Yan Busby

Interface and Composition Analysis on Perovskite Solar Cells

Organometal halide (hybrid) perovskite solar cells have been fabricated following four different deposition procedures and investigated in order to find correlations between the solar cell characteristics/performance and their structure and composition as determined by combining depth-resolved imaging with time-of-flight secondary ion mass spectrometry (ToF-SIMS), X-ray photoelectron spectroscopy (XPS), and analytical scanning transmission electron microscopy (STEM). The interface quality is found to be strongly affected by the perovskite deposition procedure, and in particular from the environment where the conversion of the starting precursors into the final perovskite is performed (air, nitrogen, or vacuum). The conversion efficiency of the precursors into the hybrid perovskite layer is compared between the different solar cells by looking at the ToF-SIMS intensities of the characteristic molecular fragments from the perovskite and the precursor materials. Energy dispersive X-ray spectroscopy in the STEM confirms the macroscopic ToF-SIMS findings and allows elemental mapping with nanometer resolution. Clear evidence for iodine diffusion has been observed and related to the fabrication procedure.

Strain relaxation in high Ge content SiGe layers deposited on Si

We have used Raman spectroscopy, transmission electron microscopy, x-ray diffraction, and x-ray photoemission spectroscopy to investigate strain relaxation mechanism of Si0.22Ge0.78 heteroepitaxial layer deposited on Si substrates in tensile, neutral, and compressive strain conditions. The three regimes have been obtained by interposing between the SiGe layer and the substrate a fully relaxed Ge layer, a partially relaxed Ge layer, or growing directly the alloy on Si. We found that the deposition of a Ge buffer layer prior to the growth of the SiGe is very promising in view of the realization of thin virtual substrates on silicon to be used for the deposition of strain-controlled high Ge content SiGe alloys. We demonstrate that this is mainly due to the strain relaxation mechanism in the Ge layer occurring via insertion of pure edge 90° misfit dislocations (MDs) and to the confinement of threading arms in to the Ge layer due to a second MD network formed at the SiGe/Ge heterointerface.

Direct observation of conductive filament formation in Alq3 based organic resistive memories

This work explores resistive switching mechanisms in non-volatile organic memory devices based on tris(8-hydroxyquinolie)aluminum (Alq3). Advanced characterization tools are applied to investigate metal diffusion in ITO/Alq3/Ag memory device stacks leading to conductive filament formation. The morphology of Alq3/Ag layers as a function of the metal evaporation conditions is studied by X-ray reflectivity, while depth profile analysis with X-ray photoelectron spectroscopy and time-of-flight secondary ion mass spectrometry is applied to characterize operational memory elements displaying reliable bistable current-voltage characteristics. 3D images of the distribution of silver inside the organic layer clearly point towards the existence of conductive filaments and allow for the identification of the initial filament formation and inactivation mechanisms during switching of the device. Initial filament formation is suggested to be driven by field assisted diffusion of silver from abundant structures formed during the top electrode evaporation, whereas thermochemical effects lead to local filament inactivation.

Conduction band intersubband transitions in Ge/SiGe quantum wells

In this letter we present the experimental evidence of intersubband absorption in the conduction band of compressively strained germanium quantum wells bounded by Ge-rich SiGe barriers. The measured absorption energies are in the terahertz range and are interpreted by means of tight binding calculations which include self-consistent band-bending and depolarization effects. From the comparison of experimental and numerical results a conduction band offset along the L line of about 120 meV has been estimated for the studied heterostructures.

Mesoscopic Perovskite Light-Emitting Diodes

Solution-processed hybrid bromide perovskite light-emitting-diodes (PLEDs) represent an attractive alternative technology that would allow overcoming the well-known severe efficiency drop in the green spectrum related to conventional LEDs technologies. In this work, we report on the development and characterization of PLEDs fabricated using, for the first time, a mesostructured layout. Stability of PLEDs is a critical issue; remarkably, mesostructured PLEDs devices tested in ambient conditions and without encapsulation showed a lifetime well-above what previously reported with a planar heterojunction layout. Moreover, mesostructured PLEDs measured under full operative conditions showed a remarkably narrow emission spectrum, even lower than what is typically obtained by nitride- or phosphide-based green LEDs. A dynamic analysis has shown fast rise and fall times, demonstrating the suitability of PLEDs for display applications. Combined electrical and advanced structural analyses (Raman, XPS depth profiling, and ToF-SIMS 3D analysis) have been performed to elucidate the degradation mechanism, the results of which are mainly related to the degradation of the hole-transporting material (HTM) and to the perovskite-HTM interface.

Controlled Distribution and Clustering of Silver in Ag-DLC Nanocomposite Coatings Using a Hybrid Plasma Approach.

Incorporation of selected metallic elements into diamond-like carbon (DLC) has emerged as an innovative approach to add unique functional properties to DLC coatings, thus opening up a range of new potential applications in fields as diverse as sensors, tribology, and biomaterials. However, deposition by plasma techniques of metal-containing DLC coatings with well-defined structural properties and metal distribution is currently hindered by the limited understanding of their growth mechanisms. We report here a silver-incorporated diamond-like carbon coating (Ag-DLC) prepared in a hybrid plasma reactor which allowed independent control of the metal content and the carbon film structure and morphology. Morphological and chemical analyses of Ag-DLC films were performed by atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy. The vertical distribution of silver from the surface toward the coating bulk was found to be highly inhomogeneous due to top surface segregation and clustering of silver nanoparticles. Two plasma parameters, the sputtered Ag flux and ion energy, were shown to influence the spatial distribution of silver particles. On the basis of these findings, a mechanism for Ag-DLC growth by plasma was proposed.

Controlling mesoscopic phase separation near electronic topological transitions via quenched disorder in ternary diborides

A phase separation driven by the negative compressibility of the electron gas, near electronic topological transitions (ETT), could drive the system at the verge of a catastrophe. We show here that the metastable phases very close to the ETT transition are observed in a mesoscopic phase separation (MePhS) driven by the quenched lattice disorder. By using high resolution synchrotron radiation x-ray powder diffraction we have identified the MePhS for the intermetallic ternary Mg1−x Alx B2 in the proximity of two ETTs: the first at x1 = 0. 1a nd the second at x2 = 0.3. We have identified the competition between a first ‘relaxed’ (R) hole poor and a second ‘tense’ (T) hole rich phase, and by micro-Raman we observe the splitting of the in-plane phonon E2g mode in the proximity of the first ETT at x = 0.1. The anisotropic quenched disorder due to a random distribution of Al 3+ and Mg 2+ ions both in the axial (c axis) direction and planar (ab plane) direction, probed by x-ray diffraction and Raman data, is proposed to be the physical variable that allows the formation of metastable phases near the critical points of electronic topological transitions, where Feshbach shape resonances in interband pairing amplifies the superconducting critical temperature. (Some figures in this article are in colour only in the electronic version) Q.1

Chemical analysis of the interface in bulk-heterojunction solar cells by X-ray photoelectron spectroscopy depth profiling

Despite the wide use of blends combining an organic p-type polymer and molecular fullerene-based electron acceptor, the proper characterization of such bulk heterojunction materials is still challenging. To highlight structure-to-function relations and improve the device performance, advanced tools and strategies need to be developed to characterize composition and interfaces with sufficient accuracy. In this work, high-resolution X-ray photoelectron spectroscopy (XPS) is combined with very low energy argon ion beam sputtering to perform a nondestructive depth profile chemical analysis on full Al/P3HT:PCBM/PEDOT:PSS/ITO (P3HT, poly(3-hexylthiophene); PCBM, [6,6]-phenyl-C61-butyric acid methyl ester; PEDOT, poly(3,4-ethylenedioxythiophene; PSS, polystyrenesulfonate; ITO, indium tin oxide) bulk-heterojunction solar cell device stacks. Key information, such as P3HT and PCBM composition profiles and Al-PCBM chemical bonding, are deduced in this basic device structure. The interface chemical analysis allows us to evidence, with unprecedented accuracy, the inhomogeneous distribution of PCBM, characterized by a strong segregation toward the top metal electrode. The chemical analysis high-resolution spectra allows us to reconstruct P3HT/PCBM ratio through the active layer depth and correlate with the device deposition protocol and performance. Results evidence an inhomogeneous P3HT/PCBM ratio and poorly controllable PCBM migration, which possibly explains the limited light-to-power conversion efficiency in this basic device structure. The work illustrates the high potential of XPS depth profile analysis for studying such organic/inorganic device stacks.

Resistive switching based on filaments in metal/PMMA/metal thin film devices

The working mechanism of unipolar organic resistive switching thin-film devices is investigated. On the basis of a metal/poly(methyl methacrylate)/metal model system, direct spectroscopic evidence for filament formation is obtained by three-dimensional (3D) imaging with time-of-flight secondary ion mass spectrometry. By means of alternative fabrication methods the claimed influence of metal implantation in the organic layer during fabrication is ruled out. Further, the stability of the resistive switches under oxygen and humidity is investigated leading to a deeper understanding of the processes governing the formation and rupture of filaments.

XPS depth profiles of organo lead halide layers and full perovskite solar cells by variable-size argon clusters

Organic and inorganic materials are more and more frequently combined in high-performance hybrid electronic and photonic devices. For such multilayered stacks, the identification of layers and interface defects by depth profile analysis is a challenging task, especially because of the possible ion beam induced modifications. This is particularly true for perovskite solar cells stacks that in a mesoscopic structure usually combine a metal electrode, a mesoscopic conductive oxide layer, an intrinsically hybrid light absorber, an organic hole extraction layer and a metal counter electrode. While depth profile analysis with X-ray photoelectron spectroscopy (XPS) was already applied to investigate these devices, the X-ray and ion beam induced modifications on such hybrid layers have not been previously investigated. In this work we compare the profiles obtained with monatomic Ar+ beam at different energies, with the ones obtained with argon ion clusters (Arn+) with different sizes (150<n<1000) and energies (up to 8 keV). A systematic study is performed on full mesoscopic perovskite (CH3NH3PbI3) solar cells and on model hybrid samples ((FAxCs1-xPbI3)0.85 (MAPbBr3)0.15)/TiO2). The results show that for monatomic beams, the implantation of positively charged atoms induces the surface diffusion of free iodine species from the perovskite which modifies the I/Pb ratio. Moreover, lead atoms in the metallic state (Pb0 ) are found to accumulate at the bottom of the perovskite layer where the Pb0 /Pbtot fraction reaches 50%. With argon clusters, the ion beam induced diffusion of iodine is reduced only when the etch rate is sufficiently high to ensure a profile duration comparable with low-energy Ar+. Convenient erosion rates are obtained only for n=300 and n=500 clusters at 8 keV, which have also the advantage of preserving the TiO2 surface chemistry. However, with argon cluster ions, Pb0 particles in the perovskite are less efficiently sputtered which leads to the increase of the Pb0 /Pbtot fraction (up to 75%) at the perovskite/TiO2 interface. Finally, ion beam and X-ray induced artifacts on perovskite absorbers can be reasonably neglected for fast analysis conditions in which the exposure time is limited to few hours.