Efficient all-small-molecule organic solar cells processed with non-halogen solvent.

All-small-molecule organic solar cells with good batch-to-batch reproducibility combined with non-halogen solvent processing show great potential for commercialization. However, non-halogen solvent processing of all-small-molecule organic solar cells are rarely reported and its power conversion efficiencies are very difficult to improve. Herein, we designed and synthesized a small molecule donor BM-ClEH that can take advantage of strong aggregation property induced by intramolecular chlorine-sulfur non-covalent interaction to improve molecular pre-aggregation in tetrahydrofuran and corresponding micromorphology after film formation. Tetrahydrofuran-fabricated all-small-molecule organic solar cells based on BM-ClEH:BO-4Cl achieved high power conversion efficiencies of 15.0% in binary device and 16.1% in ternary device under thermal annealing treatment. In contrast, weakly aggregated BM-HEH without chlorine-sulfur non-covalent bond is almost inefficient under same processing conditions due to poor pre-aggregation induced disordered π-π stacking, indistinct phase separation and exciton dissociation. This work promotes the development of non-halogen solvent processing of all-small-molecule organic solar cells and provides further guidance.

Cross-Linkable Fullerene Enables Elastic and Conductive Grain Boundaries for Efficient and Wearable Tin-Based Perovskite Solar Cells.

Tin-based perovskite solar cells (TPSCs) have received increasing attention due to their low toxicity, high theoretical efficiency, and potential applications as wearable devices. However, the inherent fast and uncontrollable crystallization process of tin-based perovskites results in high defect density in the film. Meanwhile, when fabricated into flexible devices, the prepared perovskite film exhibits inevitable brittleness and high Young's modulus, seriously weakening the mechanical stability. In this work, we design and synthesize a cross-linkable fullerene, thioctic acid functionalized C60 fulleropyrrolidinium iodide (FTAI), which has multiple interactions with perovskite components and can finely regulate the crystallization quality of perovskite film. The obtained perovskite film shows an increased grain size and a more matched energy level with the electron transport material, effectively improving the carrier extraction efficiency. The FTAI-based rigid device achieves a champion efficiency of 14.91 % with enhanced stability. More importantly, the FTAI located at the perovskite grain boundaries could spontaneously cross-link during the perovskite annealing process, which effectively improves the conductivity and elasticity of grain boundaries, thereby giving the film excellent bending resistance. Finally, the FTAI-based wearable device yields a record efficiency of 12.35 % and displays robust bending durability, retaining about 90 % of the initial efficiency after 10,000 bending times.

Suppressing Halide Segregation via Pyridine-Derivative Isomers Enables Efficient 1.68 eV Bandgap Perovskite Solar Cells.

Light-induced phase segregation is one of the main issues restricting the efficiency and stability of wide-bandgap perovskite solar cells (WBG PSCs). Small organic molecules with abundant functional groups can passivate various defects, and therefore suppress the ionic migration channels for phase segregation. Herein, a series of pyridine-derivative isomers containing amino and carboxyl are applied to modify the perovskite surface. The amino, carboxyl, and N-terminal of pyridine in all of these molecules can interact with undercoordinated Pb2+ through coordination bonds and suppress halide ions migration via hydrogen bonding. Among them, the 5-amino-3-pyridine carboxyl acid (APA-3) treated devices win the champion performance, enabling an efficiency of 22.35% (certified 22.17%) using the 1.68 eV perovskite, which represents one of the highest values for WBG-PSCs. This is believed to be due to the more symmetric spatial distribution of the three functional groups of APA-3, which provides a better passivation effect independent of the molecular arrangement orientation. Therefore, the APA-3 passivated perovskite shows the slightest halide segregation, the lowest defect density, and the least nonradiative recombination. Moreover, the APA-3 passivated device retains 90% of the initial efficiency after 985 h of operation at the maximum power point, representing the robust durability of WBG-PSCs under working conditions.

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 478 nm, a narrow full width at half-maximum (FWHM) of 22 nm 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.

Efficient Tin-Based Perovskite Solar Cells Enabled by Precisely Synthesized Single-Isomer Fullerene Bisadducts with Regulated Molecular Packing.

Designing and synthesizing fullerene bisadducts with a higher-lying conduction band minimum is promising to further improve the device performance of tin-based perovskite solar cells (TPSCs). However, the commonly obtained fullerene bisadduct products are isomeric mixtures and require complicated separation. Moreover, the isomeric mixtures are prone to resulting in energy alignment disorders, interfacial charge loss, and limited device performance improvement. Herein, we synthesized single-isomer C60- and C70-based diethylmalonate functionalized bisadducts (C60BB and C70BB) by utilizing the steric-hindrance-assisted strategy and determined all molecular structures involved by single crystal diffraction. Meanwhile, we found that the different solvents used for processing the fullerene bisadducts can effectively regulate the molecular packing in their films. The dense and amorphous fullerene bisadduct films prepared by using anisole exhibited the highest electron mobility. Finally, C60BB- and C70BB-based TPSCs showed impressive efficiencies up to 14.51 and 14.28%, respectively. These devices also exhibited excellent long-term stability. This work highlights the importance of developing strategies to synthesize single-isomer fullerene bisadducts and regulate their molecular packing to improve TPSCs' performance.

Efficient Perovskite Light-Emitting Diodes with Chemically Bonded Contact and Regulated Charge Behavior.

Efficient charge injection and radiative recombination are essential to achieving high-performance perovskite light-emitting diodes (Pero-LEDs). However, the perovskite emission layer (EML) and the electron transport layer (ETL) form a poor physically interfacial contact and non-negligible charge injection barrier, limiting the device performance. Herein, we utilize a phosphine oxide, 2,4,6-tris[3-(diphenylphosphinyl)phenyl]-1,3,5-triazine (PO-T2T), to treat the perovskite/ETL interface and form a chemically bonded contact. Specifically, PO-T2T firmly bonds on the perovskite's surface and grain boundaries through a dative bond, effectively passivating the uncoordinated lead defects. Additionally, PO-T2T has high electron mobility and establishes an electron transport highway to bridge the ETL and EML. As a result, a maximum external quantum efficiency (EQEmax) of 22.06% (average EQEmax of 20.02 ± 1.00%) and maximum luminance (Lmax) of 103286 cd m-2 have been achieved for the champion device. Our results indicate that EML/ETL interface modifications are crucial for the fabrication of highly efficient Pero-LEDs.

Ion-Diffusion Management Enables All-Interface Defect Passivation of Perovskite Solar Cells.

Perovskite solar cells (PSCs) have demonstrated over 25% power conversion efficiency (PCE) via efficient surface passivation. Unfortunately, state-of-the-art perovskite post-treatment strategies can solely heal the top interface defects. Herein, an ion-diffusion management strategy is proposed to concurrently modulate the top interfaces, buried interfaces, and bulk interfaces (i.e., grain boundaries) of perovskite film, enabling all-interface defect passivation. Specifically, this method is enabled by applying double interactive salts of octylammonium iodide (OAI) and guanidinium chloride (GACl) onto the 3D perovskite surface. It is revealed that the hydrogen-bonding interaction between OA+ and GA+ decelerates the OA+ diffusion and therefore forms a dimensionally broadened 2D capping layer. Additionally, the diffusion of GA+ and Cl- determines the composition of the bulk and buried interface of PSCs. As a result, n-inter-i-inter-p, i.e., five-layer structured PSCs can be obtained with a champion PCE of 25.43% (certified 24.4%). This approach also enables the substantially improved operational stability of perovskite solar cells.

Dissolved-Cl2 triggered redox reaction enables high-performance perovskite solar cells.

Constructing 2D/3D perovskite heterojunctions is effective for the surface passivation of perovskite solar cells (PSCs). However, previous reports that studying perovskite post-treatment only physically deposits 2D perovskite on the 3D perovskite, and the bulk 3D perovskite remains defective. Herein, we propose Cl2-dissolved chloroform as a multifunctional solvent for concurrently constructing 2D/3D perovskite heterojunction and inducing the secondary growth of the bulk grains. The mechanism of how Cl2 affects the performance of PSCs is clarified. Specifically, the dissolved Cl2 reacts with the 3D perovskite, leading to Cl/I ionic exchange and Ostwald ripening of the bulk grains. The generated Cl- further diffuses to passivate the bulk crystal and buried interface of PSCs. Hexylammonium bromide dissolved in the solvent reacts with the residual PbI2 to form 2D/3D heterojunctions on the surface. As a result, we achieved high-performance PSCs with a champion efficiency of 24.21% and substantially improved thermal, ambient, and operational stability.

Phase Regulation and Defect Passivation Enabled by Phosphoryl Chloride Molecules for Efficient Quasi-2D Perovskite Light-Emitting Diodes.

HIGHLIGHTS: The modification of perovskite precursor by a series of phosphoryl chloride molecules can indeed improve the performance of perovskite LEDs (Pero-LEDs). The bis(2-oxo-3-oxazolidinyl) phosphinic chloride can not only regulate the phase distribution by controlling the crystallization rate but also passivate the defects of the quasi-2D perovskite. Highly efficient and reproducible Pero-LEDs are achieved with an maximum external quantum efficiency (EQEmax) of 20.82% and an average EQE (EQEave) of around 20% on 50 devices. Quasi-2D perovskites have attracted tremendous interest for application as light-emission layers in light-emitting diodes (LEDs). However, the heterogeneous n phase and non-uniform distribution still severely limit the further development of quasi-2D perovskite LEDs (Pero-LEDs). Meanwhile, the increased defect density caused by the reduced dimension and grain size induces non-radiative recombination and further deteriorates the device performance. Here, we found that a series of molecules containing phosphoryl chloride functional groups have noticeable enhancement effects on the device performance of quasi-2D Pero-LEDs. Then, we studied the modification mechanism by focusing on the bis(2-oxo-3-oxazolidinyl) phosphinic chloride (BOPCl). It is concluded that the BOPCl can not only regulate the phase distribution by decreasing the crystallization rate but also remain in the grain boundaries and passivate the defects. As a result, the corresponding quasi-2D Pero-LEDs obtained a maximum external quantum efficiency (EQEmax) of 20.82% and an average EQE (EQEave) of around 20% on the optimal 50 devices, proving excellent reproducibility. Our work provides a new selection of molecular types for regulating the crystallization and passivating the defects of quasi-2D perovskite films.

Efficient Semi-Transparent Wide-Bandgap Perovskite Solar Cells Enabled by Pure-Chloride 2D-Perovskite Passivation.

Wide-bandgap (WBG) perovskite solar cells suffer from severe non-radiative recombination and exhibit relatively large open-circuit voltage (VOC) deficits, limiting their photovoltaic performance. Here, we address these issues by in-situ forming a well-defined 2D perovskite (PMA)2PbCl4 (phenmethylammonium is referred to as PMA) passivation layer on top of the WBG active layer. The 2D layer with highly pure dimensionality and halide components is realized by intentionally tailoring the side-chain substituent at the aryl ring of the post-treatment reagent. First-principle calculation and single-crystal X-ray diffraction results reveal that weak intermolecular interactions between bulky PMA cations and relatively low cation-halide hydrogen bonding strength are crucial in forming the well-defined 2D phase. The (PMA)2PbCl4 forms improved type-I energy level alignment with the WBG perovskite, reducing the electron recombination at the perovskite/hole-transport-layer interface. Applying this strategy in fabricating semi-transparent WBG perovskite solar cells (indium tin oxide as the back electrode), the VOC deficits can be reduced to 0.49 V, comparable with the reported state-of-the-art WBG perovskite solar cells using metal electrodes. Consequently, we obtain hysteresis-free 18.60%-efficient WBG perovskite solar cells with a high VOC of 1.23 V.

Efficient Perovskite Light-Emitting Diodes by Buried Interface Modification with Triphenylphosphine Oxide.

Metal halide perovskite films are prepared mainly by solution-based methods. However, the preparation process is prone to produce massive defects at the interface between the perovskite emitting layer and the charge transport layers, limiting the perovskite light-emitting diode device performance. Aiming at this problem, researchers have proposed many effective strategies to passivate these interface defects. However, most previous research studies only focus on modifying the perovskite top interface, and very few reports deal with the buried interface. Here, we deposited triphenylphosphine oxide (TPPO) molecules between the perovskite and the hole transport layer (HTL) and realized the buried interface modification. Adding TPPO avoids the contact recombination of the perovskite and HTL and improves the film quality by increasing the substrate wettability. Moreover, the lone pair electrons of P═O can interact with the uncoordinated lead (Pb2+) of the perovskite and passivate halogen vacancy defects, and the insulation property of TPPO helps to balance the injection of holes and electrons. As a result, a maximum external quantum efficiency (EQEmax) of 21.01% was obtained with an average of 18.4 ± 0.9% over 30 devices, and the device reproducibility was greatly enhanced.

Well-Defined Fullerene Bisadducts Enable High-Performance Tin-Based Perovskite Solar Cells.

Tin-based perovskite solar cells (TPSCs) are attracting intense research interest due to their excellent optoelectric properties and eco-friendly features. To further improve the device performance, developing new fullerene derivatives as electron transporter layers (ETLs) is highly demanded. Four well-defined regioisomers (trans-2, trans-3, trans-4, and e) of diethylmalonate-C60 bisadduct (DCBA) are isolated and well characterized. The well-defined molecular structure enables us to investigate the real structure-dependent effects on photovoltaic performance. It is found that the chemical structures of the regioisomers not only affect their energy levels, but also lead to significant differences in their molecular packings and interfacial contacts. As a result, the devices with trans-2, trans-3, trans-4, and e as ETLs yield efficiencies of 11.69%, 14.58%, 12.59%, and 10.55%, respectively, which are higher than that of the as-prepared DCBA-based (10.28%) device. Notably, the trans-3-based device also demonstrates a certified efficiency of 14.30%, representing one of the best-performing TPSCs.

Moisture-triggered fast crystallization enables efficient and stable perovskite solar cells.

Understanding the function of moisture on perovskite is challenging since the random environmental moisture strongly disturbs the perovskite structure. Here, we develop various N2-protected characterization techniques to comprehensively study the effect of moisture on the efficient cesium, methylammonium, and formamidinium triple-cation perovskite (Cs0.05FA0.75MA0.20)Pb(I0.96Br0.04)3. In contrast to the secondary measurements, the established air-exposure-free techniques allow us directly monitor the influence of moisture during perovskite crystallization. We find a controllable moisture treatment for the intermediate perovskite can promote the mass transportation of organic salts, and help them enter the buried bottom of the films. This process accelerates the quasi-solid-solid reaction between organic salts and PbI2, enables a spatially homogeneous intermediate phase, and translates to high-quality perovskites with much-suppressed defects. Consequently, we obtain a champion device efficiency of approaching 24% with negligible hysteresis. The devices exhibit an average T80-lifetime of 852 h (maximum 1210 h) working at the maximum power point.

Conductive Phosphine Oxide Passivator Enables Efficient Perovskite Light-Emitting Diodes.

Recently, surface passivation has been proved to be an essential approach for obtaining efficient and stable perovskite light-emitting diodes (Pero-LEDs). Phosphine oxides performed well as passivators in many reports. However, the most commonly used phosphine oxides are insulators, which may inhibit carrier transport between the perovskite emitter and charge-transporter layers, limiting the corresponding device performance. Here, 2,7-bis(diphenylphosphoryl)-9,9'-spirobifluorene (SPPO13), a conductive molecule with two phosphine oxide functional groups, is introduced to modify the perovskite emitting layer. The bifunctional SPPO13 can passivate the nonradiative defects of perovskite and promote electron injection at the interface of perovskite emitter and electron-transporter layers. As a result, the corresponding Pero-LEDs obtain a maximum external quantum efficiency (EQE) of 22.3%. In addition, the Pero-LEDs achieve extremely high brightness with a maximum of around 190 000 cd/m2.

Fullerene Derivative with Flexible Alkyl Chain for Efficient Tin-Based Perovskite Solar Cells.

Fullerene derivatives are considered excellent materials for the extraction and transportation of electrons in the production of efficient tin-based perovskite solar cells (TPSCs). However, it is not clear how the molecular structure of fullerene derivatives affects the efficiency and stability of TPSCs. In this study, the effects of fullerene derivatives, (6,6)-phenyl-C61-butyric acid hexyl ester (PCBH) and (6,6)-phenyl-C61-butyric acid methyl ester (PCBM), with different functional groups, on photovoltaic performance were investigated. The flexible alkyl chain of PCBH effectively improved the film morphology and stability, the electron extraction and transport capabilities, and the interface contact of fullerene and perovskite. As a result, the PCBH-based TPSC yielded a higher efficiency, of 9.21%, than the PCBM-based devices (7.54%). More importantly, the PCBH-based films exhibited higher stability and effectively suppressed the oxidation of Sn2+ by inhibiting oxygen permeation. Therefore, the PCBH-based devices exhibited significantly enhanced stability. This result indicates that optimizing the functional group of fullerene derivatives is crucial for improving the efficiency and stability of TPSCs.

Distribution control enables efficient reduced-dimensional perovskite LEDs.

Light-emitting diodes (LEDs) based on perovskite quantum dots have shown external quantum efficiencies (EQEs) of over 23% and narrowband emission, but suffer from limited operating stability1. Reduced-dimensional perovskites (RDPs) consisting of quantum wells (QWs) separated by organic intercalating cations show high exciton binding energies and have the potential to increase the stability and the photoluminescence quantum yield2,3. However, until now, RDP-based LEDs have exhibited lower EQEs and inferior colour purities4-6. We posit that the presence of variably confined QWs may contribute to non-radiative recombination losses and broadened emission. Here we report bright RDPs with a more monodispersed QW thickness distribution, achieved through the use of a bifunctional molecular additive that simultaneously controls the RDP polydispersity while passivating the perovskite QW surfaces. We synthesize a fluorinated triphenylphosphine oxide additive that hydrogen bonds with the organic cations, controlling their diffusion during RDP film deposition and suppressing the formation of low-thickness QWs. The phosphine oxide moiety passivates the perovskite grain boundaries via coordination bonding with unsaturated sites, which suppresses defect formation. This results in compact, smooth and uniform RDP thin films with narrowband emission and high photoluminescence quantum yield. This enables LEDs with an EQE of 25.6% with an average of 22.1 ±1.2% over 40 devices, and an operating half-life of two hours at an initial luminance of 7,200 candela per metre squared, indicating tenfold-enhanced operating stability relative to the best-known perovskite LEDs with an EQE exceeding 20%1,4-6.

Dendritic CsSnI3 for Efficient and Flexible Near-Infrared Perovskite Light-Emitting Diodes.

All-inorganic and lead-free CsSnI3 is emerging as one of the most promising candidates for near-infrared perovskite light-emitting diodes (NIR Pero-LEDs), which find practical applications including facial recognition, biomedical apparatus, night vision camera, and Light Fidelity. However, in the CsSnI3 -based Pero-LEDs, the holes injection is significantly higher than that of electrons, resulting in unbalanced charge injection, undesired exciton dissipation, and poor device performance. Herein, it is proposed to manage charge injection and recombination behavior by tuning the interface area of perovskite and charge-transporter. A dendritic CsSnI3 structure is prepared on the hole-transporter, only making a bottom contact with the hole-transporter and exposing all other available crystal surfaces to the electron-transporter. In other words, the interface area of perovskite/electron-transporter is significantly higher than that of perovskite/hole-transporter. Moreover, the embedding interface of perovskite/electron-transporter can spatially confine holes and electrons, increasing the radiation recombination. By taking advantage of the dendritic structure, efficient lead-free NIR Pero-LEDs are achieved with a record external quantum efficiency (EQE) of 5.4%. More importantly, the dendritic structure shows great superiorities in flexible devices, for there is almost no morphology change after 2000-cycles of bends, and the fabricated Pero-LEDs can keep 93.4% of initial EQEs after 50-cycles of bends.

Efficient and stable inverted perovskite solar cells enabled by inhibition of self-aggregation of fullerene electron-transporting compounds.

Fullerene-based electron-transporting layers (ETLs) significantly influence the defect passivation and device performance of inverted perovskite solar cells (PSCs). However, the π-cage structures of fullerenes lead to a strong tendency to self-aggregate, which affects the long-term stability of the corresponding PSCs. Experimental results revealed that [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)-based ETLs exhibit a certain degree of self-aggregation that affects the stability of the device, particularly under continuous irradiation stress. To modulate the aggregation behavior, we replaced a methyl hydrogen of PCBM with a phenyl group to yield [6,6]-phenyl-C61-butyric acid benzyl ester (PCBB). As verified through X-ray crystallography, this minor structural modification results in more non-covalent intermolecular interactions, which effectively enhanced the electron-transporting ability of the PCBB-based ETL and led to an efficiency approaching 20%. Notably, the enhanced intermolecular forces of PCBB suppressed its self-aggregation, and the corresponding device showed significantly improved stability, retaining approximately 90% of its initial efficiency after 600 h under one-sun irradiation with maximum power point tracking. These findings provide a viable approach for the design of new fullerene derivatives to tune their intermolecular interactions to suppress self-aggregation within the ETL for high-performance PSCs.

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.

Composition engineering to obtain efficient hybrid perovskite light-emitting diodes.

Metal halide perovskites have received considerable attention in the field of electroluminescence, and the external quantum efficiency of perovskite light-emitting diodes has exceeded 20%. CH3NH3PbBr3 has been intensely investigated as an emitting layer in perovskite light-emitting diodes. However, perovskite films comprising CH3NH3PbBr3 often exhibit low surface coverage and poor crystallinity, leading to high current leakage, severe nonradiative recombination, and limited device performance. Herein, we demonstrate a rationale for composition engineering to obtain high-quality perovskite films. We first reduce pinholes by adding excess CH3NH3Br to the actual CH3NH3PbBr3 films, and we then add CsBr to improve the crystalline quality and to passivate nonradiative defects. As a result, the (CH3NH3)1-xCsxPbBr3 based perovskite light-emitting diodes exhibit significantly improved external quantum and power efficiencies of 6.97% and 25.18 lm/W, respectively, representing an improvement in performance dozens of times greater than that of pristine CH3NH3PbBr3-based perovskite light-emitting diodes. Our study demonstrates that composition engineering is an effective strategy for enhancing the device performance of perovskite light-emitting diodes.