Efficient Large-Area (81 cm2) Ternary Copper Halides Light-Emitting Diodes with External Quantum Efficiency Exceeding 13% via Host-Guest Strategy.

Ternary copper (Cu) halides are promising candidates for replacing toxic lead halides in the field of perovskite light-emitting diodes (LEDs) toward practical applications. However, the electroluminescent performance of Cu halide-based LEDs remains a great challenge due to the presence of serious nonradiative recombination and inefficient charge transport in Cu halide emitters. Here, the rational design of host-guest [dppb]2Cu2I2 (dppb denotes 1,2-bis[diphenylphosphino]benzene) emitters and its utility in fabricating efficient Cu halide-based green LEDs that show a high external quantum efficiency (EQE) of 13.39% are reported. The host-guest [dppb]2Cu2I2 emitters with mCP (1,3-bis(N-carbazolyl)benzene) host demonstrate a significant improvement of carrier radiative recombination efficiency, with the photoluminescence quantum yield increased by nearly ten times, which is rooted in the efficient energy transfer and type-I energy level alignment between [dppb]2Cu2I2 and mCP. Moreover, the charge-transporting mCP host can raise the carrier mobility of [dppb]2Cu2I2 films, thereby enhancing the charge transport and recombination. More importantly, this strategy enables a large-area prototype LED with a record-breaking area up to 81 cm2, along with a decent EQE of 10.02% and uniform luminance. It is believed these results represent an encouraging stepping stone to bring Cu halide-based LEDs from the laboratory toward commercial lighting and display panels.

Synchronously Polishing the Lead-Rich Surface and Passivating Surface Defects of CsPb(Br/I)3 Quantum Dots for High-Performance Pure-Red PeLEDs.

Mixed-halide CsPb(Br/I)3 perovskite quantum dots (QDs) are regarded as one of the most promising candidates for pure-red perovskite light-emitting diodes (PeLEDs) due to their precise spectral tuning property. However, the lead-rich surface of these QDs usually results in halide ion migration and nonradiative recombination loss, which remains a great challenge for high-performance PeLEDs. To solve the above issues, we employ a chelating agent of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid hydrate (DOTA) to polish the lead-rich surface of the QDs and meanwhile introduce a new ligand of 2,3-dimercaptosuccinic acid (DMSA) to passivate surface defects of the QDs. This synchronous post-treatment strategy results in high-quality CsPb(Br/I)3 QDs with suppressed halide ion migration and an improved photoluminescence quantum yield, which enables us to fabricate spectrally stable pure-red PeLEDs with a peak external quantum efficiency of 23.2%, representing one of the best performance pure-red PeLEDs based on mixed-halide CsPb(Br/I)3 QDs reported to date.

Full-Spectrum White-Light Emission from Triple Self-Trapped Excitons in Hybrid Mixed-Metal Halides.

Low-dimensional metal halides with broadband emissions are expected to serve as downconversion luminescent materials for solid-state lighting (SSL). However, efficiently generating full-spectrum white-light emission with a high color-rendering index (CRI) in single-phase emitters remains a challenge. Here, we report a novel zero-dimensional (0D) hybrid mixed-metal halide (TPA)2CuAgI4 (TPA = tetrapropylammonium), in which individual [CuAgI4]2- dimers are completely isolated and surrounded by the organic cations TPA+. Cu+ and Ag+ share the same crystallographic site in [CuAgI4]2- dimers with the same statistical probability. Upon photoexcitation, single crystals exhibit a full-spectrum white-light emission with a full width at half-maximum (fwhm) of up to 314 nm and a high quantum efficiency of 46.8%. Detailed photophysical studies and theoretical calculations reveal that the ultra-broadband emission of (TPA)2CuAgI4 originates from the radiative recombination of red-, green-, and blue-emitting self-trapped excitons in [CuAgI4]2- dimers. In addition, (TPA)2CuAgI4 nanocrystals were successfully synthesized and exhibited optical properties similar to those of single-crystal counterparts. Finally, a prototype ultraviolet (UV)-pumped white-light-emitting diode (WLED) and a composite thin film employing this new white-light emitter produces a well-distributed full-spectrum white light with a high CRI of 91.4 and a warm correlated color temperature (CCT) of 4135 K, indicating the potential application of this white-light emitter in SSL. These results provide a new perspective for designing superior single-phase white-light emitters.

CsPb(Br/Cl)3 Perovskite Nanocrystals with Bright Blue Emission Synergistically Modified by Calcium Halide and Ammonium Ion.

Colloidal cesium lead halide (CsPbX3, X = Cl, Br, and I) perovskite nanocrystals (NCs) demonstrate supreme optical properties in the spectra region of infrared, red, and green. High-performance blue-emitting counterparts are still eagerly required for next-generation full-color displays. However, it is challenging to obtain efficient blue perovskite NCs, especially in a deep blue region with an emission wavelength of around 460 nm or shorter. Herein, calcium halide and ammonium ions are applied simultaneously to modify the CsPb(Br/Cl)3 NCs in situ to reduce surface defects, finally remarkably enhancing the photoluminescence quantum yield (PLQY) from 13% to 93% with an emission peak at 455 nm and the Commission Internationale de l'Eclairage (CIE) coordinates at (0.147, 0.030), which is close to the requirement of the Rec.2020 standard and also meets the requirement of blue emission in DCI-P3. Bright white emission and a wide color gamut are also achieved by combining the commercial red-emitting and green-emitting phosphors. The combination of time-resolved PL spectra and femtosecond transient absorption results discloses the reason for PLQY improvement as suppressing the nonradiative recombination.

Realizing Near-Unity Quantum Efficiency of Zero-Dimensional Antimony Halides through Metal Halide Structural Modulation.

Zero-dimensional (0D) organic metal halides have attracted significant attention because of their exceptional structure tunability and excellent optical characteristics. However, controllable synthesis of a desirable configuration of metal halide species in a rational way remains a formidable challenge, and how the unique crystal structures affect the photophysical properties are not yet well understood. Here, a reasonable metal halide structural modulation strategy is proposed to realize near-unity photoluminescence quantum efficiency (PLQE) in 0D organic antimony halides. By carefully controlling the reaction conditions, both 0D (C12H28N)2SbCl5 and (C12H28N)SbCl4 with different metal halide configurations can be prepared. (C12H28N)2SbCl5 with pyramid-shaped [SbCl5]2- species exhibits yellow emission with a near-unity PLQE of 96.8%, while (C12H28N)SbCl4 with seesaw-shaped [SbCl4]- species is not emissive at room temperature. Theoretical calculations indicate that the different photophysical properties of these two crystals can be attributed to the different symmetries of their crystal structures. (C12H28N)2SbCl5 adopts a triclinic structure with P-1 symmetry, while (C12H28N)SbCl4 possesses a monoclinic structure with P21/c symmetry, which has an inversion center, and thus the optical transitions between their band-edge states give a minimal dipole intensity because of their similar parity character. In addition, we also successfully synthesized (C12H28N)2SbCl5 nanocrystals for the first time, which are particularly appealing for their solution processibility and excellent optical properties. Furthermore, (C12H28N)2SbCl5 nanocrystals flexible composite film shows bright yellow emission under ß-ray excitation, suggesting a strong potential of (C12H28N)2SbCl5 for ß-ray detection.

Highly Luminescent Zero-Dimensional Organic Copper Halides for X-ray Scintillation.

The present work reports highly efficient flexible and reabsorption-free scintillators based on two zero-dimensional (0D) organic copper halides (TBA)CuX2 (TBA = tetrabutylammonium cation; X = Cl, Br). The (TBA)CuX2 exhibit highly luminescent green and sky-blue emissions peaked at 510 and 498 nm, with large Stokes shifts of 224 and 209 nm and high photoluminescence quantum yields (PLQYs) of 92.8% and 80.5% at room temperature for (TBA)CuCl2 and (TBA)CuBr2 single crystals (SCs), respectively. Interestingly, above room temperature, their PLQYs increase with temperature and reach near unity at 320 and 345 K for (TBA)CuCl2 and (TBA)CuBr2, respectively. The excellent properties originate from self-trapped excitons (STEs) in individual [CuX2]- quantum rods, which is demonstrated by the temperature-dependent PL, ultrafast transient absorption (TA) combined with density functional theory (DFT) calculations. The (TBA)CuX2 scintillators show bright radioluminescence (RL), impressive linear response to dose rate in a broad range, and high light yields. Their potential application in X-ray imaging is demonstrated by using (TBA)CuX2 composite scintillation screens. Importantly, flexible scintillators are demonstrated to be superior than flat ones for imaging nonplanar objects by conformally coating, which produce accurate images with negligible distortion.

Efficient Dual-Band White-Light Emission with High Color Rendering from Zero-Dimensional Organic Copper Iodide.

Broad-band white-light emissions from organic-inorganic lead halide hybrids have attracted considerable attention in energy-saving solid-state lighting (SSL) applications. However, the toxicity of lead in these hybrids hinders their commercial prospects, and the low photoluminescence quantum yields (PLQYs) cannot meet the requirements for efficient lighting. Here, we report a highly efficient dual-band white-light emission from organic copper iodide, (C16H36N)CuI2, which exhibits a high PLQY of 54.3% and excellent air stability. The single-crystalline (C16H36N)CuI2 possesses a unique zero-dimensional (0D) structure, in which the isolated [Cu2I4]2- dimers are periodically embedded in the wide band gap organic framework of C16H36N+. This perfect 0D structure can cause significant quantum confinement and strong electron-phonon coupling, which contributes to efficient emissions from self-trapped excitons (STEs). Photophysical studies revealed the presence of two self-trapped emitting states in [Cu2I4]2- dimers, whose populations are highly sensitive to the temperature that governs the molecular environment for [Cu2I4]2- dimers and the thermal activation energy of STEs. An ultraviolet (UV) excited white light-emitting diode fabricated using this single-phase white-light emitter exhibits a high color rendering index (CRI) of 78. The new material provides a promising emitter, having a high PLQY and a high CRI simultaneously, for SSL and display applications.

Cu2+-Doped CsPbI3 Nanocrystals with Enhanced Stability for Light-Emitting Diodes.

Black phase CsPbI3 perovskites have emerged as one of the most promising materials for use in optoelectronic devices due to their remarkable properties. However, black phase CsPbI3 usually possesses poor stability and involves a phase change process, resulting in an undesired orthorhombic (δ) yellow phase. Here, the enhanced stability of CsPbI3 nanocrystals is achieved by incorporating the Cu2+ ion into the CsPbI3 lattice under mild conditions. In particular, the Cu2+-doped CsPbI3 film can maintain red luminescence for 35 days in air while the undoped ones transformed into the nonluminescent yellow phase in several days. Furthermore, first-principles calculations verified that the enhanced stability is ascribed to the increased formation energy due to the successful doping of Cu2+ in CsPbI3. Benefiting from such an effective doping strategy, the as-prepared Cu2+-doped CsPbI3 as an emitting layer shows much better performance compared with that of the undoped counterpart. The turn-on voltage of the Cu2+-doped quantum-dot light-emitting diode (QLED) (1.6 V) is significantly reduced compared with that of the pristine QLED (3.8 V). In addition, the luminance of the Cu2+-doped QLED can reach 1270 cd/m2, which is more than twice that of the pristine CsPbI3 QLED (542 cd/m2). The device performance is believed to be further improved by optimizing the purification process and device structure, shedding light on future applications.

Efficiently Passivated PbSe Quantum Dot Solids for Infrared Photovoltaics.

Infrared (IR) solar cells are promising devices for significantly improving the power conversion efficiency of common solar cells by harvesting the low-energy IR photons. PbSe quantum dots (QDs) are superior IR photon absorbing materials due to their strong quantum confinement and thus strong interdot electronic coupling. However, the high chemical activity of PbSe QDs leads to etching and poor passivation in ligand exchange, resulting in a high trap-state density and a high open circuit voltage (VOC) deficit. Here we develop a hybrid ligand co-passivation strategy to simultaneously passivate the Pb and Se sites; that is, halide anions passivate the Pb sites and Cd cations passivate the Se sites. The cation and anion hybrid passivation substantially improves the quality of PbSe QD solids, giving rise to an excellent trap-state control and prolonged carrier lifetime. A high VOC and a high short circuit current density (JSC) are achieved simultaneously in the IR QD solar cells based on this hybrid ligand treatment. Finally, a IR-PCE of 1.31% under the 1100-nm-filtered solar illumination is achieved in the PbSe QD solar cells, which is the highest IR-PCE for PbSe QD IR solar cells at present. Additionally, the PbSe QD devices show a high external quantum efficiency of 80% at ∼1295 nm.

Efficient and Reabsorption-Free Radioluminescence in Cs3Cu2I5 Nanocrystals with Self-Trapped Excitons.

Radioluminescent materials (scintillators) are widely applied in medical imaging, nondestructive testing, security inspection, nuclear and radiation industries, and scientific research. Recently, all-inorganic lead halide perovskite nanocrystal (NC) scintillators have attracted great attention due to their facile solution processability and ultrasensitive X-ray detection, which allows for large area and flexible X-ray imaging. However, the light yield of these perovskite NCs is relatively low because of the strong self-absorption that reduces the light out-coupling efficiency. Here, NCs with self-trapped excitons emission are demonstrated to be sensitive, reabsorption-free scintillators. Highly luminescent and stable Cs3Cu2I5 NCs with a photoluminescence quantum yields of 73.7%, which is a new record for blue emission lead-free perovskite or perovskite-like NCs, is produced with the assistance of InI3. The PL peak of the Cs3Cu2I5 NCs locates at 445 nm that matches with the response peak of a silicon photomultiplier. Thus, Cs3Cu2I5 NCs are demonstrated as efficient scintillators with zero self-absorption and extremely high light yield (≈79 279 photons per MeV). Both Cs3Cu2I5 NC colloidal solution and film exhibit strong radioluminescence under X-ray irradiation. The potential application of Cs3Cu2I5 NCs as reabsorption-free, low cost, large area, and flexible scintillators is demonstrated by a prototype X-ray imaging with a high spatial resolution.

Quantum Confinement-Tunable Ultrafast Charge Transfer in a PbS Quantum Dots/WSe2 0D-2D Hybrid Structure: Transition from the Weak to Strong Coupling Regime.

0D-2D mixed-dimensional hybrid structures, which combine tunable optical properties of 0D quantum dots (QDs) and high transport mobilities of 2D layered materials, have shown great potential in optoelectronic applications. Understanding charge transfer dynamics at the 0D-2D interface is essential but still lacking. Here, using PbS QD/WSe2 system, by simply controlling PbS QD size, we show a tunable hole transfer (HT) rate by more than 4 orders of magnitude (from ∼1 ns to <100 fs) and, interestingly, transition from the weak to strong coupling regime due to quantum confinement effect. In contrast to reported layer-dependent energy transfer dynamics, we observe a robust HT rate against WSe2 layer number, which can be ascribed to a subtle change of WSe2 valence band structure with layer number. Our results are important to not only fundamental understanding of charge transfer behavior at nanoscale low-dimensional interface but also help design next-generation mixed-dimensional optoelectronic devices.

PbSe Quantum Dots Sensitized High-Mobility Bi2O2Se Nanosheets for High-Performance and Broadband Photodetection Beyond 2 µm.

As an emerging two-dimensional semiconductor, Bi2O2Se has recently attracted broad interests in optoelectronic devices for its superior mobility and ambient stability, whereas the diminished photoresponse near its inherent indirect bandgap (0.8 eV or λ = 1550 nm) severely restricted its application in the broad infrared spectra. Here, we report the Bi2O2Se nanosheets based hybrid photodetector for short wavelength infrared detection up to 2 µm via PbSe colloidal quantum dots (CQDs) sensitization. The type II interfacial band offset between PbSe and Bi2O2Se not only enhanced the device responsivity compared to bare Bi2O2Se but also sped up the response time to ∼4 ms, which was ∼300 times faster than PbSe CQDs. It was further demonstrated that the photocurrent in such a zero-dimensional-two-dimensional hybrid photodetector could be efficiently tailored from a photoconductive to photogate dominated response under external field effects, thereby rendering a sensitive infrared response >103 A/W at 2 µm. The excellent performance up to 2 µm highlights the potential of field-effect modulated Bi2O2Se-based hybrid photodetectors in pursuing highly sensitive and broadband photodetection.

Hybrid Growth Modes of PbSe Nanocrystals with Oriented Attachment and Grain Boundary Migration.

The growth of nanocrystals has widely been researched recently through an in situ high-resolution transmission electron microscopy technique, which reveals the process of morphological and structural evolutions. For nanocrystals, the underlying growth modes are mostly determined by growth environment and crystal morphology. Here, the direct growth process of the PbSe nanocrystals via controlling the temperature is clearly observed. The results show that the PbSe nanocrystals start growth following oriented attachment growth mode, and then change to growth with grain boundary migration at moderate temperature as the heat activated nanocrystals gather together with decreased degree of freedom for crystal rotation. During the grain boundary migration, the smaller nanocrystals are inclined to be assimilated by larger ones through interfacial atom reconfigurations, which are observed to take place through strain mediated atom migration. The growth mode changes in different growth states with a hybrid growth mode of oriented attachment and grain boundary migration during the whole growth process.