Triplet-triplet annihilation upconversion (TTA-UC) is an important type of optical process with applications in biophotonics, solar energy harvesting and photochemistry. In most of the TTA-UC systems, the formation of triplet excited states takes place via spin-orbital interactions promoted by heavy atoms. Given the crucial role of heavy atoms (especially noble metals, such as Pd and Pt) in promoting intersystem crossing (ISC) and, therefore, in production of UC luminescence, the feasibility of using more readily available and inexpensive sensitizers without heavy atoms remains a challenge. Here, we investigated sensitization of TTA-UC using BODIPY-pyrene heavy-atom-free donor-acceptor dyads with different numbers of alkyl groups in the BODIPY scaffold. The molecules with four and six alkyl groups are unable to sensitize TTA-UC in the investigated solvents (tetrahydrofuran (THF) and dichloromethane (DCM)) due to negligible ISC. In contrast, the dyad with two methyl groups in the BODIPY scaffold and the dyad with unsubstituted BODIPY demonstrate efficient intersystem crossing (ISC) of 49-58%, resulting in TTA-UC with quantum yields of 4.7% and 6.9%, respectively. The analysis of the elementary steps of the TTA-UC process indicates that heavy-atom-free donor-acceptor dyads are less effective than their noble metal counterparts, but may equal them in the future if the right combination of solvent, donor-acceptor sensitizer structure, and new luminescent molecules as TTA-UC emitters can be found.
Charge carrier mobility is an important figure of merit to evaluate organic semiconductor (OSC) materials. In aggregated OSCs, this quantity is determined by inter-chromophoric electronic and vibrational coupling. These key parameters sensitively depend on structural properties, including the density of defects. We have employed a new type of crystalline assembly strategy to engineer the arrangement of the OSC pentacene in a structure not realized as crystals to date. Our approach is based on metal-organic frameworks (MOFs), in which suitably substituted pentacenes act as ditopic linkers and assemble into highly ordered π-stacks with long-range order. Layer-by-layer fabrication of the MOF yields arrays of electronically coupled pentacene chains, running parallel to the substrate surface. Detailed photophysical studies reveal strong, anisotropic inter-pentacene electronic coupling, leading to efficient charge delocalization. Despite a high degree of structural order and pronounced dispersion of the 1D-bands for the static arrangement, our experimental results demonstrate hopping-like charge transport with an activation energy of 64 meV dominating the band transport over a wide range of temperatures. A thorough combined quantum mechanical and molecular dynamics investigation identifies frustrated localized rotations of the pentacene cores as the reason for the breakdown of band transport and paves the way for a crystal engineering strategy of molecular OSCs that independently varies the arrangement of the molecular cores and their vibrational degrees of freedom.
We present a coordination polymer based on rare-earth metal centers and carboxylated 4,4'-diphenyl-2,2'-bipyridine ligands. We investigate Y3+, Lu3+, Eu3+, and a statistical mixture of Y3+ with Eu3+ as metal centers. When Y3+ or Lu3+ is exclusively present in the coordination polymer, biluminescence from the ligand is observed: violet emission from the singlet state (417 nm, 0.9 ns lifetime) and orange emission from the triplet state (585 nm, 76 ms (Y3+) and 31 ms (Lu3+)). When Eu3+ is present in a statistical mixture with Y3+, red emission from the Eu3+ (611 nm, â¼ 500 µs ) is observed in addition to the ligand emissions. We demonstrate that this multi-mode emission is enabled by the immobility of singlet and triplet states on the ligand. Eu3+ only receives energy from adjacent ligands. Meanwhile, in the broad inhomogeneous distribution of ligand energies, higher energy states favor singlet emission, whereas faster intersystem crossing in the more stabilized ligands enhances their contribution to triplet emission.
The spatial orientation of chromophores defines the photophysical and optoelectronic properties of a material and serves as the main tunable parameter for tailoring functionality. Controlled assembly for achieving a predefined spatial orientation of chromophores is rather challenging. Metal-organic frameworks (MOFs) are an attractive platform for exploring the virtually unlimited chemical space of organic components and their self-assembly for device optimization. Here, we demonstrate the impact of interchromophore interactions on the photophysical properties of a surface-anchored MOF (SURMOF) based on 3,9-perylenedicarboxylicacid linkers. We predict the structural assembly of the perylene molecules in the MOF via robust periodic density functional theory calculations and discuss the impact of unit topology and π-π interaction patterns on spectroscopic and semiconducting properties of the MOF films. We explain the dual nature of excited states in the perylene MOF, where strong temperature-modulated excimer emission, enhanced by the formation of perylene J-aggregates, and low stable monomer emission are observed. We use band-like and hopping transport mechanisms to predict semiconducting properties of perylene SURMOF-2 films as a function of inter-linker interactions, demonstrating both p-type and n-type conduction mechanisms. Hole carrier mobility up to 7.34 cm2Vs-1is predicted for the perylene SURMOF-2. The results show a promising pathway towards controlling excimer photophysics in a MOF while controlling charge carrier mobility on the basis of a predictive model.
Several photophysical properties of chromophores depend crucially on intermolecular interactions. Thermally-activated delayed fluorescence (TADF) is often influenced by close packing of the chromophore assembly. In this context, the metal-organic framework (MOF) approach has several advantages: it can be used to steer aggregation such that the orientation within aggregated structures can be predicted using rational approaches. We demonstrate this design concept for a DPA-TPE (diphenylamine-tetraphenylethylene) chromophore, which is non-emissive in its solvated state due to vibrational quenching. Turning this DPA-TPE into a ditopic linker makes it possible to grow oriented MOF thin films exhibiting pronounced green electroluminescence with low onset voltages. Measurements at different temperatures clearly demonstrate the presence of TADF. Finally, this work reports that the layer-by-layer process used for MOF thin film deposition allows the integration of the TADF-DPA-TPE in a functioning LED device.
Silicon nanocrystals (SiNCs) are regarded as a green and environmentally friendly material when compared with other semiconductor nanocrystals. Ultra-small SiNCs (with the size 4.6-5.2 nm) demonstrate strong UV absorption and photoluminescence in the near infrared (NIR) range with the high photoluminescence quantum yield (PLQY) up to 60%. In contrast to nanoporous silicon, ultra-small SiNCs do not possess an intrinsic ability to generate singlet oxygen (1O2). However, we demonstrate that SiNC-dye conjugates synthesized via microwave assistant hydrosilylation reaction produce 1O2 with moderate quantum yield (ΦΔ) up to 27% in cyclohexane. These interesting results were obtained via measurements of singlet oxygen phosphorescence at 1,270 nm. SiNCs play an important role in the production of singlet oxygen as SiNCs harvest UV and blue radiation and transfer absorbed energy to a triplet state of the attached dyes. It increases the population of the triplet states and leads to the enhancement of the singlet oxygen generation. Simultaneously, the SiNC-dye conjugates demonstrate NIR luminescence with the PLQY up to 22%. Thus, the luminescence behavior and photosensitizing properties of the SiNC-dye conjugates can attract interest as a new multifunctional platform in the field of bio-applications.
Beyond their applications in organic light-emitting diodes (OLEDs), thermally activated delayed fluorescence (TADF) materials can also make good photonic markers. Time-gated measurement of their delayed emission enables "background-free" imaging in, for example, biological systems, because no naturally-occurring compounds exhibit such long-lived emission. Attaching a strongly-absorbing antenna, such as a phenylene ethynylene oligomer, to the TADF core would be of interest to increase their brightness as photonic markers. With this motivation, we study a sequence of TADF-oligomer conjugates with oligomers of varying length and show that, even when the absorption of the oligomer is almost resonant with the charge-transfer absorption of the TADF core, the antenna transfers energy to the TADF core. We study this series of compounds with time resolved emission and transient absorption spectroscopy and find that the delayed fluorescence is essentially turned-off for the longer antennae. Interestingly, we find that the turn-off of the delayed fluorescence is not caused by quenching of the TADF charge-transfer triplet state due to triplet energy transfer of the lower-lying triplet state to the antenna, but must be associated with a decrease in the reverse intersystem crossing rate. These results are of relevance for the further development of TADF "dyes" and also, in the broader context, for understanding the dynamics of TADF molecules in the vicinity of energy donors/acceptors (i.e., in fluorescent OLEDs wherein TADF molecules are used as an assistant dopant).
Herein, we report a method to produce luminescent silicon nanocrystals (SiNc) that strongly absorb ultraviolet-visible light (300-550 nm) and emit in the near-infrared range (700-1000 nm) with a high photoluminescence quantum yield (PLQY). Using microwave-assisted hydrosilylation and employing reactive chromophores - such as ethenyl perylene, ethynyl perylene and ethylene-m-phenyl BODIPY - we are able to achieve a 10- and 3-fold enhancement of the absorption in the blue and green spectral range, respectively. The investigated dyes function both as passivating agents and highly efficient antenna, which absorb visible light and transfer the energy to SiNc with an efficiency of >95%. This enhanced absorption leads to a significant photoluminescence enhancement, up to â¼270% and â¼140% under excitation with blue and green light, respectively. Despite the gain in absolute brightness of the emission, we demonstrate that back energy transfer from the SiNc to the dyes leads to a decrease in the PLQY for dye-modified SiNc, as compared to unmodified SiNc. The synthesis of the SiNc-dye conjugates opens up new possibilities for applications of this abundant and non-toxic material in the field of solar energy harvesting, optical sensing and bioimaging via achieving strong NIR PL excited with visible light.
Achieving efficient devices while maintaining a high fabrication yield is a key challenge in the fabrication of solution-processed, perovskite-based light-emitting diodes (PeLEDs). In this respect, pinholes in the solution-processed perovskite layers are a major obstacle. These are usually mitigated using organic electron-conducting planarization layers. However, these organic interlayers are unstable under applied bias in air and suffer from limited charge carrier mobility. In this work, we present a high brightness p-i-n PeLED based on a novel blade-coated silver microflake (SMF) rear electrode, which allows for a low-cost nanocrystalline ZnO inorganic electron-transporting layer to be used. This novel SMF contact is crucial for achieving high performance as it prevents the electrical shorting suffered when standard thermally evaporated silver rear contacts are used. The fabricated PeLEDs exhibit an excellent maximum luminance of 98,000 cd/m2, a maximum current efficiency of 22.3 cd/A, and a high external quantum efficiency of 4.6% under 5.9 V forward bias. The SMF rear contact can be printed and scaled at low cost to large areas and applied to flexible devices.
Understanding triplet exciton diffusion between organic thermally activated delayed fluorescence (TADF) molecules is a challenge due to the unique cycling between singlet and triplet states in these molecules. Although prompt emission quenching allows the singlet exciton diffusion properties to be determined, analogous analysis of the delayed emission quenching does not yield accurate estimations of the triplet diffusion length (because the diffusion of singlet excitons regenerated after reverse-intersystem crossing needs to be accounted for). Herein, we demonstrate how singlet and triplet diffusion lengths can be accurately determined from accessible experimental data, namely the integral prompt and delayed fluorescence. In the benchmark materials 4CzIPN and 4TCzBN, we show that the singlet diffusion lengths are (9.1 ± 0.2) and (12.8 ± 0.3) nm, whereas the triplet diffusion lengths are negligible, and certainly less than 1.0 and 1.2 nm, respectively. Theory confirms that the lack of overlap between the shielded lowest unoccupied molecular orbitals (LUMOs) hinders triplet motion between TADF chromophores in such molecular architectures. Although this cause for the suppression of triplet motion does not occur in molecular architectures that rely on electron resonance effects (e.g. DiKTa), we find that triplet diffusion is still negligible when such molecules are dispersed in a matrix material at a concentration sufficiently low to suppress aggregation. The novel and accurate method of understanding triplet diffusion in TADF molecules will allow accurate physical modeling of OLED emitter layers (especially those based on TADF donors and fluorescent acceptors).
We report the synthesis of five dicarboxylic acid-substituted dipolar molecular rotors for the use as linker molecules in metal-organic frameworks (MOFs). The rotor molecules exhibit very low rotational barriers and decent to very high permanent, charge free dipole moments, as shown by density functional theory calculations on the isolated molecules. Four rotors are fluorescent in the visible region. The linker designs are based on push-pull-substituted phenylene cores with ethynyl spacers as rotational axes, functionalized with carboxylic acid groups for implementation in MOFs. The substituents at the phenylene core are chosen to be small to leave rotational freedom in solids with confined free volumes. The dipole moments are generated by electron-donating substituents (benzo-1,3-dioxole, benzo-1,4-dioxane, or benzo-2,1,3-thiadiazole annelation) and withdrawing substituents (difluoro, or dicyano substitution) at the opposite positions of the central phenylene core. A combination of 1,4-dioxane annelation and dicyano substitution generates a theoretically predicted, very high dipole moment of 10.1 Debye. Moreover, the molecules are sufficiently small to fit into cavities of 10 Å3. Hence, the dipolar rotors should be ideally suited as linkers in MOFs with potential applications as ferroelectric materials and for optical signal processing.
In molecular solids, the intense photoluminescence (PL) observed for solvated dye molecules is often suppressed by nonradiative decay processes introduced by excitonic coupling to adjacent chromophores. We have developed a strategy to avoid this undesirable PL quenching by optimizing the chromophore packing. We integrated the photoactive compounds into metal-organic frameworks (MOFs) and tuned the molecular alignment by introducing adjustable "steric control units" (SCUs). We determined the optimal alignment of core-substituted naphthalenediimides (cNDIs) to yield highly emissive J-aggregates by a computational analysis. Then, we created a large library of handle-equipped MOF chromophoric linkers and computationally screened for the best SCUs. A thorough photophysical characterization confirmed the formation of J-aggregates with bright green emission, with unprecedented photoluminescent quantum yields for crystalline NDI-based materials. This data demonstrates the viability of MOF-based crystal engineering approaches that can be universally applied to tailor the photophysical properties of organic semiconductor materials.
Sustained stimulated emission under continuous-wave (CW) excitation is a prerequisite for new semiconductor materials being developed for laser gain media. Although hybrid organic-inorganic lead-halide perovskites have attracted much attention as optical gain media, the demonstration of room-temperature CW lasing has still not been realized. Here, we present a critical step towards this goal by demonstrating CW amplified spontaneous emission (ASE) in a phase-stable perovskite at temperatures up to 120 K. The phase-stable perovskite maintains its room-temperature phase while undergoing cryogenic cooling and can potentially support CW lasing also at higher temperatures. We find the threshold level for CW ASE to be 387 W cm-2 at 80 K. These results indicate that easily-fabricated single-phase perovskite thin films can sustain CW stimulated emission, potential at higher temperatures as well, by further optimization of the material quality in order to extend the carrier lifetimes.
An ideal material for photon harvesting must allow control of the exciton diffusion length and directionality. This is necessary in order to guide excitons to a reaction center, where their energy can drive a desired process. To reach this goal both of the following are required; short- and long-range structural order in the material and a detailed understanding of the excitonic transport. Here we present a strategy to realize crystalline chromophore assemblies with bespoke architecture. We demonstrate this approach by assembling anthracene dibenzoic acid chromophore into a highly anisotropic, crystalline structure using a layer-by-layer process. We observe two different types of photoexcited states; one monomer-related, the other excimer-related. By incorporating energy-accepting chromophores in this crystalline assembly at different positions, we demonstrate the highly anisotropic motion of the excimer-related state along the [010] direction of the chromophore assembly. In contrast, this anisotropic effect is inefficient for the monomer-related excited state.
The fact that organic solar cells perform efficiently despite the low dielectric constant of most photoactive blends initiated a long-standing debate regarding the dominant pathways of free charge formation. Here, we address this issue through the accurate measurement of the activation energy for free charge photogeneration over a wide range of photon energy, using the method of time-delayed collection field. For our prototypical low bandgap polymer:fullerene blends, we find that neither the temperature nor the field dependence of free charge generation depend on the excitation energy, ruling out an appreciable contribution to free charge generation though hot carrier pathways. On the other hand, activation energies are on the order of the room temperature thermal energy for all studied blends. We conclude that charge generation in such devices proceeds through thermalized charge transfer states, and that thermal energy is sufficient to separate most of these states into free charges.
An electron donor-acceptor dyad based on BODIPY (acceptor) and anthracene (donor) plays either the role of sensitizer or emitter in triplet-triplet annihilation photon up-conversion (TTA-UC). This Janus-like behavior was achieved via altering the relative ordering of charge-transfer and local excited state energies in the dyad through the polarity of TTA-UC media.
