Blue Perovskite Light-emitting Diodes Research Articles

Restraint of Nonradiative Recombination via Modulation of n-Phase Distribution through Interfacial Lithium Salt Insertion for High-Performance Pure-Blue Perovskite LEDs.

Quasi-two-dimensional perovskite has been widely used in blue perovskite light-emitting diodes. However, the performance of these devices is still hampered by random phase distribution, nonradiative recombination, and imbalanced carrier transport. In this work, an effective strategy is proposed to mitigate these limitations by inserting lithium salts at the interfaces between the hole transport layer (HTL) and the perovskite layer. The perovskite film on the inserted Li2CO3 layer exhibits reasonable n-value redistribution, which leads to the repressive nonradiation recombination and enhanced carrier transport. Moreover, the inserted Li2CO3 layer also improves the electrical conductivity of PEDOT:PSS and hinders indium ion diffusion from the PEDOT:PSS layer to the perovskite film, which inhibits exciton quenching and nonradiative recombination loss at the HTL/perovskite interface. Taking advantage of these merits, we have successfully fabricated efficient pure-blue PeLEDs with an external quantum efficiency of 6.2% at 472 nm and a luminance of 726 cd cm-2. The restraint of nonradiative recombination at the interface offers a promising approach for efficient pure-blue PeLEDs.

The synergy of pre-frozen substrates and post-annealing for high-efficiency co-evaporated blue perovskite LEDs

The co-evaporation technique shows great potential for producing perovskite films. However, there is a lack of research on the growth process and the film characteristics of co-evaporated perovskite. Herein, we found that pre-frozen substrates and post-annealing can synergically improve the performance of co-evaporated blue perovskite light-emitting diodes (PeLEDs). The optimized blue PeLEDs obtained an impressive peak external quantum efficiency (EQE) of 7.2%, which is the best reported for co-evaporated blue PeLEDs till now. The systematic investigation found that the pre-frozen substrates can facilitate the exotherm of vaporized precursor molecules near the interface, leading to more efficient nucleation and constraining grain enlargement. Furthermore, low-temperature annealing (LTA) can efficiently suppress compositional segregation and release residual compressive strain in co-evaporated perovskite films while retaining the advantages of pre-frozen substrates. This work provided deeper insights into perovskite films prepared by co-evaporation and offered a feasible strategy for enhancing the performance of the co-evaporated PeLEDs.

Phosphonic Chloride Assisted Fabrication of Highly Emissive Mixed Halide Perovskite Films in Ambient Air for Blue Light-Emitting Diodes.

Blue perovskite light-emitting diodes (LEDs) have emerged as promising candidates for full-color display and lighting applications. However, the fabrication of blue-emitting perovskite films typically requires an inert environment, leading to increased complexity and cost in the manufacturing process, which is undesirable for applications of perovskite LEDs. Herein, we report a strategy to fabricate bright blue-emitting perovskite films in ambient air by incorporating phosphonic chlorides in a perovskite precursor solution. We used two different phosphonic chlorides, diphenylphosphonic chloride (DPPC) and phenylphosphonic dichloride (PPDC), and comparatively studied their effects on the properties of perovskite films and the blue LEDs. It is found that PPDC possesses a stronger chlorination ability due to higher hydrolysis reactivity; meanwhile, it has a stronger interaction with the perovskite compared to DPPC, resulting in an improved film quality and enhanced blue emission with a photoluminescence quantum yield of 45%, which represents the record value for the air-processed blue perovskite films. Blue perovskite LEDs are fabricated, and the emission wavelengths are effectively tuned by controlling the concentration of phosphonic chlorides. Benefiting from the optimized perovskite films with reduced nonradiative recombination and promoted charge injection and transport, the PPDC-derived blue perovskite LEDs exhibit improved performance with an external quantum efficiency of 3.3% and 1.2% for the 490 and 480 nm emission wavelength, respectively.

Enhanced Efficiency and Stability of Sky Blue Perovskite Light-Emitting Diodes via Introducing Lead Acetate.

All-inorganic metal halide perovskite is promising for highly efficient and thermally stable perovskite light-emitting diodes (PeLEDs). However, there is still great room for improvement in the film quality, including low coverage and high trap density, which play a vital role in achieving high-efficiency PeLEDs. In this work, lead acetate (Pb(Ac)2) was introduced into the perovskite precursor solution as an additive. Experimental results show that perovskite films deposited from a one-step anti-solvent free solution process with increased surface coverage and reduced trap density were obtained, leading to enhanced photoluminescence (PL) intensity. More than that, the valence band maximum (VBM) of perovskite films was reduced, bringing about a better energy level matching the work function of the hole-injection layer (HIL) poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate) (PEDOT: PSS), which is facilitated for the hole injection, leading to a decrease in the turn-on voltage (Vth) of PeLEDs from 3.4 V for the control device to 2.6 V. Finally, the external quantum efficiency (EQE) of the sky blue PeLEDs (at 484 nm) increased from 0.09% to 0.66%. The principles of Pb(Ac)2 were thoroughly investigated by using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). This work provides a simple and effective strategy for improving the morphology of perovskite and therefore the performance of PeLEDs.

Blue Lead‐Free Perovskite Derivatives: Structural Diversity, Luminescence Properties and Light‐Emitting Diode Applications

AbstractHalide perovskite light‐emitting diodes (LEDs) have made remarkable advancements in both efficiency and stability. However, when compared to green and red LEDs, blue perovskite LEDs still lag behind in terms of efficiency and stability. Presently, efficient blue LEDs primarily rely on lead‐based perovskites, which goes against the environmentally friendly practices and restricts potential industrial applications. Consequently, there has been a surge of interest in academic research toward developing blue LEDs using lead‐free perovskites. This paper provides a comprehensive review of the structural diversity of lead‐free perovskite derivatives used for blue emission, encompassing Sn‐, Zr‐, Bi‐, Sb‐, Cu‐, Zn‐based halides as well as double perovskites. Various material synthesis techniques are discussed, such as nanocrystal preparation and film preparation. Additionally, the photoluminescence properties for different energy band structures are outlined, along with the luminescence mechanism involving energy transfer and strategies for enhancing luminous efficiency. The advancement in efficiency and stability of lead‐free perovskite LEDs is also examined in this review. Finally, the current challenges and future opportunities in advancing research on blue lead‐free perovskite derivatives and their potential application in LED technology is emphasized.

Buried interface modification and light outcoupling strategy for efficient blue perovskite light-emitting diodes

Perovskite light-emitting diodes (PeLEDs) exhibit remarkable potential in the field of displays and solid-state lighting. However, blue PeLEDs, a key element for practical applications, still lag behind their green and red counterparts, due to a combination of strong nonradiative recombination losses and unoptimized device structures. In this report, we propose a buried interface modification strategy to address these challenges by focusing on the bottom-hole transport layer (HTL) of the PeLEDs. On the one hand, a multifunctional molecule, aminoacetic acid hydrochloride (AACl), is introduced to modify the HTL/perovskite interface to regulate the perovskite crystallization. Experimental investigations and theoretical calculations demonstrate that AACl can effectively reduce the nonradiative recombination losses in bulk perovskites by suppressing the growth of low-n perovskite phases and also the losses at the bottom interface by passivating interfacial defects. On the other hand, a self-assembly nanomesh structure is ingeniously developed within the HTLs. This nanomesh structure is meticulously crafted through the blending of poly-(9,9-dioctyl-fluorene-co-N-(4-butyl phenyl) diphenylamine) and poly (n-vinyl carbazole), significantly enhancing the light outcoupling efficiency in PeLEDs. As a result, our blue PeLEDs achieve remarkable external quantum efficiencies, 20.4% at 487 nm and 12.5% at 470 nm, which are among the highest reported values. Our results offer valuable insights and effective methods for achieving high-performance blue PeLEDs.

Perfluorooctanoic acid interface modification enabling efficient true-blue perovskite light-emitting diodes and air-processing compatibility

The pure-bromide quasi-2D perovskite has shown advantages in fabrication of blue perovskite light-emitting diodes (PeLEDs) due to its relatively good color stability and capability of moisture resistance. However, the performances of efficiency and luminance of pure-bromide quasi-2D PeLEDs with true-blue (470 nm−480 nm) emission are still inferior. Here, we show a interfacial modification strategy of involving perfluorooctanoic acid (PFOA) to a hole transport layer of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), to improve the performances of the true-blue PeLEDs. The PFOA regulates the molecular conformation of PEDOT:PSS, forming ordered PEDOT domains that improves the carrier transport and a more favorable band alignment with the perovskite emissive layers. The achieved true-blue PeLEDs show peak EQE of 6.86 % and maximum luminance of 854.10 cd/m2 at wavelength of 478 nm, which are the record values for the pure-bromide quasi-2D PeLEDs in true-blue region. Moreover, owing to the hydrophobic fluorine-carbon (C-F) chains of PFOA, we successfully fabricate the blue PeLEDs in air condition without inert gas protection. This work paves the way for commercial applications in next-generation display technologies.

Energy Transfer-Dominated Quasi-2D Blue Perovskite Light-Emitting Diodes.

The bromide-chloride mixed quasi-two-dimensional (2D) perovskite, with a natural quantum well structure and tunable exciton binding energy, has gained significant attention for high-performance blue perovskite light-emitting diodes (PeLEDs). However, the relative importance of having a low trap state density or efficient exciton transfer for high-efficiency electroluminescence (EL) performance remains elusive. Here, two molecules with the benzoic acid group, sodium 4-fluorobenzoate (SFB) and 3,5-dibromobenzoic acid (DBA), are used to modulate the phase distribution and trap state to explore the effect between energy transfer and defect passivation. As a result, when the n = 1 phase is inhibited in both films, the DBA@SFB-modified perovskite films achieve a higher photoluminescence quantum yield (PLQY) than the SFB-modified perovskite films due to effective defect passivation. However, DBA@SFB-modified PeLEDs exhibit lower external quantum efficiency (EQE) compared to SFB-modified PeLEDs due to the poor exciton transfer between the low-dimensional phase. This demonstrates that passivation strategies may enhance photoluminescence through reducing nonradiative recombination, but the effect of phase distribution is pivotal for EL performance by efficient energy transfer in quasi-2D perovskites. Femtosecond time-resolved transient absorption measurements confirm the fastest carrier dynamics in SFB-modified perovskite films, further corroborating the above result. This work provides useful information about phase modulation and defect passivation for high-efficiency blue quasi-2D PeLEDs.

Reduced phonon coupling via controlled defect levels in blue emitting CsPbBr3 nanoplatelets

Metal-halide perovskites (MHPs) are promising materials for light-emitting diodes (LEDs) because of their high color purity, wide gamut, and low-cost processing. However, blue-emitting MHP LEDs exhibit low external quantum efficiencies because they are more susceptible to defect states with a larger energy bandgap compared to their green and red counterparts. Current strategies for achieving blue-emitting MHP LEDs involve compositional engineering; however, the ion migration of mixed halides imposes significant challenges related to abundant trap states. Therefore, in this study, we systematically investigated the effects of short organic and inorganic ligands with characteristic molecular structures and adjacent moieties on the optoelectronic characteristics of low-dimensional CsPbBr3 nanoplatelets (NPLs) used as blue emitters in PeLEDs. Inorganic ligand (i.e., hydrazine monohydrobromide; HZBr) treatment achieved the most significant photoluminescence enhancement (∼10 fold) while preserving crystalline morphology and colloidal stability. Temperature-dependent photophysical properties reveal that HZBr treatment eliminates band tail states arising from lower defect levels in highly confined CsPbBr3 NPLs. Therefore, it suppresses defect trapping and electron–phonon coupling, thereby reducing thermal quenching properties. The HZBr-treated NPLs were integrated into blue perovskite LEDs and demonstrated a narrow emission peak at 471 nm.

In-Situ passivation of mixed-halide perovskite nanocrystals for high-performance blue light-emitting diodes

In halide perovskite nanocrystals (NCs), insulating long chain ligands such as oleic acid (OA) and oleylamine (OAm) often remove the halide ions during the purification process, leading to surface vacancy defects. This hinders their application in light-emitting devices. Herein, we report an in-situ passivation strategy using ethyl trifluoroacetate, which is hydrolyzed to trifluoroacetic acid, as an antisolvent in the purification process to passivate defects by reacting with uncoordinated Pb2+ and OAm on the surface of NCs, thus anchoring Br− to the surface of NCs. This achieves a mild removal of OAm and OA while passivating both anionic and cationic vacancies. Consequently, we achieved high-performance blue perovskite light-emitting diodes (PeLEDs). The PeLEDs based on these NCs exhibit pure blue electroluminescence at 463 nm with an external quantum efficiency of 4.14 % and a luminance of 1035 cd m−2. This study provides insights and a foundation for the development of high-performance PeLEDs.

Phosphonic acid based bifunctional additive for high-performance blue perovskite light-emitting diodes

Quasi-two-dimensional (quasi-2D) Ruddlesden-Popper (RP) phase perovskite materials exhibiting quantum confinement effect are promising candidates for realizing high-performance blue perovskite light-emitting diodes (PeLEDs). However, the performance of blue PeLEDs based on quasi-2D perovskites remains unsatisfactory, as it is limited by non-ideal charge transport, energy transfer, and defect. Here, a series of bifunctional phosphonic acid additives with synergistic effects are reported. These additives passivate defects and reduce non-radiative recombination losses by coordinating PO functional group with unsaturated Pb2+, and they promote energy transfer and radiative recombination by optimizing the proportion of small n phases and large n phases. Owing to the synergistic effects of passivation and energy transfer, optimized blue PeLEDs (∼486 nm) with 3-phosphonopropionic acid (3-PA) additive exhibits a champion EQE of 13.11%, which is exceptionally high for blue PeLEDs.

Suppressing interfacial nonradiative recombination by alkali hydroxides for efficient blue perovskite light-emitting diodes

Blue perovskite light-emitting diodes (PeLEDs) provide unlimited possibility in the field of optoelectronic devices due to their excellent characteristics. However, the widely used hole-transport material, poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), has strong acidity and poor conductivity which deteriorate the efficiency and stability of perovskite devices. In this work, we modified PEDOT:PSS layer using alkalis, LiOH, NaOH, and KOH, to address these issues. Our findings indicated that the indium defect from indium tin oxide substrate was passivated after the introduction of LiOH, which resulted in the suppression of nonradiative recombination. In addition, the conductivity was improved owing to the increased phase separation of PEDOT:PSS. Taking advantage of optimized interface, the small-n phases of quasi-two-dimensional (quasi-2D) perovskite films were redistributed in quantities and dimensions. As results of these improvements, blue PeLEDs possessed the external quantum efficiencies of 5.95 % and an extended half-lifetime with emission-light wavelength of 473 nm. These findings offer an effective strategy to achieve highly efficient blue light-emitting diode.

In Situ Hydrolysis of Phosphate Enabling Sky-Blue Perovskite Light-Emitting Diode with EQE Approaching 16.32.

The performance of blue perovskite light-emitting diodes (PeLEDs) lags behind the green and red counterparts owing to high trap density and undesirable red shift of the electroluminescence spectrum under operation conditions. Organic molecular additives were employed as passivators in previous reports. However, most commonly have limited functions, making it challenging to effectively address both efficiency and stability issues simultaneously. Herein, we reported an innovatively dynamic in situ hydrolysis strategy to modulate quasi-2D sky-blue perovskites by the multifunctional passivator phenyl dichlorophosphate that not only passivated the defects but also underwent in situ hydrolysis reaction to stabilize the emission. Moreover, hydrolysis products were beneficial for low-dimensional phase manipulation. Eventually, we obtained high-performance sky-blue PeLEDs with a maximum external quantum efficiency (EQE) of 16.32% and an exceptional luminance of 5740 cd m-2. More importantly, the emission peak of devices located at 485 nm remained stable under different biases. Our work signified the significant advancement toward realizing future applications of PeLEDs.

Phase Engineering Reinforced Energy Transfer for High-Performance Blue Perovskite Light-Emitting Diodes.

Layered metal-halide perovskites, a category of self-assembled quantum wells, are of paramount importance in emerging photonic sources, such as lasers and light-emitting diodes (LEDs). Despite high trap density in two-dimensional (2D)perovskites, efficient non-radiative energy funneling from wide- to narrow-bandgap components, sustained by the Förster resonance energy transfer (FRET) mechanism, contributes to efficient luminescence by light or electrical injection. Herein, it is demonstrated that bandgap extension of layered perovskites to the blue-emitting regime will cause sluggish and inefficient FRET, stemming from the tiny spectral overlap between different phases. Motivated by the importance of blue LEDs and inefficient energy transfer in materials with phase polydispersity, wide-bandgap quasi-2D perovskites with narrow phase distribution, improved crystallinity, and the pure crystal orientation perpendicular to the charge transport layer are developed. Based on this emitter, high-performance blue perovskite LEDs with improved electroluminescence (EL) external quantum efficiency (EQE) of 7.9% at 478nm, a narrow full width at half-maximum (FWHM) of 22nm and a more stable EL spectra are achieved. These results provide an important insight into spectrally stable and efficient blue emitters and EL devices based on perovskites.

Top-Down Exfoliation Process Constructing 2D/3D Heterojunction toward Ultrapure Blue Perovskite Light-Emitting Diodes.

3D perovskites with low energy disorder and high ambipolar charge mobility represent a promising solution for efficient and bright light-emitting diodes. However, the challenges of regulating the nanocrystal size to trigger the quantum confinement effect and control the surface trap states to reduce charge loss hinder the applications of 3D perovskites in blue perovskite light-emitting diodes (PeLEDs). In this study, we present a top-down exfoliation method to obtain blue 3D perovskite films with clipped nanocrystals and tunable bandgaps by employing methyl cyanide (MeCN) for post-treatment. In this method, the MeCN solvent exfoliates the surface components of the 3D perovskite grains through a partial dissolution process. Moreover, the dissolved precursor can be further utilized to construct an ingenious 2D/3D heterostructure by incorporating an organic spacer into the MeCN solvent, contributing to efficient defect passivation and improved energy transfer. Consequently, efficient PeLEDs featuring ultrapure blue emission at 478 nm achieve a record external quantum efficiency of 12.3% among their 3D counterparts. This work emphasizes the significance of inducing the quantum confinement effect in 3D perovskites for efficient blue PeLEDs and provides a viable scheme for the in situ regulation of perovskite crystals.

High-Performance Blue Perovskite Light-Emitting Diodes Enabled by Synergistic Effect of Additives.

While quasi-two-dimensional (quasi-2D) perovskites have good properties of cascade energy transfer, high exciton binding energy, and high quantum efficiency, which will benefit high-efficiency blue PeLEDs, inefficient domain distribution management and unbalanced carrier transport impede device performance improvement. Herein, (2-(9H-carbazol-9-yl)ethyl)phosphonic acid (2PACz) and methyl 2-aminopyridine-4-carboxylate (MAC) were simultaneously introduced to a blue quasi-2D perovskite film. Relying on the synergistic effect of 2PACz and MAC, it not only modulates the phase distribution inhibiting the n = 2 phase but also greatly improves the electrical property of the quasi-2D perovskite film. As a result, the as-modified blue quasi-2D PeLED demonstrated an external quantum efficiency (EQE) of 17.08% and a luminance of 10142 cd m-2. This study exemplifies the synergistic effect among dual additives and offers a new effective additive strategy modulating phase distribution and building balanced carrier transport, which paves the way for the fabrication of highly efficient blue PeLEDs.

Regulating the continuous and concentrated distribution of Quasi-2D perovskite phases to achieve Sky-Blue Light-Emitting diodes with efficiency approaching 17%

Blue perovskite light-emitting diodes (PeLEDs) are increasingly crucial for manufacturing high-definition full-color displays due to their outstanding electroluminescent properties. Quasi-two-dimensional (quasi-2D) perovskite stands out as the most promising material for blue light-emitting layer, given its robust quantum/dielectric confinement. In this study, we present the preparation of PeLEDs with a tunable blue emission wavelength using pure bromide perovskite components by adjusting the content of halogenated organic ammonium bromide [2-bromoethylamine hydrobromide (BEABr)]. The bifunctional ligand BEABr not only achieves an excellent phase distribution of quasi-2D perovskite but also reduces the weak van der Waals gap between individual perovskite layers, facilitating effective energy transfer in perovskite films. Additionally, the bifunctional groups passivate perovskite defects and inhibit phase separation, leading to efficient and stable sky-blue luminescence. The BEABr-doped sky-blue PeLED demonstrated superior device performance, achieving a maximum external quantum efficiency of 16.98 % at 493 nm. This work serves as inspiration for further exploration of efficient and stable commercial blue PeLED devices.

Regulating Perovskite Crystallization through Interfacial Engineering Using a Zwitterionic Additive Potassium Sulfamate for Efficient Pure-Blue Light-Emitting Diodes.

Quasi-two-dimensional (quasi-2D) perovskites are emerging as efficient emitters in blue perovskite light-emitting diodes (PeLEDs), while the imbalanced crystallization of the halide-mixed system limits further improvements in device performance. The rapid crystallization caused by Cl doping produces massive defects at the interface, leading to aggravated non-radiative recombination. Meanwhile, unmanageable perovskite crystallization is prone to facilitate the formation of nonuniform low-dimensional phases, which results in energy loss during the exciton transfer process. Here, we propose a multifunctional interface engineering for nucleation and phase regulation by incorporating the zwitterionic additive potassium sulfamate into the hole transport layer. By using potassium ions (K+ ) as heterogeneous nucleation seeds, finely controlled growth of interfacial K+ -guided grains is achieved. The sulfamate ions can simultaneously regulate the phase distribution and passivate defects through coordination interactions with undercoordinated lead atoms. Consequently, such synergistic effect constructs quasi-2D blue perovskite films with smooth energy landscape and reduced trap states, leading to pure-blue PeLEDs with a maximum external quantum efficiency (EQE) of 17.32 %, spectrally stable emission at 478 nm and the prolonged operational lifetime. This work provides a unique guide to comprehensively regulate the halide-mixed blue perovskite crystallization by manipulating the characteristics of grain-growth substrate.

Shape-controlled synthesis of CsPbBr3 nanorods with bright pure blue emission and high stability

CsPbBr3 NRs synthesized at 80 °C show bright blue emission at 462 nm and exhibit a high PLQY of 62.65%. The 1 : 1 mixed anti-solvents of EAC and IPA can change the state of NR surface ligands and improve the stability of NRs.

Synergistic interaction of multi-functional additives at the buried interface for efficient blue perovskite light-emitting diodes

The synergistic effect of the doping strategy of basic amino acid salts at the interface enables the simultaneous modification of PEDOT:PSS and the bottom interface of the perovskite film to achieve efficient sky-blue PeLEDs.