Investigations performed in order to understand the electronic and optoelectronic properties of field effect transistors based on few layers of 2D Copper Indium Selenide (CuIn7Se11) are reported. In general, field effect transistors (FETs), electric double layer field effect transistors (EDL-FETs), and photodetectors are crucial part of several electronics based applications such as tele-communication, bio-sensing, and opto-electronic industry. After the discovery of graphene, several 2D semiconductor materials like TMDs (MoS2, WS2, and MoSe2 etc.), group III-VI materials (InSe, GaSe, and SnS2 etc.) are being studied rigorously in order to develop them as components in next generation FETs. Traditionally, thin films of ternary system of Copper Indium Selenide have been extensively studied and used in optoelectronics industry as photoactive component in solar cells. Thus, it is expected that atomically thin 2D layered structure of Copper Indium Selenide can have optical properties that could potentially be more advantageous than its thin film counterpart and could find use for developing next generation nano devices with utility in opto/nano electronics. Field effect transistors were fabricated using few-layers of CuIn7Se11 flakes, which were mechanically exfoliated from bulk crystals grown using chemical vapor transport technique. Our FET transport characterization measurements indicate n-type behavior with electron field effect mobility µFE ≈ 36 cm^2 V^-1 s^-1 at room temperature when Silicon dioxide (SiO2) is used as a back gate. We found that in such back gated field effect transistor an on/off ratio of ~ 10^4 and a subthreshold swing ≈ 1 V/dec can be obtained. Our investigations further indicate that Electronic performance of these materials can be increased significantly when gated from top using an ionic liquid electrolyte [1-Butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6)]. We found that electron field effect mobility µFE can be increased from ~ 3 cm^2 V^-1 s^-1 in SiO2 back gated device to ~ 18 cm^2 V^-1 s^-1 in top gated electrolyte devices. Similarly, subthreshold swing can be improved from ~ 30 V/dec to 0.2 V/dec and on/off ratio can be increased from 10^2 to 10^3 by using an electrolyte as a top gate. These FETs were also tested as phototransistors. Our photo-response characterization indicate photo-responsivity ~ 32 A/W with external quantum efficiency exceeding 10^3 % when excited with a 658 nm wavelength laser at room temperature. Our phototransistor also exhibit response times ~ tens of µs with specific detectivity (D*) values reaching ~ 10^12 Jones. The CuIn7Se11 phototransistor properties can be further tuned & enhanced by applying a back gate voltage along with increased source drain bias. For example, photo-responsivity can gain substantial improvement up to ~ 320 A/W upon application of a gate voltage (Vg = 30 V) and/or increased source-drain bias. The photo-responsivity exhibited by these photo detectors are at least an order of magnitude better than commercially available conventional Si based photo detectors coupled with response times that are orders of magnitude better than several other family of layered materials investigated so far. Further photocurrent generation mechanisms, effect of traps is discussed in detail.

La structure de bande et les propriétés électroniques des nanofils d’InAs et d’InSb sont étudiées par transport électronique en régime quasi-balistique et sous un champ magnétique montant jusqu’à 55T. Le régime quasi-balistique est mis en évidence par la quantification de la conductance. La structure de bande est sondée par l’analyse des plateaux de conductance en fonction de la concentration électronique. L’application du champ magnétique lève la dégénérescence de spin et la dégénérescence orbitale. Sous champ magnétique perpendiculaire à l’axe du nanofil, les bandes évoluent vers la quantification de Landau, accompagnée d’une réduction de la rétrodiffusion. Des fluctuations quasi-périodiques de la conductance sont mesurées en fonction du champ magnétique parallèle à l’axe du nanofil. Elles révèlent le confinement des porteurs à l’intérieur du nanofil et la formation d’orbites de Landau dans la direction du transport. Le transport électronique cohérent est mis en évidence par l’observation de fluctuations universelles de conductance et du régime de Fabry-Pérot électronique. Enfin, la mesure de photoconductivité révèle la présence de barrières de Schottky au niveau des contacts et une anisotropie en fonction de la direction de polarisation linéaire inattendue pour des nanofils d’InSb de structure cristalline Blende de Zinc. / The subband structure and electronic properties of InAs and InSb nanowires are studied experimentally by measuring the electronic transport in the quasi-ballistic regime and under magnetic field up to 55T.The quasi-ballistic regime is highlighted by the conductance quantization. The band structure is probed by analyzing the conductance plateaus as a function of the gate voltage. The application of a magnetic field lifts the orbital and spin degeneracy. Under a magnetic field perpendicular to the NW axis subbands evolved towards Landau quantization together with backscattering reduction. Fluctuations of the magneto-conductance are observed in function of magnetic field parallel to the nanowire axis. They reveal the carriers confinement within the nanowire and Landau orbits emergence in the transport direction. The coherent electron transport is jointly studied in these systems. It is highlighted by the observation of universal conductance fluctuations and electronic Fabry-Pérot oscillations. Finally the low-temperature photoconductivity measurement reveals the presence of Schottky barriers at the contacts and unexpected anisotropy according to the direction of linear polarization for InSB Zinc Blende nanowires.

Ce manuscrit porte sur la conception d’un transistor à effet de champ destiné à l’observation de la photoluminescence de l’exciton et des complexes excitoniques chargés du ZnO sous l’influence d’un champ électrique. Pour cela, des simulations ont permis de définir un cahier des charges de la structure du transistor afin de bloquer la conductivité dans le canal de ZnO et d’appliquer un champ électrique intense. La seconde partie concerne le choix du matériau de grille et de l’électrode transparente de surface pour l’observation de la photoluminescence dans le canal. L’oxyde de gallium (-Ga2O3) a été choisi car il présente un grand gap, des propriétés d’isolant et de semi-conducteur avec dopage. Cependant les films de Ga2O3 dopés avec Ti, Sn, Zn et Mg élaborés par MOCVD n’ont pas révélé de conductivité. Les films d’alliages (Ga,Sn)2O3 n’ont pas non plus montré de conductivité et leur structure est étudiée intensivement. Des traitements plasma radiofréquence sous flux d’argon, d’oxygène ou d’hydrogène ont permis de montrer que l’implantation de l’hydrogène donne lieu à un niveau donneur avec une énergie d’activation de 7 meV. La conductivité est toutefois modulée par le dopage en Sn et les traitements s’accompagnent d’un changement de la sous-stœchiométrie en oxygène qui diminue la transparence à cause de la formation de niveau profond de lacune d’oxygène. La structure finale de la grille transparente dans l’ultraviolet pour l’observation de la photoluminescence du ZnO peut donc être élaborée par une grille diélectrique de -Ga2O3 puis une électrode conductrice transparente de (Ga,Sn)2O3 traitée superficiellement par un plasma d’hydrogène. / This manuscript covers the design of a field transistor for the observation of photoluminescence of the exciton and the charged excitonic complex of ZnO under the influence of an electric field. For this, simulations have helped to define the specifications of the transistor structure to block the conductivity in the ZnO channel and applying a strong electric field. The second part concerns the choice of gate material and the surface transparent electrode for the observation of photoluminescence in the channel. The gallium oxide (-Ga2O3) was chosen because it has a large gap, insulating properties and semiconductor properties with doping. However, Ga2O3 films doped with Ti, Sn, Zn and Mg MOCVD did not show conductivity. Films of alloys (Ga,Sn)2O3 have not shown either conductivity and their structure is studied intensively. Radio frequency plasma treatment under a flux of argon, oxygen or hydrogen have shown that implantation of hydrogen gives rise to a donor level with 7 meV activation energy. However, the conductivity is modulated by doping Sn and treatments are accompanied by a change of sub-stoichiometry in oxygen, which reduces the transparency due to the formation of deep level of oxygen vacancy. The final structure of the transparent gate in the ultraviolet for the observation of photoluminescence of ZnO can be prepared by a dielectric gate -Ga2O3 and a transparent conductive electrode of (Ga,Sn)2O3 surface treated by a plasma of hydrogen.

No description available.

Au cours de cette étude, nous avons montré que dans les oxydes de fer type perovskite, les ions sulfates (SO42-) pouvaient être utilisés à escient pour apporter de l'anisotropie cristalline et électronique ou bien au contraire pour casser les mises en ordre à longue distance et provoquer l'isotropie du matériau. Ainsi, ce travail a permis d'isoler les composés bidimensionnels : Sr4Fe2.5-x□xO7.25-(3x/2)(SO4)0.5 (avec x=0, 0.25 et 0.5). Ils peuvent être décrits comme une intercroissance SrO/SrFeO2,5/SrFe0,5-x□xO1,25-(3x/2)(SO4)0,5/SrFeO2,5 et cristallisent dans une maille moyenne quadratique I4/mmm (a=ap et c≈29 Å). Les tétraèdres de sulfates non-pontés se présentent de façon transversale par rapport à c ⃗ pour x=0,5 et longitudinale pour x=0 et 0,25 parce que pontés aux pyramides de fer de la couche partagée. Les atomes de fer des couches non-mixtes SrFeO2,5 se situent eux en coordinence pyramidale pour x=0 et pyramidale et octaédrique pour x=0.5 et x=0.25 afin de respecter la trivalence du fer. Quel que soit x, les composés sont antiferromagnétiques de type G (les spins se situant dans le plan (a,b)). Cependant, pour x=0,5, deux configurations magnétiques sont observées, tandis que les composés x=0 et x=0.25 n'en montrent qu'une seule. Dans le composé Sr4Fe2.5□xO7.25(SO4)0.25(CO3)0.25, l'influence des carbonates (CO32-) se ressent directement sur le paramètre d'empilement, qui est plus petit. Cela n'entraîne cependant aucun changement sensible dans les propriétés physiques. Les composés sont des semi-conducteurs présentant de fortes valeurs de résistivité électronique (de l'ordre de 106Ω.cm) et ne sont pas conducteurs ioniques.La phase ordonnée "15R" SrFe0.6Cr0.4O2.8 se désordonne lorsque l'on substitue 10% du fer par des sulfates (SrFe0.5Cr0.4O2.1(SO4)0.1) et adopte une structure pseudo-cubique. Ses propriétés physiques sont alors bouleversées puisque l'on passe d'un comportement ferromagnétique à antiferromagnétique (TN=800K). Ce composé très lacunaire en oxygène montre des défauts structuraux plus ou moins étendus et un comportement de type semi-conducteur. Aucun phénomène de conduction ionique n'est observé. / In this study, we have shown that in perovskite-type iron oxides, sulfate ions (SO42-) can be used to bring structural and electronic anisotropy, or on the contrary to break long distance ordering and cause the isotropy of the material.Thus, this work made it possible to isolate the two-dimensional compounds: Sr4Fe2.5-x□x07.25-(3x/2)(SO4)0.5 (with x = 0.25 and 0.5). They can be described as an intergrowth SrO/SrFeO2,5/SrFe0,5-x□xO1,25-(3x/2)(SO4)0.5/SrFeO2,5 and crystallize in a quadratic mean cell I4/mmm (a=ap et c≈29 Å). The unbridged sulfates tetrahedra are oriented transversely with respect to c ⃗ for x=0.5 and longitudinal for x=0 and 0.25 because bridged to the iron pyramids of the shared layer. The iron atoms of the non-mixed layers SrFeO2,5 are in pyramidal coordination for x=0 and pyramidal and octahedral coordination for x=0.5 and x=0.25, in order to respect the trivalence of iron. However, for x=0.5, two magnetic configurations are observed whereas the compounds x=0 and x=0.25 show only one. In the compound Sr4Fe2.5□xO7.25(SO4)0.25(CO3)0.25, the influence of the carbonates (CO32-) is directly felt on the stacking parameter, which is smaller. The compounds are semiconductors with high electronic resistivity values (of the order of 106Ω.cm) and are not ionic conductors.The ordered phase "15R" SrFe0.6Cr0.4O2.8 becomes disordered when 10% of the iron is substituted with sulfates (SrFe0.5Cr0.4O2.1(SO4)0.1) and adopts a pseudo-cubic structure. Its physical properties are then modified because we switch from a ferromagnetic to an antiferromagnetic behavior (TN=800K). This oxygen-deficient compound shows more or less large structural defects and a semiconductor behavior. No ionic conduction phenomenon is observed.

La compétence du laboratoire dans le domaine du transport électronique a été étendue par un travail métrologique permettant de préciser l’échelle de thermoélectricité notamment en corrigeant l’alumel. Dans une deuxième partie nous avons utilisé l’excellente précision du dispositif expérimental pour mesurer le Pouvoir Thermoélectrique Absolu (PTA) d’échantillons d’Arcelor auparavant caractérisés à haute température par résistivité. Puis nous avons déterminé, pour la première fois, les propriétés de transport électronique de 4 pseudo-alliages en fonction de la température et avons étudié l’effet de leur vieillissement à haute température / The competence of the laboratory in the field of electronic transport has been extended by a metrological work to specify the scale of thermoelectricity correcting that of alumel. In a second part, we used the excellent precision of the experimental device to measure the Absolute Thermoelectric Power (ATP) of Arcelor samples previously characterized at high temperature by resistivity. Then we determined, for the first time, the electronic transport properties of four pseudo-alloys as function of temperature and studied the effect of their ageing at high temperatures

Molybdenum chalcohalide nanowires are systems, which structural, electronic and optical properties have been analyzed in detail. However, their potential as building blocks for electronic devices has not been investigated so far. This question is raised in Dissertation, focusing on unique electronic transport properties of these systems, and comparing them with those of the popular carbon nanotubes.

Cette thèse rapporte les mesures de transport réalisées sur des jonctions moléculaires à l'état solide large échelle, mettant en évidence des effets d'interférence quantique. Le premier chapitre pose les bases théoriques de ce phénomène et introduit le formalisme des fonctions de green hors équilibre adapté à la description du couplage molécules/interfaces métalliques. Le second chapitre présente l'état de l'art expérimental dans ce domaine et résume les principales expériences ayant permis de mettre en évidence des effets d'interférences à l'échelle moléculaire. Le troisième chapitre décrit les étapes de fabrication mises en place pour construire les dispositifs mesures pendant ce travail de thèse. Les résultats expérimentaux obtenus sur les mesures de conductance des jonctions moléculaires sont décrits dans le quatrième chapitre et compares a plusieurs modèles théoriques qui confirme la présence d'interférences quantiques. Le dernier chapitre aborde les effets de thermoélectricité qui peuvent avoir lieu dans ces jonctions en présence d'interférence / This thesis reports the transport measurement performed on large scale solid state molecular junctions, highlighting quantum interference effect. First chapter set the theoretical basis of such a phenomenon and introduces the out of equilibrium green's functions formalism which is adapted to the description of coupling molecules/metallic interfaces. Second chapter presents the corresponding experimental state of the art and summarizes the experiments that have contributed to highlight interference effect at the molecular scale. Third chapter describes the fabrication steps optimized to build the devices measured during the thesis work. Experimental results obtained on conductance measurements are described and compared to several theoretical models that confirm the presence of quantum interference. Last chapter deals with thermoelectric effect that can occur in presence of interference

Replacing electronic components with molecule-sized analogs or hybrids is often seen as a promising alternative to further miniaturization of conventional electronics in the effort to achieve functional nanoscale circuit elements. In this thesis, electronic transport through self-assembled networks with tunable thiolated (alkane(di)thiol and benzenedithiol) molecule-to-colloidal gold (Au) nanoparticle ratios (1:5–50:1) is studied using a combination of broad area and scanning probe microscope-based measurements. The electronic transport paths through the network can be altered by adjusting the (di)thiol molecule–gold nanoparticle ratio and/or type of molecules in the network. Resistance can be controllably tuned by several orders of magnitude (~105 to 1011 ohms for the Au-thiolated structures studied). Two-terminal current–voltage (I-V) measurements of the Au-thiolated networks display linear behavior at low bias. High bias measurements in case of benzenedithiol networks show nonlinear negative differential resistance (NDR) and hysteresis behavior for different benzenedithiol concentrations, which can be attributed to a combination of field-assisted tunneling and charge trapping occurring in the nanoscale networks. Circuit simulations that account for different network morphologies, tunable via molecule-to-nanoparticle ratio, and defects show good agreement with the experiment and provide a guide to engineer network properties using different molecules. In addition, electronic transport properties of nanoscale networks, which are composed of Au metal clusters interconnected with thiolated molecules (benzene/alkanedithiol) and connected in linear chains and branched extended networks, are examined via first-principles density functional theory-based simulations. Calculated I-V characteristics of the metal-molecular networks exhibited nonlinearities and rectification with NDR peaks that became more pronounced with increasing chain length. The transmission spectra of the linear chains and branched networks showed an increase in the number and width of transmission peaks near the Fermi energy, as the structures were extended, indicating enhanced transmission. Peak-to-valley current NDR ratios as large as ~ 500 and rectification ratios of ~ 10 (0.25 V) were shown for linear and branched circuit elements, respectively, illustrating how charge transport through molecular-scale devices could be controlled with precision by modifying the structure and geometry of molecule-nanoparticle networks. These experimental and simulation results are utilized to propose molecular-scale circuits in applications such as memory, switching, and hardware security. The metal nanoparticle molecular electronic networks presented in this thesis provide an avenue for engineering electronics at the molecular level. / Graduate

O emprego de polímeros conjugados e blendas como camada ativa de diodos emissores de luz ou células fotovoltaicas é foco de intenso desenvolvimento científico na atualidade. O desempenho eletro-ótico de tais dispositivos é fortemente dependente das características estruturais e eletrônicas dos componentes poliméricos ou moleculares, que são difíceis de serem quantificadas, demandando a integração de resultados experimentais e modelagem teórica. A desordem intrínseca desses materiais também dificulta a modelagem e a simulação, sendo necessário o emprego de diferentes e complementares métodos e técnicas de física computacional. O presente trabalho tem como objetivo o estudo, em nível atomístico, da correlação entre propriedades morfológicas e eletrônicas de filmes poliméricos com alta desordem de: I) poli-para-fenileno-vinileno (PPV); II) poli-3-hexil-tiofeno (P3HT) e sua blenda com fulereno (C60). Empregamos modelagem por Dinâmica Molecular Clássica dos sistemas desordenados em temperatura finita; implementamos para tal adaptações específicas no Campo de Forças Universal, baseadas em cálculos quânticos de primeiros princípios. Para obtermos a estrutura eletrônica de modelos selecionados utilizamos método de Hartree-Fock semiempírico. O sistema de PPV é estudado com respeito à variação das propriedades morfológicas ao longo do processo de deformação uniaxial. Estabelecemos correspondência entre os efeitos do estiramento e o surgimento de anisotropia no espectro de fotoluminescência observado experimentalmente. Para os sistemas de P3HT simulamos diferentes tipos de empacotamento, estudamos as propriedades morfológicas e calculamos os estados eletrônicos relevantes ao transporte de buracos pelo polímero. Vemos como majoritária a ocorrência de estados com comprimento conjugado de quatro e cinco meros; além disso, com a desordem estrutural os níveis eletrônicos localizados passam a exibir grande proximidade em energia, com pouca relação ao comprimento de conjugação. Isso resulta no surgimento de uma Densidade de Estados gaussiana com largura de aproximadamente 100meV que se mostra independente das diferenças morfológicas entre os modelos simulados. / The use of organic conjugated polymers and blends as active layers of light emitting diodes and photovoltaic cells has been the focus of intense scientific development in recent years. The electro-optical performance of such devices depends strongly on the structural and electronic properties of the polymeric or molecular components, and is of difficult characterization, demanding integration of experimental results and theoretical modeling. A complicating factor to the theoretical modeling is the intrinsic disorder in these materials, which demands the use of different and complementary techniques and methods of computational physics. The goal of the present work is to study at the atomistic level the correlation between morphological and electronic properties of highly disordered films of: I) poly-para-phenylene-vinylene (PPV); II) poly-3-hexyl-thiophene (P3HT) and blends with fullerenes (C60). We applied Classical Molecular Dynamics to model the disordered systems at finite temperature employing the well-known Universal Force Field, to which we implemented specific corrections based on first-principles quantum calculations. For selected models we calculated the electronic structure through semiempirical Hartree-Fock. The PPV system was studied focusing on the effect of uniaxial stretching on morphological properties. We have established a connection between morphology effects and the anisotropy of light emission detected experimentally. For P3HT systems we simulated different packing systems and studied morphological properties, and the electronic structure of the localized states relevant to hole transport in the polymer film. We found higher occurrence of 4- and 5-mer long conjugated electronic states. Moreover, the structural disorder affects the electronic levels, reducing the energy separation of conjugated segments of different lengths. This makes possible the occurrence of a gaussian Density of States of approximately 100meV width, regardless of the different morphological signatures of the different simulated models.