ABSTRACT
For the last two decades, research has addressed whether the glass transition temperature and the molecular motions on the surface of organic films are significantly different from those inside the bulk glasses. It is reported that the surface of the photochromic diarylethene film prepared by vacuum deposition has fluidity and the vacuum deposition of small amount of rubrene molecules induces surface tension fluctuations, generating dents due to the Marangoni flow in nanoscale. The depth of the dents increases in proportion to these radii for the colorless diarylethene film with a bulk glass transition temperature (Tg) close to room temperature. On the other hand, in the colored diarylethene obtained by UV irradiation to the colorless film, the depth becomes constant at a certain level. The Tg distribution in the depth direction is clarified based on an analysis of the dent depth. By approximating the obtained Tg depth distribution with an exponential function, the outermost surface Tg is about 100 K lower than the bulk Tg in the case of photoisomerized diarylethene.
ABSTRACT
Selective metal-vapor deposition signifies that metal-vapor atoms are deposited on a hard organic surface, but not on a soft (low glass transition temperature, low Tg ) surface. In this paper, we introduce the origin, extension, and applications of selective metal-vapor deposition. An amorphous photochromic diarylethene film shows light-controlled selective metal-vapor deposition, which is caused by a large Tg change based on photoisomerization, but various organic surfaces, including organic crystal and polymers, can be utilized for achieving selective metal-vapor deposition. Various applications of selective metal-vapor deposition, including cathode patterning of organic light-emitting devices, micro-thin-film fuses, multifunctional diffraction gratings, in-plane electrical bistability for memory devices, and metal-vapor integration, have been demonstrated.
ABSTRACT
We identified the mechanism of the formation of needle-shaped microcrystals on which the contact angle of a water droplet exceeds 170° [Nishikawa, N. et al. Langmuir, 2012, 28, 17817-17824]. The standing needle-shaped crystal of the closed-ring isomer of a diarylethene 3c grew at a much lower temperature than the eutectic temperature by irradiation of UV light on the thin films of the open-ring isomer 3o, due to the epitaxial growth of the 013 plane of 3c over the 110 plane of the crystal lattice of 3o in the subphase. Therefore, the new crystal-growth mechanism triggered by the photoisomerization does not require special inorganic single-crystal substrates and may be called self-epitaxial crystal growth. The needle-shaped crystals appeared well-ordered and stood inclined at an angle of about 60° to the surface. Consequently, the photo-induced rough surface shows not only the superhydrophobic lotus effect, but also the antireflection moth-eye effect, and these effects were switchable by alternate irradiation with UV and visible light.
Subject(s)
Crystallization , Ethylenes/chemistry , Photochemistry/methods , Hydrophobic and Hydrophilic Interactions , Temperature , Ultraviolet RaysABSTRACT
A superhydrophobic surface on which the contact angle of a water droplet exceeds 170° was reversibly produced by alternate irradiation with UV and visible light. Superhydrophobicity is due to the formation of densely generated submicrometer sized needle-shaped crystals (less than 0.2-0.3 µm diameter and 2.2-2.5 µm long) at 30 °C, which is much lower than the eutectic temperature of either isomers of the diarylethene. Below the eutectic temperature, the generated crystals were much smaller than those generated above the eutectic temperature. These smaller crystals more effectively enhanced the superhydrophobicity.
Subject(s)
Hydrocarbons, Aromatic/chemistry , Hydrophobic and Hydrophilic Interactions , Photochemical Processes , Water/chemistry , Surface Properties , TemperatureABSTRACT
We introduce photoreprogrammable dual-function gratings, which show different diffraction in transmission and reflection. Parallel metal lines on the photochromic diarylethene (DAE) surface were prepared by selective metal deposition, enabling one-dimensional diffraction in transmission and reflection. Then, another isomerization pattern was programmed on the DAE layer by light irradiation. This grating generated unique diffraction: one-dimensional diffraction in the reflection but two-dimensional diffraction in the transmission, and a dual-function grating was achieved. This programmed state on the DAE layer could be erased by UV irradiation and could be reprogrammed to generate different diffraction by visible laser scanning. This result shows the great potential of the photoreprogrammable dual-function grating as a key element in various future optical devices and systems.
ABSTRACT
The title compound, C(43)H(32)F(6)N(2)S(2), is a new symmetrical photochromic diaryl-ethene derivative with 9-ethyl-carbazol-3-yl substituents. The mol-ecule adopts a photoactive anti-parallel conformation [Irie (2000). Chem. Rev.100, 1685-1716; Kobatake et al. (2002). Chem. Commun. pp. 2804-2805], with a dihedral angle between the mean planes of the two thio-phene rings of 56.23â (6)°. The distance between the two reactive C atoms is 3.497â (3)â Å. In the crystal, two mol-ecules are associated through a pair of C-Hâ¯F inter-molecular hydrogen bonds, forming a centrosymmetric dimer. Dimers are linked by weak π-π inter-actions [centroid-centroid distance = 3.8872â (13)â Å], forming chains along the c axis.
ABSTRACT
Dual-functional diffraction gratings, which show different diffractions in transmission and reflection, are proposed as an essential optical element. We utilize a flattening effect of photochromic diarylethene (DAE) in the low glass transition temperature state and selective metal deposition to prepare the gratings. The uncolored lines of the colored DAE layer on a grating substrate with grooves were formed by red-laser scanning, and Mg evaporation onto the substrate without a shadow mask enabled Mg-line formation at right angles to the grooves. After being stored at 27 °C for 500 min, the sample showed two-dimensional diffraction in reflection but one-dimensional diffraction in transmission, meaning that a dual-functional grating was achieved. This result shows great potential as a key element for various future optical devices and systems.
ABSTRACT
We report on photocurrent switching based on photoisomerization for the nondestructive readout of photochromic optical memory. The photoisomerization of a diarylethene (DAE) memory layer switched the photocurrent generated in a light-absorbing phthalocyanine layer upon irradiation of a laser light. This switching is based on the ionization potential change of the DAE molecules. Switching characteristics of the photocurrent were investigated for the laser light with a wavelength of 410 nm, 630 nm, or 780 nm. Excellent on-off ratios of the photocurrent were achieved by irradiation at 630 nm and 780 nm. When the pulsed laser light with a wavelength of 780 nm was repeatedly irradiated to the colored and uncolored memory devices, no change of the photocurrent signal levels was observed, even after 8 x 10(5) cycles, indicating a successful demonstration of the nondestructive readout.
ABSTRACT
Electrical carrier separation from a photoexcited photochromic molecule could be a promising method for controlling the photosensitivity of such a molecule. We report an efficient carrier separation from a photochromic diarylethene (DAE) molecule by adopting a device structure with a heterojunction consisting of an n-type diarylethene layer and a p-type layer of N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (NPB). A photocurrent originating from carrier separation for the colored photostationary state was observed, even at zero applied voltage. The efficient carrier separation occurred at the interface between the DAE and NPB layers and was the result of the internal electrical field induced by the pn heterojunction.
ABSTRACT
We report here a novel phenomenon: selective metal deposition on photoswitchable diarylethene (DAE) surfaces. Magnesium vapor was deposited by vacuum evaporation on the colored DAE but not on the uncolored surface. The selective deposition originates in the change of the glass transition temperature of the amorphous DAE film resulting from photoisomerization and therefore from changes of surface molecular motion. We clarified that Mg atoms on the uncolored surface actively migrated on the surface and were desorbed from the surface. The possibility of depositing other metals is also discussed. Light-controllable metal-integrated deposition was demonstrated as a new function of the photoswitchable molecular surfaces. This study reveals new features of the photoswitchable molecular surfaces, and their potential suggests bright prospects for future applications in organic electronics.