Res Jöhr

Kelvin probe force microscopy of nanocrystalline TiO2 photoelectrodes

Summary Dye-sensitized solar cells (DSCs) provide a promising third-generation photovoltaic concept based on the spectral sensitization of a wide-bandgap metal oxide. Although the nanocrystalline TiO2 photoelectrode of a DSC consists of sintered nanoparticles, there are few studies on the nanoscale properties. We focus on the microscopic work function and surface photovoltage (SPV) determination of TiO2 photoelectrodes using Kelvin probe force microscopy in combination with a tunable illumination system. A comparison of the surface potentials for TiO2 photoelectrodes sensitized with two different dyes, i.e., the standard dye N719 and a copper(I) bis(imine) complex, reveals an inverse orientation of the surface dipole. A higher surface potential was determined for an N719 photoelectrode. The surface potential increase due to the surface dipole correlates with a higher DSC performance. Concluding from this, microscopic surface potential variations, attributed to the complex nanostructure of the photoelectrode, influence the DSC performance. For both bare and sensitized TiO2 photoelectrodes, the measurements reveal microscopic inhomogeneities of more than 100 mV in the work function and show recombination time differences at different locations. The bandgap of 3.2 eV, determined by SPV spectroscopy, remained constant throughout the TiO2 layer. The effect of the built-in potential on the DSC performance at the TiO2/SnO2:F interface, investigated on a nanometer scale by KPFM measurements under visible light illumination, has not been resolved so far.

Characterization of individual molecular adsorption geometries by atomic force microscopy: Cu-TCPP on rutile TiO2 (110).

Functionalized materials consisting of inorganic substrates with organic adsorbates play an increasing role in emerging technologies like molecular electronics or hybrid photovoltaics. For such applications, the adsorption geometry of the molecules under operating conditions, e.g., ambient temperature, is crucial because it influences the electronic properties of the interface, which in turn determine the device performance. So far detailed experimental characterization of adsorbates at room temperature has mainly been done using a combination of complementary methods like photoelectron spectroscopy together with scanning tunneling microscopy. However, this approach is limited to ensembles of adsorbates. In this paper, we show that the characterization of individual molecules at room temperature, comprising the determination of the adsorption configuration and the electrostatic interaction with the surface, can be achieved experimentally by atomic force microscopy (AFM) and Kelvin probe force microscopy (KPFM). We demonstrate this by identifying two different adsorption configurations of isolated copper(ii) meso-tetra (4-carboxyphenyl) porphyrin (Cu-TCPP) on rutile TiO2 (110) in ultra-high vacuum. The local contact potential difference measured by KPFM indicates an interfacial dipole due to electron transfer from the Cu-TCPP to the TiO2. The experimental results are verified by state-of-the-art first principles calculations. We note that the improvement of the AFM resolution, achieved in this work, is crucial for such accurate calculations. Therefore, high resolution AFM at room temperature is promising for significantly promoting the understanding of molecular adsorption.

Ordered heteromolecular overlayers formed by metal phthalocyanines and porphyrins on rutile titanium dioxide surface studied at room temperature.

Molecular heterostructures are formed from meso-tetraphenyl porphyrins-Zn(II) (ZnTPP) and Cu(II)-phthalocyanines (CuPc) on the rutile TiO2(011) surface. We demonstrate that ZnTPP molecules form a quasi-ordered wetting layer with flat-lying molecules, which provides the support for growth of islands comprised of upright CuPc molecules. The incorporation of the ZnTPP layer and the growth of heterostructures increase the stability of the system and allow for room temperature scanning tunneling microscopy (STM) measurements, which is contrasted with unstable STM probing of only CuPc species on TiO2. We demonstrate that within the CuPc layer the molecules arrange in two phases and we identify molecular dimers as basic building blocks of the dominant structural phase.

Electrospray deposition of structurally complex molecules revealed by atomic force microscopy

Advances in organic chemistry allow the synthesis of large, complex and highly functionalized organic molecules having potential applications in optoelectronics, molecular electronics and organic solar cells. Their integration into devices as individual components or highly ordered thin-films is of paramount importance to address these future prospects. However, conventional sublimation techniques in vacuum are usually not applicable since large organic compounds are often non-volatile and decompose upon heating. Here, we prove by atomic force microscopy and scanning tunneling microscopy, the structural integrity of complex organic molecules deposited onto an Au(111) surface using electrospray ionisation deposition. High resolution AFM measurements with CO-terminated tips unambiguously reveal their successful transfer from solution to the gold surface in ultra-high vacuum without degradation of their chemical structures. Furthermore, the formation of molecular structures from small islands to large and highly-ordered self-assemblies of those fragile molecules is demonstrated, confirming the use of electrospray ionisation to promote also on-surface polymerization reactions of highly functionalized organic compounds, biological molecules or molecular magnets.

Thermally induced anchoring of a zinc-carboxyphenylporphyrin on rutile TiO2 (110)

Functionalization of surfaces has become of high interest for a wealth of applications such as sensors, hybrid photovoltaics, catalysis, and molecular electronics. Thereby molecule-surface interactions are of crucial importance for the understanding of interface properties. An especially relevant point is the anchoring of molecules to surfaces. In this work, we analyze this process for a zinc-porphyrin equipped with carboxylic acid anchoring groups on rutile TiO2 (110) using scanning probe microscopy. After evaporation, the porphyrins are not covalently bound to the surface. Upon annealing, the carboxylic acid anchors undergo deprotonation and bind to surface titanium atoms. The formation of covalent bonds is evident from the changed stability of the molecule on the surface as well as the adsorption configuration. Annealed porphyrins are rotated by 45° and adopt another adsorption site. The influence of binding on electronic coupling with the surface is investigated using photoelectron spectroscopy. The o...

Scanning probe microscopy studies on the adsorption of selected molecular dyes on titania.

Titanium dioxide, or titania, sensitized with organic dyes is a very attractive platform for photovoltaic applications. In this context, the knowledge of properties of the titania–sensitizer junction is essential for designing efficient devices. Consequently, studies on the adsorption of organic dyes on titania surfaces and on the influence of the adsorption geometry on the energy level alignment between the substrate and an organic adsorbate are necessary. The method of choice for investigating the local environment of a single dye molecule is high-resolution scanning probe microscopy. Microscopic results combined with the outcome of common spectroscopic methods provide a better understanding of the mechanism taking place at the titania–sensitizer interface. In the following paper, we review the recent scanning probe microscopic research of a certain group of molecular assemblies on rutile titania surfaces as it pertains to dye-sensitized solar cell applications. We focus on experiments on adsorption of three types of prototypical dye molecules, i.e., perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), phtalocyanines and porphyrins. Two interesting heteromolecular systems comprising molecules that are aligned with the given review are discussed as well.

Ordering of Zn-centered porphyrin and phthalocyanine on TiO2(011): STM studies

Zn(II)phthalocyanine molecules (ZnPc) were thermally deposited on a rutile TiO2(011) surface and on Zn(II)meso-tetraphenylporphyrin (ZnTPP) wetting layers at room temperature and after elevated temperature thermal processing. The molecular homo- and heterostructures were characterized by high-resolution scanning tunneling microscopy (STM) at room temperature and their geometrical arrangement and degree of ordering are compared with the previously studied copper phthalocyanine (CuPc) and ZnTPP heterostructures. It was found that the central metal atom may play some role in ordering and growth of phthalocyanine/ZnTPP heterostructures, causing differences in stability of upright standing ZnPc versus CuPc molecular chains at given thermal annealing conditions.