Inverted organic photovoltaic device with a new electron transport layer

We demonstrate that there is a new solution-processed electron transport layer, lithium-doped zinc oxide (LZO), with high-performance inverted organic photovoltaic device. The device exhibits a fill factor of 68.58%, an open circuit voltage of 0.86 V, a short-circuit current density of −9.35 cm/mA² along with 5.49% power conversion efficiency. In addition, we studied the performance of blend ratio dependence on inverted organic photovoltaics. Our device also demonstrates a long stability shelf life over 4 weeks in air.     

Triplet-induced degradation: An important consideration in the design of solution-processed hole injection materials for organic light-emitting devices

Solution-processed organic light-emitting devices (OLEDs) still require improvements in their operational lifetime in order for them to become commercially viable. One factor that limits the lifetime of these devices is the instability of the hole injection layer (HIL). Therefore, understanding its degradation mechanism is crucial for the development of more stable solution-processed OLEDs. In this work, we use an archetypal fluorescent OLED in conjunction with an experimental solution-processed HIL in order to elucidate the degradation mechanism in these HILs. Our studies show that degradation is caused by triplet excitons. This new triplet-induced hole injection degradation is expected to be a common phenomenon in OLEDs, and therefore should have important implications for the design of stable HILs.     

Ethylthio-substituted sandwich phthalocyaninato europium (III) semiconductors for sensing NO2 and NH3: Effect of the extended π-conjugate systems on tuning the conductivity and sensing behavior

By using the π-conjugated phthalocyanine macrocycle as the versatile building block, a series of five sandwich-type ethylthio substituted phthalocyaninato europium complexes, namely double-decker Eu[Pc(SC₂H₅)₈]₂ (Pc-1), triple-decker Eu₂[Pc(SC₂H₅)₈]₃ (Pc-2), and their corresponding dimers, [Pc(SC₂H₅)₈]₂Eu₂[BiPc(SC₂H₅)₁₂] (Pc-1@Pc-1), [Pc(SC₂H₅)₈]₃Eu₃[BiPc(SC₂H₅)₁₂] (Pc-1@Pc-2) and [Pc(SC₂H₅)₈]₄Eu₄[BiPc(SC₂H₅)₁₂] (Pc-2@Pc-2), are synthesized and prepared into the solution-processed films by a simple quasi-Langmuir-Shäfer (QLS) method. Combination between the extending π-conjugated system in the longitudinal and transverse directions of Pc macrocycles and/or radical nature of Pc-1 unit among different semiconducting molecules result in unusually small energy gaps (0.345–0.91 eV). Consequently, all of the semiconductors exhibit excellent conductivities. Among these materials, the conductivity for the radical species Pc-1@Pc-1, Pc-1@Pc-2 and Pc-1 is about 3–4 times larger than that for the non-radical compounds Pc-2@Pc-2 and Pc-2. Moreover, the QLS films of five semiconductors take excellent linear responses for both oxidizing NO₂ (100–300 ppb) and reducing NH₃ (4–8.6 ppm). Respectively, the sensitivity (in % ppm⁻¹) gets increased in the order of Pc-1 < Pc-2 < Pc-1@Pc-1 < Pc-1@Pc-2 < Pc-2@Pc-2 for NO₂, and Pc-1@Pc-2 < Pc-1 < Pc-1@Pc-1 < Pc-2@Pc-2 < Pc-2 for NH₃. Depending on the highly extended π-conjugated systems, Pc-2@Pc-2 and Pc-2 films achieve the highest sensitivity of 208.2% ppm⁻¹ and 0.97% ppm⁻¹ to NO₂ and NH₃, respectively. In addition, with a less than 2 min response time within a limit of detection at 10 ppb for NO₂ and 0.48 ppm for NH₃, good reproducibility and selectivity have been revealed for the Pc-2@Pc-2 and Pc-2 films among the best gas sensors obtained so far for all the solution-processed films based on organic semiconductors in dry air at room temperature. More importantly, it is firstly demonstrated that the high NO₂ sensing is resulted from low Oxd₁, and high NH₃ sensing is resulted from high Red₁ among the sandwich Pc-based semiconductors.     

Two different donor subunits substituted unsymmetrical squaraines for solution-processed small molecule organic solar cells

Two unsymmetrical squaraines (USQs) with different donor (D) subunits as photovoltaic materials, namely USQ-11 and USQ-12, were designed and synthesized to investigate the effect of different D subunits on the optoelectronic properties of USQs for the first time. The two USQs compounds were characterized for optical, electrochemical, quantum chemical and optoelectronic properties. By changing the two different D subunits attached to the squaric acid core from 2,3,3-trimethylindolenine to 2-methylbenzothiazole, the HOMO energy levels could be tuned with a stepping of 0.07 eV, and quite different solid state aggregations (H- or J-aggregation) were observed in the thin film by UV-Vis absorption spectra, which were attributed to their distinct steric effects and dipole moments. Solution-processed bulk-heterojunction small molecule organic solar cells fabricated with the USQ-11/PC₇₁BM (1:5, wt%) exhibited extremely higher PCE (4.27%) than that of the USQ-12/PC₇₁BM (2.78%). The much enhanced PCE should be attributed to the simultaneously improved V_oc, J_sc and FF.     

New host materials based on fluorene and benzimidazole units for efficient solution-processed green phosphorescent OLEDs

New green host materials 1-(9,9-diphenyl-9H-fluorene-2-yl)-2-phenyl-1H-benzimidazole and 1-(9,9′-spirobifluorene-2-yl)-2-phenyl-1H-benzimidazole for solution-processed green phosphorescent organic light-emitting devices have been designed and synthesized by attaching the electron transporting benzimidazole units to the rigid fluorene units. Owing to the non-planar structures, which decrease the π conjugation length of fluorene and benzimidazole rings, these fluorene derived derivatives show high triplet energy. The high triplet energy of newly host materials ensures efficient energy transfer from the host to the triplet emitter tris(2-phenylpyridine)iridium. Furthermore, the thermal, photophysical, electrochemical properties and crystal structures of 1-(9,9-diphenyl-9H-fluorene-2-yl)-2-phenyl-1H-benzimidazole and 1-(9,9′-spirobifluorene-2-yl)-2-phenyl-1H-benzimidazole were investigated. The solution-processed single-layer green device using 1-(9,9-diphenyl-9H-fluorene-2-yl)-2-phenyl-1H-benzimidazole as the host for the phosphorescence emitter tris(2-phenylpyridine)iridium showed the maximum luminance efficiencies of 10.1 cd/A. This result demonstrated that the newly synthesized, fluorene-based rigid host materials are advantageous for fabrication of highly efficient green phosphorescent organic light-emitting diodes.     

High-efficiency inverted polymer solar cells with solution-processed metal oxides

The selection of carrier transporting layer in polymer solar cells is an important issue because the nature and direction of carrier transport can be manipulated by inserting different functional layers in the device structure. In this work, we report a very efficient inverted polymer solar cell (PSC) system based on regioregular poly(3-hexylthiophene) and a n-type acceptor, bis-indene[C₆₀]. With a pair of metal oxides and the insertion of TiO₂ nanorods electron collecting layer between the ZnO thin film and the active layer, the device efficiency can be greatly improved. The contact area between the active layer and the electron collecting layer, as well as the thickness of active layer, can be increased with the incorporation of TiO₂ nanorods. As a result, photocurrent can be enhanced due to more absorption of light and more charge separation interface. In addition, the larger contact area and the crystalline TiO₂ nanorods provide a more efficient transporting route for the carriers to the cathode. The most efficient device demonstrated shows a high power conversion efficiency of 5.6% with the inverted structure.     

Open-circuit voltage up to 1.07 V for solution processed small molecule based organic solar cells

With the goal of increasing the open-circuit voltage, two new solution-processable A–D–A structure small molecule donor materials, named DCAO3TF and DCAO3TCz, using two weak electron-donating units, fluorene and carbazole as the central block have been designed and synthesized for photovoltaic applications. While bulk heterojunction photovoltaic devices based on DCAO3TF:PC₆₁BM and DCAO3TCz:PC₆₁BM as the active layers exhibit moderate power conversion efficiencies of 2.38% and 3.63%, respectively, devices based on DCAO3TF:PC₆₁BM do exhibit an impressively high open-circuit voltage (V_oc) up to 1.07 V, which is one of the highest V_oc in organic solar cells based on donor:PCBM blend films.     

Large-area,high-quality self-assembly electron transport layer for organic optoelectronic devices

We propose a self-assembly method for forming large-area high-quality solution-processed titanium oxide (TiO₂) films as efficient electron transport layer for organic solar cells. The self-assembled solution-processed TiO₂ layers are highly ordered and significantly improved in surface morphology over commonly-used spin-coating process resulting in better charge collection and significant material saving. When incorporated into polymer solar cells, the TiO₂ device shows enhanced performance. Furthermore, we demonstrate the TiO₂ can form large-area films, and achieve very uniform and improved device performances. Consequently, the self-assembled TiO₂ films can be efficient and low-cost electron transport layer potentially for large-area organic optoelectronics.     

Highly efficient,solution-processed orange–red phosphorescent OLEDs by using new iridium phosphor with thieno[3,2-c]pyridine derivative as cyclometalating ligand

A new orange iridium phosphor of (EtPy)₂Ir(acac) with thieno[3,2-c]pyridine derivative as cyclometalating ligand was designed and synthesized. The combination of thieno[3,2-c]pyridine with rigid fluorene moiety enlarged the π conjugation of ligand, and consequently caused the peak emission of (EtPy)₂Ir(acac) red-shift to 588 nm. By using (EtPy)₂Ir(acac) as the orange phosphor, the fully solution-processed PhOLEDs were fabricated with the following device configuration: ITO/PEDOT:PSS/PVK: PBD: (EtPy)₂Ir(acac)/CsF/Al. With PEDOT:PSS 8000 as the hole-injecting material, the orange device achieved a maximum current efficiency of 13.4 cd A⁻¹, a maximum power efficiency of 5.9 lm W⁻¹ and a maximum external quantum efficiency (EQE) of 11.2% with a CIE coordinate of (0.62, 0.38) that falls into the orange–red region. Moreover, at high luminance of 1000 cd m⁻², the device still remained high current efficiency of 8.7 cd A⁻¹ and EQE of 7.3%. To the best of our knowledge, these efficiencies were among the highest ever reported for solution-processed orange–red PhOLEDs.     

Low-temperature cross-linkable hole transporting materials through chemical doping for solution-processed green PHOLEDs

Since the inter-layer mutual solubility is an obstacle to the development of solution-processed OLED, cross-linking is considered to be the best method to obtain solvent resistance. Vinyl is the most widely reported crosslinking group, but a problem raised that crosslinking usually need a high temperature. Here, two vinyl-crosslinked hole transporting materials, 3,3'-(1,3,4-oxadiazole-2,5-diyl)bis (N-phenyl-N-(4-vinylphenyl)aniline) (OXZ-VPAN), 3,3'-(4-phenyl-4H-1,2,4-triazole-3,5-diyl)bis (N-phenyl-N-(4-vinylphenyl)aniline) (TRZ-VPAN) were designed and synthesized. The introduction of pentaerythritol tetra(3-mercaptopropionate) (PETMP) and vinyl groups by thiol-ene reaction to reduce the crosslinking temperature. As a result, crosslinking can be achieved at 120 °C with the solvent resistance higher than 99%. The surface morphology of the films before and after crosslinking were characterized by atomic force microscope, and it was found that the roughness of the film was improved after dopped with PETMP. The solution-processed green phosphorescent OLEDs devices based on the obtained HTM exhibit excellent performance. Maximum current efficiency of 57.1 cd A⁻¹ and external quantum efficiency of 16.0% (Ir (mppy)₃) are obtained when OXZ-VPAN served as HTL. This low temperature feasible cross-linking process to prepare HTLs promotes the development solution-processed OLEDs.