Progress in small-molecule luminescent materials for organic light-emitting diodes

Organic light-emitting diodes(OLEDs) have been extensively studied since the first efficient device based on small molecular luminescent materials was reported by Tang. Organic electroluminescent material, one of the centerpieces of OLEDs, has been the focus of studies by many material scientists. To obtain high luminosity and to keep material costs low, a few remarkable design concepts have been developed. Aggregation-induced emission(AIE) materials were invented to overcome the common fluorescence-quenching problem, and cross-dipole stacking of fluorescent molecules was shown to be an effective method to get high solid-state luminescence. To exceed the limit of internal quantum efficiency of conventional fluorescent materials, phosphorescent materials were successfully applied in highly efficient electroluminescent devices. Most recently, delayed fluorescent materials via reverse-intersystem crossing(RISC) from triplet to singlet and the "hot exciton" materials based on hybridized local and charge-transfer(HLCT) states were developed to be a new generation of low-cost luminescent materials as efficient as phosphorescent materials. In terms of the device-fabrication process, solution-processible small molecular luminescent materials possess the advantages of high purity(vs. polymers) and low procession cost(vs. vacuum deposition), which are garnering them increasing attention. Herein, we review the progress of the development of small-molecule luminescent materials with different design concepts and features, and also briefly examine future development tendencies of luminescent materials.

Tailoring Excited State Properties and Energy Levels Arrangement via Subtle Structural Design on D-π-A Materials

The donor-n-conjugated-acceptor （D-n-A） structure is an important design for the luminescent materials be- cause of its diversity in the selections of donor, n-bridge and acceptor groups. Herein, we demonstrate two examples of D-^-A structures capable to finely modulate the excited state properties and arrangement of energy levels, TPA-AN-BP and CZP-AN-BP, which possess the same acceptor and n-bridge but different donor. The investigation of their photophysical properties and DFT calculation revealed that the D-n-A structure with proper donor, n-bridge and acceptor can result in separation of frontier molecular orbitals on the corresponding donor and acceptor with an obvious overlap on the n-bridge, resulting in a hybridized local and charge-transfer （HLCT） excited state with high photoluminescent （PL） efficiencies. Meanwhile, their singlet and triplet states are arranged on corresponding moie- ties with large energy gap between T2 and T1, and a small energy gap between S1 and T2, which favor the reverse intersystem crossing （RISC） from high-lying triplet levels to singlet levels. As a result, the sky-blue emission non-doped OLED based on the TPA-AN-BP reached maximum external quantum efficiency （EQE） of 4.39% and a high exciton utilization efficiency （EUE） of 77%. This study demonstrates a new strategy to construct highly effi- cient OLED materials.

Simultaneous red-green-blue electroluminescent enhancement directed by surface plasmonic ＂far-field＂ of facile gold nanospheres

Based on the ＂far-field＂ effect of surface plasma resonance, simultaneous red-green-blue electroluminescence enhancement by facile synthesized gold nanospheres were realized in this work, which would be difficult and complex to attain using wavelength-selected localized surface plasma resonance. The plasmonic ＂far-field＂ effect can simultaneously enhance the whole emission region in the white light range, because the enhancing regions from blue to red emission are largely overlapped. By doping gold nanospheres embedded in a poly（3,4-ethylene dioxythiophene）：polystyrene sulfonic acid （PEDOT：PSS） layer, yield enhancement is achieved in more than 95% devices with the best enhancing ratio of 60% and the commission International de UEclairage （CIE） coordinate is stable at approximately （0.33, 0.36）. The plasmonic ＂far-field＂ effect requires an ultra-low working concentration of Au NPs in picomolar magnitude, and shows little negative effect on the electronic process and light scattering, which has big potential in realizing highly efficient white organic light emitting diodes.

Enhancing photovoltaic performance via aggregation dynamics control in fused-ring electron acceptor

A new fused-ring electron acceptor FNIC3 with dynamics controlled aggregation behavior was synthesized.FNIC3 shows strong absorption in 600–900 nm,HOMO/LUMO energy levels of−5.59/−4.04 eV,and electron mobility of 1.2×10^(−3) cm^(2) V^(−1) s^(−1).The aggregation of FNIC3 shows strong dependency on film formation time.Prolongation of film formation time promotes the crystallization of FNIC3,leading to improved crystallinity and enlarged aggregate sizes.Aggregation of FNIC3 significantly influences the photovoltaic device parameters.Appropriate aggregation red-shifts the absorption and improves the mobilities of the blend,which contributes to high photocurrent and fill factor thus high power conversion efficiency(PCE).Overaggregation leads to increased nonradiative energy loss and insufficient charge generation,resulting in decreased open-circuit voltage and short-circuit current density.The blends based on PM6:FNIC3 fabricated under proper film formation time exhibit a PCE of 12.3%,higher than those fabricated under short and long film formation time(10.0–10.5%).

The effect of interfacial diffusion on device performance of polymer solar cells: a quantitative view by active-layer doping

The diffusion of constituent materials at interfaces is one of the key factors for device performance and stability.In this work,the effect of interfacial diffusion of a classic interfacial material PFN on device performance of polymer solar cells was studied quantitatively by doping PFN into active layer based on P3HT:PC61BM blend.The PCEs of devices with 550 ppm PFN decrease to half compared to those of the control devices without PFN,which are mainly attributed to the decrease of short-circuit current(Jsc)and fill factor(FF).Advanced analyses of equivalent circuit,absorption spectra,and atomic force microscopy indicates that the presence of PFN in the active layer increases the leakage current,decreases the aggregation of P3HT,and reduces the phase separation.This research reveals the physical mechanism of interfacial diffusion in device performance and provides a basis for further improving the performance and stability of PSCs.

Preparation and electronic characteristics of anionic perylene bisimide films

Neutral perylene bisimides(PBI) are well-known n-type organic semiconductors, with number of challenging electronic properties in their neutral and reduced states. We report the characteristic electronic properties of PBI anionic films. We unexpectedly discovered that pristine PBI dianion film showed p-type character, while oxidized dianion film(dominant neutral state with few radical anions) showed normal n-type semiconductor character based on Seebeck effect measurements. Both kinds of films exhibit high electrical conductivity with a potential for thermoelectric applications. The mechanism of polarity reversal is proposed.

Precursor synthesis strategy for polycyclic aromatic conjugated polymers on the application of supercapacitors

Polycyclic aromatics (PCAs) possess excellent photoelectric properties, but the construction of such compounds has been a quite challenging subject of study, mainly due to very low solubility. Herein we report a precursor synthesis strategy for polycyclic aromatic conjugated polymers. A soluble precursor polymer, that containing fusible "double U-shaped aromatic"(DUA) and perylenetetracarboxydiimide (PDI) units, was firstly synthesized by Suzuki coupling. The stereo aromatic units in polymer backbone were found to be converted into polycyclic aromatic units, i.e. hexa-peri-hexabenzocoronene (HBC), by chemical or electrochemical oxidation, which resulted in a formation of insoluble polycyclic aromatic conjugated polymers. The electrochemical oxidations that occurred at the interface of electrode and solution exhibited higher cyclization reactivity and leads to the formation of high quality films on the electrode surface. Characterization by Raman and UV-visible (UV-Vis) spectroscopy validated the successful formation of this HBC structure. Some potential applications of such thin films are being explored, and here we focus on the characteristics of supercapacitors based on their excellent electrochemical properties.

A solution-processed nanoscale COF-like material towards optoelectronic applications

Two-dimensional(2 D)covalent organic frameworks(COFs)with periodic functionalπ-electron systems are an emerging class of optoelectronic materials.However,almost all conjugated COFs so far are insoluble and hard to process,which hampers severely their optoelectronic applications.Here,a solution-processable,nanoscale and sp2 carbon-conjugated COF-like material,PDPP-C20 was successfully designed and synthesized.The solution-processed PDPP-C20 films exhibit high crystallinity and excellent charge transport properties along out-of-plane directions,combined with the highest occupied molecular orbital(HOMO)/lowest unoccupied molecular orbital(LUMO)levels of-5.36/-3.75 e V,making PDPP-C20 suitable for electronic device applications.An efficiency as high as 21.92%has been demonstrated when it was used as a functional interfacial layer in perovskite solar cells,coupled with dramatically improved stability in comparison with the control device due to the superior hydrophobicity of PDPP-C20 layer as well as its passivation effect on perovskite surface.Furthermore,the soluble PDPP-C20 could also be used as donor in bulk-heterojunction organic solar cells and an initial efficiency of 2.46%has been achieved.These results indicate that this new class of soluble and nanoscale COF-like materials should offer a new arena of functional materials for optoelectronic devices.

A Cathodic Electrochromic Material Based on Thick Perylene Bisimide Film with High Optical Contrast and High Stability

Cathodic electrochromic materials realized by n-type doping of conducting polymers are scarce.Even with limited cases reported in the literature,long-term stability is an urgent problem to be solved.Herein,we report a high performance and stable cathodic electrochromic material,poly(Th-Cl-PBI),based on a perylene bisimide function core.Due to its high electropolymerization efficiency and low steric hindrance of thiophene groups,perylene bisimide,which generally does not dissolve and form film easily,can grow to the sufficient thickness of 350 nm for wide-range spectral modulation and large-capacity energy storage.The optical contrast of optimized film with a thickness of 240 nm reaches as high as 69.1% at 520 nm,94.1% at 760 nm,and 95.7% at 680 nm.Theoretical simulation based on the Lambert–Beer law also verifies this optical contrast dependent on film thickness.Besides,during the transition between the neutral state and radical anion state,it maintains 90.2% of the electrochemical activity after 4000 cycles,and the transmittance spectrum remains stable after 2000 cycles.The cation size effect on cathodic electrochromic process and cyclic stability has been investigated.

Isomerism: Minor Changes in the Bromine Substituent Positioning Lead to Notable Differences in Photovoltaic Performance

An isomerism strategy was employed to develop single,end‐group bromine-substituted non‐fullerene two isomeric acceptors,2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,"3′′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(4-bromo-3-oxo-2,3-dihydro-1H-inden-1-ylidene)dimalononitrile(BTIC-2Br-β)and 2,2′-((2Z,2′Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,"3′′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5-bromo-3-oxo-2,3-dihydro-1Hinden-1-ylidene)dimalononitrile(BTIC-2Br-γ).

Long-range ordering of composites for organic electronics:TIPS-pentacene single crystals with incorporated nano-fibers

Multi-component active materials are widely used for organic electronic devices, with every component contributing complementary and synergistic optoelectronic functions. Mixing these components generally leads to lowered crystallinity and weakened charge transport. Therefore, preparing the active materials without substantially disrupting the crystalline lattice is highly desired. Here, we show that crystallization of TIPS-pentacene from solutions in the presence of fluorescent nanofibers of a perylene bisimide derivative （PBI） leads to formation of composites with nanoflber guest incorporated in the crystal host. In spite of the binary composite structure, the TIPS-pentacene maintains the single- crystalline nature. As a result, the incorporation of the PB1 guest introduces additional fluorescence function but does not significantly reduce the charge transport property of the TIPS-pentacene host, exhibiting field-effect mobility as high as 3.34 cm^2 V^-1 s^-1 even though 26.4% of the channel area is taken over by the guest. As such, this work provides a facile approach toward high-performance multifunctional organic electronic materials.