Using a vertical titania (TiO(2)) nanotube array, an inverted polymer solar cell was constructed with power conversion efficiency up to 2.71%. In this study, self-organized TiO(2) nanotubes arrays were grown by anodizing Ti metal in glycerol electrolyte containing 0.5 wt% NH(4)F and 1.0 wt% H(2)O with 20 V potential. The tube length (∼100 nm) was controlled by the thickness of the sputtered titanium layer on the indium-tin oxide (ITO) substrate. The diameter of the tube was approximately 15-25 nm. After annealing in air at 500 °C for 1 h, nanotubes arrays were crystallized to the anatase phase from the initial amorphous state. Following the infiltration of polymeric semiconductor (poly(3-hexylthiophene) and (6,6)-phenyl C(60) butyric acid methyl ester, P3HT:PCBM), the filled TiO(2) layer had an optical absorption over a range from UV to visible light. The high surface-to-volume ratio of the nanotube arrays structure increased the effective area of the active region. The high efficiency of our solar cell is attributed to the vertical TiO(2) nanotube array's enhanced conduction of photo-induced current due to its charge transport capability.

Solution processable fullerene and copolymer bulk heterojunctions are widely used as the active layers of solar cells. In this work, scanning time-of-flight secondary ion mass spectrometry (ToF-SIMS) is used to examine the distribution of [6,6]phenyl-C61-butyric acid methyl ester (PCBM) and regio-regular poly(3-hexylthiophene) (rrP3HT) that forms the bulk heterojunction. The planar phase separation of P3HT:PCBM is observed by ToF-SIMS imaging. The depth profile of the fragment distribution that reflects the molecular distribution is achieved by low energy Cs(+) ion sputtering. The depth profile clearly shows a vertical phase separation of P3HT:PCBM before annealing, and hence, the inverted device architecture is beneficial. After annealing, the phase segregation is suppressed, and the device efficiency is dramatically enhanced with a normal device structure. The 3D image is obtained by stacking the 2D ToF-SIMS images acquired at different sputtering times, and 50 nm features are clearly differentiated. The whole imaging process requires less than 2 h, making it both rapid and versatile.

Alkanethiol anchored self-assembled monolayers (SAMs) on gold are widely used to immobilize and detect molecules including DNA and proteins. Most of these molecules are covalently bonded with the SAM on the Au surface and cannot be released easily. By using different functional groups, the interfacial charge of SAMs can be selected, and thus, they can be considered as adaptors for immobilizing and releasing materials selectively through electrostatic interaction under given conditions. In this work, as an additional factor to control the surface charge, SAMs with mixed functional groups are presented, and it is demonstrated that the isoelectric point (IEP) can be tailored by the ratio of functional groups. Using carboxylic acid- and amine-SAM on gold substrates as an example, isoelectric points (IEPs) from 3.5 to 6.5 can be obtained arbitrarily. The ratio between the functional groups on the surface was quantified by X-ray photoelectron spectrometry (XPS) and was found to be slightly different from the deposition solution. The homogeneous spatial distribution of the functional groups was determined with scanning electrical potential microscopy (SEPM). The interfacial charge of SAMs with mixed functional groups on gold was investigated by electrokinetic analysis in aqueous electrolyte solutions.

By sputtering organic films with 10 kV, 10 nA C60+ and 0.2 kV, 300 nA Ar+ ion beams concurrently and analyzing the newly exposed surface with X-ray photoelectron spectroscopy, organic thin-film devices including an organic light-emitting diode and a polymer solar cell with an inverted structure are profiled. The chemical composition and the structure of each layer are preserved and clearly observable. Although C60+ sputtering is proven to be useful for analyzing organic thin-films, thick organic-devices cannot be profiled without the low-energy Ar+ beam co-sputtering due to the nonconstant sputtering rate of the C60+ beam. Various combinations of ion-beam doses are studied in this research. It is found that a high dosage of the Ar+ beam interferes with the C60+ ion beam, and the sputtering rate decreases with increasing the total ion current. The results suggest that the low-energy single-atom projectile can disrupt the atom deposition from the cluster ion beams and greatly extend the application of the cluster ion-sputtering. By achievement of a steady sputtering rate while minimizing the damage accumulation, this research paves the way to profiling soft matter and organic electronics.

Amine-terminated self-assembled monolayers (SAMs) on Au surfaces are commonly used to immobilize various types of molecules, including DNA and proteins. However, little is known about the stability of these types of surfaces. In this work, it was observed that the surface potential (as well as the isoelectric point) of amine-bearing SAMs on flat gold substrates changed significantly with time, indicating that the surface functional group is not stable under ambient conditions (standard temperature and pressure). Contact angle analysis indicated that after degradation, the polar component of the interfacial force decreased and the dispersion component increased. These results indicate that the surface has undergone a chemical transformation. X-ray photoelectron spectroscopy (XPS) was used to detect changes in the chemical state of the surface nitrogen atoms. The chemical shift of the binding energy indicates that the nitrogen is partially oxidized. Using time-of-flight secondary ion mass spectrometry (ToF-SIMS), the oxidation of the amino groups to nitroso groups was evident, as was the previously reported oxidation of the thiol groups to sulfonate groups. Two methods for retarding the oxidation of the amine functional group are presented in this work. By isolating the SAM from either light or air, the oxidation is suppressed and the surface properties are preserved. In other words, the shelf life of the amine-modified gold substrates is prolonged. This result suggests that the oxidation is either photocatalyzed or photoinduced.

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on CBP, were studied. In all cases, a clear multilayer structure was observed. The chemical composition and elemental state were preserved after C 60 + ion sputtering. The sputter rate was found to decrease with sputtering time. This is due to the deposition of amorphous carbon on the surface, with the rate of implantation highly dependent on the surface interacting with the ion beam.Owing to its high surface sensitivity, X-ray photoelectron spectroscopy (XPS, electron spectroscopy for chemical analysis) is one of the most common techniques for studying the outer surface of metals, semiconductors, ceramics, and polymers. There is often interest in not only the top atomic or molecular layers but also the depth distribution of elements in the region close to the surface. For this application, in situ ion sputtering is generally used.Argon sputtering is the most accepted technique for removing surface contaminants and obtaining information on the depth distribution of an element in a sample. However, this erosion technique is known to cause severe damage to organic samples 1 owing to preferential sputtering or sputter reduction. Hence, information on the chemical composition and the chemical state of elements is lost and argon sputtering cannot be used for depth profiling of polymer materials. Such damage is still observable at low (0.25 kV) beam energy 2 and with other ion species. 3Recently, buckminsterfullerene (C 60 ) ion guns were constructed by Ionoptika Ltd. 4,5 and were used to generate secondary ions for studying polymer surfaces. Molecular dynamics calculations suggested that C 60 + ions are more efficient in removing material 6 and leave behind a relatively thin damage layer. 7 The calculations also suggest that a C 60 + ion beam allows chemical imaging at higher sensitivity and better depth resolution. 8 Using C 60 as the primary ion in secondary ion mass spectroscopy (SIMS), organic materials including Irganox 1010, 9 PMMA, 10,11 barium arachidate, 12 and biological membranes 13 were studied. The results confirm that the sputter yield is increased and damage to the chemical structure is reduced. However, the composition of mixtures cannot be quantitatively analyzed with SIMS due to the nature of the ionization process. In order to gain more insights of composite systems, a direct quantifiable technique like XPS is desirable. Bulk polymers including PET 4 and PTFE 14 were also cleaned with a C 60 ion beam, and the chemical states of elements observed by XPS remained the same after the cleaning. In the present study, materials important for thin-film organic electronics, e.g., organic light-emitting diode (OLED) devices, were investigated by XPS using C 60 + sputtering. EXPERIMENTAL SECTIONXPS spectra were recorded on a PHI 5000 VersaProbe (ULVAC-PHI, Chigasaki, Japan) system using a microfocused (100 µm, 25 W) Al X-ray beam with a photoelectron takeoff angle of 45°. A dual-beam charge neutralizer (7-V Ar + and 30-V electron

In response to the growing need for metal oxide nanotubes and nanowires for nanoelectronic applications, polycrystalline titanate nanotubes are synthesized in this work at near-ambient conditions without the application of an external electric field or pre-existing solids. Nanotubes of complicated metal oxides including strontium titanate and barium titanate are fabricated inside anodic aluminum oxide (AAO) templates from aqueous solutions using a simple, inexpensive, reproducible, and environmentally friendly procedure. The deposition solution is prepared by dissolving ammonium hexafluorotitanate and strontium nitrate in a boric acid solution at a pH of 2.5. The typical lengths of SrTiO(3) nanotubes are 5-30 microm, with an average diameter of approximately 250 nm, which is defined by the pore diameter of the AAO template. After annealing at 800 degrees C in air, the resulting nanotubes are polycrystalline cubic SrTiO(3). The Sr:Ti ratio in the nanotube is controlled by the hydrolysis of TiF(6)(2-) ions, and the concentration of Sr(2+) and stoichiometric SrTiO(3) nanotubes can be obtained. As an additional controlling factor, the surface properties of the AAO can be modified by (octadecyl)trichlorosilane. Barium titanate is also prepared in a similar manner with barium nitrate and ammonium hexafluorotitanate as precursors. The polycrystalline cubic BaTiO(3) nanotubes are 12-30 microm long and approximately 250 nm in diameter.