Room temperature triplet state spectroscopy of organic semiconductors

Organic light-emitting devices and solar cells are devices that create, manipulate, and convert excited states in organic semiconductors. It is crucial to characterize these excited states, or excitons, to optimize device performance in applications like displays and solar energy harvesting. This is complicated if the excited state is a triplet because the electronic transition is ‘dark’ with a vanishing oscillator strength. As a consequence, triplet state spectroscopy must usually be performed at cryogenic temperatures to reduce competition from non-radiative rates. Here, we control non-radiative rates by engineering a solid-state host matrix containing the target molecule, allowing the observation of phosphorescence at room temperature and alleviating constraints of cryogenic experiments. We test these techniques on a wide range of materials with functionalities spanning multi-exciton generation (singlet exciton fission), organic light emitting device host materials, and thermally activated delayed fluorescence type emitters. Control of non-radiative modes in the matrix surrounding a target molecule may also have broader applications in light-emitting and photovoltaic devices.United States. Dept. of Energy. Center for Excitonics (Award DE-SC0001088

Photoinduced absorption and photoluminescence in poly(2,5-dimethoxy-p- phenylene vinylene)

We report a study of the photoexcited states in the conjugated polymer poly(2,5-dimethoxy-p-phenylene vinylene). Photoluminescence due to radiative recombination of singlet excitons is observed at energiesjust below the onset of the pi-pi* absorption band at 2.1 eV. Photoinduced absorption at 80 K shows bands peaking at 0.68, 1.35, and 1.80 eV. The features at 0.68 and 1.8 eV are associated with the same excited state which we propose is a doubly charged bipolaron, while the third at 1.35 eV is unrelated. We assign this 1.35-eV absorption to a triplet-triplet transition of a triplet exciton. The bipolarons are long lived with significant numbers surviving in excess of 100 ms at 80 K, and have a weak temperature dependence such that photoinduced absorption is readily detectable even at room temperature. The triplet exciton has a lifetime of order 2.5 ms at 80 K but this falls rapidly at higher temperature and the response is not detected at room temperature. We contrast these results with those obtained previously for the related poly(arylene vinylene) polymers poly(p-phenylene vinylene), and poly(2,5-thienylene vinylene) and for other conjugated polymers, and draw attention to the important role played in the photophysics of these materials by neutral excited states

Management of singlet and triplet excitons for efficient white organic light-emitting devices

Lighting accounts for approximately 22 per cent of the electricity consumed in buildings in the United States, with 40 per cent of that amount consumed by inefficient (similar to 15 lm W-1) incandescent lamps(1,2). This has generated increased interest in the use of white electroluminescent organic light-emitting devices, owing to their potential for significantly improved efficiency over incandescent sources combined with low-cost, high-throughput manufacturability. The most impressive characteristics of such devices reported to date have been achieved in all-phosphor-doped devices, which have the potential for 100 per cent internal quantum efficiency(2): the phosphorescent molecules harness the triplet excitons that constitute three-quarters of the bound electron-hole pairs that form during charge injection, and which (unlike the remaining singlet excitons) would otherwise recombine non-radiatively. Here we introduce a different device concept that exploits a blue fluorescent molecule in exchange for a phosphorescent dopant, in combination with green and red phosphor dopants, to yield high power efficiency and stable colour balance, while maintaining the potential for unity internal quantum efficiency. Two distinct modes of energy transfer within this device serve to channel nearly all of the triplet energy to the phosphorescent dopants, retaining the singlet energy exclusively on the blue fluorescent dopant. Additionally, eliminating the exchange energy loss to the blue fluorophore allows for roughly 20 per cent increased power efficiency compared to a fully phosphorescent device. Our device challenges incandescent sources by exhibiting total external quantum and power efficiencies that peak at 18.7 +/- 0.5 per cent and 37.6 +/- 0.6 lm W-1, respectively, decreasing to 18.4 +/- 0.5 per cent and 23.8 +/- 0.5 lm W-1 at a high luminance of 500 cd m(-2).Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/62889/1/nature04645.pd

Excimer formation by steric twisting in carbazole and triphenylamine-based host materials

This paper presents a detailed spectroscopic investigation of luminescence properties of 4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP) and N,N,N’,N’-tetraphenylbenzidine (TAD) in solutions and neat films. These compounds are compared to their derivatives CDBP and TDAD that contain methyl groups in the 2 and 2’ position of the biphenyl core. We find that whereas steric twisting in CDBP and TDAD leads to a high triplet energy of about 3.0 and 3.1 eV, respectively, these compounds also tend to form triplet excimers in a neat film, in contrast to CBP and TAD. By comparison with N-phenylcarbazole (NPC) and triphenylamine (TPA), on which these compounds are based, as well as with the rigid spiro analogs to CBP and TAD we show that the reduced excimer formation in CBP and TAD can be attributed to a localization of the excitation onto the central biphenyl part of the molecule.We acknowledge support from the Federal Ministry of Education and Research (BMBF) through the project ‘Trip-Q’, the German Science Foundation (DFG) through the Research and Training Group GRK 1640 and the UK Engineering and Physical Sciences Research Council (grant number EP/G060738/1).This is the final published version. It first appeared at http://pubs.acs.org/doi/abs/10.1021/jp512772j

Fingerprints for Structural Defects in Poly(thienylene vinylene) (PTV): A Joint Theoretical–Experimental NMR Study on Model Molecules

In the field of plastic electronics, low band gap conjugated polymers like poly(thienylene vinylene) (PTV) and its derivatives are a promising class of materials that can be obtained with high molecular weight via the so-called dithiocarbamate precursor route. We have performed a joint experimental- theoretical study of the full NMR chemical shift assignment in a series of thiophene-based model compounds, which aims at (i) benchmarking the quantum-chemical calculations against experiments, (ii) identifying the signature of possible structural defects that can appear during the polymerization of PTV's, namely head-to-head and tail-to-tail defects, and (iii) defining a criterion regarding regioregularity

Flexible and Printed Organic Nonvolatile Memory Transistor with Bilayer Polymer Dielectrics

In this study, printed organic nonvolatile memory thin-film transistors (TFTs) with phase-separated tunneling layer is presented. Finely patterned electrodes are fabricated by reverse-offset printing with 15 mu m line width and 10 mu m channel length. Memory devices are configured in a bottom-gate bottom-contact TFT structure with a high-k gate blocking insulator poly(vinylidene fluoride-co-trifluoroethylene). A blended ink, which consisted of a small-molecule p-type organic semiconductor dithieno[2,3-d;2 ',3 '-d ']benzo[1,2-b;4,5-b ']dithiophene and a polystyrene dielectric, is fabricated using air-pulse nozzle printing. The tunneling layer is formed during the active layer printing process with the blended ink by phase separation of small-molecule and polymer. The printed memory TFTs with the phase-separated tunneling layer exhibit significantly improved V-TH shifts (approximate to 3 times), programmed/erased current ratio (>10(3) A A(-1)), switching speed (10 years). This memory device can be applied to wearable electronics, smart Internet-of-Things devices, and neuromorphic computing devices.11Nsciescopu

Low Bandgap Bistetracene‐Based Organic Semiconductors Exhibiting Air Stability, High Aromaticity and Mobility

International audienc