Rozprawy doktorskie na temat „Semiconductors - Advance Device Applications”

Organic semiconductors are being investigated as an alternative to more traditional materials such as silicon, for the fabrication of different types of electronic devices. The advantages of such materials are flexibility, lightness and quick and low cost device production methods. In this thesis we analyze some small molecule organic semiconductors for their use in devices such as thin film transistors and photovoltaic cells. These materials, deposited in thin films on glass by thermal vacuum evaporation, are copper phthalocyanine (CuPc) and pentacene, p-type materials, fullerene (C60), PTCDA and PTCDI-C13, that are n-type. We analyze their optical properties by optical transmittance measurement and photothermal deflection spectroscopy (PDS). By such means we obtain the absorption coefficient of the materials in sub-gap region (near infrared - NIR), directly related with the density of electronic states. Furthermore, we examine thin film microstructure by X-ray diffraction (XRD) in order to observe if it is amorphous or polycrystalline. The data obtained by optical methods are used to calculate optical gap (Eg) and Urbach energy (Eu). The former of these parameters gives important information about the absorption properties of the material in the visible and NIR ranges of the spectrum, while the latter about the structural disorder in the film. Since a clear model for organic semiconductors is still not defined, in both cases we employ models that are usually considered in the case of inorganic semiconductors. The XRD analysis indicates that, in the deposition conditions used in this work, only C60 grows with amorphous structure while all the other materials are polycrystalline. Such result is used to determine which law can be used to estimate the optical gap: the general law for direct allowed electronic transitions in semiconductors for polycrystalline materials or the Tauc law for amorphous ones. The Urbach law, usually employed to have an idea about the amount of disorder in amorphous films, is used for all our materials as an indicator of thin film quality. Furthermore, we examine the stability of the materials over time under exposure to direct radiation and atmosphere and to compare the results with the ones obtained for samples simply exposed to atmosphere. PTCDA and CuPc have demonstrated to be stable against oxidizing agents that are present in atmosphere while the other materials suffer modifications in their optical properties. Such variations, principally located in the sub-gap region of the absorption region, indicate that an increase in the absorption level is obtained, probably due to the presence of defects that could work as charge carrier traps. Annealing treatments are performed on the degraded materials to observe that the degradation process is not reversible. Organic photovoltaic cells always include a heterojunction between two semiconductors, so the same study is performed on mixtures of two materials, a p-type and an n-type one, testing all the possible combinations between the investigated materials. The films are obtained by co-evaporating the two materials in 1:1 proportion. A mixture containing a degrading material also degrades. Heat treatments performed on the samples yield a partial crystallization of some materials but not of others and fail to recover the original optical properties when degradation occurs. Finally, two types of devices are fabricated: thin film transistors (TFTs) using PTCDI-C13 and diodes with CuPc. In the first case we obtain very interesting results, determining that the devices work as typical n-type channel transistors. An analysis of the device characterizations allows us to determine the density of electronic states in the channel obtaining a result that is very similar to the one obtained by optical means on the same material. In the second case we observe the typical diode behaviour but the response with light of such devices, characterized by having a structure similar to the one of Schottky type solar cells, is very low.
Los semiconductores orgánicos están siendo investigados como alternativos a materiales más tradicionales, como el silicio, para la fabricación de varios tipos de dispositivos electrónicos. Las ventajas que presentan tales materiales son flexibilidad, ligereza, rapidez y bajo coste de los métodos de producción de los dispositivos orgánicos. En esta tesis se analizan algunos semiconductores orgánicos de molécula pequeña para su aplicación en dispositivos como los transistores en capa delgada y las células fotovoltaicas. Tales materiales, depositados en capa delgada por evaporación térmica en vacío, son ftalocianina de cobre (CuPc) y pentaceno, de tipo p, fullereno (C60), PTCDA y PTCDI-C13, de tipo n. Se analizan las propiedades ópticas de ellos por medio de la medida de Trasmitancia Óptica y de la Espectroscopia de Deflección Fototérmica (PDS). Además se analiza la microestructura de las capas delgadas por difracción de rayos X (XRD) con el objetivo de observar si las capas tienen estructura amorfa o policristalina. Los datos son utilizados para calcular el gap óptico (Eg) y la energía de Urbach (Eu). Se analiza la estabilidad de los materiales con el pasar del tiempo y la exposición a irradiación directa, por un lado, y a la atmosfera, por otro lado. El fullereno es el único material que se deposita con estructura amorfa. Además se ha observado que CuPc y PTCDA son estables frente a la degradación por exposición a agentes oxidantes. Las células fotovoltaicas orgánicas incluyen siempre una heterounión entre dos semiconductores, así que se repite el mismo estudio sobre mezclas de dos materiales, uno de tipo p y otro de tipo n, probando todas las combinaciones posibles con los materiales analizados. Se observa que en una mezcla que incluya un material que presenta inestabilidad también hay degradación. Los tratamientos térmicos efectuados sobre las muestras han permiten obtener una parcial cristalización de algunos materiales pero no de otros y no llevan a recuperar las propiedades ópticas originarias, perdidas con la degradación. Finalmente, se fabrican dos tipos de dispositivos: TFTs de PTCDI-C13 y diodos de CuPc. En el primer caso se obtienen resultados interesantes, detectando que los dispositivos funcionan como típicos transistores en capa delgada de tipo n. En el segundo caso se observa el típico comportamiento de los diodos. Sin embargo, la respuesta con luz de tales dispositivos, de estructura análoga a fotocélulas de tipo Schottky, es muy escasa.

In recent years, the use of novel organic conjugated materials as semiconductors in electronic devices has become a continuingly growing and interesting field of research; the attraction derives from the ability of the materials to be easily manipulated and tailored to suit the desired outcome. Organic semiconductors have tunable band gaps and redox properties that can be influenced through variation of the substituents; accompanying this with the ease and reduced cost of processability required for these materials, it makes them very favourable for device fabrication. Organic semiconductors have found use in devices such as electrochromics, light emitting diodes, field effect transistors, photovoltaics, and sensors. In this thesis, the synthesis and characterisation of many compounds suitable for the aforementioned applications are reported. Chapter two is the characterisation of monomers and polymers based on the incorporation of tetrathianaphthalene and its open and cyclic forms. Chapter three is the study of conjugated monomers and polymers, containing BODIPY in the main chain, towards the use in photovoltaic devices. Chapter four reports on unusual extended conjugated architectures, the first section is the characterisation of two new dendralene compounds that adopt two different conformers in solution and solid state and the second section reports on a new series of diindenothienothiophene based materials with interesting electrochemical and photophysical properties. In chapter five, a series of compounds that contain a benzobisthiazole core are investigated and in chapter six, the development of two new biological sensors are discussed.

This thesis studies lead suphide (PbS) colloidal quantum dots and their photovoltaic applications. Different sizes of PbS QDs were synthesised and characterised using absorption spectroscopy and transmission electron microscopes. PbS QD Schottky junction devices were fabricated with AM1.5 power conversion efficiency up to 1.8 %. The Schottky junction geometry limits the device performance. A semiconductor heterojunction using ZnO as an electron acceptor was built and the device efficiency increased to 3%. By studying the light absorption and charge extraction profile of the bilayer device, the absorber layer has a charge extraction dead zone which is beyond the reach of the built-in electric field. Therefore, strategies to create a QD bulk heterojunction were considered to address this issue by distributing the junction interface throughout the absorber layer. However, the charge separation mechanism of the QD heterojunction is not clearly understood: whether it operates as an excitonic or a depleted p-n junction, as the junction operating mechanism determines the scale of phase separation in the bulk morphology. This study shows a transitional behaviour of the PbS/ZnO heterojunction from excitonic to depletion by increasing the doping density of ZnO. To utilise the excitonic mechanism, a PbS/ZnO nanocrystal bulk heterojunction was created by blending the two nanocrystals in solution such that a large interface between the two materials could facilitate fast exciton dissociation. However, the devices show poor performance due to a coarse morphology and formation of germinate pairs. To create a bulk heterojunction where a built-in electric field could assist the charge separation, a TiO₂ porous structure with the pore size matching with the depletion width was fabricated and successfully in-filled by PbS QDs. The porous device produces 5.7% power conversion efficiency, among one of the highest in literature. The enhancement comes from increased light absorption and suppression of charge recombination.

Les sources d'énergie renouvelable connaissent un essor grandissant. Parmi celles-ci se trouvent les cellules photovoltaïques. Elles ont pour objet la transformation de la lumière en électricité. Les dispositifs actuels, basés sur le silicium, nécessitent des matériaux de très grande pureté et de hautes températures de mise en œuvre, les empêchant de concurrencer les principales sources d’énergie actuelles (fossile, nucléaire).

Une alternative pourrait provenir des matériaux semi-conducteurs organiques. En effet, l’utilisation de méthodes de mise en œuvre à partir de solutions pourrait permettre la fabrication de dispositifs flexibles et bon marché. Des résultats encourageants ont été obtenus avec des polymères conjugués et de petites molécules organiques. Les cristaux liquides discotiques CLDs forment une catégorie particulièrement intéressante de matériaux. Ils ont en effet la capacité de s’organiser spontanément en colonnes de molécules, formant des semi-conducteurs à une dimension. Leurs propriétés intéressantes en tant que semi-conducteurs, combinées à une mise en œuvre facile, en font de bons candidats pour de futures applications.

Dans ce travail, deux familles complémentaires de matériaux discotiques ont été développées, formant une paire de semi-conducteurs de type n et p. Leurs structures chimiques ont été étudiées en vue d'obtenir des matériaux possédant un ensemble de propriétés choisies afin d’optimiser les paramètres clefs du processus de photo-génération de charges. Ces propriétés sont les suivantes: forte absorption de la lumière dans le visible, fort caractère semi-conducteur de type n ou p, pas de phase cristalline à température ambiante, présence d'une phase cristal liquide colonne, phase isotrope en dessous de 200°C. De plus, les matériaux doivent être accessibles en un nombre minimum d’étapes d’une synthèse efficace, et ce avec un haut niveau de pureté. Ils doivent également être fortement solubles dans les solvants organiques usuels.

Cette étude comporte, pour chacune des deux familles de matériaux, le design de leur structure chimique, leur synthèse et la caractérisation de leurs propriétés physiques (thermotropes, optoélectroniques, électrochimiques). Comme possible semi-conducteur de type p, cinq dérivés tétrasubstitués de la phthalocyanine non-métallée ont été synthétisés, donnant un matériau possédant l’ensemble des propriétés recherchées. Comme possible semi-conducteur de type n, six dérivés hexasubstitués de l’hexaazatrinaphthylène ont été étudiés. L’un d’eux possède les propriétés requises.

Finalement, les propriétés optoélectroniques et photovoltaïques de mélanges des deux matériaux les plus prometteurs, ensemble ou avec d’autres matériaux, ont été étudiées. Des cellules solaires de rendement maximum de 1 % ont été obtenues pour deux dispositifs de compositions différentes.

Ces rendements, bien qu’inférieurs à ceux obtenus précédemment par d’autres groupes (jusqu’à 34 % à ce jour), sont néanmoins révélateurs des potentialités des matériaux organiques, et plus particulièrement des cristaux liquides discotiques, pour de futures applications dans le domaine des dispositifs électroniques.

Doctorat en sciences, Spécialisation chimie
info:eu-repo/semantics/nonPublished

Harnessing solar energy has become a promising clean and renewable energy source alternative to fossil fuels since the development of low-cost dye sensitized solar cells (DSSC) and organic photovoltaic solar cell devices. Their power-conversion efficiencies, below 13% and 9% respectively, still limit the economic viability of these technologies. The geometry and optical properties of photonic crystals can be used to improve the absorption and charge collection efficiencies of these devices. This thesis describes the fabrication of TiO2 DSSC and ZnO-polymer solar cell devices based on a three-dimensional photonic crystal structure. Photonic crystal polymer structures were produced by holographic lithography and thermally stabilized in order to be used as templates for atomic layer deposition (ALD) of various metal oxides. For this purpose, an ALD apparatus was built and ALD processes for the growth of TiO2, ZnO, Al2O3, ZnO:Al, and Zr3N4 were established and deposited on photonic crystal templates. After ALD, the template was removed by calcination at 500°C, at which ZnO:Al films lost their conductivity of 250 S/cm preventing their use as transparent conducting oxide (TCO) electrodes. The produced 90 nm TiO2 photonic crystal shell DSSC and TiO2 inverse replica devices based on the dye N-719 and iodine/iodide redox electrolyte provided power-conversion efficiencies of 0.9% and 0.49% respectively and their diffusion lengths were 2× and 3× longer than that of a nanocrystalline reference device respectively. ZnO-polymer devices, comprising a P3HT layer as absorber and PEDOT:PSS film as hole-transporter, were also investigated.

Thin film transistors (TFTs) can be used to determine the bulk-like mobilities of amorphous semiconductors. Different organic hole transporters (HTs) are under investigation including spiro-TPD, 2TNATA, NPB and TPD which are commonly used in organic light-emitting diodes (OLEDs). In addition, we also measure the TFT hole mobilities of two iridium phosphors: Ir(ppy)3 and Ir(piq)3. These materials were grown on two different gate dielectric surfaces which were SiO2 and polystyrene (PS). On SiO2, the TFT mobilities are found to be 1-2 orders smaller than the bulk hole mobilities as evaluated independently by time-of-flight (TOF) technique. On the other hand, on PS gate dielectric layer, the TFT mobilities of these hole transporters are found to be in good agreement with TOF data. A thickness dependence measurement was carried out on TFT with PS. We found that only 10nm of organic semiconductor is sufficient for TFTs to achieve TOF mobilities. We further investigate why organic semiconductors on SiO2 have such huge reduction of mobilities. Temperature dependent mobility measurements were carried out and the data were analyzed by the Gaussian Disorder Model (GDM). We found that on SiO2 surface, when compared to the bulk values, the energetic disorders (σ) of the HTs increase and simultaneously, the high temperature limits (∞) of the carrier mobilities decrease. Both σ and ∞ contribute to the reduction of the carrier mobility. The increase in σ is related to the presence of randomly oriented polar Si-O bonds. The reduction of ∞ is topological in origin and is related to the orientations of the more planar molecules on SiO2. The more planar molecules tend to lie horizontally on the surface and such orientation is unfavorable for charge transport in TFT configuration. Hybrid organic/inorganic perovskites have emerged as an outstanding material for photovoltaic cells. In the second part of this work, we setup a repeatable perovskite recipe and optimized the system under different conditions. Under certain circumstances, a perovskite solar cell with power conversion efficiency ~9% can be achieved with PEDOT:PSS as hole transporting layer with the conventional structure.

Novel carborane (B10C2H12) and aromatic compounds (benzene, pyridine, diaminobenzene) copolymers and composite materials have been fabricated by electron beam induced cross-linking and plasma enhanced chemical vapor deposition (PECVD) respectively. Chemical and electronic structure of these materials were studied using X-ray and ultra-violet photoelectron spectroscopy (XPS and UPS). UPS suggest that the systematic tuning of electronic structure can be achieved by using different aromatic compounds as co-precursors during the deposition. Furthermore, top of valence band is composed of states from the aromatic moieties implying that states near bottom of the conduction band is derived from carborane moieties. Current- voltage (I-V) measurements on the ebeam derived B10C2HX: Diaminobenzene films suggest that these films exhibit enhanced electron hole separation life time. Enhanced electron hole separation and charge transport are critical parameters in designing better neutron voltaic devices. Recently, PECVD composite films of ortho-carborane and pyridine exhibited enhanced neutron detection efficiency even under zero bias compared to the pure ortho-carborane derived films. This enhancement is most likely due to longer electron-hole separation, better charge transport or a combination of both. The studies determining the main factors for the observed enhanced neutron detection are in progress by fabricating composite films of carborane with other aromatic precursors and by altering the plasma deposition conditions. This research will facilitate the development of highly sensitive and cost effective neutron detectors, and has potential applications in spintronics and photo-catalysis.

Thesis (M. S.)--Electrical and Computer Engineering, Georgia Institute of Technology, 2009.
Committee Chair: Cressler, John; Committee Member: Papapolymerou, John; Committee Member: Ralph, Stephen.

Organic photovoltaics have attracted considerable research and commercial interest due to their lightness, mechanical flexibility and low production costs. There are two main approaches for the fabrication of organic solar cells – solution and vacuum processing. The former relies on morphology control in polymer-fullerene blends resulting from natural phase separation in these systems. The latter takes advantage of solvent-free processing allowing highly complex multi-junction architectures similar to inorganic solar cells. This work aims to combine the benefits of both by depositing conjugated polymers using vacuum thermal evaporation. By employing this unconventional approach it aims to enhance the efficiency of organic photovoltaics through increased complexity of the thin-film architecture while improving the nanoscale morphology control of the individual active layers. The thesis explores the vacuum thermal deposition of polythiophenes, mainly poly(3-hexylthiophene) (P3HT) and side-group free poly(thiophene) (PTh). A variety of chemical techniques, such as NMR, FT-IR, GPC, DSC and TGA, are used to examine the effect of heating on chemical structure of the polymers. Optimal processing parameters are identified and related to the resulting thin-film morphology and charge transport properties. Efficient photovoltaic devices based on polythiophene donors and fullerene acceptors are fabricated. Materials science techniques AFM, XRD, SEM, TEM and MicroXAM are used to characterize topography and morphology of the thin films, and UV-Vis, EQE, I-V and C-V measurements relate these to the optical and electronic properties. The results of the study show that polymer side groups have a strong influence on molecular packing and charge extraction in vacuum-deposited polymer thin films. Unlike P3HT, evaporated PTh forms highly crystalline films. This leads to enhanced charge transport properties with hole mobility two orders of magnitude higher than that in P3HT. The effect of molecular order is demonstrated on polymer/fullerene planar heterojunction solar cells. PTh-based devices have significantly better current and recombination characteristics, resulting in improved overall power conversion efficiency (PCE) by 70% as compared to P3HT. This confirms that the chemical structure of the molecule is a crucial parameter in deposition of large organic semiconductors. It is also the first-ever example of vacuum-deposited polymer photovoltaic cell. Next, vacuum co-deposited PTh:C60 bulk heterojunctions with different donor-acceptor compositions are fabricated, and the effect of post-production thermal annealing on their photovoltaic performance and morphology is studied. Co-deposition of blended mixtures leads to 60% higher photocurrents than in thickness-optimized PTh/C60 planar heterojunction counterparts. Furthermore, by annealing the devices post-situ the PCE is improved by as much as 80%, achieving performance comparable to previously reported polythiophene and oligothiophene equivalents processed in solution and vacuum, respectively. The enhanced photo-response is a result of favourable morphological development of PTh upon annealing. In contrast to standard vacuum-processed molecular blends, annealing-induced phase separation in PTh:C60 does not lead to the formation of coarse morphology but rather to an incremental improvement of the already established interpenetrated nanoscale network. The morphological response of the evaporated PTh within the blend is further verified to positively differ from that of its small-molecule counterpart sexithiophene. This illustrates the morphological advantage of polymer-fullerene combination over all other vacuum-processable material systems. In conclusion, this processing approach outlines the conceptual path towards the most beneficial combination of solution/polymer- and vacuum-based photovoltaics. It opens up a fabrication method with considerable potential to enhance the efficiency of large-scale organic solar cells production.

Nanomaterials have attracted great interest due to the unique physical properties and great potential in the applications of nanoscale devices. Two dimensional atomic crystals, which are atomic thickness, especially graphene, have triggered the gold rush recently due to the fascinating high mobility at room temperature for future electronics. The crystal structure of nanomaterials will have great influence on their physical properties. Thus, this thesis is focused on developing the methods to control the crystal structure of nanomaterials, namely quantum dots as semiconductor, boron nitride (BN) as insulator, graphene as semimetal, with low cost for their applications in photonics, structural support and electronics. In this thesis, firstly, Mn doped ZnSe quantum dots have been synthesized using colloidal synthesis. The shape control of Mn doped ZnSe quantum dots has been achieved from branched to spherical by switching the injection temperature from kinetics to thermodynamics region. Injection rates have been found to have effect on controlling the crystal phase from zinc blende to wurtzite. The structural-property relationship has been investigated. It is found that the spherical wurtzite Mn doped ZnSe quantum dots have the highest quantum yield comparing with other shape or crystal phase of the dots. Then, the Mn doped ZnSe quantum dots were deposited onto the BN sheets, which were micron-sized and fabricated by chemical exfoliation, for high resolution imaging. It is the first demonstration of utilizing ultrathin carbon free 2D atomic crystal as support for high resolution imaging. Phase contrast images reveal moiré interference patterns between nanocrystals and BN substrate that are used to determine the relative orientation of the nanocrystals with respect to the BN sheets and interference lattice planes using a newly developed equation method. Double diffraction is observed and has been analyzed using a vector method. As only a few microns sized 2D atomic crystal, like BN, can be fabricated by the chemical exfoliation. Chemical vapour deposition (CVD) is as used as an alternative to fabricate large area graphene. The mechanism and growth dynamics of graphene domains have been investigated using Cu catalyzed atmospheric pressure CVD. Rectangular few layer graphene domains were synthesized for the first time. It only grows on the Cu grains with (111) orientation due to the interplay between atomic structure of Cu lattice and graphene domains. Hexagonal graphene domains can form on nearly all non-(111) Cu surfaces. The few layer hexagonal single crystal graphene domains were aligned in their crystallographic orientation over millimetre scale. In order to improve the alignment and reduce the layer of graphene domains, a novel method is invented to perform the CVD reaction above the melting point of copper (1090 ºC) and using molybdenum or tungsten to prevent the balling of the copper from dewetting. By controlling the amount of hydrogen during the growth, individual single crystal domains of monolayer over 200 µm are produced determined by electron diffraction mapping. Raman mapping shows the monolayer nature of graphene grown by this method. This graphene exhibits a linear dispersion relationship and no sign of doping. The large scale alignment of monolayer hexagonal graphene domains with epitaxial relationship on Cu is the key to get wafer-sized single crystal monolayer graphene films. This paves the way for industry scale production of 2D single crystal graphene.

Les dispositifs thermoélectriques, légers et flexibles, peuvent être particulièrement intéressants aujourd’hui dans le contexte de l’émergence de l’informatique ubiquitaire, ainsi que de la crise environnementale liée à la consommation d’énergie électrique. Cependant, beaucoup de problèmes doivent encore être résolus pour rendre les dispositifs de récupération de chaleur commercialement viables. Dans cette thèse nous avons élaboré une méthode de conception et de fabrication par impression jet d’encre de générateurs flexibles à base de semi-conducteurs organiques et hybrides. En premier lieu, les travaux ont été consacrés au développement de matériaux thermoélectriques efficaces, stables et synthétisés par voie liquide. Les stratégies d’optimisation employées reposent sur la modulation de la concentration de porteurs de charge et le contrôle de la morphologie microscopique du matériau. En second lieu, nous avons effectué un travail de conception et de modélisation de dispositifs thermoélectriques ainsi que de leurs paramètres géométriques en utilisant des outils numériques. La modélisation numérique a été réalisée par la méthode des éléments finis 3D et par couplage d’effets physiques multidimensionnels. L’aboutissement de notre projet a été la formulation des matériaux en encres pour la fabrication de générateurs thermoélectriques par la technique de dépôt par impression jet d’encre. Différentes structures et architectures ont été expérimentalement caractérisées et systématiquement comparées aux évaluations numériques. Ainsi, nous présentons une approche intégrale de conception et de fabrication de dispositifs thermoélectriques opérant à des températures proches de l’ambiant
Flexible lightweight printed thermoelectric devices can become particularly interesting with the advent of ubiquitous sensing and within the context of current energy and environmental issues. However, major drawbacks of state of the art thermoelectric materials must be addressed to make waste heat recovery devices commercially feasible. In this PhD thesis, we’ve elaborated and described a method to fabricate optimized, fully inkjetprinted flexible thermoelectric generators based on organic and hybrid semiconductors. This research project can be divided into three stages: First is the development of effective, stable and solution-processed p-type and n-type thermoelectric materials. Our effort in optimizing thermoelectric materials were based on modulation of charge carrier concentration and on control of morphology. Second, design and modeling of thermoelectric devices and their geometric parameters using numerical simulation methods. Numerical simulations were based on a 3D-finite element analysis and simulation software for coupled physical problems to model and design thermoelectric devices. Finally, formulation of materials into ink in order to produce thermoelectric generators by inkjet printing deposition. Various structures and architectures were experimentally characterized and systematically compared to numerical evaluations. Hence, we produced an extensive study on designing and producing thermoelectric devices operating at near ambient temperature and conditions

Cette thèse porte sur l’évaluation des techniques pour la tomographie chimique par STEM EDX : mise au point des procédures expérimentales, traitement des données, reconstruction des volumes, analyse de la qualité des résultats obtenus et évaluation de la complexité globale. Les performances très limitées de l’analyse STEM EDX font que peu d’études, jusqu’à aujourd’hui, se sont portées sur cette technique. Cependant, les avancées très notables procurées par les nouveaux détecteurs ‘SDD’ ainsi que les sources électroniques X-FEG haute brillance, rendant l’analyse STEM EDX 2D très rapide, ont relancé la possibilité de la tomographie chimique ; la technique demande toutefois à être mise au point et évaluée (performances et complexité). Nous avons travaillé sur un microscope Tecnai Osiris permettant d’acquérir des cartographies chimiques EDX de centaines de milliers de pixels avec une résolution de l’ordre du nanomètre en quelques minutes. Nous avons choisi de préparer par FIB des échantillons en forme de pointe et d’utiliser un porte-objet permettant une exploration angulaire de 180° sans ombrage. Puis, à l’aide d’échantillons modèles (billes de SiO2 dans une résine), nous avons évalué les déformations d’échantillon par l’irradiation du faisceau électronique. Ceci nous a permis de proposer une méthode pour limiter cet effet par déposition d’une couche de 20 nm de chrome. Des simulations d’images ont permis d’évaluer les logiciels et méthodes de reconstruction. La méthodologie de chaque étape d’une analyse de tomographie STEM EDX a ensuite été expliquée, et l’intérêt de la technique démontré grâce à la comparaison de l’analyse 2D et 3D d’un transistor FDSOI 28 nm. La qualité des reconstructions (rapport signal-sur-bruit, résolution spatiale) a été évaluée en fonction des paramètres expérimentaux à l’aide de simulations et d’expériences. Une résolution de 4 nm est démontrée grâce à l’analyse d’une mire et d’un transistor « gate all around ». Pour ce même transistor, la possibilité et l’intérêt d’analyse de défaillance à l’échelle nanométrique est prouvée. Une analyse d’un défaut de grille d’une SRAM ou de trous dans un pilier en cuivre permettent d’expliquer l’intérêt d’une combinaison d’un volume HAADF (morphologie et résolution < 4 nm) et du volume EDX (information chimique). La conclusion est que cette technique, qui reste encore à améliorer du point de vue de sa simplicité, montre déjà son utilité pour l’analyse et la mise au point des technologies avancées (nœud 20 nm et après)
This thesis focuses on the evaluation of the STEM EDX chemical tomography technique: development of experimental procedures, data processing and volumes reconstruction, quality analysis of the results and evaluation of the overall complexity. Until now, STEM EDX analysis performances were very limited, so only few studies about this technique have been realized. However, very significant progress procured by the new SDD detectors as well as by the high brightness electronic sources (X-FEG), making the STEM EDX 2D analysis very fast, have revived the possibility of the chemical tomography, although the technique has to be developed and evaluated (performance and complexity). We have worked on a Tecnai Osiris which acquires EDX chemical mapping of hundreds of thousands of pixels with resolution of one nanometer and in a few minutes. We chose to prepare the rod-shaped samples by FIB and use a sample holder allowing an angle of exploration of 180° without shadowing effects. Then, using model samples (SiO2 balls in resin), we evaluated the sample deformation due to the electron beam irradiation. This allowed us to propose a method to reduce this effect by depositing a 20 nm chromium layer. Images simulations were used to evaluate the software and the reconstruction methods. The methodology of each step of the STEM EDX tomography analysis is then explained and the technique interest is demonstrated by comparing the 2D and the 3D analysis of a transistor 28 nm FDSOI. The quality of the reconstructions (signal-to-noise ratio, spatial resolution) was evaluated, in function of experimental parameters, using simulations and experiments. A resolution of 4 nm is demonstrated through the analysis of a test pattern and a "gate all around” transistor. For the same transistor, the possibility and the interest of a failure analysis at the nanoscale is proven. Analyses of a SRAM gate fail or of the holes in a copper pillar explain the benefits of a combination between a HAADF volume (morphology and resolution < 4 nm) and an EDX volume (chemical information). To conclude, this technique, which still needs to be improved in terms of simplicity, is already showing its usefulness for the analysis and the development of advanced technologies (20nm node and beyond)

Through the history of mankind, novel materials have played a key role in techno- logical progress. As we approach the limits of scaling it becomes difficult to squeeze out any more extensions to Moore’s law by just reducing device feature sizes. It is important to look for an alternate semiconductor to silicon in order to continue making the progress predicted by Moore’s law. Among the various semiconductor options being explored world-wide, the III-nitride semiconductor material system has certain unique characteristics that make it one of the leading contenders. We explore the III-nitride semiconductor material system for the unique advantages that it offers over the other alternatives available to us. This thesis studies the device applications of epitaxial III-nitride films and nanos- tructures grown using plasma assisted molecular beam epitaxy (PAMBE) The material characterisation of the PAMBE grown epitaxial III-nitrides was car- ried out using techniques like high resolution X-ray diffraction (HR-XRD), field emis- sion scanning electron microscopy (FESEM), room temperature photoluminescence (PL) and transmission electron microscopy (TEM). The epitaxial III-nitrides were then further processed to fabricate devices like Schottky diodes, photodetectors and surface acoustic wave (SAW) devices. The electrical charcterisation of the fabricated devices was carried out using techniques like Hall measurement, IV and CV measure- ments on a DC probe station and S-parameter measurements on a vector network analyser connected to an RF probe station. We begin our work on Schottky diodes by explaining the motivation for adding an interfacial layer in a metal-semiconductor Schottky contact and how high-k di- electrics like HfO2 have been relatively unexplored in this application. We report the work carried out on the Pt/n-GaN metal-semiconductor (MS) Schottky and the Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diode. We report an improvement in the diode parameters like barrier height (0.52 eV to 0.63 eV), ideality factor (2.1 to 1.3) and rectification ratio (35.9 to 98.9 @2V bias) after the introduction of 5 nm of HfO2 as the interfacial layer. Temperature dependent I-V measurements were done to gain a further understanding of the interface. We observe that the barrier height and ideality factor exhibit a temperature dependence. This was attributed to inhomogeneities at the interface and by assuming a Gaussian distribution of barrier heights. UV and IR photodetectors using III-nitrides are then studied. Our work on UV photodetectors describes the growth of epitaxial GaN films. Au nanoparticles were fabricated on these films using thermal evaporation and annealing. Al nanostruc- tures were fabricated using nanosphere lithography. Plasmonic enhancement using these metallic nanostructures was explored by fabricating metal-semiconductor-metal (MSM) photodetectors. We observed plasmonic enhancement of photocurrent in both cases. To obtain greater improvement, we etched down on the GaN film using reac tive ion etching (RIE). This resulted in further increase in photocurrent along with a reduction in dark current which was attributed to creation of new trap states. IR photodetectors studied in this thesis are InN quantum dots whose density can be controlled by varying the indium flux during growth. We observe that increase in InN quantum dot density results in increase in photocurrent and decrease in dark current in the fabricated IR photodetectors. We then explore the advantages that InGaN offers as a material that supports surface acoustic waves and fabricate InGaN based surface acoustic wave devices. We describe the growth of epitaxial In0.23 Ga0.77 N films on GaN template using molecular beam epitaxy. Material characterisation was carried out using HR-XRD, FESEM, PL and TEM. The composition was determined from HR-XRD and PL measurements and both results matched each other. This was followed by the fabrication of interdigited electrodes with finger spacing of 10 µm. S-parameter results showed a transmission peak at 104 MHz with an insertion loss of 19 dB. To the best of our knowledge, this is the first demonstration of an InGaN based SAW device. In summary, this thesis demonstrates the practical advantages of epitaxially grown film and nanostructured III-nitride materials such as GaN, InN and InGaN using plasma assisted molecular beam epitaxy for Schottky diodes, UV and IR photodetec- tors and surface acoustic wave devices.

Through the history of mankind, novel materials have played a key role in techno- logical progress. As we approach the limits of scaling it becomes difficult to squeeze out any more extensions to Moore’s law by just reducing device feature sizes. It is important to look for an alternate semiconductor to silicon in order to continue making the progress predicted by Moore’s law. Among the various semiconductor options being explored world-wide, the III-nitride semiconductor material system has certain unique characteristics that make it one of the leading contenders. We explore the III-nitride semiconductor material system for the unique advantages that it offers over the other alternatives available to us. This thesis studies the device applications of epitaxial III-nitride films and nanos- tructures grown using plasma assisted molecular beam epitaxy (PAMBE) The material characterisation of the PAMBE grown epitaxial III-nitrides was car- ried out using techniques like high resolution X-ray diffraction (HR-XRD), field emis- sion scanning electron microscopy (FESEM), room temperature photoluminescence (PL) and transmission electron microscopy (TEM). The epitaxial III-nitrides were then further processed to fabricate devices like Schottky diodes, photodetectors and surface acoustic wave (SAW) devices. The electrical charcterisation of the fabricated devices was carried out using techniques like Hall measurement, IV and CV measure- ments on a DC probe station and S-parameter measurements on a vector network analyser connected to an RF probe station. We begin our work on Schottky diodes by explaining the motivation for adding an interfacial layer in a metal-semiconductor Schottky contact and how high-k di- electrics like HfO2 have been relatively unexplored in this application. We report the work carried out on the Pt/n-GaN metal-semiconductor (MS) Schottky and the Pt/HfO2/n-GaN metal-insulator-semiconductor (MIS) Schottky diode. We report an improvement in the diode parameters like barrier height (0.52 eV to 0.63 eV), ideality factor (2.1 to 1.3) and rectification ratio (35.9 to 98.9 @2V bias) after the introduction of 5 nm of HfO2 as the interfacial layer. Temperature dependent I-V measurements were done to gain a further understanding of the interface. We observe that the barrier height and ideality factor exhibit a temperature dependence. This was attributed to inhomogeneities at the interface and by assuming a Gaussian distribution of barrier heights. UV and IR photodetectors using III-nitrides are then studied. Our work on UV photodetectors describes the growth of epitaxial GaN films. Au nanoparticles were fabricated on these films using thermal evaporation and annealing. Al nanostruc- tures were fabricated using nanosphere lithography. Plasmonic enhancement using these metallic nanostructures was explored by fabricating metal-semiconductor-metal (MSM) photodetectors. We observed plasmonic enhancement of photocurrent in both cases. To obtain greater improvement, we etched down on the GaN film using reac tive ion etching (RIE). This resulted in further increase in photocurrent along with a reduction in dark current which was attributed to creation of new trap states. IR photodetectors studied in this thesis are InN quantum dots whose density can be controlled by varying the indium flux during growth. We observe that increase in InN quantum dot density results in increase in photocurrent and decrease in dark current in the fabricated IR photodetectors. We then explore the advantages that InGaN offers as a material that supports surface acoustic waves and fabricate InGaN based surface acoustic wave devices. We describe the growth of epitaxial In0.23 Ga0.77 N films on GaN template using molecular beam epitaxy. Material characterisation was carried out using HR-XRD, FESEM, PL and TEM. The composition was determined from HR-XRD and PL measurements and both results matched each other. This was followed by the fabrication of interdigited electrodes with finger spacing of 10 µm. S-parameter results showed a transmission peak at 104 MHz with an insertion loss of 19 dB. To the best of our knowledge, this is the first demonstration of an InGaN based SAW device. In summary, this thesis demonstrates the practical advantages of epitaxially grown film and nanostructured III-nitride materials such as GaN, InN and InGaN using plasma assisted molecular beam epitaxy for Schottky diodes, UV and IR photodetec- tors and surface acoustic wave devices.

博士
國立臺灣大學
化學工程學研究所
103
Polymeric semiconductors have received great attentions for organic electronic and optoelectronic devices, such as field-effect transistors (FETs), photovoltaic cells (PVs), and memory devices. In the recent progress of polymer community, side chains are act as a crucial component in the design of novel conjugated polymers. They not only directly relate to the solubility but also affect the molecular packing motifs and thin film morphologies. The goal of this thesis is to address the effect of conjugated or alkyl side chain structures on the polymer thin film morphologies and the optoelectronic properties. In addition, the field-effect mobilities, photovoltaic, or memory characteristics are also probed to investigate the side chain engineering design on polymeric semiconductors for optoelectronic devices systematically. Three different strategies are explored in this thesis, as shown in followings: 1. Syntheses of two-dimensional branched thiophene extended octithiophene‐based conjugated polymers for field-effect transistors and photovoltaic cells: In Chapter 2, three octithiophene (8T)-based conjugated copolymers, including P8TSe, P8TT, and P8TTT, have been synthesized. The larger atomic radius selenium (Se) atom possesses higher polarizability than sulfur (T), inducing stronger intermolecular interactions in solid state. Also, 8T moiety could significantly lower the HOMO level and lead to the enhanced open circuit voltage because of its branched conformation. The hole mobilities of these 8T-based copolymers were in the range of 1.32×10-5 to 5.00×10-5 cm2V-1s-1 with on/off ratio of 104. Among them, P8TTT showed better characteristics than the other polymers due to the fused-ring TT can promote self-organization and minimize the steric interactions. The power conversion efficiencies (PCE) of the copolymers/PC71BM based photovoltaic cells were in the range of 1.28 - 2.30% under the illumination of AM 1.5G (100 mW cm-2). In particular, P8TTT showed the best PCE of 2.81%, as the blend films are prepared from the mixed solvent of o-dichlorobenzene (DCB) and 1,8-diiodoctane (DIO) (DCB/DIO = 97%:3% by volume). In Chapter 3, the synthesis, morphology and optoelectronic device applications of 2D extended quaterthiophene (4T)- and octithiophene (8T)-vinylene conjugated polymers, P4TV and P8TV, were explored. P4TV and P8TV exhibited smaller energy band gaps of 1.69 and 1.78 eV than that of parent polythiophenes, respectively, due to the reduced conformation distortion by the vinylene linkage. The highest field-effect hole mobilities of P4TV and P8TV were 0.12 and 0.0018 cm2V-1s-1, respectively, with on/off ratios around 104-105. In addition, the power conversion efficiency (PCE) of the P4TV/PC71BM based photovoltaic cells under the illumination of AM 1.5G (100 mW cm-2) was 4.04 %, which was significantly higher than that of P8TV/PC71BM with 2.69 %, due to its superior charge transport ability. However, P8TV had a better environmental stability attributed to its low-lying HOMO energy level. 2. Syntheses of main chain donor tethered side chain phenanthro[9,10-d]imidazole acceptor conjugated polymers for high performance flexible resistive memory devices: In Chapter 4, a bipolar-recorded resistive memory device consisting of a single-layer donor-acceptor conjugated polymer fabricated on plastic polyethylene naphthalate (PEN) have been developed. The newly designed conjugated polymer with a main-chain donor of fluorene and thiophene and a side-chain acceptor of phenanthro[9,10-d]-imidazole (PFT-PI) was synthesized as an active memory material. The reproducible, nonvolatile flash switching characteristics of each sandwiched PEN/Al/PFT-PI/Al memory device was demonstrated under bending. The flexible nonvolatile resistor memory devices with low threshold voltages (±2 V), low switching powers ( 100 μW cm−2), large ON/OFF memory windows (104), good retention (>104 s) and excellent endurance against electric and mechanical stimulus. The simple and facile device fabrication was obtained from a single PFT-PI memory material, without using charge injection layers or a complex multilayer structure. In Chapter 5, the synthesis and resistive memory device characteristics of new donor-acceptor conjugated poly(arylene vinylene), PVC-PI, PVT-PI, and PVTPA-PI, have been explored. The studied polymers possess similar HOMO energy levels (-5.08 ~ -5.18 eV), but with different LUMO energy levels (-2.24, -3.40, and -2.60 eV for PVC-PI, PVT-PI, and PVTPA-PI, respectively). The PVC-PI flexible memory with the sandwich configuration of PEN/Al/polymer/Al reveals the volatile static random access memory (SRAM) characteristic while the PVTPA-PI device exhibits the nonvolatile write-once-read-many-times (WORM) switching behavior. The above two devices could operate at low voltages (less than 2.5 V) with high ON/OFF current ratios (over 104) and exhibit excellent durability upon repeated bending tests. The PVT-PI device, however, only shows a diode-like electrical behavior. The polymer conformation affects the strength of D-A electrical polarization and charge trapping ability, leading to the variation on the volatility of the memory devices. 3. Effects of alkyl side chain design on charge transport: Synthesis, morphology, and stretchable transistor applications: In Chapter 6, three polymers with variant alkyl side chain structures (i.e. short linear, long linear, and branched alkyl side chains), namely P3HT, PTDPPTFT4, and PII2T, are evaluated for stretchable field-effect transistors. In addition, a facile method to efficiently identify suitable semiconducting polymers for organic stretchable transistors using soft contact lamination is described. In this method, the various polymers investigated are first transferred on elastomeric poly(dimethylsiloxane) (PDMS) slab, and subsequently stretched (up to 100 %) along with the PDMS. The polymer/PDMS matrix is then laminated on source/drain electrode-deposited Si substrates equipped with a PDMS dielectric layer. The polymer semiconductors can be repeatedly interrogated with laminate/delaminate cycles under different amounts of tensile strain, and the strain limitation of semiconductors enable different side chain structures can be derived. In Chapter 7, a series of isoindigo-based conjugated polymers (PII2F-CmSi, m=3-11) with alkyl siloxane-terminated side chains have been prepared, in which the branching point is systematically “moved away” from the conjugated backbone by one carbon atom. All soluble PII2F-CmSi (m=5-11) polymers exhibited hole charge carrier mobilities over 1 cm2V-1s-1, while the reference polymer with the same polymer backbone showed a much lower mobility of 0.13 cm2V-1s-1. PII2F-C9Si showed the highest mobility of 4.76 cm2V-1s-1, even though PII2F-C11Si exhibited the smallest π-π stacking distance at 3.379 Å. We concluded that it is beneficial that the branching site was further away from conjugated backbones to improve charge transport characteristics. The above studies demonstrate that the optoelectronic properties, charge carrier transport ability, solar cell efficiency, and memory behaviors can be manipulated using side chain engineering design. The device performances were tuned by controlling the chemical structures of conjugated side chains. Moreover, with variant alkyl side chain structures, the charge carrier mobility in stretched polymer thin films were changed, indicating the design of side chain on polymeric semiconductors plays a crucial role for next-generation electronic device application.

碩士
臺灣大學
光電工程學研究所
98
Organic Light Emitting Device (OLED) technology is emerging as a promising technology for displays and lighting. OLEDs possess key performance features including vibrant color, high contrast ratios, full-motion video, and wide viewing angles. In two different light-emitting mechanisms, phosphorescent OLEDs can have up to four times higher efficiency than fluorescent OLEDs, because the incorporation of heavy metal-containing complexes into appropriate host materials allows the harvesting of both singlet and triplet excitons and make it possible to achieve nearly 100% internal quantum efficiency. The development of PHOLED therefore has attracted a great deal of attention, and the adoption of bipolar host materials is becoming an important method to improve device performances. Two novel materials were under studied in this research. Materials combining carbazole-based main structures, which are considered to give hole-transport ability, and sulfone group, which is expected to be electron-transport part of the molecule, is believed to give bipolar ability, and the large triplet energy (> 2.8 eV) is suitable for PHOLED host materials. Both two materials have high PLQY about 80% when doping with Ir(ppy)3 and FIrpic, but the devices can’t reach equal performances. The properties of these two materials in devices were studied by applying different materials into the hole-transport layer and the electron-transport layer. Having more sulfone groups, cbz-di-SO2 shows stronger electron-transport property than SO2mCP.

One of the ways of countering the ever increasing computational requirements in the simulation and modeling of electrical and electromagnetic devices and phenomena, is the development of simulation and modeling tools on parallel computing platforms. In this thesis, a previously developed Monte Carlo parallel device simulator is utilized, enhanced, and evolved, to render it applicable to the modeling and simulation of certain key applications. A three-dimensional Monte Carlo simulation of GaAs MESFETs is first presented to study small-geometry effects. Then, a finite-difference time-domain numerical solution of Maxwell's equations is developed and coupled to Monte Carlo particle simulation, to illustrate a photoconductive switching experiment. As the third and major application of the Monte Carlo code, high-field electron transport simulations of the ZnS phosphor of AC thin film electroluminescent devices are presented. A full band structure (of ZnS) computed using a nonlocal empirical pseudopotential technique is included in the Monte Carlo simulation. The band structure is computed using a set of form factors, that were tuned to fit experimentally measured critical point transitions in ZnS. The Monte Carlo algorithms pertaining to the full band model are developed. Most of the scattering mechanisms, pertinent to ZnS are included to model the electron kinetics. The hot electron distributions are computed as a function of the electric field in the ZnS phosphor layer, to estimate the percentage of hot electrons that could potentially contribute to excitation of luminescent impurity centers in the ZnS phosphor layer. Impact excitation, a key process in electroluminescence, is included in the Monte Carlo simulation to estimate the quantum yield of the devices. Preliminary results based on the full band k-space model exhibit experimentally observed trends.
Graduation date: 1996

博士
國立臺灣大學
電子工程學研究所
99
OLEDs can produce polarized electroluminescence via aligning the light-emitting molecules, and the performance of organic thin-film transistors and organic photovoltaic cells can also be improved by aligning the active molecules. Liquid crystal (LC) phases can be applied to achieve these purposes. In this thesis, we studied four organic materials possessing LC phases. In chapter two, we studied the photophysical and charge-transport properties of two self-assembly materials with LC phases. They were the first kind of their own family possessing LC properties. In chapter three, we successfully fabricated the first polarized phosphorescent OLED by using a mesogenic host/guest system. In chapter four, we reported efficient solution-processed phosphorescent OLEDs using a Pt(II) complex with LC properties and high photoluminescence (PL) quantum yields in the solid state. We truly believe that exploiting and studying the organic materials with LC properties will be a key factor to create novel organic electro-optical devices in the future.

The research of amorphous metal oxide semiconductors for printed electronics applications, such as transparent and flexible devices, has been increasing to allow the low-cost production, good performance and large area upscaling of these materials. The most commonly used solution-based semiconductors rely on toxic solvents and are indium-based. To avoid this critical raw material ZTO is the preferred alternative. Nevertheless, replacing the toxic solvent and the chloride-based tin precursor wich also contributes to the toxicity of the solution remains a challenge. This work focuses on the development of eco-friendly ZTO precursor solutions to produce electronic devices at low temperature and optimization of flexographic printing of these ZTO inks. ZTO/SiO2 TFTs were successfully produced at 300 °C with non-toxic solvent, presenting a mobility of 2.98 ± 0.05 cm2/V.s and flexoprinted Ag/ZTO/ITO Schottky diodes were successfully produced at low temperature (150 °C + DUV) with a current on/off ratio of 1000. These devices show equivalent performance to the current state-of-the-art of ZTO devices produced with toxic solvents. Finally, TFTs and Schottky diodes using non-toxic solvent and chloride-free ZTO precursors were successfully demonstrated for the first time. This work clearly shows that it is possible to produce 100 % eco-friendly inks for high performance devices at low temperature suitable for large area printing.