Morphology and material stability in polymer solar cells

Polymer solar cells are promising in that they are inexpensive to produce, and due to their mechanical flexibility have the potential for use in applications not possible for more traditional types of solar cells. The performance of polymer solar cells depends strongly on the distribution of electron donor and acceptor material in the active layer. Understanding the connection between morphology and performance as well as how to control the morphology, is therefore of great importance. Furthermore, improving the lifetime of polymer solar cells has become at least as important as improving the efficiency.   In this thesis, the relation between morphology and solar cell performance is studied, and the material stability for blend films of the thiophene-quinoxaline copolymer TQ1 and the fullerene derivatives PCBM and PC70BM. Atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) are used to investigate the lateral morphology, secondary ion mass spectrometry (SIMS) to measure the vertical morphology and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to determine the surface composition. Lateral phase-separated domains are observed whose size is correlated to the solar cell performance, while the observed TQ1 surface enrichment does not affect the performance. Changes to the unoccupied molecular orbitals as a result of illumination in ambient air are observed by NEXAFS spectroscopy for PCBM, but not for TQ1. The NEXAFS spectrum of PCBM in a blend with TQ1 changes more than that of pristine PCBM. Solar cells in which the active layer has been illuminated in air prior to the deposition of the top electrode exhibit greatly reduced electrical performance. The valence band and absorption spectrum of TQ1 is affected by illumination in air, but the effects are not large enough to account for losses in solar cell performance, which are mainly attributed to PCBM degradation at the active layer surface.

Trasporte eléctrico y magnetismo en sistemas electrodo - aislante - electrodo: hacia el desarrollo de dispositivos del tipo juntura tunel.

La presente tesis es un estudio dedicado a la optimización y desarrollo de sistemas del tipo juntura túnel. La metodología utilizada para la realización de la tesis consistió, en primer lugar, en la optimización de las componentes independientes de la juntura túnel: electrodo y barrera aislante. Posteriormente se optimizaron los procesos de fabricación para el desarrollo y caracterización de dispositivos del tipo juntura túnel en su forma final. En la primera parte de la tesis se analizan detalladamente los resultados obtenidos de la caracterización eléctrica y topografica de barreras aislantes en sistemas electrodo - barrera. Los sistemas bicapas estudiados, GdBa_2Cu_3_7/SrTiO_3, Nb/Ba_0,05Sr_0,95TiO_3 y YBa_2Cu_3O_7/SrTiO_3, fueron caracterizados utilizando un microscopio de fuerza atómica en modo conductor. Se propuso un modelo fenomenológico basado en los resultados experimentales, que permitió la obtención de parámetros críticos para el desarrollo de dispositivos del tipo juntura túnel con nuevas funcionalidades. La información obtenida de la caracterización de los sistemas bicapas (homogeneidad de crecimiento, baja densidad de defectos y de pinholes) indican un muy buen control de los parámetros de crecimiento de las barreras. Por otro lado, se obtuvo un buen comportamiento aislante para espesores mayores a 2 nm sin la presencia de pinholes en la barrera. La similitud en la estequiometría de las barreras (SrTiO_3) permitió comparar los distintos sistemas estudiados en términos de conductividad eléctrica. Se verificó que el modelo fenomenológico permite comparar la conductividad eléctrica de los sistemas mediante uno de los parámetros definidos en el modelo fenomenológico (obtenido de los ajustes lineales de las curvas I(V)). De los 3 sistemas estudiados, las bicapas GdBa_2Cu_3O_7/SrTiO_3 presentaron un mayor valor de longitud de atenuación de los portadores de carga a través de la barrera y una muy baja densidad de defectos superficiales. Las bicapas YBa_2Cu_3O_7/SrTiO_3 y Nb/Ba_0,05Sr_0,95TiO_3 permitieron validar el modelo fenomenológico propuesto para el análisis de la respuesta corriente - voltaje obtenida con el microscopio de fuerza atómica en modo conductor. La segunda parte de la tesis abarca conceptos de magnetismo y microfabricación para el desarrollo de junturas túnel magnéticas. Durante la caracterización de las películas ferromagnéticas individuales de Co_90Fe_10 (CoFe) se logró aumentar valor del campo coercitivo de films de 10 nm de espesor al incrementar la temperatura de depósito. Esto se debe a un aumento del tamaño de grano de los films. El aumento de la temperatura del sustrato durante el crecimiento influye en la morfología y las propiedades magnéticas de los films de CoFe favoreciendo la formación de granos y la pérdida del eje preferencial de magnetización. Estos resultados permitieron la fabricación de sistemas Co_90Fe_10/M_gO/Co_90Fe_10 con distintas orientaciones relativas accesibles con campo magnético para el estudio del acople magnético entre los films de CoFe. La caracterización eléctrica de estos sistemas, particularmente la respuesta corriente - voltaje obtenida con el microscopio de fuerza atómica en modo conductor, indicó que las propiedades de transporte eléctrico de las junturas presentan un alto grado de reproducibilidad. Se analizó además la inuencia del sustrato utilizado en la corriente túnel que atraviesa la barrera aislante. Por otro lado, se discuten los fenómenos relacionados a la optimización de las propiedades magnéticas de electrodos ferromagnéticos para la fabricación de junturas túnel Co_90Fe_10/MgO/Co_90Fe_10 y Co_90Fe_10/MgO /Fe_20Ni_80. En particular, se estudió el acople magnético entre capas ferromagnéticas y la inuencia del sustrato utilizado para el crecimiento de las tricapas. La optimización de los electrodos magnéticos involucró el análisis de la inuencia de la presencia de un aislante entre dos capas magnéticas en el acople de los electrodos. Se logró el desacople de films de 10 nm de Co_90Fe_10 y Fe_20Ni_80 separados por un espaciador de MgO de 2 nm. Finalmente se detallan los pasos para la fabricación de una red de junturas túnel magnéticas y su caracterización eléctrica a bajas temperaturas. El sistema estudiado fue la tricapa Co_90Fe_10 (10 nm)/M_gO (8 nm)/ Fe_20Ni_80 (10 nm) crecido sobre un sustrato de M_gO. La caracterización eléctrica confirmó la buena calidad de la junturas fabricadas. Las junturas obtenidas presentaron un comportamiento altamente resistivo (~ MΩ). Las mediciones de la corriente túnel en función de la temperatura permitieron descartar la presencia de pinholes en la barrera. El transporte de los portadores de carga es por efecto túnel a través de la barrera aislante. Las curvas de conductancia diferencial permitieron calcular el valor medio de la altura de la barrera de potencial (φ = 3.1 eV) a partir del modelo de Brinkman. Los resultados obtenidos en cada uno de los capítulos se complementan y son relevantes para la optimización de junturas túnel, debido a que brindan información crítica para su correcto funcionamiento. En la presente tesis se lograron obtener los primeros avances para la fabricación de arreglos de junturas túnel que permitan el desarrollo de dispositivos.

Size effects on self-assembly and melting of silver-alkanethiolate on inert surfaces

Self-assembled materials produced in the reaction between alkanethiol and Ag are characterized and compared. It is revealed that the size of the Ag substrate has a significant role in the self-assembly process and determines the reaction products. Alkanethiol adsorbs on the surface of Ag continuous planar thin films and only forms self-assembled monolayers (SAMs), while the reaction between alkanethiol and Ag clusters on inert surfaces is more aggressive and generates a significantly larger amount of alkanethiolate. Two dissimilar products are yielded depending on the size of the clusters. Small Ag clusters are more likely to be converted into multilayer silver-alkanethiolate (AgSR, R = CnH2n+1) crystals, while larger Ag clusters form monolayer-protected clusters (MPCs). The AgSR crystals are initially small and can ripen into large lamellae during thermal annealing. The crystals have facets and flat terraces with extended area, and have a strong preferred orientation in parallel with the substrate surface. The MPCs move laterally upon annealing and reorganize into a single-layer network with their separation distance approximately equal to the length of an extended alkyl chain. AgSR lamellar crystals grown on inert surfaces provide an excellent platform to study the melting characteristics of crystalline lamellae of polymeric materials with the thickness in the nanometer scale. This system is also unique in that each crystal has integer number of layers – magic-number size (thickness). The size of the crystals is controlled by adjusting the amount of Ag and the annealing temperature. X-ray diffraction (XRD) and atomic force microscopy (AFM) are combined to accurately determine the size (number of layers) of the lamellar crystals. The melting characteristics are measured with nanocalorimetry and show discrete melting transitions which are attributed to the magic-number sizes of the lamellar crystals. The discrete melting temperatures are intrinsic properties of the crystals with particular sizes. Smaller lamellar crystals with less number of layers melt at lower temperatures. The melting point depression is inversely proportional to the total thickness of the lamellae – the product of the number of layers and the layer thickness.

Plasma diagnostics and ITO film deposition by RF-assisted closed-field dual magnetron system

Deposition of indium tin oxide (ITO) among various transparent conductive materials on flexible organic substrates has been intensively investigated among academics and industrials for a whole new array of imaginative optoelectronic products. One critical challenge coming with the organic materials is their poor thermal endurances, considering that the process currently used to produce industry-standard ITO usually involves relatively high substrate temperature in excess of 200°C and post-annealing. A lower processing temperature is thus demanded, among other desires of high deposition rate, large substrate area, good uniformity, and high quality of the deposited materials. For this purpose, we developed an RF-assisted closed-field dual magnetron sputtering system. The “prototype” system consists of a 3-inch unbalanced dual magnetron operated at a closed-field configuration. An RF coil was fabricated and placed between the two magnetron cathodes to initiate a secondary plasma. The concept is to increase the ionization faction with the RF enhancement and utilize the ion energy instead of thermal energy to facilitate the ITO film growth. The closed-field unbalanced magnetrons create a plasma in the intervening region rather than confine it near the target, thus achieving a large-area processing capability. An RF-compensated Langmuir probe was used to characterize and compare the plasmas in mirrored balanced and closed-field unbalanced magnetron configurations. The spatial distributions of the electron density ne and electron temperature Te were measured. The density profiles reflect the shapes of the plasma. Rather than intensively concentrated to the targets/cathodes in the balanced magnetrons, the plasma is more dispersive in the closed-field mode with a twice higher electron density in the substrate region. The RF assistance significantly enhances ne by one or two orders of magnitude higher. The effect of various other parameters, such as pressure, on the plasma was also studied. The ionization fractions of the sputtered atoms were measured using a gridded energy analyzer (GEA) combined with a quartz crystal microbalance (QCM). The presence of the RF plasma effectively increases the ITO ionization fraction to around 80% in both the balanced and closed-field unbalanced configurations. The ionization fraction also varies with pressure, maximizing at 5-10 mTorr. The study of the ionization not only facilitates understanding the plasma behaviors in the RF-assisted magnetron sputtering, but also provides a criterion for optimizing the film deposition process. ITO films were deposited on both glass and plastic (PET) substrates in the 3-inch RF-assisted closed-field magnetrons. The electrical resistivity and optical transmission transparency of the ITO films were measured. Appropriate RF assistance was shown to dramatically reduce the electrical resistivity. An ITO film with a resistivity of 1.2×10-3 Ω-cm and a visible light transmittance of 91% was obtained with a 225 W RF enhancement, while the substrate temperature was monitored as below 110°C. X-ray photoelectron spectroscopy (XPS) was employed to confirm the ITO film stoichiometry. The surface morphology of the ITO films and its effect on the film properties were studied using atomic force microscopy (AFM). The prototype of RF-assisted closed-field magnetron was further extended to a larger rectangular shaped dual magnetron in a flat panel display manufacturing system. Similar improvement of the ITO film conductivities by the auxiliary RF was observed on the large-area PET substrates. Meanwhile, significant deposition rates of 25-42 nm/min were achieved.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.

Nanofiltration membranes modified with aromatic polyamide dendrimers active layers

This thesis describes the modification of the commercial TFC-S nanofiltration membrane with shape-persistent dendritic architectures. Amphiphilic aromatic polyamide dendrimers (G1-G3) are synthesized via a divergent approach and used for membrane modification by direct percolation. The permeate samples collected from the percolation experiments are analyzed by UV-Vis spectroscopy to instantly monitor the influence of dendrimer generations on percolation behaviors and new active layer formation. The membrane structures are further characterized by Rutherford backscattering spectrometry (RBS) and atomic force microscopy (AFM) techniques, suggesting a low-level accumulation of dendrimers inside the TFC-S NF membranes and subsequent formation of an additional aramide dendrimer active layer. Thus, all the modified TFC-S membranes have a double active layer structure. A PES-PVA film is used as a control membrane showing that structural compatibility between the dendrimer and supports plays an important role in the membrane modification process. The performance of modified TFC-S membrane is evaluated on the basis of rejection abilities of a variety of water contaminants having a range of sizes and chemistry. As the water flux is inversely proportional to the thickness of the active layer, we optimize the amount of dendrimers deposited for specific contaminants to improve the solute rejection while maintaining high water flux.

Sustained release of TGF-β1 from biodegradable microparticles prepared by a new green process in CO2 medium

International audience

Superlattice structures in twisted bilayers of folded graphene

The electronic properties of bilayer graphene strongly depend on relative orientation of the two atomic lattices. Whereas Bernal-stacked graphene is most commonly studied, a rotational mismatch between layers opens up a whole new field of rich physics, especially at small interlayer twist. Here we report on magnetotransport measurements on twisted graphene bilayers, prepared by folding of single layers. These reveal a strong dependence on the twist angle, which can be estimated by means of sample geometry. At small rotation, superlattices with a wavelength in the order of 10 nm arise and are observed by friction atomic force microscopy. Magnetotransport measurements in this small-angle regime show the formation of satellite Landau fans. These are attributed to additional Dirac singularities in the band structure and discussed with respect to the wide range of interlayer coupling models.

Role of Platinum Deposited on TiO2 in Photocatalytic Methanol Oxidation and Dehydrogenation Reactions

Titania modified nanoparticles have been prepared by the photodeposition method employing platinum particles on the commercially available titanium dioxide (Hombikat UV 100). The properties of the prepared photocatalysts were investigated by means of the Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), atomic force microscopy (AFM), and UV-visible diffuse spectrophotometry (UV-Vis). XRD was employed to determine the crystallographic phase and particle size of both bare and platinised titanium dioxide. The results indicated that the particle size was decreased with the increasing of platinum loading. AFM analysis showed that one particle consists of about 9 to 11 crystals. UV-vis absorbance analysis showed that the absorption edge shifted to longer wavelength for 0.5% Pt loading compared with bare titanium dioxide. The photocatalytic activity of pure and Pt-loaded TiO2 was investigated employing the photocatalytic oxidation and dehydrogenation of methanol. The results of the photocatalytic activity indicate that the platinized titanium dioxide samples are always more active than the corresponding bare TiO2 for both methanol oxidation and dehydrogenation processes. The loading with various platinum amounts resulted in a significant improvement of the photocatalytic activity of TiO2. This beneficial effect was attributed to an increased separation of the photogenerated electron-hole charge carriers.

Coerced Mechanical Coarsening of Nanoparticle Assemblies

Coarsening is a ubiquitous phenomenon [1-3] that underpins countless processes in nature, including epitaxial growth [1,3,4], the phase separation of alloys, polymers and binary fluids [2], the growth of bubbles in foams5, and pattern formation in biomembranes6. Here we show, in the first real-time experimental study of the evolution of an adsorbed colloidal nanoparticle array, that tapping-mode atomic force microscopy (TM-AFM) can drive the coarsening of Au nanoparticle assemblies on silicon surfaces. Although the growth exponent has a strong dependence on the initial sample morphology, our observations are largely consistent with modified Ostwald ripening processes [7-9]. To date, ripening processes have been exclusively considered to be thermally activated, but we show that nanoparticle assemblies can be mechanically coerced towards equilibrium, representing a new approach to directed coarsening. This strategy enables precise control over the evolution of micro- and nanostructures.

Dispositifs optoélectroniques à base de semi-conducteurs organiques en couches minces

Les petites molécules de type p à bandes interdites étroites sont de plus en plus perçues comme des remplaçantes possibles aux polymères semi-conducteurs actuellement utilisés conjointement avec des dérivés de fullerènes de type n, dans les cellules photovoltaïques organiques (OPV). Par contre, ces petites molécules tendent à cristalliser facilement lors de leur application en couches minces et forment difficilement des films homogènes appropriés. Des dispositifs OPV de type hétérojonction de masse ont été réalisés en ajoutant différentes espèces de polymères semi-conducteurs ou isolants, agissant comme matrices permettant de rectifier les inhomogénéités des films actifs et d’augmenter les performances des cellules photovoltaïques. Des polymères aux masses molaires spécifiques ont été synthétisés par réaction de Wittig en contrôlant précisément les ratios molaires des monomères et de la base utilisée. L’effet de la variation des masses molaires en fonction des morphologies de films minces obtenus et des performances des diodes organiques électroluminescentes reliées, a également été étudié. La microscopie électronique en transmission (MET) ou à balayage (MEB) a été employée en complément de la microscopie à force atomique (AFM) pour suivre l’évolution de la morphologie des films organiques minces. Une nouvelle méthode rapide de préparation des films pour l’imagerie MET sur substrats de silicium est également présentée et comparée à d’autres méthodes d’extraction. Motivé par le prix élevé et la rareté des métaux utilisés dans les substrats d’oxyde d’indium dopé à l’étain (ITO), le développement d’une nouvelle méthode de recyclage eco-responsable des substrats utilisés dans ces études est également présenté.

Modificação de membranas de quitosana por plasma para uso biológico

Chitosan membranes have been modified by plasma, utilizing the following gases: nitrogen (N2), methane (CH4), argon (Ar), oxygen (O2) and hydrogen. The modified membranes by plasma were compared to the unmodified ones. The membranes were characterized by absorption assay, contact angle, atomic force microscopy (AFM). Also, permeability assay of sodium sulfamerazine from such membranes were carried out. Through the absorption assay and contact angle it was possible to obtain information of the wettability of the membranes and what changes the plasma treatment can promote in relation to it. The plasma treatment using oxygen promoted increase of the wetability and swelling while the samples treated with methane decrease of the wetability and swelling. Through the Optical Emission Spectroscopy (OES) it was possible to identify which species were present in the plasma during the treatment. And through the AFM analysis it was possible to observe the changes nanotopography occurred on the surface of the samples. Permeability assay were archived for all treated membranes and compared to no treated ones. Due to that assay it was possible verify which the plasma treatment increased the permeability spectrum of the membranes which has varied from 1,4548 *10-5cm2.min-1 to 2,7713*10-5cm2.min-1. Chitosan membranes with permeability varied are importance in systems drug delivery, to liberate a wide variety of drugs

Structure of the N-terminal oligomerization domain of DnaD reveals a unique tetramerization motif and provides insights into scaffold formation

DnaD is a primosomal protein that remodels supercoiled plasmids. It binds to supercoiled forms and converts them to open forms without nicking. During this remodeling process, all the writhe is converted to twist and the plasmids are held around the periphery of large scaffolds made up of DnaD molecules. This DNA-remodeling function is the sum of a scaffold-forming activity on the N-terminal domain and a DNA-dependent oligomerization activity on the C-terminal domain. We have determined the crystal structure of the scaffold-forming N-terminal domain, which reveals a winged-helix architecture, with additional structural elements extending from both N- and C-termini. Four monomers form dimers that join into a tetramer. The N-terminal extension mediates dimerization and tetramerization, with extensive interactions and distinct interfaces. The wings and helices of the winged-helix domains remain exposed on the surface of the tetramer. Structure-guided mutagenesis and atomic force microscopy imaging indicate that these elements, together with the C-terminal extension, are involved in scaffold formation. Based upon our data, we propose a model for the DnaD-mediated scaffold formation.