Passivating Defects of Perovskite Solar Cells with Functional Donor-Acceptor–Donor Type Hole Transporting Materials

In this study, a series of donor–acceptor–donor (D-A-D) type small molecules based on the fluorene and diphenylethenyl enamine units, which are distinguished by different acceptors, as holetransporting materials (HTMs) for perovskite solar cells is presented. The incorporation of the malononitrile acceptor units is found to be beneficial for not only carrier transportation but also defects passivation via Pb–N interactions. The highest power conversion efficiency of over 22% is achieved on cells based on V1359, which is higher than that of spiro-OMeTAD under identical conditions. This st shows that HTMs prepared via simplified synthetic routes are not only a low-cost alternative to spiro-OMeTAD but also outperform in efficiency and stability state-of-art materials obtained via expensive cross-coupling methods.     

Diphenylamino-substituted derivatives of 9-phenylcarbazole as glass-forming hole-transporting materials for solid state dye sensitized solar cells

The synthesis and properties of glass-forming diphenylamino-substituted derivatives of 9-phenylcarbazole with methoxy groups in the different position of diphenylamino moieties are reported. A comparative study on their thermal, optical, photoelectrical and electrochemical properties is presented. The synthesized compounds exhibit high thermal stability with 5% weight loss temperatures ranging from 344 to 475 °C. The derivatives absorb electromagnetic irradiation in the range of 225–425 nm with the band gaps of 2.94–3.08 eV. The ionization energies of the synthesized compounds range from 5.04 to 5.56 eV. The lowest ionization energies and band gaps are observed for compounds containing para methoxy-substituted phenyl rings of diphenylamino moieties and for disubstituted carbazole derivatives. Charge-transporting properties of the selected compounds were tested by time-of-flight technique. Hole drift mobilities in the amorphous layers of the materials reach 10⁻³ cm²/V s at high electric fields. The derivatives were tested as hole transport materials in solid-state dye sensitized solar cells and showed conversion efficiency up to 0.54%.     

Ultrahigh Efficiency Fluorescent Single and Bi‐Layer Organic Light Emitting Diodes: The Key Role of Triplet Fusion

A new family of anthracene core, highly fluorescent emitters is synthesized which include diphenylamine hole transport end groups. Using a very simple one or two layer organic light emitting diode (OLED) structure, devices without outcoupling achieve an external quantum efficiency of 6% and photonic efficiencies of 20 cd/A. The theoretical maximum efficiency of such devices should not exceed 3.55%. Detailed photophysical characterization shows that for these anthracene based emitters 2T₁≤T_n and so in this special case, triplet fusion can achieve a singlet production yield of 0.5. Indeed, delayed electroluminescence measurements show that triplet fusion contributes 59% of all singlets produced in these devices. This demonstrates that when triplet fusion becomes very efficient, fluorescent OLEDs even with very simple structures can approach an internal singlet production yield close to the theoretical absolute maximum of 62.5% and rival phosphorescent‐based OLEDs with the added advantage of much improved stability.     

Critical Role of Triplet Exciton Interface Trap States in Bilayer Films of NPB and Ir(piq)3

Investigations are carried out into triplet transfer in bilayer films of NPB (N,N´‐diphenyl‐N,N´‐bis(1‐naphthyl)‐1,1´‐biphenyl‐4,4?‐diamine) and Ir(piq)₃ (Iridium (III) Tris(1‐phenylisoquinoline) using laser light pulses to excite the upper surface of the NPB, and thereafter observing the decay dynamics in the Ir(piq)₃ layer situated beneath the NPB. The NPB layer thickness is varied from 13 nm to 80 nm. The results show that up to 200 ns after excitation, the multiexponential decay of directly excited Ir(piq)₃ is observed, thereafter the decay is monoexponential. It is concluded that this monoexponential decay after 200 ns is due to triplets that are transferred to the Ir(piq)₃ via migration from the NPB. The thicker the NPB layer the longer it takes for the reservoir of NPB triplets to deplete via the Ir(piq)₃, with the result that the apparent monoexponential lifetime of the Ir(piq)₃ increases as the thickness of the NPB films increases. Based on time resolved spectra and decays, it is concluded that triplets arriving from NPB are trapped at interface sites of Ir(piq)₃ and do not migrate directly to the bulk states of Ir(piq)₃. A model based on exciton diffusion kinetics, including the presence of interface trap sites, is described, which accurately predicts this behavior.     

Synthesis of new hole-transporting molecular glass with pendant carbazolyl moieties

The synthesis and properties of amorphous hole-transporting 4,4′-bis[11-carbazol-9-yl)-6,8,10-tri(carbazol-9-methyl)-3-hydroxy-5,7,9-trioxa-1-thia]thiobisbenzene with two end and six pendant carbazolyl moieties, separated from the main chain by CH₂ spacers, is reported. It was prepared by a multistep synthesis route from 1,6-di(carbazol-9-yl)-5-(carbazol-9-methyl)-4-oxa-2-hexanol glycidyl ether. Glass transition temperatures of intermediate and final products established by differential scanning calorimetry are reported. The hole drift mobility, measured by the time of flight technique, in this well defined molecular glass depends little on the strength of the electric field and exceeds 10⁻⁵ cm² V⁻¹ s⁻¹. The ionization potentials measured by electron photoemission method, light absorption and fluorescence spectra are closed to those reported for the other organic photoconductors containing electronically isolated carbazole moieties.     

Is Poly(vinylcarbazole) a Good Host for Blue Phosphorescent Dopants in PLEDs? Dimer Formation and Their Effects on the Triplet Energy Level of Poly(N‐vinylcarbazole) and Poly(N‐Ethyl‐2‐Vinylcarbazole)

The detailed measurement and analysis of the delayed emission from poly(vinylcarbazole) (PVK) and poly(N‐ethyl‐2‐vinyl‐carbazole) (P2VK) thin films is described. PVK has rapidly become a “polymer of choice” for hosting phosphorescent dopants in PLEDs, especially blue emitters. In this respect it is important to have a full understanding of the triplet properties of this host. It is concluded that in films, the electronic 0–0 peak energy of PVK phosphorescence is found at 2.88 eV (14 K). With an increase of temperature, >44 K, increasing emission from new long lived, lower energy species, previously ascribed to “trap states” in the literature, is observed. Increasing temperature enables thermally assisted triplet exciton hopping to these trap states. Critically it is shown that some of these triplet trap species are ground state triplet dimers in origin for both PVK (2.46 eV) and P2VK (2.1 eV), and not all of them are of excimer nature as previously thought. These species can quench the emission of blue heavy metal complexes doped in PVK and drastically effect performance over lifetime if the dimer formation increases over time and at elevated operating temperature. It is therefore concluded that PVK might not be such an ideal host material for blue phosphorescent emitters.     

Oxetanyl-functionalized 9-aryl[3,3′]bicarbazolyl derivatives as building blocks for electro-active polymers

9-Aryl[3,3′]bicarbazolyl derivatives containing reactive functional groups were synthesized by the multi-step synthetic rout. The monomers were examined by various techniques including thermogravimetry, differential scanning calorimetry, UV and fluorescence spectrometry as well as electron photoemission and time of flight techniques. The electron photoemission spectra of the layers showed the ionisation potentials of 5.2–5.5 eV. Time-of-flight hole drift mobilities in amorphous layers of bisphenol Z polycarbonate containing 50 wt. % of the electroactive materials exceed 10⁻⁵ cm²/Vs at high electric fields.     

Charge-transporting 3,4-ethylenedioxythiophene-based hydrazone monomers and oligomers

3,4-Ethylenedioxythiophene-based hydrazones, containing reactive functional groups were synthesized and their optical, thermal, photophysical and electrochemical properties were studied. The monomers were subjected to cationic polymerization using boron trifluoride etherate as an initiator. The ionization potentials of the films of the hydrazones, measured by the electron photoemission technique, range from 5.53 to 5.62 eV. Room temperature time-of-flight hole mobilities in the solid solutions of 3,4-ethylenedioxythiophene hydrazone monomers in bisphenol-Z polycarbonate exceed 10^?5 cm² V^?1 s^?1 at high applied electric fields.     

Energy Upconversion via Triplet Fusion in Super Yellow PPV Films Doped with Palladium Tetraphenyltetrabenzoporphyrin: a Comprehensive Investigation of Exciton Dynamics

One of the key issues concerning the development of efficient polymer solar cell technology is the lack of viable materials which absorb in the near‐infrared (NIR) region. This could be resolved by up‐converting energy from the NIR into visible using triplet fusion (TF) with an additional layer that is fabricated separately from the solar cell and deposited on top. Theoretically a maximum upconversion (UC) via TF efficiency of 50% could be obtained. Here, it is demonstrated that in a film of commercially available poly(para‐phenylene vinylene) copolymer “super yellow” (SY) doped with 4% palladium(meso‐tetraphenyl‐tetrabenzoporphyrin) (PdTPBP) sensitizer, an UC efficiency of 6% can be achieved. By using femtosecond and nanosecond spectroscopies it is shown that the main UC efficiency loss mechanism is due to triplet quenching in PdTPBP aggregates. The PdTPBP intersystem crossing rate constant is determined to be 1.8 × 10¹¹ s^?1 and the triplet energy transfer rate constant from PdTPBP to SY to be 10⁹ s^?1. Quenching in PdTPBP aggregates can account for a triplet concentration loss in the range of 76‐99%. As such, preventing sensitizer aggregation in NIR‐to‐visible upconverting films is crucial and may lead to substantial increase of UC efficiencies in films.