Maciej Krzywiecki

Zinc oxide as a defect-dominated material in thin films for photovoltaic applications – experimental determination of defect levels, quantification of composition, and construction of band diagram

In the present work, thin ZnO layers were synthesized by the sol-gel method with subsequent spin-coating on Si(100). We show that the detailed analysis of lab-recorded photoemission spectra in combination with Kelvin probe data yielded the work function, ionization energy, and valence band - Fermi level separation - and hence enabled the construction of band diagrams of the examined layers. With small modifications in preparation, very different films can be obtained. One set shows a homogeneous depth-dependent n carrier distribution, and another a significant carrier concentration gradient from n-type conductivity to almost metal-like n(+) character. Likewise, the surface morphology can be tuned from a uniform, compact surface with spherical single-nm sized grain-like features to a structured surface with 5-10 nm tall crystallites with (002) dominating crystal orientation. Based on the band-bending and the energy levels observed, defects of contradictory nature, i.e. acceptor-donor-trap (ADT) properties, were identified. These defects may be groups of point defects, with opposite character. The ADT states affect the energy levels of the oxide layers and due to their nature cannot be considered in the photoemission experiment as mutually independent. The versatile nature of the synthesis provides us with the opportunity to tune the properties with a high degree of freedom, at low processing costs, yielding layers with an exotic electronic structure. Such layers are interesting candidates for applications in photovoltaic and nanoelectronic devices.

Correlation between morphology and local thermal properties of iron (II) phthalocyanine thin layers

The effect of substrate temperature and post-deposition annealing temperature on the surface morphology, topography and local thermal properties of iron(II) phthalocyanine (FePc) 500 nm thick films was investigated. The investigations were conducted by a combination of scanning probe microscopies (atomic force microscopy, scanning thermal microscopy) and scanning electron microscopy with structural (x-ray diffraction) and chemical (energy-dispersive x-ray spectroscopy) analysis. FePc is always obtained in its α-form. While for heated substrates, FePc crystallites lie flat on the surface, so post-deposition annealing leads to vertically oriented crystallites. The total surface area obtained does not depend significantly on the substrate temperature, while it is strongly dependent on the annealing temperature. For both groups of samples, the increase of roughness was accompanied by a decrease of the samples thermal resistivity, which is in agreement with the picture of a decreased number of grain boundaries resulting in higher heat transport. The results obtained here show that the exposed surface area of an organic film strongly depends on the thermal treatments; hence surface morphology can be tailored to particular needs.

Application of scanning thermal microscopy for investigation of thermal boundaries in multilayered photonic structures

In current work the application of modified Scanning Thermal Microscopy (SThM) technique for thermal imaging of multilayered periodic photonic structures is presented. The measurements were carried out using non-standard operation mode of the SThM. The thermal probe was driven by the sum of DC and small AC currents. The main advantages of presented approach are mechanical stability of the probe during measurements and high sensitivity of AC signal detection by the use of lock-in amplifier. The amplitude and phase components of probe response signal are used for visualization and analysis of the thermal properties of the layer interfaces. Basing on topographic and thermal signals the thermal boundaries between layers were revealed and the periodicity of the structure was analyzed. Presented experiment indicates that the proposed method provides spatial resolution at least about 30% better than 100 nm, which is considered for standard nanofabricated thermal probes. Therefore, proposed technique may be successfully used for the thermal boundaries mapping, as well as for the high-resolution nanoscale imaging of thermal properties distribution. The results prove that thermal imaging provides additional information to that obtained by standard AFM imaging.

Impact of air exposure and annealing on the chemical and electronic properties of the surface of SnO2 nanolayers deposited by rheotaxial growth and vacuum oxidation

In this paper the SnO2 nanolayers were deposited by rheotaxial growth and vacuum oxidation (RGVO) and analyzed for the susceptibility to ambient-air exposure and the subsequent recovery under vacuum conditions. Particularly the surface chemistry of the layers, stoichiometry and level of carbon contamination, was scrutinized by X-ray photoelectron spectroscopy (XPS). The layers were tested i) pristine, ii) after air exposure and iii) after UHV annealing to validate perspective recovery procedures of the sensing layers. XPS results showed that the pristine RGVO SnO2 nanolayers are of high purity with a ratio [O]/[Sn] = 1.62 and almost no carbon contamination. After air exposure the relative [O]/[Sn] concentration increased to 1.80 while maintaining a relatively low level of carbon contaminants. Subsequent UHV annealing led to a relative [O]/[Sn] concentration comparable to the pristine samples. The oxidation resulted in a variation of the distance between the valence band edge and the Fermi level energy. This was attributed to oxygen diffusion through the porous SnO2 surface as measured by atomic force microscopy.

Towards monomaterial p-n junctions: Single-step fabrication of tin oxide films and their non-destructive characterisation by angle-dependent X-ray photoelectron spectroscopy

The application of a non-destructive method for characterization of electronic structure of an ultra-thin SnO1<x<2 layer synthesized by spin coating on Si wafers was demonstrated. Utilizing angle dependent XPS, we quantified stoichiometry changes inside the SnO1<x<2 layers of thickness comparable with the electron attenuation length. The O/Sn concentration varied from 1.25 near the SnOx surface to 1.10 near the substrate/overlayer interface. Deviations from ideal stoichiometry are caused by defects, and defect levels affect the band structure of the SnOx layers. By investigation of the valence band region, followed by main core level position tracking, changes of electronic parameters like energy levels shift were identified. The results indicated a downward energy levels shift by 0.45 eV in SnOx layers at the SiO2/SnOx interface. In combination with the detected upward energy levels shift in the substrates electronic structure, these results suggest a negative charge displacement across the SiO2 layer. ...

Chirality-sorted carbon nanotube films as high capacity electrode materials

Carbon nanomaterials show great promise for a wide range of applications due to their excellent physicochemical and electrical properties. Since their discovery, the state-of-the-art has expanded the scope of their application from scientific curiosity to impactful solutions. Due to their tunability, carbon nanomaterials can be processed into a wide range of formulations and significant scope exists to couple carbon structures to electronic and electrochemical applications. In this paper, the electrochemical performance of various types of CNT films, which differ by the number of walls, diameter, chirality and surface chemistry is presented. Especially, chirality-sorted (6,5)- and (7,6)-based CNT films are shown to possess a high charge storage capacity (up to 621.91 mC cm−2), areal capacitance (262 mF cm−2), significantly increased effective surface area and advantageous charge/discharge characteristics without addition of any external species, and outperform many other high capacity materials reported in the literature. The results suggest that the control over the CNT structure can lead to the manufacture of macroscopic CNT devices precisely tailored for a wide range of applications, with the focus on energy storage devices and supercapacitors. The sorted CNT macroassemblies show great potential for energy storage technologies to come from R&D laboratories into real life.

Cyclodextrin inhibits zinc corrosion by destabilizing point defect formation in the oxide layer

Corrosion inhibitors are added in low concentrations to corrosive solutions for reducing the corrosion rate of a metallic material. Their mechanism of action is typically the blocking of free metal surface by adsorption, thus slowing down dissolution. This work uses electrochemical impedance spectroscopy to show the cyclic oligosaccharide β-cyclodextrin (β-CD) to inhibit corrosion of zinc in 0.1M chloride with an inhibition efficiency of up to 85%. Only a monomolecular adsorption layer of β-CD is present on the surface of the oxide covered metal, with Raman spectra of the interface proving the adsorption of the intact β-CD. Angular dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to extract a band-like diagram of the β-CD/ZnO interface, showing a large energy level shift at the interface, closely resembling the energy level alignment in an n–p junction. The energy level shift is too large to permit further electron transfer through the layer, inhibiting corrosion. Adsorption hence changes the defect density in the protecting ZnO layer. This mechanism of corrosion inhibition shows that affecting the defect chemistry of passivating films by molecular inhibitors maybe a viable strategy to control corrosion of metals.