Pattern-Matched Polymer Ligpands Toward Near-Perfect Synergistic Passivation for High-Performance and Stable Br/Cl Mixed Perovskite Light-Emitting Diodes.

Mixed Br/Cl perovskite nanocrystals (PeNCs) exhibit bright pure-blue emission benefiting for fulfilling the Rec. 2100 standard. However, phase segregation remains a significant challenge that severely affects the stability and emission spectrum of perovskite light-emitting diodes (PeLEDs). Here, we demonstrate the optimization of the spacing between polydentate functional groups of polymer ligands to match the surface pattern of CsPbBr1.8Cl1.2 PeNCs, resulting in effective synergistic passivation effect and significant improvements in PeLED performances. The block and alternating copolymers with different inter-functional group spacing are facilely synthesized as ligands for PeNCs. Surprisingly, block copolymers with a higher functional group density do not match PeNCs, while alternating copolymers enable efficient PeNCs with the high photoluminescence intensity, low non-radiative recombination rate and high exciton binding energy. Density functional theory calculations clearly confirm the almost perfect match between alternating copolymers and PeNCs. Finally, pure-blue PeLEDs are achieved with the emission at 467 nm and Commission Internationale de l'Eclairage (CIE) coordinates of (0.131, 0.071), high external quantum efficiency (9.1%) and record spectral and operational stabilities (~ 80 mins) in mixed-halide PeLEDs. Overall, this study contributes to designing the polymer ligands and promoting the development of high-performance and stable pure-color PeLEDs towards display applications.

Spin Quantum Dot Light-Emitting Diodes Enabled by 2D Chiral Perovskite with Spin-Dependent Carrier Transport.

Chiral-induced spin selectivity (CISS) effect provides innovative approach to spintronics and quantum-based devices for chiral materials. Different from the conventional ferromagnetic devices, the application of CISS effect is potential to operate under room temperature and zero applied magnetic field. Low dimensional chiral perovskites by introducing chiral amines are beginning to show significant CISS effect for spin injection, but research on chiral perovskites is still in its infancy, especially on spin-light emitting diode (spin-LED) construction. Here, the spin-QLEDs enabled by 2D chiral perovskites as CISS layer for spin-dependent carrier injection and CdSe/ZnS quantum dots (QDs) as light emitting layer are reported. The regulation pattern of the chirality and thickness of chiral perovskites, which affects the circularly polarized electroluminescence (CP-EL) emission of spin-QLED, is discovered. Notably, the spin injection polarization of 2D chiral perovskites is higher than 80% and the CP-EL asymmetric factor (gCP-EL ) achieves up to 1.6 × 10-2 . Consequently, this work opens up a new and effective approach for high-performance spin-LEDs.

Quenching Detrimental Reactions and Boosting Hole Extraction via Multifunctional NiOx /Perovskite Interface Passivation for Efficient and Stable Inverted Solar Cells.

Nickel oxide (NiOx ) is one of the most promising hole transport materials for inverted perovskite solar cells (PSCs). However, its application is severely restrained due to unfavorable interfacial reactions and insufficient charge carrier extraction. Herein, a multifunctional modification at the NiOx /perovskite interface is developed via introducing fluorinated ammonium salt ligand to synthetically solve the obstacles. Specifically, the interface modification can chemically convert detrimental Ni≥3+ to lower oxidation state, resulting in the elimination of interfacial redox reactions. Meanwhile, interfacial dipole is incorporated simultaneously to tune the work function of NiOx and optimize energy level alignment, which effectively promotes the charge carrier extraction. Therefore, the modified NiOx -based inverted PSCs achieve a remarkable power conversion efficiency (PCE) of 22.93%. Moreover, the unencapsulated devices obtain a significantly enhanced long-term stability, maintaining over 85% and 80% of the initial PCEs after storage in ambient air with a high relative humidity of 50-60% for 1000 h and continuous operation at maximum power point under one-sun illumination for 700 h, respectively.

A Multiple Mechanism Enhanced Arithmetic Optimization Algorithm for Numerical Problems.

The Arithmetic Optimization Algorithm (AOA) is a meta-heuristic algorithm inspired by mathematical operators, which may stagnate in the face of complex optimization issues. Therefore, the convergence and accuracy are reduced. In this paper, an AOA variant called ASFAOA is proposed by integrating a double-opposite learning mechanism, an adaptive spiral search strategy, an offset distribution estimation strategy, and a modified cosine acceleration function formula into the original AOA, aiming to improve the local exploitation and global exploration capability of the original AOA. In the proposed ASFAOA, a dual-opposite learning strategy is utilized to enhance population diversity by searching the problem space a lot better. The spiral search strategy of the tuna swarm optimization is introduced into the addition and subtraction strategy of AOA to enhance the AOA's ability to jump out of the local optimum. An offset distribution estimation strategy is employed to effectively utilize the dominant population information for guiding the correct individual evolution. In addition, an adaptive cosine acceleration function is proposed to perform a better balance between the exploitation and exploration capabilities of the AOA. To demonstrate the superiority of the proposed ASFAOA, two experiments are conducted using existing state-of-the-art algorithms. First, The CEC 2017 benchmark function was applied with the aim of evaluating the performance of ASFAOA on the test function through mean analysis, convergence analysis, stability analysis, Wilcoxon signed rank test, and Friedman's test. The proposed ASFAOA is then utilized to solve the wireless sensor coverage problem and its performance is illustrated by two sets of coverage problems with different dimensions. The results and discussion show that ASFAOA outperforms the original AOA and other comparison algorithms. Therefore, ASFAOA is considered as a useful technique for practical optimization problems.

Electric dipole modulation for boosting carrier recombination in green InP QLEDs under strong electron injection.

Enhanced and balanced carrier injection is essential to achieve highly efficient green indium phosphide (InP) quantum dot light-emitting diodes (QLEDs). However, due to the poor injection of holes in green InP QLEDs, the carrier injection is usually balanced by suppressing the strong electron injection, which decreases the radiation recombination rate dramatically. Here, an electric dipole layer is introduced to enhance the hole injection in the green InP QLED with a high mobility electron transport layer (ETL). The ultra-thin MoO3 electric dipole layer is demonstrated to form a positive built-in electric field at the interface of the hole injection layer (HIL) and hole transport layer (HTL) due to its deep conduction band level. Simulation and experimental results support that strong electric fields are produced for efficient hole hopping, and the carrier recombination rate is substantially increased. Consequently, the green InP QLEDs based on enhanced electron and hole injection have achieved a high luminance of 52 730 cd m-2 and 1.7 times external quantum efficiency (EQE) enhancement from 4.25% to 7.39%. This work has provided an effective approach to enhance carrier injection in green InP QLEDs and indicates the feasibility to realize highly efficient green InP QLEDs.

Solvent Modulation of Chiral Perovskite Films Enables High Circularly Polarized Luminescence Performance from Chiral Perovskite/Quantum Dot Composites.

Materials with circularly polarized luminescence (CPL) activity are promising in many chiroptoelectronics fields, such as for biological probes, asymmetric photosynthesis, information storage, spintronic devices, and so on. Promoting the value of the dissymmetry factor (glum) for the CPL-active materials based on chiral perovskite draws increasing attention since a higher glum value indicates better CPL. In this work, we find that, after being treated with a facile solvent modulation strategy, the chirality of 2D chiral perovskite films has been enhanced a lot, which we attribute to an increased lattice distortion degree. By forming chiral perovskite/quantum dot (QD) composites, the CPL-active material is successfully obtained. The calculated maximum |glum| of these composites increased over 4 times after solvent modulation treatment (1.53 × 10-3 for the pristine sample of R-DMF and 6.91 × 10-3 for R-NMP) at room temperature. Moreover, the enhancement of the CPL intensity is ascribed to two aspects: one is the generation and transportation of spin-polarized charge carriers from chiral perovskite films to combine in the QD layer, and the other is the solvent modulation strategy to enlarge the lattice distortion of chiral perovskite films. This facile route provides an effective way to construct CPL-active materials. More importantly, this kind of composite material (chiral perovskite film/QD layer) can be easily applied for fabricating circularly polarized light-emitting diode devices for electroluminescence.

Revealing the Hidden Mechanism of Enhanced Responsivity of Doped p-i-n Perovskite Photodiodes via Coupled Opto-Electronic Model.

Organic-inorganic halide perovskites have demonstrated preeminent optoelectronic performance in recent years due to their unique material properties, and have shown great potential in the field of photodetectors. In this study, a coupled opto-electronic model is constructed to reveal the hidden mechanism of enhancing the performance of perovskite photodetectors that are suitable for both inverted and regular structure doped p-i-n perovskite photodiodes. Upon illumination, the generation rate of photogenerated carriers is calculated followed by carrier density distribution, which serves as a coupled joint to further analyze the recombination rate, electric field strength, and current density of carriers under different doping types and densities. Moreover, experiments were carried out in which the doping types and densities of the active layer were regulated by changing the precursor ratios. With optimal doping conditions, the inverted and regular perovskite photodiodes achieved an external quantum efficiency of 74.83% and 73.36%, and a responsivity of 0.417 and 0.404 A/W, respectively. The constructed coupled opto-electronic model reveals the hidden mechanism and along with the doping strategy, this study provides important guidance for further analysis and improvement of perovskite-based photodiodes.

Thermally Processed Quantum-Dot Polypropylene Composite Color Converter Film for Displays.

Quantum dots (QDs) have attracted much attention as one of the most promising candidates for next-generation display materials. However, stability is still a big challenge for QDs. Herein, we encapsulated QDs in a thermoplastic polypropylene (PP) matrix by thermal processing technology to prepare a stabler color conversion film for the first time. Thermal processing technology expands the packaging materials of QDs from traditional soluble polymers to thermoplastic polymers such as PP with easy processing and a low cost. We showed that the QDs in the PP film exhibited longer-lasting stability than the traditional PMMA film. After 216 h of blue light accelerated aging test, the QDs maintained more than 90% of the initial performance in the PP film but dropped to less than 25% in the PMMA film. Moreover, the reasons for the improved stability have been further discussed. It was found that the PP-H film not only possessed better barriers to moisture and oxygen, but the absence of ester groups also led to a milder environment around the QDs. The results show that ester groups have stronger electronegativity and easily cause the ligands on the surface of QDs to fall off, which lead to performance degradation.

In Situ Growth Mechanism for High-Quality Hybrid Perovskite Single-Crystal Thin Films with High Area to Thickness Ratio: Looking for the Sweet Spot.

The development of in situ growth methods for the fabrication of high-quality perovskite single-crystal thin films (SCTFs) directly on hole-transport layers (HTLs) to boost the performance of optoelectronic devices is critically important. However, the fabrication of large-area high-quality SCTFs with thin thickness still remains a significant challenge due to the elusive growth mechanism of this process. In this work, the influence of three key factors on in situ growth of high-quality large-size MAPbBr3 SCTFs on HTLs is investigated. An optimal "sweet spot" is determined: low interface energy between the precursor solution and substrate, a slow heating rate, and a moderate precursor solution concentration. As a result, the as-obtained perovskite SCTFs with a thickness of 540 nm achieve a record area to thickness ratio of 1.94 × 104  mm, a record X-ray diffraction peak full width at half maximum of 0.017°, and an ultralong carrier lifetime of 1552 ns. These characteristics enable the as-obtained perovskite SCTFs to exhibit a record carrier mobility of 141 cm2 V-1 s-1 and good long-term structural stability over 360 days.

High-Performance Blue Quasi-2D Perovskite Light-Emitting Diodes via Balanced Carrier Confinement and Transfer.

Extensive investigation of the passivating agents has been performed to suppress the perovskite defects. However, very few attentions have been paid to rationally design the passivating agents for the balance of the carrier confinement and transfer in quasi-2D perovskites, which is essential to achieve high-performance perovskite LEDs (PeLEDs). In this work, tributylphosphine oxide (TBPO) with moderate carbon chain length is demonstrated as a decent passivator for the quasi-2D perovskites by strengthening the carrier confinement for massive radiative recombination within the perovskites, and more importantly providing efficient carrier transfer in the quasi-2D perovskites. Benefiting from these interesting optoelectronic properties of TBPO-incorporated perovskites, we achieve high-efficient blue PeLEDs with an external quantum efficiency up to 11.5% and operational stability as long as 41.1 min without any shift of the electroluminescence spectra. Consequently, this work contributes an effective approach to promote the carrier confinement and transfer for high-performance and stable blue PeLEDs.

Analyzing and modulating energy transfer in ternary-emissive system of quantum dot light-emitting diodes towards efficient emission.

The mechanisms for energy transfer including Förster resonance energy transfer (FRET) and radiative energy transfer in ternary-emissive system consists of blended-quantum dots (QDs, red-QDs blended with blue-QDs) emissive layer (EML) and blue-emissive hole-transport material that contained in quantum dot light-emitting diodes (QLEDs) are complicated. As the energy transfer could exhibit either positive or negative impact on QD's photoluminescence (PL) and electroluminescence (EL), it is important to analyze and modulate energy transfer in such ternary-emissive system to obtain high-efficiency QLEDs. In this work, we have demonstrated that proper B-QDs doping has a positive impact on R-QDs' PL and EL, where these improvements were attributed to the B-QDs' spacing effect on R-QDs which weakens homogeneous FRET among R-QDs and near 100% efficient heterogeneous FRET from B-QDs to R-QDs. With optimization based on the analysis of energy transfer, the PL quantum yield of blended-QDs (with R:B blending ratio of 90:10, in quality) film has been enhanced by 35% compared with that of unblended R-QDs film. Moreover, thanks to the spacing effect and high-efficiency FRET from B-QDs to R-QDs, the external quantum efficiency of QLEDs that integrate optimized blended-QDs (R:B=90:10) EML reaches 22.1%, which is 15% higher than that of the control sample (19.2%) with unblended R-QDs EML. This work provides a systematically analytical method to study the energy transfer in ternary-emissive system, and gives a valid reference for the analysis and development of the emerging QLEDs that with blended-QDs EML.

Antioxidation and Energy-Level Alignment for Improving Efficiency and Stability of Hole Transport Layer-Free and Methylammonium-Free Tin-Lead Perovskite Solar Cells.

Tin-lead (Sn-Pb) perovskites have shown great potential in applications of single-junction perovskite solar cells (PSCs) and tandem devices due to outstanding photoelectrical properties and low band gaps. Currently, Sn-Pb PSCs typically have a p-i-n structure, but choices of hole transport layer (HTL) materials are very limited and there are different concerns in each of them. Eliminating the HTL is a direct and promising strategy to address the concerns, but is rarely studied. In this work, we demonstrate HTL-free and MA-free based Sn-Pb PSCs and a synergistic integration strategy of simultaneously introducing a reducing agent and in situ surface passivation. With the integration strategy, Sn-Pb perovskite films with enhanced antioxidation, reduced trap density, prolonged carrier lifetime, and improved energy-level alignment are achieved. Consequently, final HTL-free PSCs exhibit a champion power conversion efficiency (PCE) of 17.4%, which is a new record for HTL-free and MA-free Sn-Pb PSCs. Meanwhile, the integration strategy-based HTL-free device maintains excellent stability with efficiency unchanged for the first 200 h, and finally retaining 81% of the efficiency after 480 h aging in the air. This study shows the potential of achieving desirable HTL-free and MA-free Sn-Pb PSCs and offers more opportunities for tandem solar cells and other photovoltaic devices.

Efficient and Stable Red Perovskite Light-Emitting Diodes with Operational Stability >300 h.

The long-term operational stability of perovskite light-emitting diodes (PeLEDs), especially red PeLEDs with only several hours typically, has always faced great challenges. Stable ß-CsPbI3 nanocrystals (NCs) are demonstrated for highly efficient and stable red-emitting PeLEDs through incorporation of poly(maleic anhydride-alt-1-octadecene) (PMA) in synthesizing the NCs. The PMA can chemically interact with PbI2 in the precursors via the coupling effect between O groups in PMA and Pb2+ to favor crystallization of stable ß-CsPbI3 NCs. Meanwhile, the cross-linked PMA significantly reduces the PbCs anti-site defect on the surface of the ß-CsPbI3 NCs. Benefiting from the improved crystal phase quality, the photoluminescence quantum yield for ß-CsPbI3 NCs films remarkably increases from 34% to 89%. The corresponding red-emitting PeLEDs achieves a high external quantum efficiency of 17.8% and superior operational stability with the lifetime, the time to half the initial electroluminescence intensity (T50 ) reaching 317 h at a constant current density of 30 mA cm-2 .

High-Performance Blue Perovskite Light-Emitting Diodes Enabled by Efficient Energy Transfer between Coupled Quasi-2D Perovskite Layers.

While there has been extensive investigation into modulating quasi-2D perovskite compositions in light-emitting diodes (LEDs) for promoting their electroluminescence, very few reports have studied approaches involving enhancement of the energy transfer between quasi-2D perovskite layers of the film, which plays very important role for achieving high-performance perovskite LEDs (PeLEDs). In this work, a bifunctional ligand of 4-(2-aminoethyl)benzoic acid (ABA) cation is strategically introduced into the perovskite to diminish the weak van der Waals gap between individual perovskite layers for promoting coupled quasi-2D perovskite layers. In particular, the strengthened interaction between coupled quasi-2D perovskite layers favors an efficient energy transfer in the perovskite films. The introduced ABA can also simultaneously passivate the perovskite defects by reducing metallic Pb for less nonradiative recombination loss. Benefiting from the advanced properties of ABA incorporated perovskites, highly efficient blue PeLEDs with external quantum efficiency of 10.11% and a very long operational stability of 81.3 min, among the best performing blue quasi-2D PeLEDs, are achieved. Consequently, this work contributes an effective approach for high-performance and stable blue PeLEDs toward practical applications.

Effective Surface Ligand-Concentration Tuning of Deep-Blue Luminescent FAPbBr3 Nanoplatelets with Enhanced Stability and Charge Transport.

Metal-halide perovskite-based green and red light-emitting diodes (LEDs) have witnessed a rapid development because of their facile synthesis and processability; however, the blue-band emission is constrained by their unstable chemical properties and poorly conducting emitting layers. Here, we show a trioctylphosphine oxide (TOPO)-mediated one-step approach to realize bright deep-blue luminescent FAPbBr3 nanoplatelets (NPLs) with enhanced stability and charge transport. The concentration of NPL surface ligands is shown to be progressively tuned via varying the amount of intermediate TOPO due to the acid-base equilibrium between protic acid and TOPO. By effectively optimizing the concentration of surface ligands, the structural integrity of NPL solids can be preserved in ambient air for a week, mainly because of the highly ordered and dense solid assembly and the reduced defects. The removal of excess organic ligands also enables the improvement of charge mobility by orders of magnitude. Ultimately, ultrapure deep-blue perovskite LEDs (439 nm) with a narrow emission width of 14 nm and a peak EQE of 0.14% are achieved at low driving voltage. Our finding expands the current understanding of surface ligand modulation in the development of pure bromide deep-blue perovskite optoelectronics.

In Situ Growth of All-Inorganic Perovskite Single Crystal Arrays on Electron Transport Layer.

Directly growing perovskite single crystals on charge carrier transport layers will unravel a promising route for the development of emerging optoelectronic devices. Herein, in situ growth of high-quality all-inorganic perovskite (CsPbBr3) single crystal arrays (PeSCAs) on cubic zinc oxide (c-ZnO) is reported, which is used as an inorganic electron transport layer in optoelectronic devices, via a facile spin-coating method. The PeSCAs consist of rectangular thin microplatelets of 6-10 µm in length and 2-3 µm in width. The deposited c-ZnO enables the formation of phase-pure and highly crystallized cubic perovskites via an epitaxial lattice coherence of (100)CsPbBr3∥(100)c-ZnO, which is further confirmed by grazing incidence wide-angle X-ray scattering. The PeSCAs demonstrate a significant structural stability of 26 days with a 9 days excellent photoluminescence stability in ambient environment, which is much superior to the perovskite nanocrystals (PeNCs). The high crystallinity of the PeSCAs allows for a lower density of trap states, longer carrier lifetimes, and narrower energetic disorder for excitons, which leads to a faster diffusion rate than PeNCs. These results unravel the possibility of creating the interface toward c-ZnO heterogeneous layer, which is a major step for the realization of a better integration of perovskites and charge carrier transport layers.

Ultrathin PEDOT:PSS Enables Colorful and Efficient Perovskite Light-Emitting Diodes.

Recently, metal halide perovskite light-emitting diodes (Pero-LEDs) have achieved significant improvement in device performance, especially for external quantum efficiency (EQE). And EQE is mostly determined by internal quantum efficiency of the emitting material, charge injection balancing factor (ηc), and light extraction efficiency (LEE) of the device. Herein, an ultrathin poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (UT-PEDOT:PSS) hole transporter layer is prepared by a water stripping method, and the UT-PEDOT:PSS can enhance ηc and LEE simultaneously in Pero-LEDs, mostly due to the improved carrier mobility, more matched energy level alignment, and reduced photon loss. More importantly, the performance enhancement from UT-PEDOT:PSS is quite universal and applicable in different kinds of Pero-LEDs. As a result, the EQEs of Pero-LEDs based on 3D, quasi-3D, and quasi-2D perovskites obtain enhancements of 42%, 87%, and 111%, and the corresponding maximum EQE reaches 17.6%, 15.0%, and 6.8%, respectively.

Printable CsPbBr3 perovskite quantum dot ink for coffee ring-free fluorescent microarrays using inkjet printing.

Printable perovskite quantum dot (QD) ink is very important for achieving high quality coffee ring-free fluorescent microarrays for different kinds of emerging perovskite optoelectronic applications using inkjet printing. In this work, we prepared a printable CsPbBr3 perovskite QD ink by mixing high-boiling point dodecane with low-boiling point toluene as a solvent. The evaporation rate, viscosity and surface tension of the ink were carefully optimized by tuning the volume ratio of these two solvents for forming appropriate Marangoni flow, so as to balance the capillary flow and eliminate the coffee ring effect further. Successfully, CsPbBr3 perovskite microarrays with uniform surface, low roughness and no coffee rings were achieved by inkjet printing the optimized perovskite QD ink on a PVK (poly-(9-vinylcarbazole)) layer. Furthermore, we patterned the CsPbBr3 perovskite QD ink, and the printed patterns were only visible under ultraviolet (UV) light, which can be applied in invisible anti-counterfeiting labels and encryption in the future.