吉田 弘幸

Carbazole-based self-assembled monolayers have received considerable attention as hole-selective layers (HSLs) in inverted perovskite solar cells. As an HSL, the electron-blocking capability is important and directly related to electron affinity (EA). Low-energy inverse photoelectron spectroscopy (LEIPS) is the most reliable method for EA measurement. However, the intense electron-impact-induced fluorescence from carbazole interferes with their measurement. By improving the photon detector, we were able to measure 2PACz and MeO-2PACz LEIPS spectra and determine their respective EAs of 1.72 and 1.48 eV. These small EA values ensure effective electron-blocking capability of HSLs regardless of the type of perovskite layer.

Illumination stress (IS) and negative bias under illumination stress (NBIS) cause considerable device instability in thin-film transistors based on amorphous In–Ga–Zn–O (a-IGZO). Models using in-gap states are suggested to explain device instability. Therefore, to provide reliably their density of states (DOS), this study investigated the valence band, conduction band, and in-gap states of an a-IGZO thin film. The DOS of in-gap states was directly determined in a dynamic range of six orders of magnitude through constant final state yield spectroscopy (CFS-YS) using low-energy and low-flux photons. Furthermore, light irradiation irreversibly induced extra in-gap states near the Fermi level and shifted the Fermi level to the vacuum level side, which should be related to the device instability due to IS and NBIS. Hard x-ray photoemission spectroscopy and ultraviolet photoemission spectroscopy using synchrotron radiation observed the large DOS of in-gap states near the Fermi level as in previous works. Here, we reveal that they are not intrinsic electronic states of undamaged a-IGZO, but induced by the intense measurement light of synchrotron radiation. This study demonstrates that CFS-YS is useful for determining the reliable DOS of the in-gap states for samples that are sensitive to light irradiation. The absorption spectrum measured through photothermal deflection spectroscopy is interpreted based on DOS directly determined via photoemission spectroscopies. This indicates that the line shape in the energy region below the region assigned to the Urbach tail in previous works actually roughly reflects the DOS of occupied in-gap states.

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2′,7,7′-tetrakis( N , N -di- p -methoxyphenyl-amine)9,9′-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4- tert -butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.

Porphyrin derivatives are promising materials for various thin-film-based devices such as solar cells, field-effect transistors, and gas sensors. Since the molecular aggregation structure in a thin film significantly influences the device performance, controlling the aggregation structure is of crucial importance. In this study, we show that three different crystalline polymorphs of free-base tetraphenylporphyrin (H2TPP) can be made to form in spin-coated thin films depending on the evaporation time of the solvent. The results show that the aggregation structure in the as-spun films is controlled by the solvent evaporation time, and the initial film structure determines the polymorphs obtained after thermal annealing.

<jats:title>Abstract</jats:title> <jats:p>Quasi-2D perovskites passivate the perovskite surface and improve the lifetime of perovskite solar cells. However, their detailed surface structures have never been reported. We studied the surfaces of the solution-processed quasi-2D PEA<jats:sub>2<jats:italic>m</jats:italic> </jats:sub>MA<jats:sub> <jats:italic>n</jats:italic>−2<jats:italic>m</jats:italic> </jats:sub>Pb<jats:italic> <jats:sub>n</jats:sub> </jats:italic>I<jats:sub>3<jats:italic>n</jats:italic> </jats:sub> (PEA: C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>CH<jats:sub>3</jats:sub>CH<jats:sub>2</jats:sub>NH<jats:sub>3</jats:sub>, MA: CH<jats:sub>3</jats:sub>NH<jats:sub>3</jats:sub>) perovskites as well as the 2D perovskite formed on top of 3D MAPbI<jats:sub>3</jats:sub> with the thicknesses relevant to practical solar cell (<jats:italic>n</jats:italic> ≈ 400) using ultraviolet photoelectron and metastable-atom electron spectroscopies. We confirmed that PEA segregates to the surface and that the phenyl group (C<jats:sub>6</jats:sub>H<jats:sub>5</jats:sub>) covers the outermost surface of the quasi-2D perovskite. We discuss plausible structures from the concentration dependence of PEA.</jats:p>

Perylene dyes are a representative framework of electron transport (n-type) organic semiconductors. The energy of their electron transport level is the electron affinity (EA), which is an important parameter in selecting the electron transport materials for device application and of the material's electron-accepting ability. Recent studies show that EA may vary by as much as 1 eV depending on the molecular orientation owing to the electrostatic potential generated by the quadrupole moments. Because perylene dyes have a large quadrupole moment, it is essential to discuss EA combined with the molecular orientation in the sample film. In this work, we determine the EAs of perylene diimide derivatives in the solid phase using low-energy inverse photoelectron spectroscopy (LEIPS), which was developed by one of the authors. By changing the substrate and the alkyl-chain length, we systematically investigate the relationship between EA and molecular arrangement in the film to derive the general trend of the EA of perylene dyes. The results show that most of the perylene dyes' EAs are in the range from 3.7 to 4.0 eV.

Information concerning the unoccupied states of condensed matter is of great relevance to its electronic, optical and chemical properties. These unoccupied states can be directly examined by inverse photoelectron spectroscopy (IPES), which is often regarded as the time-inversion process of photoelectron spectroscopy. The fundamental drawback of IPES is its low signal intensity. Other spectroscopic intensities are enhanced by surface plasmon resonance (SPR), so the intensity of the IPES signal may also be enhanced by SPR. This was, however, impossible because the photon energy involved in conventional IPES exceeds 9 eV and is much higher than the SPR energy of existing materials. In 2012, we developed low-energy IPES (LEIPS), in which the photon energy is <5 eV, which can then be matched with the SPR energy. We demonstrate a five-fold enhancement of the LEIPS signal from a prototypical organic semiconductor, copper phthalocyanine (CuPc), by SPR of Ag nanoparticles.

Eliminating the excess energetic driving force in organic solar cells leads to a smaller energy loss and higher device performance; hence, it is vital to understand the relation between the interfacial energetics and the photoelectric conversion efficiency. In this study, we systematically investigate 16 combinations of four donor polymers and four acceptors in planar heterojunction. The charge generation efficiency and its electric field dependence correlate with the energy difference between the singlet excited state and the interfacial charge transfer state. The threshold energy difference is 0.2 to 0.3 eV, below which the efficiency starts dropping and the charge generation becomes electric field-dependent. In contrast, the charge generation efficiency does not correlate with the energy difference between the charge transfer and the charge-separated states, indicating that the binding of the charge pairs in the charge transfer state is not the determining factor for the charge generation.

Methylammonium lead triiodide (CH3NH3PbI3) is an essential material in prototype perovskite solar cells, and its intrinsic electronic structures have been of great interest. In this study, the clean surface of single crystal samples of CH3NH3PbI3 was elucidated by X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy (UPS), and photoelectron yield spectroscopy (PYS), and was closely compared with as-prepared single crystal surfaces with considerable native impurities. Low-energy UPS and PYS successfully revealed a presence of electronic states exceeding the Fermi level, which are presumably attributed to electrons transferring from the surface impurities into the conduction band of CH3NH3PbI3.

Pentacene attracts a great deal of attention as a basic material used in organic thin-film transistors for many years. Pentacene is known to form a highly ordered structure in a thin film, in which the molecular long axis aligns perpendicularly to the substrate surface, i.e., end-on orientation. On the other hand, the face-on oriented thin film, where the molecular plane is parallel to the substrate, has never been found on an inert substrate represented by SiO2. As a result, the face-on orientation has long been believed to be generated only on specific substrates such as a metal single crystal. In the present study, the face-on orientation grown on a SiO2 surface has first been identified by means of visible and infrared p-polarized multiple-angle incidence resolution spectrometry (pMAIRS) together with two-dimensional grazing incidence X-ray diffraction (2D-GIXD). The combination of the multiple techniques readily reveals that the face-on phase is definitely realized as the dominant component. The face-on film is obtained when the film growth is kinetically restricted to be prevented from transforming into the thermodynamically stable structure, i.e., the end-on orientation. This concept is useful for controlling the molecular orientation in general organic semiconductor thin films.

© 2018 American Chemical Society. A molecular anion of tris(8-hydroxyquinolinato)aluminum (Alq3) was generated by a pulsed discharge to the solid sample under supersonic expansion and its photoelectron spectrum was recorded after mass selection. The vertical detachment energy of Alq3- and the adiabatic electron affinity of Alq3 were determined to be 1.24 ± 0.01 and 0.89 ± 0.04 eV, respectively. By using these energies determined for monomeric Alq3, the reorganization energy for the intermolecular electron transport in bulk Alq3 was estimated to be 0.70 ± 0.08 eV.

Designing donor/acceptor (D/A) interfaces that can efficiently generate free carriers is an attractive research target for organic photovoltaics (OPVs). While many reports suggest that the molecular orientation of the donor at the D/A interface influences the free-charge generation and recombination, the effects of the acceptor orientation on these processes remain elusive. In this work, we demonstrate that [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) changes its molecular orientation at the film surface on crystallization, resulting in the preferential surface exposure of the side chains. Photoelectron spectra of amorphous- and crystalline-PC61BM/sexithiophene (6T) interfaces and analysis of the external quantum efficiency and electroluminescence of bilayer OPVs in the charge-transfer absorption range reveal that the orientational change of PC61BM raises the energy of the charge-transfer state at the D/A interface. In addition, the PC61BM side chain at the crystalline-PC61BM/6T interface reduces the electronic coupling between the charge-transfer and ground states, suppressing carrier recombination without sacrificing photocurrent. These two factors lead to the higher open-circuit voltage of crystalline-PC61BM/6T OPV compared with its amorphous counterpart. This work directly links the interface and photovoltaic properties, highlighting the role of the acceptor’s orientation in determining the efficiency of OPVs.

The solvent vapor annealing (SVA) technique is one of the useful post processing techniques of a thin film, which is an alternative technique of the thermal annealing one. SVA has a great advantage that the molecular rearrangement in the film is made moderately by employing an appropriate solvent without the sample heating. The moderate processing is expected to yield a benefit that the molecular coalescence would be suppressed, which would readily keep the continuous surface topography of the film during the annealing, and another benefit that a metastable structure would be obtained. To make the best use of the SVA-specific characteristics, in the present study, a material having a metastable structure is chosen. The sample is zinc tetraphenylporphyrin (ZnTPP) that yields a metastable triclinic crystal structure, which can easily be converted to a monoclinic crystal structure by thermal annealing. A triclinic-structure film of ZnTPP by the combination of a wet process and the thermal annealing has thus never been reported. By choosing a fluorine-containing solvent, which has a low affinity to ZnTPP, a triclinic-structure film has first been obtained by a wet process while the surface continuity is protected.

Energy levels of organic molecular films exert paramount influence on the electronic properties of organic semiconductors. Recently the effect of electrostatic energy was highlighted as an origin of such peculiar phenomena as the molecular-orientation dependence and continuous tuning of energy levels. However, the mechanism has been discussed mostly based on theoretical work and has not been adequately supported by experiments. In this work, we propose a procedure to evaluate the electrostatic and electronic polarization energies in organic films solely from the experimental data obtained by ultraviolet photoelectron and low-energy inverse photoelectron spectroscopies. We apply it to the energy levels of thin films of 6,13-pentacenequinone on SiO2 substrates with three different molecular orientations. The obtained electrostatic energies are fully consistent with the theoretical results at different levels such as the first-principles calculations and the electrostatic energy of charge-multipole interactions. The present work also underlines the importance of the charge-permanent quadrupole interaction which is the leading term of the electrostatic energy in the film of nonpolar molecules.

In organic semiconductors, the hole and electron transport occurs through the intermolecular overlaps of highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO), respectively. A measure of such intermolecular electronic coupling is the transfer integral, which can experimentally be observed as energy level splittings or the width of the respective energy bands. Quantum chemistry textbooks describe how an energy level splits into two levels in molecular dimers, into three levels in trimers and evolves into an energy band in infinite systems, a process that has never been observed for the LUMO or beyond dimers for the HOMO. In this work, our new technique, low-energy inverse photoelectron spectroscopy, was applied to observe the subtle change of the spectral line shape of a LUMO-derived feature while we used ultraviolet photoelectron spectroscopy to investigate the occupied states. We show at first that tin-phthalocyanine molecules grow layer-by-layer in quasi-one-dimensional stacks on graphite, and then discuss a characteristic and systematic broadening of the spectral line shapes of both HOMO and LUMO. The results are interpreted as energy-level splittings due to the intermolecular electronic couplings. On the basis of the Hückel approximation, we determined the transfer integrals for HOMO-1, HOMO, and LUMO to be ≤15 meV, (100 ± 10) meV, and (128 ± 10) meV, respectively.

Charge trap in amorphous perfluoro-polymer electret is studied, focusing on electron trap site and trap energy. Low-energy inverse photoelectron spectroscopy is adopted to measure solid-state electron affinity (EA) of cyclic transparent optical polymer (CYTOP). EA of CYTOP CTL-S is discovered by compensating the unwanted charge-up effect. Negatively-charged electret materials (polyethylene, ethylene-tetra-fluoro-ethylene, poly-tetra-fluoro-ethylene, and CYTOP) are analyzed by quantum mechanical calculation. Density functional theory with long-range correction is adopted to analyze orbital energies of single molecular systems. Intramolecular distribution of trapped electron and EA are investigated. Calculated electron affinities of CYTOP polymers with different end group are qualitatively in accordance with trapped charge stability measured with thermal stimulated discharge, signifying that electron affinities obtained with the present simulation can be used as an index of amorphous polymer electret.

Understanding of the electronic structures is indispensable for complete elucidation of the charge carrier behaviors in organic semiconductors. Although recent progress enabling accurate photoemission demonstrations of organic single crystals has greatly promoted such understanding, it had been achieved merely on partially oxidized surfaces by exposure to ambient conditions. In this study, we successfully prepared an oxide-free surface of the pentacene single crystal (PnSC) by cleavage in vacuum. X-ray and ultraviolet photoelectron spectroscopy measurements on the PnSC clean surface revealed improved energetic homogeneity of the C1s level and highest-occupied state in comparison to those of the partially oxidized surface.

The development of semiconducting polymers is imperative to improve the performance of polymer-based solar cells (PSCs). In this study, new semiconducting polymers based on naphtho[1,2-c:5,6-c′]bis[1,2,5]thiadiazole (NTz), PNTz4TF2 and PNTz4TF4, having 3,3′-difluoro-2,2′-bithiophene and 3,3′,4,4′-tetrafluoro-2,2′-bithiophene, respectively, are designed and synthesized. These polymers possess a deeper HOMO energy level than their counterpart, PNTz4T, which results in higher open-circuit voltages in solar cells. This concequently reduces the photon energy loss that is one of the most important issues surrounding PSCs. The PNTz4TF4 cell exhibits up to 6.5% power conversion efficiency (PCE), whereas the PNTz4TF2 cell demonstrates outstanding device performance with as high as 10.5% PCE, which is quite high for PSCs. We further discuss the performances of the PSCs based on these polymers by correlating the charge generation and recombination dynamics with the polymer structure and ordering structure. We believe that the results provide new insights into the design of semiconducting polymers and that there is still much room for improvement of PSC efficiency.

A novel electron-deficient building unit, dithienylthienothiophenebisimide, and its polymers (PTBIs) are reported. Organic photovoltaic (OPV) cells based on PTBIs as p-type material exhibit 8.0% efficiencies with open-circuit voltages higher than 1 V. Interestingly, PTBIs also function as n-type material in OPVs depending on the molecular structure. These polymers also exhibit p-channel, n-channel, and ambipolar behaviors in field-effect transistors.

We report on the results of experimental and theoretical studies on the electronic structure of gas-phase diindenoperylene (DIP) and DIP-monolayer (ML) on Cu(111). Vapor-phase ultraviolet photoelectron spectroscopy (UPS) was realized for 11.3 mg of DIP, giving reference orbital energies of isolated DIP, and UPS and inverse photoemission spectroscopy of DIP-ML/graphite were performed to obtain DIP-ML electronic states at a weak interfacial interaction. Furthermore, first-principles calculation clearly demonstrates the interfacial rearrangement. These results provide evidence that the rearrangement of orbital energies, which is realized in HOMO-LUMO and HOMO-HOMO-1 gaps, brings partially occupied LUMO through the surface-induced aromatic stabilization of DIP, a pure hydrocarbon molecule, on Cu(111). (C) 2016 The Japan Society of Applied Physics

Information about the unoccupied states is crucial to both fundamental and applied physics of organic semiconductors. However, there were no available experimental methods that meet the requirement of such research. In this review, we describe a new experimental method to examine the unoccupied states, called low-energy inverse photoemission spectroscopy (LEIPS). An electron having the kinetic energy lower than the damage threshold of organic molecules is introduced to a sample film, and an emitted photon in the near-ultraviolet range is detected with high resolution and sensitivity. Unlike the previous inverse photoemission spectroscopy, the sample damage is negligible and the overall resolution is a factor of two improved to 0.25 eV. Using LEIPS, electron affinity of organic semiconductor can be determined with the same precision as photoemission spectroscopy for ionization energy. The instruments including an electron source and photon detectors as well as application to organic semiconductors are presented. (C) 2015 Published by Elsevier B.V.

When a thin layer of bathocuproine (BCP) is inserted between the metal electrode and the organic layer of the organic semiconductor device, the electron injection/collection efficiency at the interface is significantly improved. However, the mechanism of electron transport through the BCP layer has not been clarified yet. In this study, we directly observed the unoccupied electronic states of the Ag/BCP interface using low-energy inverse photo emission spectroscopy. The result shows that Ag strongly interacts with the BCP molecule and the lowest unoccupied molecular orbital (LUMO) level of the Ag-BCP complex aligns with the Fermi level, indicating that the electron transport occurs through the LUMO level of the complex. With the aid of DFT calculation, we identify the reaction product.

Ionization energy and electron affinity in organic solids are understood in terms of a single molecule perturbed by solid-state effects such as polarization energy, band dispersion, and molecular orientation as primary factors. However, no work has been done to determine the individual contributions experimentally. In this work, the electron affinities of thin films of pentacene and perfluoropentacene with different molecular orientations are determined to a precision of 0.1 eV using low-energy inverse photoemission spectroscopy. Based on the precisely determined electron affinities in the solid state together with the corresponding data of the ionization energies and other energy parameters, we quantitatively evaluate the contribution of these effects. It turns out that the bandwidth as well as the polarization energy contributes to the ionization energy and electron affinity in the solid state while the effect of the surface dipole is at most a few eV and does not vary with the molecular orientation. As a result, we conclude that the molecular orientation dependence of the ionization energy and electron affinity of organic solids originates from the orientation-dependent polarization energy in the film.

In diverse classes of organic optoelectronic devices, controlling charge injection, extraction, and blocking across organic semiconductor-inorganic electrode interfaces is crucial for enhancing quantum efficiency and output voltage. To this end, the strategy of inserting engineered interfacial layers (IFLs) between electrical contacts and organic semiconductors has significantly advanced organic light-emitting diode and organic thin film transistor performance. For organic photovoltaic (OPV) devices, an electronically flexible IFL design strategy to incrementally tune energy level matching between the inorganic electrode system and the organic photoactive components without varying the surface chemistry would permit OPV cells to adapt to ever-changing generations of photoactive materials. Here we report the implementation of chemically/environmentally robust, low-temperature solution-processed amorphous transparent semiconducting oxide alloys, In-Ga-O and Ga-Zn-Sn-O, as IFLs for inverted OPVs. Continuous variation of the IFL compositions tunes the conduction band minima over a broad range, affording optimized OPV power conversion efficiencies for multiple classes of organic active layer materials and establishing clear correlations between IFL/photoactive layer energetics and device performance.