Local work function control of indium tin oxide by micro-contact printing for electroluminescent devices.

We demonstrate here that light emission of an electroluminescent (EL) device was enhanced on chemically modified ITO areas over a patterned ITO anode with a self-assembled monolayer (SAM) of 4-chlorophenylphosphoryl dichloride (ClC(6)H(4)OPOCl(2): CPPDC) prepared by micro-contact printing (mu-CP). The EL device was fabricated by vapor-depositing a hole transport layer, a light emitting and electron transport layer, and a C(6)H(5)COOLi/Al bilayer cathode on the patterned ITO anode. The enhanced light emission under lower drive voltages on the modified areas can be interpreted by the increase in the work function of the ITO covered with the SAM measured with a Kelvin probe force microscope (KPFM) and thus the decrease in the hole injection barrier height. In addition, we could demonstrate the much smaller pattern images than the previously reported ones [F. Nüesch, Y. Li, L.J. Rothberg, Appl. Phys. Lett. 75 (1999) 1799] by the use of ink-pads.

Single molecular conductance measurements of molecular junction of Au/1,4-phenylenediamine/Au.

It was reported recently that the diamine-terminated molecules show two sets of single molecular conductance peaks in the conductance histogram. Although we found another set of conductance value of 1,4-diaminobutane in a lower current range, it was difficult to determine the conductivity definitely because the compound has different conformations with different gauche contents within its molecular chain. To make it easier to determine and analyze a single molecular conductance we measured here the conductance of 1,4-phenylenediamine, whose conformation cannot be changed in terms of the gauche contents. As a result, new sets of conductance other than those reported recently [L. Venkataraman, J.E. Klare, C. Nuckolls, M.S. Hybertsen, M.L. Steigerwald, Nature 442 (2006) 904] were observed.

Topographic effects on adhesive force mapping of stretched DNA molecules by pulsed-force-mode atomic force microscopy.

Adhesive interaction between a tip and a sample surface was examined on a microscopic scale by pulsed-force-mode atomic force microscopy (PFM-AFM). The signal measured by monitoring pull-off force is influenced by various factors such as topography, elasticity, electrostatic charges, and adsorbed water on surfaces. Here, we focus on the topographic effects on the adhesive interaction. To clarify the topographic influence, the adhesive force measurement of a stretched DNA molecule with a smaller radius of curvature than that of a tip was carried out at low relative humidity (RH) with an alkanethiol-modified tip. The experimental conditions such as low RH and the use of the alkanethiol-modified tip were required to minimise the influence of water capillary force on hydrated DNA strands. The hydrophobic modification of a substrate surface was also important to minimise the adsorbed water effect. The DNA molecules were stretched on the substrate surfaces by an immobilisation process called a dynamic molecular combing method. The two-component vapour-phase surface modification with an alkylsilane mixed with a silane derivative containing an amino end group enhanced the DNA adsorption due to the electrostatic interaction. The experimental results for the topographic effects on the adhesive force mapping were reproducible.

Observation of removal of an Fmoc protecting group by scanning tunneling microscopy.

We demonstrate here by imaging successive surface reactions in self-assembled monolayers (SAMs) on Au(111) at molecular scale with a scanning tunneling microscope (STM): (i) SAM matrices formation with 1-octanethiol on Au(111) in ethanol, (ii) insertion of N-Fmoc-aminooctanethiol into the SAM matrices in ethanol, and (iii) removal of the Fmoc protecting group with tris(2-aminoethyl)amine (TAEA). The total reaction is formation of SAMs containing a small amount of NH2 terminated molecules in the CH3 terminated SAM matrices. After the reaction of the protecting group with TAEA, STM imaging revealed the decrease in heights of the inserted molecules on average. We attributed this observation to removal of the protecting group by taking account of a convolution of electronic and topographic contributions to observed STM heights. Apparent areas of the terminal groups, however, became larger on removal. The increase in the areas was attributed to water adsorption to the NH2 terminal group under air.

The effect of permanent dipole moments of adsorbates upon I-V characteristics of a bilayer tunneling junction between self-assembled monolayers on an Au(111) substrate and a gold tip.

It is important to understand an electronic property of an interface between an organic material and a metal electrode. In the present work, we measured current-voltage (I-V) curves of self-assembled monolayers (SAMs) on Au(111) using a conducting atomic force microscope (AFM) with chemically modified Au-coated AFM tips. This contact resulted in a bilayer junction between the Au(111) substrate covered with one SAM and the Au-coated tip with the other SAM. An alkanethiol (octanethiol) and benzenemethanethiols with various terminal groups (-H, -CH(3), -Cl, -CF(3)) were used as the adsorbates. The shapes of the I-V curves depended on the terminal groups. This phenomenon was attributed to the change in the work function of gold due to different permanent dipole moments of the terminal groups.

Imaging stretched single DNA molecules by pulsed-force-mode atomic force microscopy.

The effect of a surface water layer on DNA strands deposited on a substrate was studied by atomic force microscopy (AFM). DNA molecules were deposited and stretched on chemically modified glass coverslips by a molecular combing method. Lambda bacteriophage DNA molecules were aligned on the organosilane-modified substrate surfaces by chemical and physical adsorption during the molecular combing. The combed DNA molecules were observed in humidity-controlled air and in aqueous solutions by pulsed-force-mode AFM (PFM-AFM). Chemical modification of cantilevers with an Au-coated tip by organothiol compounds was also applied to DNA observation. Mapping adhesive forces in aqueous media was useful to discriminate chemically the DNA strands from the substrate surface. The results suggest that PFM-AFM can be used widely to image the stretched DNA molecules on the silane-modified substrates.

Scanning surface potential microscopic studies of photo-voltaic Langmuir-Blodgett assemblies containing an A-S-D triad molecule.

Scanning surface potential microscopy was applied to detect the photo-voltaic response of Langmuir-Blodgett (LB) monolayer assemblies containing an amphiphilic A-S-D triad molecule (ASD) with two different concentrations. The triad acts as a charge separation unit in the same way as the photosynthetic reaction center. In addition, the photo-induced multistep electron transfer systems can be organized in the LB monolayers: first electrons and holes are separated across the monolayer through the ASD triads upon photo-excitation and then the resultant electrons and holes are further separated by lateral diffusion among the concentrated A and the D moieties, respectively. The change in surface potential was clearly observed on an LB assembly with the high ASD concentration in a mixed ASD monolayer with omega-tricosenoic acid (T) (the molar ratio of ASD:T = 1:5), while the photo-response could not be observed on an LB monolayer with the low ASD concentration (the molar ratio of ASD:T = 1:30). It was interesting to note that the average surface concentration of ASD in the latter diluted monolayer was decreased only to 6 of that of the former concentrated monolayer. If the photo-response depended linearly on the ASD concentration, the surface potential would be readily detected in the latter monolayer. The nonlinearity can be attributed to the effect of succeeding lateral diffusion of the separated charges among the ASD triads. To clarify the effect of the lateral diffusion, the other type of LB assemblies, i.e., A/A-S-D double layers, was fabricated by alternate deposition of an additional acceptor (A) layer and the ASD layer. In the A/A-S-D assemblies, significant photo-induced surface potential change was observed with an A layer of a high A concentration (A:T = 1:2) even when the ASD concentration was low in the ASD layer (ASD:T = 1:30). This result supported an idea that the additional A layer enhanced lateral electron diffusion and resulted in electron accumulation in A layer and hole accumulation in the diluted ASD layer in the A/A-S-D system.

Rectified photocurrent of molecular photodiode consisting of cytochrome c/GFP hetero thin films.

Photoinduced electron transfer in the molecular electronic device consisting of protein-adsorbed hetero Langmuir-Blodgett (LB) film was investigated. Three kinds of functional molecules, cytochrome c, viologen, and green fluorescent protein (GFP) were used as an electron acceptor, a mediator, and a sensitizer, respectively. The hetero-LB film was fabricated by subsequently depositing cytochrome c and viologen onto the pretreated ITO or quartz glass. GFP adsorbed hetero-LB films were prepared by soaking the hetero-LB films into the buffer solution containing GFP. The MIM (metal/insulator/metal) structured molecular device was constructed by depositing aluminum onto the surface of the GFP-adsorbed hetero LB films. Due to the excitation by irradiation with a 460 nm monochromic light source, the photoinduced unidirectional flow of electrons in the MIM device could be achieved and was detected as photocurrents. The photoswitching function was achieved and the rectifying characteristic was observed in the molecular device. Based on the measurement of transient photocurrent of molecular device, the unidirectional flow of electrons was verified.

Study of energy transfer from excited TPD to Alq in organic electroluminescent devices by time-resolved fluorescence spectroscopy using a scanning near-field optical atomic force microscope.

We demonstrate the direct measurement of molecular diffusion at organic/organic interfaces of organic electroluminescence devices by use of a scanning near-field optical atomic force microscope. Our preliminary study shows that the degradation of an electroluminescence device is partly caused by crystallization of the organic layers. Because the initial stage of degradation cannot be observed by microscopic methods, nanoscale optical properties of the interface in multilayer systems are currently receiving a great deal of attention. Defects of organic electroluminescence devices were investigated using a scanning near-field optical atomic force microscope. This instrument is capable of measuring both a topographic and a fluorescence image at the same time. The defect area and other areas are clearly observed and time-resolved near-field fluorescence spectra demonstrate emission of the different species. These results suggest that defects occur at the organic solid interface, and that energy transfer occurs from excited TPD, as donor, to Alq, as acceptor.

Near-field fluorescence imaging and simultaneous observation of surface potentials.

We present a new detection method to measure simultaneously surface potential and fluorescence intensity distributions using a combined scanning near-field optical microscope-atomic force microscope (SNOM-AFM). A surface potential image of phospholipid monolayers was obtained in non-contact mode using the SNOM-AFM with a thin-step etched optical fibre probe. For applying this technique, a phospholipid of dipalmitoylphosphatidylethanolamine labelled at the head with a nitrobenzoxadiazole group was used as a fluorescent and single component Langmuir-Blodgett film. It is well known that aggregation of the lipid molecules and their fluorescence intensities are very sensitive to its environmental conditions such as humidity and temperature. We demonstrated for the first time the near-field optical imaging and simultaneous observation of surface potentials with Maxwell stress microscopy.

Chemical force microscopy of self-assembled monolayers on sputtered gold films patterned by phase separation.

Patterned self-assembled monolayers (SAMs) were formed on gold films and observed by friction force microscopy (FFM) and adhesive force mapping with pulsed-force mode atomic force microscopy (PFM-AFM). The substrate gold films were prepared by sputtering gold on flat surfaces of osmium-coated cover glass with surface roughness, Ra, of 0.3 nm. The patterned samples with the CH3 and COOH terminated regions were prepared using the Langmuir-Blodgett (LB) method, partial removal of the LB film by ultrasonication, and SAM formation. The CH3 and COOH terminated regions of the patterned SAMs in air and in water were observed by mapping friction and adhesive forces with FFM and PFM-AFM, respectively, using gold-coated AFM tips chemically modified with a thiol compound terminating in CH3 or COOH. The adhesive forces measured in air increased in the order of CH3/CH3, CH3/COOH (or COOH/CH3) and COOH/COOH, while those in water increased in reverse order. The enormous high adhesive force observed in water for CH3/CH3 was attributed to hydrophobic interaction between the CH3 tip and the CH3 terminated sample surface. With CH3 tip, the lower friction force was observed, however, in water on the CH3 terminated region than on the COOH terminated region. This experimental finding raises a question as to what is the effective normal load in friction measurements in water.

Study of microcontact printed patterns by chemical force microscopy.

Patterned self-assembled monolayers (SAMs) on sputtered gold films prepared by microcontact printing (microCP) were studied by mapping adhesive forces with pulsed-force-mode atomic force microscopy. A stamp for microCP was fabricated by pouring polydimethylsiloxane (PDMS) over a photolithographically prepared master. The patterned SAMs were prepared by two methods. One is called the wet-inking method, in which inking was done by placing a thiol ethanol solution for 30 s on the stamp and then removing the excess ink solution under a stream of nitrogen. The other is called the contact-inking method, in which a pad made of PDMS was dipped overnight in a thiol ethanol solution and then the stamp was placed on the inker pad impregnated with the thiol ethanol solution. The second step for pattern formation was the same for both of the two different microCP methods. Namely, the gold surfaces stamped with alkanethiols were further reacted with a thiol terminating in COOH in ethanol. The resulting patterns with CH3- and COOH-terminated regions were analyzed by imaging the adhesive forces with the chemically modified gold coated AFM tips with a SAM of CH3 or COOH terminal functional groups.

Novel self-assembled monolayers of disulfides with bicyclo[2.2.2]octane moieties of Au(111).

A series of disulfides containing bicyclo[2.2.2]octane moieties have been synthesised and their self-assembled monolayers (SAMs) on Au(111) have been characterized using scanning tunnelling microscopy (STM).

A novel cleaning method of gold-coated atomic force microscope tips for their chemical modification

For chemical modification of gold-coated AFM tips with thiol or sulfide compounds, a new two-step precleaning procedure was studied. The two-step cleaning procedure involves (i) oxidation of organic contaminants on the AFM tips with ozone treatment and (ii) reduction of the oxidized gold surface by immersing the oxidized tip into pure hot ethanol at ca. 65 degrees C. The chemically modified tips prepared from gold-coated AFM tips precleaned by the two-step procedure gave almost the same tip characteristics as those chemically modified immediately after gold vapor deposition in a factory. The present two-step cleaning procedure can be used widely for chemical modification of commercially available gold-coated AFM tips with thiol or disulfide compounds for chemical force microscopy.

Chemical force microscopy of microcontact-printed self-assembled monolayers by pulsed-force-mode atomic force microscopy

A novel chemically sensitive imaging mode based on adhesive force detection by previously developed pulsed-force-mode atomic force microscopy (PFM-AFM) is presented. PFM-AFM enables simultaneous imaging of surface topography and adhesive force between tip and sample surfaces. Since the adhesive forces are directly related to interaction between chemical functional groups on tip and sample surfaces, we combined the adhesive force mapping by PFM-AFM with chemically modified tips to accomplish imaging of a sample surface with chemical sensitivity. The adhesive force mapping by PFM-AFM both in air and pure water with CH3- and COOH-modified tips clearly discriminated the chemical functional groups on the patterned self-assembled monolayers (SAMs) consisting of COOH- and CH3-terminated regions prepared by microcontact printing (microCP). These results indicate that the adhesive force mapping by PFM-AFM can be used to image distribution of different chemical functional groups on a sample surface. The discrimination mechanism based upon adhesive forces measured by PFM-AFM was compared with that based upon friction forces measured by friction force microscopy. The former is related to observed difference in interactions between tip and sample surfaces when the different interfaces are detached, while the latter depends on difference in periodic corrugated interfacial potentials due to Pauli repulsive forces between the outermost functional groups facing each other and also difference in shear moduli of elasticities between different SAMs.

Imaging of various surface properties of fluorescently labelled phospholipid Langmuir-Blodgett films with a combined scanning probe microscope.

We present results of phase separation of a single-component system of 1,2-dihexadecanoyl-sn-glycero-3-phospho-[N-(4-nitrobenz)-2-oxa-1,3-diazolyl]ethanolamine in which a liquid-condensed (LC) phase co-exists with a liquid-expanded (LE) phase. Domain formation in the co-existence region was studied using a newly developed combined scanning near-field optical microscope-atomic force microscope (SNOM-AFM). We demonstrate for the first time that the topographic, friction, fluorescence and surface potential distributions for a phase-separated single-component Langmuir-Blodgett film between the LE and LC phases can be simultaneously observed using the SNOM-AFM with a thin-step etched optical fibre probe.

Fluorescence imaging and spectroscopy of biomaterials in air and liquid by scanning near-field optical/atomic force microscopy.

We have developed scanning near-field optical/atomic force microscopy (SNOM/AFM). The SNOM/AFM uses a bent optical fiber simultaneously as a dynamic force AFM cantilever and a SNOM probe. Resonant frequency of the optical fiber cantilever is 15-40 kHz. Optical resolution of the SNOM/AFM images shows less than 50 nm. The SNOM/AFM system contains photon counting system and polychrometer/intensified coupled charge devise (ICCD) system to observe fluorescence image and spectrograph of micro areas, respectively. Cultured cells were stained with fluorescein isothiocyanate (FITC)-labeled anti-keratin antibody or FITC-labeled phalloidin after treatment with Triton X-100. Fluorescence and topographic images were obtained in air and water. The fluorescence images showed clear images of keratin and actin filaments. The SNOM/AFM is perfect to observe biomaterials in liquid with a liquid chamber while the topographic Images showed subcellular structures which correspond to keratin and actin filaments.

Development of near-field optic/atomic force microscope for biological materials in aqueous solutions.

This paper reports improvements of optical fiber cantilevers and the scanning near-field optical microscopy imaging of biological materials in liquid. In our scanning near-field optical/atomic-force microscope (SNOAM), the scanning of an optical fiber cantilever over the specimen was controlled by dynamic mode AFM to reduce damage to the probe and soft specimens. The typical resonant frequency of the optical fiber cantilever was 19.5 kHz, while it was 23.0 kHz in air. The Q-factor of the cantilever depended on the vibration amplitude and was typically 260-600 in air and 40-240 in water. The relationship between the vibration amplitude and the average sample-probe separation indicated that the cantilever worked in the non-contact mode in water, while it worked in the cyclic-contact mode in air. Cultured cells in aqueous solutions were visualized by the SNOAM, indicating that the SNOAM is suitable to observe soft specimens.