Controllable p- and n-type behaviours in emissive perovskite semiconductors.

Reliable control of the conductivity and its polarity in semiconductors is at the heart of modern electronics1-7, and has led to key inventions including diodes, transistors, solar cells, photodetectors, light-emitting diodes and semiconductor lasers. For archetypal semiconductors such as Si and GaN, positive (p)- and negative (n)-type conductivities are achieved through the doping of electron-accepting and electron-donating elements into the crystal lattices, respectively1-6. For halide perovskites, which are an emerging class of semiconductors, mechanisms for reliably controlling charge conduction behaviours while maintaining high optoelectronic qualities are yet to be discovered. Here we report that the p- and n-type characteristics in a wide-bandgap perovskite semiconductor can be adjusted by incorporating a phosphonic acid molecular dopant with strong electron-withdrawing abilities. The resultant carrier concentrations were more than 1013 cm-3 for the p- and n-type samples, with Hall coefficients ranging from -0.5 m3 C-1 (n-type) to 0.6 m3 C-1 (p-type). A shift of the Fermi level across the bandgap was observed. Importantly, the transition from n- to p-type conductivity was achieved while retaining high photoluminescence quantum yields of 70-85%. The controllable doping in the emissive perovskite semiconductor enabled the demonstration of ultrahigh brightness (more than 1.1 × 106 cd m-2) and exceptional external quantum efficiency (28.4%) in perovskite light-emitting diodes with a simple architecture.

High-efficiency and thermally stable FACsPbI3 perovskite photovoltaics.

α-FA1-xCsxPbI3 is a promising absorber material for efficient and stable perovskite solar cells (PSCs)1,2. However, the most efficient α-FA1-xCsxPbI3 PSCs require the inclusion of methylammonium chloride (MACl) additive3,4, which generates volatile organic residues (i.e., MA) that limit device stability at elevated temperatures5. To date, the highest certified power-conversion efficiency (PCE) of α-FA1-xCsxPbI3 PSCs without MACl was only ~24% (ref.6,7), and has yet to exhibit any stability advantages. Here, we identify interfacial contact loss caused by the Cs+ accumulation for the conventional α-FA1-xCsxPbI3 PSCs, which deteriorates the device performance and stability. Through in-situ GIWAXS analysis and DFT calculations, we demonstrate an intermediate phase-assisted crystallization pathway enabled by acetate surface coordination to fabricate high-quality α-FA1-xCsxPbI3 film, without using MA-additive. We herein report a certified stabilized power output (SPO) efficiency of 25.94% and a reverse-scanning PCE of 26.64% for α-FA1-xCsxPbI3 PSCs, exhibiting negligible contact losses and enhanced operational stability. The devices retain >95% of their initial PCEs after over 2,000 hours operating at maximum power point under 1 sun, 85 °C, and 60% relative humidity (ISOS-L-3).

A Graded Redox Interfacial Modifier for High-Performance Perovskite Solar Cells.

Perovskite solar cells have emerged as a potential competitor to the silicon photovoltaic technology. The most representative perovskite cells employ SnO2 and spiro-OMeTAD as the charge-transport materials. Despite their high efficiencies, perovskite cells with such a configuration show unsatisfactory lifespan, normally attributed to the instability of perovskites and spiro-OMeTAD. Limited attention was paid to the influence of SnO2, an inorganic material, on device stability. Here we show that improving SnO2 with a redox interfacial modifier, cobalt hexammine sulfamate, simultaneously enhances the power-conversion efficiency (PCE) and stability of the perovskite solar cells. Redox reactions between the bivalent cobalt complexes and oxygen lead to the formation of a graded distribution of trivalent and bivalent cobalt complexes across the surface and bulk regions of the SnO2. The trivalent cobalt complex at the top surface of SnO2 raises the concentration of (SO3NH2)- which passivates uncoordinated Pb2+ and relieves tensile stress, facilitating the formation of perovskite with improved crystallinity. Our approach enables perovskite cells with PCEs of up to 24.91%. The devices retained 93.8% of their initial PCEs after 1000 hours of continuous operation under maximum power point tracking. These findings showcase the potential of cobalt complexes as redox interfacial modifiers for high-performance perovskite photovoltaics.

Efficient Near-Infrared Electroluminescence from Lanthanide-Doped Perovskite Quantum Cutters.

Perovskite nanocrystals (PeNCs) deliver size- and composition-tunable luminescence of high efficiency and color purity in the visible range. However, attaining efficient electroluminescence (EL) in the near-infrared (NIR) region from PeNCs is challenging, limiting their potential applications. Here we demonstrate a highly efficient NIR light-emitting diode (LED) by doping ytterbium ions into a PeNCs host (Yb3+ : PeNCs), extending the EL wavelengths toward 1000 nm, which is achieved through a direct sensitization of Yb3+ ions by the PeNC host. Efficient quantum-cutting processes enable high photoluminescence quantum yields (PLQYs) of up to 126 % from the Yb3+ : PeNCs. Through halide-composition engineering and surface passivation to improve both PLQY and charge-transport balance, we demonstrate an efficient NIR LED with a peak external quantum efficiency of 7.7 % at a central wavelength of 990 nm, representing the most efficient perovskite-based LEDs with emission wavelengths beyond 850 nm.

Stabilized Low-Dimensional Species for Deep-Blue Perovskite Light-Emitting Diodes with EQE Approaching 3.4.

Despite recent encouraging developments, achieving efficient blue perovskite light-emitting diodes (PeLEDs) have been widely considered a critical challenge. The efficiency breakthrough only occurred in the sky-blue region, and the device performance of pure-blue and deep-blue PeLEDs lags far behind those of their sky-blue counterparts. To avoid the negative effects associated with dimensionality reduction and excess chloride typically needed to achieve deep-blue emission, here we demonstrate guanidine (GA+)-induced deep-blue (∼457 nm) perovskite emitters enabling spectrally stable PeLEDs with a record external quantum efficiency (EQE) over 3.41% through a combination of quasi-2D perovskites and halide engineering. Owing to the presence of GA+, even a small inclusion of chloride ions is sufficient for generating deep-blue electroluminescence (EL), in clear contrast to the previously reported deep-blue PeLEDs with significant chloride inclusion that negatively affects spectral stability. Based on the carrier dynamics analysis and theoretical calculation, GA+ is found to stabilize the low-dimensional species during annealing, retarding the cascade energy transfer and facilitating the deep-blue EL. Our findings open a potential third route to achieve deep-blue PeLEDs beyond the conventional methods of dimensionality reduction and excessive chloride incorporation.

Copper and Gold Cyclic (Alkyl)(amino)carbene Complexes with Sub-Microsecond Photoemissions: Structure and Substituent Effects on Redox and Luminescent Properties.

Copper and gold halide and pseudo-halide complexes stabilised by methyl-, ethyl- and adamantyl-substituted cyclic (alkyl)(amino)carbene (CAAC) ligands are mostly linear monomers in the solid state, without aurophilic Au⋅⋅⋅Au interactions. (Et2 L)CuCl shows the highest photoluminescence quantum yield (PLQY) in the series, 70 %. The photoemissions of Me2 L and Et2 L copper halide complexes show S1 →S0 fluorescence on the ns time scale, in agreement with theory, as well as a long-lived emission. Monomeric (Me2 L)CuNCS is a white emitter, whereas dimeric [(Et2 L)Cu(µ-NCS)]2 shows intense yellow emission with a photoluminescence (PL) quantum yield of 49 %. The reaction of (Ad L)MCl (M=Cu or Au) with phenols ArOH (Ar=Ph, 2,6-F2 C6 H3 , 2,6-Me2 C6 H3 , 3,5-tBu2 C6 H3 , 2-tBu-5-MeC6 H3 , 2-pyridyl), thiophenol, or aromatic amines H2 NAr'' (Ar'=Ph, 3,5-(CF3 )2 C6 H3 , C6 F5 , 2-py) afforded the corresponding phenolato, thiophenolato and amido complexes. Although the emission wavelengths are only marginally affected by the ring substitution pattern, the PL intensities respond sensitively to the presence of substituents in the ortho or meta positions. In gold aryloxides, PL is controlled by steric factors, with strong luminescence in compounds with Au-O-C-C torsion angles <50°. Calculations confirm the dependence of oscillator strength on the torsion angle, as well as the inter-ligand charge transfer nature of the emission. The HOMO/LUMO energy levels were estimated based on first reduction and oxidation potentials.

Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix.

Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

Reduced-Toxicity and Highly Luminescent Germanium-Lead Perovskites Enabled by Strain Reduction for Light-Emitting Diodes.

Germanium-lead (Ge-Pb) perovskites provide a promising solution for perovskite optoelectronic devices with reduced toxicity. However, Ge-Pb perovskite light-emitting diodes (PeLEDs) with >30 mol % Ge showed low emission efficiencies [Yang, D.; Zhang, G.; Lai, R.; Cheng, Y.; Lian, Y.; Rao, M.; Huo, D.; Lan, D.; Zhao, B.; Di, D. Germanium-Lead Perovskite Light-Emitting Diodes. Nat. Commun. 2021, 12 (1), 4295]. Here, we apply strain engineering to effectively improve the light emission efficiency and stability of Ge-Pb perovskite films and PeLEDs with 30 and 60 mol % Ge, through A-site modulation. The maximum external quantum efficiencies of the Ge-Pb PeLEDs with 30 and 60 mol % Ge are 8.5% and 3.0% at 3.32 mA cm-2 (∼922 cd m-2) and 0.53 mA cm-2 (∼60 cd m-2), respectively. Time-resolved transient absorption spectroscopy analysis of Ge-Pb perovskite films on different hole-transport layers shows that incorporating 30 mol % Ge into the perovskite with mixed A-site cations can effectively suppress trap-assisted recombination. Further analysis of their current density-voltage (J-V) curves reveals the efficiency loss mechanisms of Ge-Pb PeLEDs with high Ge fractions, indicating the possibility of further improvements.

Highly efficient blue light-emitting diodes based on mixed-halide perovskites with reduced chlorine defects.

Perovskite light-emitting diodes (PeLEDs) provide excellent opportunities for low-cost, color-saturated, and large-area displays. However, the performance of blue PeLEDs lags far behind that of their green and red counterparts. Here, we show that the external quantum efficiencies (EQEs) of blue PeLEDs scale linearly with the photoluminescence quantum yields (PL QYs) of CsPb(BrxCl1-x)3 nanocrystals emitting at 460 to 480 nm. The recombination efficiency of carriers is highly sensitive to the chlorine content and the related deep-level defects in nanocrystals, causing notable EQE drops even with minor increases in chlorine defects. Minor adjustments of chlorine content through rubidium compensation on the A-site effectively suppress the formation of nonradiative defects, improving PL QYs while retaining desirable bandgaps for blue-emitting nanocrystals. Our PeLEDs with record-high efficiencies span the blue spectrum, achieving peak EQEs of 12.0% (460 nm), 16.7% (465 nm), 21.3% (470 nm), 24.3% (475 nm), and 26.4% (480 nm). This work exemplifies chlorine-defect control as a key design principle for high-efficiency blue PeLEDs.

Improved Molecular Packing of Self-Assembled Monolayer Charge Injectors for Perovskite Light-Emitting Diodes.

Self-assembled monolayers (SAMs) have shown great potential as hole injection materials for perovskite light-emitting diodes due to their low parasitic absorption and ability to adjust energy level alignment. However, the head and anchoring groups on SAM molecules with significant differences in polarity can lead to the formation of micelles in the commonly used alcoholic processing solvent, inhibiting the formation of an intact SAM. In this work, the introduction of methyl groups on carbazole in the phosphonic-acid-based SAM materials is found to facilitate energy level alignment and promote the formation of compact SAMs. The alternative molecular structure also enhances the solvent resistance of poly(9-vinylcarbazole), suppressing interfacial defect densities and nonradiative recombination processes in the emissive perovskites. PeLEDs based on the methyl-containing SAMs exhibit ∼30% enhancement in efficiency. These findings contribute to a better understanding of the design of SAM materials for PeLED applications.

Bright and Stable Red Perovskite LEDs under High Current Densities.

Perovskite LEDs (PeLEDs) have emerged as a next-generation light-emitting technology. Recent breakthroughs were made in achieving highly stable near-infrared and green PeLEDs. However, the operational lifetimes (T50) of visible PeLEDs under high current densities (>10 mA cm-2) remain unsatisfactory (normally <100 h), limiting the possibilities in solid-state lighting and AR/VR applications. This problem becomes more pronounced for mixed-halide (e.g., red and blue) perovskite emitters in which critical challenges such as halide segregation and spectral instability are present. Here, we demonstrate bright and stable red PeLEDs based on mixed-halide perovskites, showing measured T50 lifetimes of up to ∼357 h at currents of ≥25 mA cm-2, a record for the operational stability of visible PeLEDs under high current densities. The devices produce intense and stable emission with a maximum luminance of 28,870 cd m-2 (radiance: 1584 W sr-1 m-2), which is record-high for red PeLEDs. Key to this demonstration is the introduction of sulfonamide, a dipolar molecular stabilizer that effectively interacts with the ionic species in the perovskite emitters. It suppresses halide segregation and migration into the charge-transport layers, resulting in enhanced stability and brightness of the mixed-halide PeLEDs. These results represent a substantial step toward bright and stable PeLEDs for emerging applications.

Stabilizing FASnI3-based perovskite light-emitting diodes with crystallization control.

The toxicity of lead presents a critical challenge for the application of perovskite optoelectronics. Lead-free perovskite solar cells were achieved with formamidinium tin iodide (FASnI3) perovskites, exhibiting decent power-conversion efficiencies (PCEs) of up to 14%, with >98% of the initial PCE retained after 3000 h of storage. However, when employed in light-emitting applications, FASnI3-based perovskite LEDs (PeLEDs) show limited stability, with T50 lifetimes of up to 0.25 h at 10 mA cm-2. Here, we improve the stability of FASnI3-based PeLEDs through the inclusion of a two-dimensional precursor phenethylamine iodide (PEAI), allowing controlled crystallization of the mixed-dimensional perovskite emitters. The density of defects is found to be reduced, accompanied by the suppression of oxidation from Sn2+ to Sn4+. Using an optimized perovskite composition, we achieve an EQE of 1.5% (a ∼10-fold improvement over the control devices), a maximum radiance of 145 W sr-1 m-2, and a record-long T50 lifetime of 10.3 h at 100 mA cm-2 for FASnI3-based PeLEDs. Our results illuminate an alternative path toward lead-free PeLED applications.

Light management for perovskite light-emitting diodes.

Perovskite light-emitting diodes (LEDs) have reached external quantum efficiencies of over 20% for various colours, showing great potential for display and lighting applications. Despite the internal quantum efficiencies of the best-performing devices already approaching unity, around 80% of the internally generated photons are trapped in the devices and lose energy through a variety of lossy channels. Significant opportunities for improving efficiency and maximizing photon extraction lie in the effective management of light. In this Review we analyse light management strategies based on the intrinsic optical properties of the perovskite materials and the extrinsic properties related to device structures. These approaches should allow the external quantum efficiencies of perovskite LEDs to substantially exceed the conventional limits of planar organic LED devices. By revisiting lessons learned from organic LEDs and perovskite solar cells, we highlight possible directions of future research towards perovskite LEDs with ultrahigh efficiencies.

Electronic State Engineering in Perovskite-Cerium-Composite Nanocrystals toward Enhanced Triplet Annihilation Upconversion.

Wavelength conversion based on hybrid inorganic-organic sensitized triplet-triplet annihilation upconversion (TTA-UC) is promising for applications such as photovoltaics, light-emitting-diodes, photocatalysis, additive manufacturing, and bioimaging. The efficiency of TTA-UC depends on the population of triplet excitons involved in triplet energy transfer (TET), the driving force in TET, and the coupling strength between the donor and acceptor. Consequently, achieving highly efficient TTA-UC necessitates the precise control of the electronic states of inorganic donors. However, conventional covalently bonded nanocrystals (NCs) face significant challenges in this regard. Herein, a novel strategy to exert control over electronic states is proposed, thereby enhancing TET and TTA-UC by incorporating ionic-bonded CsPbBr3 and lanthanide Ce3+ ions into composite NCs. These composite-NCs exhibit high photoluminescence quantum yield, extended single-exciton lifetime, quantum confinement, and uplifted energy levels. This engineering strategy of electronic states engendered a comprehensive impact, augmenting the population of triplet excitons participating in the TET process, enhancing coupling strength and the driving force, ultimately leading to an unconventional, dopant concentration-dependent nonlinear enhancement of UC efficiency. This work not only advances fundamental understanding of hybrid TTA-UC but also opens a door for the creation of other ionic-bonded composite NCs with tunable functionalities, promising innovations for next-generation optoelectronic applications.

Advances in the Application of Perovskite Materials.

Nowadays, the soar of photovoltaic performance of perovskite solar cells has set off a fever in the study of metal halide perovskite materials. The excellent optoelectronic properties and defect tolerance feature allow metal halide perovskite to be employed in a wide variety of applications. This article provides a holistic review over the current progress and future prospects of metal halide perovskite materials in representative promising applications, including traditional optoelectronic devices (solar cells, light-emitting diodes, photodetectors, lasers), and cutting-edge technologies in terms of neuromorphic devices (artificial synapses and memristors) and pressure-induced emission. This review highlights the fundamentals, the current progress and the remaining challenges for each application, aiming to provide a comprehensive overview of the development status and a navigation of future research for metal halide perovskite materials and devices.

Transient Suppression of Carrier Mobility Due to Hot Optical Phonons in Lead Bromide Perovskites.

In lead halide perovskites, owing to the strong Fröhlich coupling, carrier dynamics that governs the optoelectronic performance is greatly affected by the lattice vibrations. In this emerging class of materials, injected hot carriers quickly relax by emitting optical phonons, and if this process is sufficiently fast, hot optical phonons can be generated, which may in turn hamper the carrier transport. However, the transient interaction between hot phonons and carriers has not yet been investigated. Herein, we identified the transient absorption feature of hot phonons in lead bromide perovskites and then extracted the hot-phonon dynamics. The hot-phonon decay mechanism was uncovered by temperature-dependent measurements. The hot-phonon decay in lead bromide perovskites was an order of magnitude faster than that in GaAs, attributed to the large anharmonicity arising from the lattice softness and structural fluctuation. The carrier mobility was also transiently suppressed by hot phonons, and the mobility recovery was accompanied by the decay of hot phonons.

Tuning Precursor-Amine Interactions for Light-Emitting Lead Bromide Perovskites.

Organic additives with amino moieties are effective in improving the properties of archetypical formamidinium (FA)-based hybrid perovskites for photovoltaic and light-emitting applications. However, a detailed understanding of how amino additives affect the perovskite materials is lacking, impeding developments in this area. Here, by investigating the interactions of lead bromide perovskite precursors with phenethylamine (PEA) and its derivatives with small variations in chemical structure, we reveal that only the secondary amine (N-methyl-2-phenylethylamine (N-PEA)) results in strengthened hydrogen bonds with FABr in precursor solutions, allowing the formation of high-quality perovskite films. The photoluminescence quantum efficiencies (PLQEs) of the resultant perovskite samples on widely used charge-transport substrates are retained to 82% of their original values, indicating reduced sensitivity to interfacial nonradiative traps critical to device applications. Using a standard device structure, green perovskite light-emitting diodes with peak external quantum efficiencies of 12.7% at ∼500 cd m-2 and operational lifetimes (T50) exceeding 10 h (at 100 cd m-2) are obtained.

Ultralow-voltage operation of light-emitting diodes.

For a light-emitting diode (LED) to generate light, the minimum voltage required is widely considered to be the emitter's bandgap divided by the elementary charge. Here we show for many classes of LEDs, including those based on perovskite, organic, quantum-dot and III-V semiconductors, light emission can be observed at record-low voltages of 36-60% of their bandgaps, exhibiting a large apparent energy gain of 0.6-1.4 eV per photon. For 17 types of LEDs with different modes of charge injection and recombination (dark saturation currents of ~10-39-10-15 mA cm-2), their emission intensity-voltage curves under low voltages show similar behaviours. These observations and their consistency with the diode simulations suggest the ultralow-voltage electroluminescence arises from a universal origin-the radiative recombination of non-thermal-equilibrium band-edge carriers whose populations are determined by the Fermi-Dirac function perturbed by a small external bias. These results indicate the potential of low-voltage LEDs for communications, computational and energy applications.

Photon-upconverters for blue organic light-emitting diodes: a low-cost, sky-blue example.

In the research ecosystem's quest towards having deployable organic light-emitting diodes with higher-energy emission (e.g., blue light), we advocate focusing on fluorescent emitters, due to their relative stability and colour purity, and developing design strategies to significantly improve their efficiencies. We propose that all triplet-triplet annihilation upconversion (TTA-UC) emitters would make good candidates for triplet fusion-enhanced OLEDs ("FuLEDs"), due to the energetically uphill nature of the photophysical process, and their common requirements. We demonstrate this with the low-cost sky-blue 1,3-diphenylisobenzofuran (DPBF). Having satisfied the criteria for TTA-UC, we show DPBF as a photon upconverter (I th 92 mW cm-2), and henceforth demonstrate it as a bright emitter for FuLEDs. Notably, the devices achieved 6.5% external quantum efficiency (above the ∼5% threshold without triplet contribution), and triplet-exciton-fusion-generated fluorescence contributes up to 44% of the electroluminescence, as shown by transient measurements. Here, triplet fusion translates to a quantum yield (Φ TTA-UC) of 19%, at an electrical excitation of ∼0.01 mW cm-2. The enhancement is meaningful for commercial blue OLED displays. We also found DPBF to have decent hole mobilities of ∼0.08 cm2 V-1 s-1. This additional finding can lead to DPBF being used in other capacities in various printable electronics.

Ultrahigh Stability of Perovskite Nanocrystals by Using Semiconducting Molecular Species for Displays.

The instability of perovskite nanocrystals (NCs) to moisture, heat, and blue light severely hinders their commercial applications in quantum dot displays. Here, organic semiconducting molecules are introduced onto CsPbBr3 NCs, and the as-obtained CsPbBr3 NCs have a high photoluminescent quantum yield (PLQY) of 82% and extremely high stability in harsh commercial accelerated operational stability tests (such as high temperature (85 °C) and high humidity (85%)). The products can survive and maintain more than 80% of the initial PL intensity value under high temperature, high humidity, and long-term blue light irradiation for hundreds to thousands of hours. They are among the most stable perovskite NCs and even superior to those encapsulated by inert shells and commercial green-emissive CdSe@ZnS quantum dots (QDs). The mechanism of the exceptional stability has been proposed, mainly including the strong interaction and moderate photocarrier transfer between the quasi type II heterostructure formed by the molecule and CsPbBr3. By using these stable CsPbBr3 NCs, a QD-enhanced liquid crystal display prototype has been successfully fabricated with a wide color gamut. This work provides understandings on the functionality of ligands in perovskite fields and a promising prospect in perovskite-based display technologies.