Hyunbok Lee

The origin of the hole injection improvements at indium tin oxide/molybdenum trioxide/N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl- 4,4′-diamine interfaces

We investigated the interfacial electronic structures of indium tin oxide (ITO)/molybdenum trioxide (MoO3)/N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) using in situ ultraviolet and x-ray photoemission spectroscopy to understand the origin of hole injection improvements in organic light-emitting devices (OLEDs). Inserting a MoO3 layer between ITO and NPB, the hole injection barrier was remarkably reduced. Moreover, a gap state in the band gap of NPB was found which assisted the Ohmic hole injection at the interface. The hole injection barrier lowering and Ohmic injection explain why the OLED in combination with MoO3 showed improved performance.

Formation of SEI on Cycled Lithium-Ion Battery Cathodes: Soft X-ray Absorption Study

The formation of a solid electrolyte interface (SEI) on LiNi 0 . 8 5 Co 0 . 1 5 O 2 cathodes from lithium-ion cells cycled at 40 and 70°C was observed and characterized using soft X-ray absorption spectroscopy (XAS). XAS measurements were made in the energy region between 500 and 950 eV, encompassing the Ni and Co L 3 - and L 2 -edges and at the K-edges of O and F. Measurements, obtained in the total electron yield mode, are surface sensitive, probing to a depth of ∼5 nm. XAS at the F K-edge demonstrates the presence of poly(vinylidene fluoride) (PVdF) in addition to LiF on the surface of cycled electrodes. The results indicate that the PVdF in the cycled electrodes is largely intact and that the LiF comes from decomposition of LiPF 6 from the electrolyte. XAS also suggests Fe contamination of cycled cathodes.

TiO2/BiVO4 Nanowire Heterostructure Photoanodes Based on Type II Band Alignment.

Metal oxides that absorb visible light are attractive for use as photoanodes in photoelectrosynthetic cells. However, their performance is often limited by poor charge carrier transport. We show that this problem can be addressed by using separate materials for light absorption and carrier transport. Here, we report a Ta:TiO2|BiVO4 nanowire photoanode, in which BiVO4 acts as a visible light-absorber and Ta:TiO2 acts as a high surface area electron conductor. Electrochemical and spectroscopic measurements provide experimental evidence for the type II band alignment necessary for favorable electron transfer from BiVO4 to TiO2. The host–guest nanowire architecture presented here allows for simultaneously high light absorption and carrier collection efficiency, with an onset of anodic photocurrent near 0.2 V vs RHE, and a photocurrent density of 2.1 mA/cm2 at 1.23 V vs RHE.

Electrochemical and In Situ Synchrotron XRD Studies on Al2 O 3-Coated LiCoO2 Cathode Material

Using a commercial available LiCoO2 as starting material, surface-modified cathode material was obtained by coating its surface with a nanosize layer of amorphous Al2O3. Electrochemical performances and structural evolutions of the modified cathode material were characterized and compared with that of pristine LiCoO2. Specific capacity of 190 mAh/g was obtained in Li/ (Al2O3-coated LiCoO2) experimental cells when charged to 4.5 V. The relationship between the structural evolution and the electrochemical performances at overcharged state was investigated using in situ synchrotron X-ray diffraction (XRD). After charging the half-cell using uncoated LiCoO2 as cathode, the variation of the c value in hexagonal structure is significantly reduced during subsequent cycles. This reduction in c variation range is concurrently related to the capacity fading. In contrast, the variation range of c is preserved in the Al2O3-coated cathodes, and so is capacity. Based on these results, a capacity fading mechanism of LiCoO2-type cathode materials after overcharge is proposed, and an explanation of the surface coating effects is given

Synthesis of a Series of Fluorinated Boronate Compounds and Their Use as Additives in Lithium Battery Electrolytes

A new series of anion receptors based on boronate compounds have been synthesized. These compounds can be used as anion receptors in lithium battery electrolytes. The so-called boronate means that the compounds contain a boron bonded with two oxygen atoms and one carbon atom. This series includes various boronate compounds with different fluorinated aryl and fluorinated alkyl groups. When these anion receptors are used as additives in 1,2-dimethoxyethane (DME) solutions containing various lithium salts, the ionic conductivities of these solutions are greatly increased. The electrolytes tested in this study were DME solutions containing the following lithium salts: LiF, CF 3 COOLi, and C 2 F 5 COOLi. Without the additive, the solubility of LiF in DME (and all other nonaqueous solvents) is very low. With some of these boronate compounds as additives, LiF solutions in DME with concentration as high as 1 M were obtained. The solubilities of the other salts were also increased by these additives. Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy studies show that I - anions are complexed with these compounds in DME solutions containing LiI salts. The degree of complexation is also closely related to the structures of the fluorinated aryl and alkyl groups which act as electron-withdrawing groups. The NEXAFS results are in good agreement with ionic conductivity studies.

The interface state assisted charge transport at the MoO 3 /metal interface

The interface formation between a metal and MoO(3) was examined. We carried out in situ ultraviolet and x-ray photoemission spectroscopy with step-by-step deposition of MoO(3) on clean Au and Al substrates. The MoO(3) induces huge interface dipoles, which significantly increase the work functions of Au and Al surfaces. This is the main origin of the carrier injection improvement in organic devices. In addition, interface states are observed at the initial stages of MoO(3) deposition on both Au and Al. The interface states are very close to the Fermi level, assisting the charge transport from the metal electrode. This explains that thick MoO(3) layers provide good charge transport when adopted in organic devices.

Poly(sulfobetaine methacrylate)s as Electrode Modifiers for Inverted Organic Electronics

We demonstrate the use of poly(sulfobetaine methacrylate) (PSBMA), and its pyrene-containing copolymer, as solution-processable work function reducers for inverted organic electronic devices. A notable feature of PSBMA is its orthogonal solubility relative to solvents typically employed in the processing of organic semiconductors. A strong permanent dipole moment on the sulfobetaine moiety was calculated by density functional theory. PSBMA interlayers reduced the work function of metals, graphene, and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) by over 1 eV, and an ultrathin interlayer of PSBMA reduced the electron injection barrier between indium tin oxide (ITO) and C70 by 0.67 eV. As a result, the performance of organic photovoltaic devices with PSBMA interlayers is significantly improved, and enhanced electron injection is demonstrated in electron-only devices with ITO, PEDOT:PSS, and graphene electrodes. This work makes available a new class of dipole-rich, counterion-free, pH insensitive polymer interlayers with demonstrated effectiveness in inverted devices.

Bandgap Engineering through Controlled Oxidation of Polythiophenes

The use of Rozens reagent (HOF⋅CH3 CN) to convert polythiophenes to polymers containing thiophene-1,1-dioxide (TDO) is described. The oxidation of polythiophenes can be controlled with this potent, yet orthogonal reagent under mild conditions. The oxidation of poly(3-alkylthiophenes) proceeds at room temperature in a matter of minutes, introducing up to 60 % TDO moieties in the polymer backbone. The resulting polymers have a markedly low-lying lowest unoccupied molecular orbital (LUMO), consequently exhibiting a small bandgap. This approach demonstrates that modulating the backbone electronic structure of well-defined polymers, rather than varying the monomers, is an efficient means of tuning the electronic properties of conjugated polymers.

Intrinsic and Extrinsic Parameters for Controlling the Growth of Organic Single-Crystalline Nanopillars in Photovoltaics

The most efficient architecture for achieving high donor/acceptor interfacial area in organic photovoltaics (OPVs) would employ arrays of vertically interdigitated p- and n- type semiconductor nanopillars (NPs). Such morphology could have an advantage in bulk heterojunction systems; however, precise control of the dimension morphology in a crystalline, interpenetrating architecture has not yet been realized. Here we present a simple, yet facile, crystallization technique for the growth of vertically oriented NPs utilizing a modified thermal evaporation technique that hinges on a fast deposition rate, short substrate-source distance, and ballistic mass transport. A broad range of organic semiconductor materials is beneficial from the technique to generate NP geometries. Moreover, this technique can also be generalized to various substrates, namely, graphene, PEDOT-PSS, ZnO, CuI, MoO3, and MoS2. The advantage of the NP architecture over the conventional thin film counterpart is demonstrated with an increase of power conversion efficiency of 32% in photovoltaics. This technique will advance the knowledge of organic semiconductor crystallization and create opportunities for the fabrication and processing of NPs for applications that include solar cells, charge storage devices, sensors, and vertical transistors.

Rubicene: a molecular fragment of C70 for use in organic field-effect transistors

Rubicene, a molecular fragment of C70, is a promising organic semiconductor material that displays excellent electronic characteristics for use in organic field-effect transistors (OFETs). Bottom-gate/bottom-contact polycrystalline thin-film OFETs using rubicene exhibit a saturation hole mobility of 0.20 cm2 V−1 s−1 and a current on/off ratio (Ion/Ioff) of 1.0 × 104. In addition, the device performance can be improved with a mobility of 0.32 cm2 V−1 s−1 and Ion/Ioff of 2.5 × 104 with pentafluorobenzenethiol (PFBT) self-assembled monolayer (SAM) treatment on Au electrodes. To characterize the interfacial electronic structure and morphology of rubicene on Au and PFBT/Au, ultraviolet photoelectron spectroscopy (UPS), theoretical calculation with density functional theory (DFT) and grazing incidence X-ray diffraction (GIXD) were performed. With PFBT SAM treatment, the hole injection barrier from Au to rubicene is significantly decreased from 1.15 to 0.48 eV due to the formation of a large interface dipole on Au that increased its work function from 4.33 to 5.67 eV. Furthermore, PFBT SAM treatment also induces an “edge-on” configuration of rubicene, which can lead to the increase in carrier mobility. These results indicate that rubicene can serve as a benchmark organic semiconductor for model charge transport studies and in various organic electronic devices.