbI3 is thermodynamically stable with a bandgap of 1.75 eV, which has great potential for photovoltaic applications, herein we report a conceptually new method for the targeted design of phase stable and near unity photoluminescence quantum yield (PLQY) two-dimensional (2D) γ-CsPbI3 nanoplatelets (NPLs) and one-dimensional (1D) γ-CsPbI3 nanobelts (NBs) by wavelength dependent light-induced assembly of CsPbI3 cubic nanocrystals. This article demonstrates for the first time that by varying the excitation wavelengths, one can design air stable desired 2D nanoplatelets or 1D nanobelts selectively. Our experimental finding indicates that 532 nm green light-driven self-assembly produces phase stable and highly luminescent γ-CsPbI3 NBs from CsPbI3 nanocrystals. Moreover, we show that a 670 nm red light-driven self-assembly process produces stable and near unity PLQY γ-CsPbI3 NPLs. Systematic time-dependent microscopy and spectroscopy studies on the morphological evolution indicates that the electromagnetic field of light triggered the desorption of surface ligands from the nanocrystal surface and transformation of crystallographic phase from α to γ. Detached ligands played an important role in determining the morphologies of final structures of NBs and NPLs from nanocrystals via oriented attachment along the [110] direction initially and then the [001] direction. In addition, XRD and fluorescence imaging data indicates that both NBs and NPLs exhibit phase stability for more than 60 days in ambient conditions, whereas the cubic phase α-CsPbI3 nanocrystals are not stable for even 3 days. The reported light driven synthesis provides a simple and versatile approach to obtain phase pure CsPbI3 for possible optoelectronic applications.

High Color-Purity and Efficient Pure-Blue Perovskite Light-Emitting Diodes Based on Strongly Confined Monodispersed Quantum Dots.

Here, we develop an in situ photoluminescence (PL) system to monitor the nucleation and growth of perovskite nanocrystals and control the monomer supply rate to achieve strongly confined and monodispersed quantum dots (QDs) with average size of 3.4 nm. Pure-blue (460 nm wavelength) CsPbBr3 QDs with near unity PL quantum yield and narrow size distribution (small size dispersion of 9.6%) were thus produced. Light-emitting diodes (LEDs) based on these QDs were prepared by using an all-solution processing route, which showed narrow electroluminescence with full width at half-maximum of 20 nm and a high color purity of 97.3%. The device also had a high external quantum efficiency of 10.1%, maximum luminance of 11 610 cd m-2, and continuous operation lifetime of 21 h at the initial luminance of 102 cd m-2, corresponding to the state-of-art for pure-blue perovskite LEDs.

TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor-Acceptor Emitter Featuring a Hybrid Sulfone-Triarylboron Acceptor.

10H-Dibenzo[b,e][1,4]thiaborinine 5,5-dioxide (SO2B)-a high triplet (T1 =3.05 eV) strongly electron-accepting boracycle was successfully utilised in thermally activated delayed fluorescence (TADF) emitters PXZ-Dipp-SO2B and CZ-Dipp-SO2B. We demonstrate the near-complete separation of highest occupied and lowest unoccupied molecular orbitals leading to a low oscillator strength of the S1 →S0 CT transition, resulting in very long ca. 83 ns and 400 ns prompt fluorescence lifetimes for CZ-Dipp-SO2B and PXZ-Dipp-SO2B, respectively, but retaining near unity photoluminescence quantum yield. OLEDs using CZ-Dipp-SO2B as the luminescent dopant display high external quantum efficiency (EQE) of 23.3 % and maximum luminance of 18600 cd m-2 with low efficiency roll off at high brightness. For CZ-Dipp-SO2B, reverse intersystem crossing (rISC) is mediated through the vibronic coupling of two charge transfer (CT) states, without involving the triplet local excited state (3 LE), resulting in remarkable rISC rate invariance to environmental polarity and polarisability whilst giving high organic light-emitting diode (OLED) efficiency. This new form of rISC allows stable OLED performance to be achieved in different host environments.

TADF Invariant of Host Polarity and Ultralong Fluorescence Lifetimes in a Donor‐Acceptor Emitter Featuring a Hybrid Sulfone‐Triarylboron Acceptor**

Abstract10H‐Dibenzo[b,e][1,4]thiaborinine 5,5‐dioxide (SO2B)—a high triplet (T1=3.05 eV) strongly electron‐accepting boracycle was successfully utilised in thermally activated delayed fluorescence (TADF) emitters PXZ‐Dipp‐SO2B and CZ‐Dipp‐SO2B. We demonstrate the near‐complete separation of highest occupied and lowest unoccupied molecular orbitals leading to a low oscillator strength of the S1→S0 CT transition, resulting in very long ca. 83 ns and 400 ns prompt fluorescence lifetimes for CZ‐Dipp‐SO2B and PXZ‐Dipp‐SO2B, respectively, but retaining near unity photoluminescence quantum yield. OLEDs using CZ‐Dipp‐SO2B as the luminescent dopant display high external quantum efficiency (EQE) of 23.3 % and maximum luminance of 18600 cd m−2 with low efficiency roll off at high brightness. For CZ‐Dipp‐SO2B, reverse intersystem crossing (rISC) is mediated through the vibronic coupling of two charge transfer (CT) states, without involving the triplet local excited state (3LE), resulting in remarkable rISC rate invariance to environmental polarity and polarisability whilst giving high organic light‐emitting diode (OLED) efficiency. This new form of rISC allows stable OLED performance to be achieved in different host environments.

Understanding and Preventing Photoluminescence Quenching to Achieve Unity Photoluminescence Quantum Yield in Yb:YLF Nanocrystals.

Ytterbium-doped LiYF4 (Yb:YLF) is a commonly used material for laser applications, as a photon upconversion medium, and for optical refrigeration. As nanocrystals (NCs), the material is also of interest for biological and physical applications. Unfortunately, as with most phosphors, with the reduction in size comes a large reduction of the photoluminescence quantum yield (PLQY), which is typically associated with an increase in surface-related PL quenching. Here, we report the synthesis of bipyramidal Yb:YLF NCs with a short axis of ∼60 nm. We systematically study and remove all sources of PL quenching in these NCs. By chemically removing all traces of water from the reaction mixture, we obtain NCs that exhibit a near-unity PLQY for an Yb3+ concentration below 20%. At higher Yb3+ concentrations, efficient concentration quenching occurs. The surface PL quenching is mitigated by growing an undoped YLF shell around the NC core, resulting in near-unity PLQY values even for fully Yb3+-based LiYbF4 cores. This unambiguously shows that the only remaining quenching sites in core-only Yb:YLF NCs reside on the surface and that concentration quenching is due to energy transfer to the surface. Monte Carlo simulations can reproduce the concentration dependence of the PLQY. Surprisingly, Förster resonance energy transfer does not give satisfactory agreement with the experimental data, whereas nearest-neighbor energy transfer does. This work demonstrates that Yb3+-based nanophosphors can be synthesized with a quality close to that of bulk single crystals. The high Yb3+ concentration in the LiYbF4/LiYF4 core/shell nanocrystals increases the weak Yb3+ absorption, making these materials highly promising for fundamental studies and increasing their effectiveness in bioapplications and optical refrigeration.

Quantum shells versus quantum dots: suppressing Auger recombination in colloidal semiconductors.

Colloidal semiconductor nanocrystals (NCs) have attracted a great deal of attention in recent decades. The quantum efficiency of many optoelectronic processes based on these nanomaterials, however, declines with increasing optical or electrical excitation intensity. This issue is caused by Auger recombination of multiple excitons, which converts the NC energy into excess heat, whereby reducing the efficiency and lifespan of NC-based devices, including lasers, photodetectors, X-ray scintillators, and high-brightness LEDs. Recently, semiconductor quantum shells (QSs) have emerged as a viable nanoscale architecture for the suppression of Auger decay. The spherical-shell geometry of these nanostructures leads to a significant reduction of Auger decay rates, while exhibiting a near unity photoluminescence quantum yield. Here, we compare the optoelectronic properties of quantum shells against other low-dimensional semiconductors and discuss their emerging opportunities in solid-state lighting and energy-harvesting applications.

A high-performance metal halide perovskite-based laser-driven display.

Laser-driven liquid crystal displays (LCDs) comprising metal halide perovskites (MHPs) as the blue-to-green/red color converters are at the forefront of ongoing intense research on the development and improvement of display devices. However, the inferior high photoluminescence quantum yield (PLQY) of MHPs under the excitation of high-power blue light and photoluminescence deterioration at high temperatures remain major concerns. Herein, we design a kind of octylamine-modified MHP via binding energy engineering, and the synthesized materials show PLQY of 97.6% under the excitation of a blue laser at 450 nm. Meanwhile, this design endows a structural self-healing ability to achieve a high PLQY and luminescence stability under high temperature (90 °C) and high flux excitation (386 mW cm-2). The blue light-excitable MHPs with a near unity PLQY, strong stability, and low PLQY deterioration are further encapsulated into a laser-driven LCD device. This prototype demonstrates excellent color gamut (132% NTSC, 98% Rec. 2020), illuminance intensity (>10 000 lux), and energy consumption (47.5% of commercial consumption), and hence is expected to be beneficial for the reduction of energy consumption in backlight display devices, particularly in large-screen outdoor displays.

Tailoring Donor‐Acceptor Emitters to Minimise Localisation Induced Quenching of Thermally Activated Delayed Fluorescence

AbstractBy inverting the common structural motif of thermally activated delayed fluorescence (TADF) materials to a rigid donor core and multiple peripheral acceptors, it has been shown possible to achieve both a reverse intersystem crossing (rISC) rate 1×107 s−1 and a unity photoluminescence quantum yield [Dos Santos et al. Adv. Sci. 5 (2018) 1700989]. However, the rISC rate in this motif is quenched by localisation of the excited state electronic structure which causes in‐equivalence between the peripheral acceptors. In this paper, we explore a series of related molecular targets which seek to reduce the effect of localisation on the rISC rates. This includes structures that contain donors exhibiting three‐fold or four‐fold symmetry and different degrees of steric hindrance around the donor‐acceptor bond with the objective of using steric hindrance to exert finer conformational control of the excited state dynamics to enhance functional properties. We demonstrate that a triazatruxene central donor is most effective for TADF owing to the energetic position of the locally excited state, while cyano‐benzonitriles are the most effective acceptors for reducing the effect of localisation on the electronic structure. These also push the emission into the blue region of the spectrum, opening the possibilities for this to be a pathway to develop efficient blue TADF emitters.

A Rational Molecular Design Strategy of TADF Emitter for Achieving Device Efficiency Exceeding 36%

AbstractAn excellent thermally activated delayed fluorescence (TADF) emitter requires a sophisticated molecular design strategy to incorporate structural features to simultaneously achieve high photoluminescence quantum yield (PLQY) and high horizontal emission dipole ratio (Θ//). This work reports the uses of heteroarenes and dicarbonitrile benzenes to design four new acceptors PymCN, PyoCN, PmmCN, and PmoCN, which are linked to a common donor dimethylacridine (DMAC) for making new TADF emitters. The emission wavelength, ΔEST, krisc, kr, and the resulting PLQY of the target TADF emitters are governed by the combined natures of the heteroaryl bridges (Py vs Pm) and the CN‐substituted patterns (o‐CN vs m‐CN). The photophysical and device characteristics reveal the best acceptor to be PyoCN, which is further coupled with spiroacridine to afford a new emitter SpiroAC‐PyoCN with an enhanced PLQY of 100% compared to that (91%) of the DMAC‐based counterpart DMAC‐PyoCN. Furthermore, linking PyoCN with spiro‐bisacridine (SBAC) gives an A–D–A‐configured TADF emitter SBAC‐PyoCN with both enhanced PLQY (100%) and Θ// (90%). The device employing SBAC‐PyoCN as emitter renders a maximum external quantum efficiency up to 36.1% owing to its unity PLQY and superior light out‐coupling efficiency. This rational molecular design strategy provides a feasible means to achieve an excellent TADF emitter design.

Bright Triplet Self-Trapped Excitons to Dopant Energy Transfer in Halide Double-Perovskite Nanocrystals.

For inorganic semiconductor nanostructure, excitons in the triplet states are known as the "dark exciton" with poor emitting properties, because of the spin-forbidden transition. Herein, we report a design principle to boost triplet excitons photoluminescence (PL) in all-inorganic lead-free double-perovskite nanocrystals (NCs). Our experimental data reveal that singlet self-trapped excitons (STEs) experience fast intersystem crossing (80 ps) to triplet states. These triplet STEs give bright green color emission with unity PL quantum yield (PLQY). Furthermore, efficient energy transfer from triplet STEs to dopants (Mn2+) can be achieved, which leads to white-light emitting with 87% PLQY in both colloidal and solid thin film NCs. These findings illustrate a fundamental principle to design efficient white-light emitting inorganic phosphors, propelling the development of illumination-related applications.

Asymmetric Spirobiacridine-based Delayed Fluorescence Emitters for High-performance Organic Light-Emitting Devices.

Recently, researchers have focused on thermally activated delayed fluorescence (TADF) for efficient future lighting and displays. Among TADF emitters, a combination of triazine and acridine is a promising candidate for realizing high-efficiency organic light-emitting devices (OLEDs). However, simultaneous development of perfect horizontal orientation (Θ=100 %) and an external quantum efficiency (EQE) of over 40 % is still challenging. Here, to obtain insights for further improvements of a triazine/acridine combination, various asymmetric spirobiacridine (SBA)-based TADF emitters with a unity photoluminescence quantum yield and high Θ ratio of over 80 % were developed. Furthermore, the substitution effects of the triazine acceptor unit on the photophysical properties were studied, including molecular orientations and OLED performance. The corresponding OLED exhibited sky-blue emission with a high EQE of over 30 %.

Stable and highly efficient blue-emitting CsPbBr3 perovskite nanomaterials via kinetic-controlled growth

Compared to the classical II-VI quantum dots (QDs), the reaction kinetics of cesium lead halide perovskite nanocrystals (NCs) are not clear yet because of the fast reaction rate. Here, an Ag+-assisted slow-release strategy is proposed to synthesize CsPbBr3 nanomaterials, where the reaction rate is decreased and the reaction time is prolonged to days. It is found that the Ag+ ions can bind with the PbBr2 precursor, which makes the formation of PbBr64- as the rate-limiting step. Shape conversion from dots to nanowires and then to platelets has been observed for the CsPbBr3. Pure blue-emitting nanoplatelets (NPLs) with near unity photoluminescence quantum yield (QY) are acquired. In addition, the blue-emitting CsPbBr3 solution is very stable, which has been stored for over 1.5 years without performance degradation. A liquid light-emitting diode (LED) prototype is further fabricated and exhibits excellent stability towards driving currents.

In situ synthesis of blue-emitting bromide-based perovskite nanoplatelets towards unity quantum efficiency and ultrahigh stability

In situ cross-linking passivation strategy for high-quality perovskite nanoplatelets with unity photoluminescence quantum yield.