Crosslinking-induced patterning of MOFs by direct photo- and electron-beam lithography.

Metal-organic frameworks (MOFs) with diverse chemistry, structures, and properties have emerged as appealing materials for miniaturized solid-state devices. The incorporation of MOF films in these devices, such as the integrated microelectronics and nanophotonics, requires robust patterning methods. However, existing MOF patterning methods suffer from some combinations of limited material adaptability, compromised patterning resolution and scalability, and degraded properties. Here we report a universal, crosslinking-induced patterning approach for various MOFs, termed as CLIP-MOF. Via resist-free, direct photo- and electron-beam (e-beam) lithography, the ligand crosslinking chemistry leads to drastically reduced solubility of colloidal MOFs, permitting selective removal of unexposed MOF films with developer solvents. This enables scalable, micro-/nanoscale (≈70 nm resolution), and multimaterial patterning of MOFs on large-area, rigid or flexible substrates. Patterned MOF films preserve their crystallinity, porosity, and other properties tailored for targeted applications, such as diffractive gas sensors and electrochromic pixels. The combined features of CLIP-MOF create more possibilities in the system-level integration of MOFs in various electronic, photonic, and biomedical devices.

Nondestructive Direct Optical Patterning of Perovskite Nanocrystals with Carbene-Based Ligand Cross-Linkers.

Microscale patterning of colloidal perovskite nanocrystals (NCs) is essential for their integration in advanced device platforms, such as high-definition displays. However, perovskite NCs usually show degraded optical and/or electrical properties after patterning with existing approaches, posing a critical challenge for their optoelectronic applications. Here we achieve nondestructive, direct optical patterning of perovskite NCs with rationally designed carbene-based cross-linkers and demonstrate their applications in high-performance light-emitting diodes. We reveal that both the photochemical properties and the electronic structures of cross-linkers need to be carefully tailored to the material properties of perovskite NCs. This method produces high-resolution (∼4000 ppi) NC patterns with preserved photoluminescent quantum efficiencies and charge transport properties. Prototype light-emitting diodes with patterned/cross-linked NC layers show a maximum luminance of over 60000 cd m-2 and a peak external quantum efficiency of 16%, among the highest for patterned perovskite electroluminescent devices. Such a material-adapted patterning method enabled by designs from a photochemistry perspective could foster the applications of perovskite NCs in system-level electronic and optoelectronic devices.

Direct Photo-Patterning of Efficient and Stable Quantum Dot Light-Emitting Diodes via Light-Triggered, Carbocation-Enabled Ligand Stripping.

Next generation displays based on quantum dot light-emitting diodes (QLEDs) require robust patterning methods for quantum dot layers. However, existing patterning methods mostly yield QLEDs with performance far inferior to the state-of-the-art individual devices. Here, we report a light-triggered, carbocation-enabled ligand stripping (CELS) approach to pattern QLEDs with high efficiency and stability. During CELS, photogenerated carbocations from triphenylmethyl chlorides remove native ligands of quantum dots, thereby producing patterns at microscale precision. Chloride anions passivate surface defects and endow patterned quantum dots with preserved photoluminescent quantum yields. It works for both cadmium-based and heavy-metal-free quantum dots. CELS-patterned QLEDs show remarkable external quantum efficiencies (19.1%, 17.5%, 12.0% for red, green, blue, respectively) and a long operation lifetime (T95 at 1000 nits up to 8700 h). Both are among the highest for patterned QLEDs and approach the records for nonpatterned devices, which makes CELS promising for building high-performance QLED displays and related integrated devices.

Direct Patterning of Colloidal Nanocrystals via Thermally Activated Ligand Chemistry.

Precise patterning with microscale lateral resolution and widely tunable heights is critical for integrating colloidal nanocrystals into advanced optoelectronic and photonic platforms. However, patterning nanocrystal layers with thickness above 100 nm remains challenging for both conventional and emerging direct photopatterning methods, due to limited light penetration depths, complex mechanical and chemical incompatibilities, and others. Here, we introduce a direct patterning method based on a thermal mechanism, namely, the thermally activated ligand chemistry (or TALC) of nanocrystals. The ligand cross-linking or decomposition reactions readily occur under local thermal stimuli triggered by near-infrared lasers, affording high-resolution and nondestructive patterning of various nanocrystals under mild conditions. Patterned quantum dots fully preserve their structural and photoluminescent quantum yields. The thermal nature allows for TALC to pattern over 10 µm thick nanocrystal layers in a single step, far beyond those achievable in other direct patterning techniques, and also supports the concept of 2.5D patterning. The thermal chemistry-mediated TALC creates more possibilities in integrating nanocrystal layers in uniform arrays or complex hierarchical formats for advanced capabilities in light emission, conversion, and modulation.

Beyond a Linker: The Role of Photochemistry of Crosslinkers in the Direct Optical Patterning of Colloidal Nanocrystals.

Surface chemistry mediated direct optical patterning represents an emerging strategy for incorporating colloidal nanocrystals (NCs) in integrated optoelectronic platforms including displays and image sensors. However, the role of photochemistry of crosslinkers and other photoactive species in patterning remains elusive. Here we show the design of nitrene- and carbene-based photocrosslinkers can strongly affect the patterning capabilities and photophysical properties of NCs, especially quantum dots (QDs). Their role beyond physical linkers stems from structure-dictated electronic configuration, energy alignment and associated reaction kinetics and thermodynamics. Patterned QD layers with designed carbene-based crosslinkers fully preserve their photoluminescent and electroluminescent properties. Patterned light emitting diodes (QLEDs) show a maximum external quantum efficiency of ≈12 % and lifetime over 4800 h, among the highest for reported patterned QLEDs. These results would guide the rational design of photoactive species in NC patterning and create new possibilities in the monolithic integration of NCs in high-performance device platforms.

Direct optical patterning of perovskite nanocrystals with ligand cross-linkers.

Precise microscale patterning is a prerequisite to incorporate the emerging colloidal metal halide perovskite nanocrystals into advanced, integrated optoelectronic platforms for widespread technological applications. Current patterning methods suffer from some combination of limitations in patterning quality, versatility, and compatibility with the workflows of device fabrication. This work introduces the direct optical patterning of perovskite nanocrystals with ligand cross-linkers or DOPPLCER. The underlying, nonspecific cross-linking chemistry involved in DOPPLCER supports high-resolution, multicolored patterning of a broad scope of perovskite nanocrystals with their native ligands. Patterned nanocrystal films show photoluminescence (after postpatterning surface treatment), electroluminescence, and photoconductivity on par with those of conventional nonpatterned films. Prototype, pixelated light-emitting diodes show peak external quantum efficiency of 6.8% and luminance over 20,000 cd m-2. Both are among the highest for patterned perovskite nanocrystal devices. These results create new possibilities in the system-level integration of perovskite nanomaterials and advance their applications in various optoelectronic and photonic platforms.

Unraveling the influence of non-fullerene acceptor molecular packing on photovoltaic performance of organic solar cells.

In non-fullerene organic solar cells, the long-range structure ordering induced by end-group π-π stacking of fused-ring non-fullerene acceptors is considered as the critical factor in realizing efficient charge transport and high power conversion efficiency. Here, we demonstrate that side-chain engineering of non-fullerene acceptors could drive the fused-ring backbone assembly from a π-π stacking mode to an intermixed packing mode, and to a non-stacking mode to refine its solid-state properties. Different from the above-mentioned understanding, we find that close atom contacts in a non-stacking mode can form efficient charge transport pathway through close side atom interactions. The intermixed solid-state packing motif in active layers could enable organic solar cells with superior efficiency and reduced non-radiative recombination loss compared with devices based on molecules with the classic end-group π-π stacking mode. Our observations open a new avenue in material design that endows better photovoltaic performance.

An Optimized Fibril Network Morphology Enables High-Efficiency and Ambient-Stable Polymer Solar Cells.

Morphological stability is crucially important for the long-term stability of polymer solar cells (PSCs). Many high-efficiency PSCs suffer from metastable morphology, resulting in severe device degradation. Here, a series of copolymers is developed by manipulating the content of chlorinated benzodithiophene-4,8-dione (T1-Cl) via a random copolymerization approach. It is found that all the copolymers can self-assemble into a fibril nanostructure in films. By altering the T1-Cl content, the polymer crystallinity and fibril width can be effectively controlled. When blended with several nonfullerene acceptors, such as TTPTT-4F, O-INIC3, EH-INIC3, and Y6, the optimized fibril interpenetrating morphology can not only favor charge transport, but also inhibit the unfavorable molecular diffusion and aggregation in active layers, leading to excellent morphological stability. The work demonstrates the importance of optimization of fibril network morphology in realizing high-efficiency and ambient-stable PSCs, and also provides new insights into the effect of chemical structure on the fibril network morphology and photovoltaic performance of PSCs.

Effect of the Energy Offset on the Charge Dynamics in Nonfullerene Organic Solar Cells.

The energy offset, considered as the driving force for charge transfer between organic molecules, has significant effects on both charge separation and charge recombination in organic solar cells. Herein, we designed material systems with gradually shifting energy offsets, including both positive and negative values. Time-resolved spectroscopy was used to monitor the charge dynamics within the bulk heterojunction. It is striking to find that there is still charge transfer and charge generation when the energy offset reached -0.10 eV (ultraviolet photoelectron spectroscopy data). This work not only indicates the feasibility of the free carrier generation and the following charge separation under the condition of a negative offset but also elucidates the relationship between the charge transfer and the energy offset in the case of polymer chlorination.

Optimized active layer morphology toward efficient and polymer batch insensitive organic solar cells.

Morphology control in laboratory and industry setting remains as a major challenge for organic solar cells (OSCs) due to the difference in film-drying kinetics between spin coating and the printing process. A two-step sequential deposition method is developed to control the active layer morphology. A conjugated polymer that self-assembles into a well-defined fibril structure is used as the first layer, and then a non-fullerene acceptor is introduced into the fibril mesh as the second layer to form an optimal morphology. A benefit of the combined fibril network morphology and non-fullerene acceptor properties was that a high efficiency of 16.5% (certified as 16.1%) was achieved. The preformed fibril network layer and the sequentially deposited non-fullerene acceptor form a robust morphology that is insensitive to the polymer batches, solving a notorious issue in OSCs. Such progress demonstrates that the utilization of polymer fibril networks in a sequential deposition process is a promising approach towards the fabrication of high-efficiency OSCs.

Ternary Organic Solar Cells with Efficiency >16.5% Based on Two Compatible Nonfullerene Acceptors.

A ternary structure has been demonstrated as being an effective strategy to realize high power conversion efficiency (PCE) in organic solar cells (OSCs); however, general materials selection rules still remain incompletely understood. In this work, two nonfullerene small-molecule acceptors 3TP3T-4F and 3TP3T-IC are synthesized and incorporated as a third component in PM6:Y6 binary blends. The photovoltaic behaviors in the resultant ternary OSCs differ significantly, despite the comparable energy levels. It is found that incorporation of 15% 3TP3T-4F into the PM6:Y6 blend results in facilitating exciton dissociation, increasing charge transport, and reducing trap-assisted recombination. All these features are responsible for the enlarged PCE of 16.7% (certified as 16.2%) in the PM6:Y6:3TP3T-4F ternary OSCs, higher than that (15.6%) in the 3TP3T-IC containing ternary devices. The performance differences are mainly ascribed to the compatibility between the third component and the host materials. The 3TP3T-4F guest acceptor exhibits an excellent compatibility with Y6, tending to form well-mixed phases in the ternary blend without disrupting the favored bicontinuous transport networks, whereas 3TP3T-IC displays a morphological incompatibility with Y6. This work highlights the importance of considering the compatibility for materials selection toward high-efficiency ternary organic OSCs.

Benzothiadiazole Versus Thiophene: Influence of the Auxiliary Acceptor on the Photovoltaic Properties of Donor-Acceptor-Based Copolymers.

Two donor-acceptor (D-A) type conjugated copolymers, P1 and P2, are designed and synthesized. A classical benzothiadiazole acceptor is used to replace a thiophene unit in the polymer chain of P1 to obtain P2 terpolymer. Compared with P1, P2 exhibits broader absorption spectra, higher absorption coefficient, deeper lowest unoccupied molecular orbital level, and a relatively lower band gap. As a result, the P2-based solar cell exhibits a high power conversion efficiency (PCE) of 6.60%, with a short-circuit current (J sc ) of 12.43 mA cm-2 , and a fill factor (FF) of 73.1%, which are higher than those of the P1-based device with a PCE of 4.70%, a J sc of 9.43 mA cm-2 , and an FF of 61.6%.