Les diodes électroluminescentes hybrides organiques-inorganiques ou Quantum Dot- Light-Emitting Diodes (QD-LED) sont le parangon de dispositifs qui associeraient les propriétés semi-conductrices des matériaux organiques conjugués, ainsi que leur facilité de mise en oeuvre en couche mince, aux propriétés exceptionnelles (couleur accordable par la taille, bon rendement quantique de photoluminescence) des nanoparticules nanométriques de semi-conducteurs inorganiques, telles que CdSe/ZnS (TOPO). Diverses approches ont été explorées pour optimiser les QD-LEDs ; elles reposent sur la réalisation d'architectures diverses (uni, bi, tri couches) combinant matériaux organiques et QDs (en couche compacte ou dispersés dans une matrice), obtenues par diverses méthodes de dépôt (spin coating, tampon, impression jet d'encre). Dans ce travail de thèse, nous avons d'abord réalisé une structure originale sous forme de diodes comportant une couche hybride nanocomposite, obtenue en incorporant les QDs dans une matrice diélectrique de PMMA. Le but était de contrôler les flux de porteurs pour maximiser leur recombinaison sur les QDs. Les mesures des caractéristiques électriques, d'électro- et photoluminescence sont discutées, conjointement à des études de la morphologie des dépôts par AFM qui ont montré comment la microstructure dépendait des caractéristiques du, ou des, solvant(s) utilisé(s) pour le spin coating. D'une façon générale, les nanoparticules sont agrégées et la couche apparait inhomogène et rugueuse, ce qui permet des contacts entre les couches de transport. La faible électroluminescence résulterait de transferts d'excitation à partir d'états excités produits par les recombinaisons à ces endroits. Dans une seconde partie, nous avons déposé les QDs par spin coating à partir de solutions dans l'heptane, un solvant qui ne perturbe pas les couches organiques préalablement déposées. Les morphologies observées sont celles d'ilots compacts, avec des taux de couverture allant de 0 à 100%. La diminution, puis la disparition, de l'électroluminescence aux fortes couvertures confirme que l'émission des QDs provient exclusivement de transferts d'excitation à partir d'espèces excitées générées à l'interface organique-organique, en fonction de la nature des matériaux organiques. Les mécanismes d'injection des porteurs à la cathode, dépendant de la nature de celle-ci et de la couche de transport d'électrons, sont variables eux-aussi.

To reproduce color images in print, the continuous tone image is first transformed into a binary halftone image, producing various colors by discrete dots with varying area coverage. In halftone prints on paper, physical and optical dot gains generally occur, making the print look darker than expected, and making the modeling of halftone color reproduction a challenge. Most available models are based on macroscopic color measurements, averaging the reflectance over an area that is large in relation to the halftone dots. The aim of this study is to go beyond the macroscopic approach, and study halftone color reproduction on a micro-scale level, using high resolution images of halftone prints. An experimental imaging system, combining the accuracy of color measurement instruments with a high spatial resolution, opens up new possibilities to study and analyze halftone color prints. The experimental image acquisition offers a great flexibility in the image acquisition setup. Besides trichromatic RGB filters, the system is also equipped with a set of 7 narrowband filters, for multi-channel images. A thorough calibration and characterization of all the components in the imaging system is described. The spectral sensitivity of the CCD camera, which can not be derived by direct measurements, is estimated using least squares regression. To reconstruct spectral reflectance and colorimetric values from the device response, two conceptually different approaches are used. In the model-based characterization, the physical model describing the image acquisition process is inverted, to reconstruct spectral reflectance from the recorded device response. In the empirical characterization, the characteristics of the individual components are ignored, and the functions are derived by relating the device response for a set of test colors to the corresponding colorimetric and spectral measurements, using linear and polynomial least squares regression techniques. Micro-scale images, referring to images whose resolution is high in relation to the resolution of the halftone, allow for measurements of the individual halftone dots, as well as the paper between them. To capture the characteristics of large populations of halftone dots, reflectance histograms are computed as well as 3D histograms in CIEXYZ color space. The micro-scale measurements reveal that the reflectance for the halftone dots, as well as the paper between the dots, is not constant, but varies with the dot area coverage. By incorporating the varying micro-reflectance in an expanded Murray-Davies model, the nonlinearity caused by optical dot gain can be accounted for without applying the nonphysical exponentiation of the reflectance values, as in the commonly used Yule-Nielsen model. Due to their different intrinsic nature, physical and optical dot gains need to be treated separately when modeling the outcome of halftone prints. However, in measurements of reflection colors, physical and optical dot gains always co-exist, making the separation a difficult task. Different methods to separate the physical and optical dot gain are evaluated, using spectral reflectance measurements, transmission scans and micro-scale images. Further, the relation between the physical dot gain and the halftone dot size is investigated, demonstrated with FM halftones of various print resolutions. The physical dot gain exhibits a clear correlation with the dot size and the dot gain increase is proportional to the increase in print resolution. The experimental observations are followed by discussions and a theoretical explanation.

Photon detectors based on single-crystalline materials are of great interest for high performance imaging applications due to their low noise and fast response. The major detector materials for sensing in the long-wavelength infrared (LWIR) band (8-14 µm) are currently HgCdTe (MCT) and AlGaAs/GaAs quantum wells (QW) used in intraband-based quantum-well infrared photodetectors (QWIPs). These either suffer from compositional variations that are detrimental to the system performance as in the case of MCT, or, have an efficient dark current generation mechanism that limits the operating temperature as for QWIPs. The need for increased on-wafer uniformity and elevated operating temperatures has resulted in the development of various alternative approaches, such as type-II strained-layer superlattice detectors (SLSs) and intraband quantum-dot infrared photodetectors (QDIPs). In this work, we mainly explore two self-assembled quantum-dot (QD) materials for use as the absorber material in photon detectors for the LWIR, with the aim to develop low-dark current devices that can allow for high operating temperatures and high manufacturability. The detection mechanism is here based on type-II interband transitions from bound hole states in the QDs to continuum states in the matrix material. Metal-organic vapor-phase epitaxy (MOVPE) was used to fabricate (Al)GaAs(Sb)/InAs and In(Ga)Sb/InAs QD structures for the development of an LWIR active material. A successive analysis of (Al)GaAs(Sb) QDs using absorption spectroscopy shows strong absorption in the range 6-12 µm interpreted to originate in intra-valence band transitions. Moreover, record-long photoluminescence (PL) wavelength up to 12 µm is demonstrated in InSb- and InGaSb QDs. Mesa-etched single-pixel photodiodes were fabricated in which photoresponse is demonstrated up to 8 µm at 230 K with 10 In0.5Ga0.5Sb QD layers as the active region. The photoresponse is observed to be strongly temperature-dependent which is explained by hole trapping in the QDs. In the current design, the photoresponse is thermally limited at typical LWIR sensor operating temperatures (60-120 K), which is detrimental to the imaging performance. This can potentially be resolved by selecting a matrix material with a smaller barrier for thermionic emission of photo-excited holes. If such an arrangement can be achieved, type-II interband InGaSb QD structures can turn out to be interesting as a high-operating-temperature sensor material for thermal imaging applications. / <p>QC 20130521</p>

The commercially available solar cells suffer from low conversion efficiency due to the thermalization and transmission losses arising from the mismatch between the band gap of the semiconductor materials and the solar spectrum. Advanced device architectures based on nanomaterial have been proposed and being successfully used to enhance the efficiency of the solar cells. Quantum dots (QDs) and nanowires (NWs) are the nanosclae structures that have been exploited for the development of the third generation solar cell devices and nanowire based solar cells, respectively. The optical and electrical properties of these materials can be tuned by their size and geometry; hence they have great potential for the production of highly efficient solar cell. Application of QDs and NWs with enhanced optoelectronic properties and development of low-cost fabrication processes render a new generation of economic highly efficient PV devices. The most significant contribution of this PhD study is the development of simple and cost effective methods for fabrication of nanowires and quantum dots for advanced solar cell architectures. In advanced silicon nanowires (SiNWs) array cell, SiNWs have been widely synthesised by the well-known vapor-liquid-solid method. Electron beam lithography and deep reactive ion etching have also been employed for fabrication of SiNWs. Due to the high price and complexity of these methods, simple and cost effective approaches are needed for the fabrication of SiNWs. In another approach, to enhance the cell efficiency, organic dyes and polymers have been widely used as luminescent centers and host mediums in the luminescent down shifting (LDS) layers. However, due to the narrow absorption band of the dyes and degradation of the polymers by moisture and heat, these materials are not promising candidates to use as LDS. Highly efficient luminescent materials and transparent host materials with stable mechanical properties are demanded for luminescent down shifting applications. In this project, simple fabrication processes were developed to produce SiNWs and QDs for application in advanced cell architectures. The SiNWs array were successfully fabricated, characterized and deployed in new cell architectures with radial p-n junction geometry. The luminescence down shifting of layers containing QDs in oxide and glass mediums was verified. The silica coated quantum dots which are suitable for luminescence down shifting, were also fabricated and characterized for deployment in new design architectures. Silicon nanowires were fabricated using two simplified methods. In the first approach, a maskless reactive ion etching process was developed to form upright ordered arrays of the SiNWs without relying on the complicated nano-scale lithography or masking methods. The fabricated structures were comprehensively characterized. Light trapping and photoluminescence properties of the medium were verified. In the second approach, combination of the nanosphere lithography and etching techniques were utilized for wire formation. This method provides a better control on the wire diameters and geometries in a very simple and cost effective way. The fabricated silicon nanowires were used for formation of the radial p-n junction array cells. The functionality of the new cell structures were confirmed through experimental and simulation results. Quantum dots are promising candidates as luminescent centers due to their tunable optical properties. Oxide/glass matrices are also preferred as the host medium for QDs because of their robust mechanical properties and their compatibility with standard silicon processing technology. Besides, the oxide layers are transparent mediums with good passivation and anti-reflection coating properties. They can also be used to encapsulate the cell. In this work, ordered arrays of QDs were incorporated in an oxide layer to form a luminescent down shifting layer. This design benefits from the enhanced absorption of a periodic QD structure in a transparent oxide. The down shifting properties of the layer after deployment on a crystalline silicon solar cell were examined. For this purpose, crystalline silicon solar cells were fabricated to use as test platform for down shifting. In order to examine the down-shifting effect, different approaches for formation of a luminescence down shifting layer were developed. The LDS layer consist of cadmium selenide- zinc sulfide (CdSe/ZnS) quantum dots in oxide and glass layers to act as luminescent centers and transparent host medium, respectively. The structural and optical properties of the fabricated layers were studied. The concept of spectral engineering was proved by the deployment of the layer on the solar cell. To further benefit from the LDS technique, quantum efficiency of the QDs and optical properties of the layer must be improved. Demand for the high quantum efficiency material with desired geometry leaded us to synthesis quantum dots coated with a layer of grown oxide. As the luminescence quantum efficiency of the QDs is correlated to the surface defects, one advantage of having oxide on the outer shell of the QDs, is to passivate the surface non-radiative recombination centers and produce QDs with high luminescent quantum yield. In addition, nanoparticles with desired size can be obtained only by changing the thickness of the oxide shell. This method also simplifies the fabrication of QD arrays for luminescence down shifting application, since it is easier to form ordered arrays from larger particles. QD superlattices in an oxide medium can be fabricated on a large area by a simple spin-coating or dip coating methods. The photonic crystal properties of the proposed structure can greatly increase the absorption in the QDs layer and enhance the effect of down shifting.

Semiconductor quantum dots and metal nanoparticles feature very strong light-matter interactions, which has led to their use in many photonic applications such as photodetectors, biosensors, components for telecommunications etc.Under illumination both structures exhibit collective electron-photon resonances, described in the frameworks of quasiparticles as exciton-polaritons for semiconductors and surface plasmon-polaritons for metals.To date these two approaches to controlling light interactions have usually been treated separately, with just a few simple attempts to consider exciton-plasmon interactions in a system consisting of both semiconductor and metal nanostructures.In this work, the exciton-polaritons and surface \\plasmon-polaritons are first considered separately, and then combined using the Finite Difference Time Domain numerical method coupled with a master equation for the exciton-polariton population dynamics.To better understand the properties of excitons and plasmons, each quasiparticle is used to investigate two open questions - the source of the Stokes shift between the absorption and luminescence peaks in quantum dots, and the source of the photocurrent increase in quantum dot infrared photodetectors coated by a thin metal film with holes. The combined numerical method is then used to study a system consisting of multiple metal nanoparticles close to a quantum dot, a system which has been predicted to exhibit quantum dot-induced transparency, but is demonstrated to just have a weak dip in the absorption. / <p>QC 20120417</p>

Herein, we report the first solution-processed broadband photodetectors to break the past compromise between sensitivity and speed of response. Specifically, we report photodiodes having normalized detectivity (D*) > 1012 Jones and a 3dB bandwidth of > 2.9 MHz. This finding represents a 170,000 fold improvement in response speed over the most sensitive colloidal quantum dot (CQD) photodetector reported1 and a 100,000 fold improvement in sensitivity over the fastest CQD photodetector reported2. At the outset of this study, sensitive, solution-processed IR photodetectors were severely limited by low response speeds1. Much faster response speeds had been demonstrated by solution-processed photodetectors operating in the visible3, but these devices offered no benefits for extending the spectral sensitivity of silicon. No available solution-processed photodetector combined high sensitivity, high operating speed, and response to illumination across the UV, visible and IR. We developed a fast, sensitive, solution-processed photodetector based on a photodiode formed by a Schottky barrier to a CQD film. Previous attempts to form sensitive photodetectors based on CQD photodiodes had demonstrated low quantum efficiencies that limited sensitivity4,5. Efficient, sensitive semiconductor photodiodes are based on two fundamental characteristics: a large built-in potential that separates photogenerated charge carriers and minimizes internal noise generation, and high semiconductor conductivity for efficient collection of photogenerated charge. Schottky barriers to CQD films were developed to provide high, uniform built-in potentials. A multi-step CQD ligand exchange procedure was developed to allow deposition of tightly packed films of CQDs with high mobility and sufficiently well-passivated surfaces to form high-quality metallurgical junctions. The temporal response of the CQD photodiodes showed separate drift and diffusion components. Combined with detailed measurements of the Schottky barrier, these characteristics provided the physical basis for a numerical model of device operation. Based on this understanding, devices that excluded the slow diffusive component were fabricated, exploiting only the sub-microsecond field-driven transient to achieve MHz response bandwidth. These devices are the first to combine megahertz-bandwidth, high sensitivity, and spectral-tunability in photodetectors based on semiconducting CQDs. Record performance is achieved through advances in materials and device architecture based on a detailed understanding the physical mechanisms underlying the operation of CQD photodiodes.

Herein, we report the first solution-processed broadband photodetectors to break the past compromise between sensitivity and speed of response. Specifically, we report photodiodes having normalized detectivity (D*) > 1012 Jones and a 3dB bandwidth of > 2.9 MHz. This finding represents a 170,000 fold improvement in response speed over the most sensitive colloidal quantum dot (CQD) photodetector reported1 and a 100,000 fold improvement in sensitivity over the fastest CQD photodetector reported2. At the outset of this study, sensitive, solution-processed IR photodetectors were severely limited by low response speeds1. Much faster response speeds had been demonstrated by solution-processed photodetectors operating in the visible3, but these devices offered no benefits for extending the spectral sensitivity of silicon. No available solution-processed photodetector combined high sensitivity, high operating speed, and response to illumination across the UV, visible and IR. We developed a fast, sensitive, solution-processed photodetector based on a photodiode formed by a Schottky barrier to a CQD film. Previous attempts to form sensitive photodetectors based on CQD photodiodes had demonstrated low quantum efficiencies that limited sensitivity4,5. Efficient, sensitive semiconductor photodiodes are based on two fundamental characteristics: a large built-in potential that separates photogenerated charge carriers and minimizes internal noise generation, and high semiconductor conductivity for efficient collection of photogenerated charge. Schottky barriers to CQD films were developed to provide high, uniform built-in potentials. A multi-step CQD ligand exchange procedure was developed to allow deposition of tightly packed films of CQDs with high mobility and sufficiently well-passivated surfaces to form high-quality metallurgical junctions. The temporal response of the CQD photodiodes showed separate drift and diffusion components. Combined with detailed measurements of the Schottky barrier, these characteristics provided the physical basis for a numerical model of device operation. Based on this understanding, devices that excluded the slow diffusive component were fabricated, exploiting only the sub-microsecond field-driven transient to achieve MHz response bandwidth. These devices are the first to combine megahertz-bandwidth, high sensitivity, and spectral-tunability in photodetectors based on semiconducting CQDs. Record performance is achieved through advances in materials and device architecture based on a detailed understanding the physical mechanisms underlying the operation of CQD photodiodes.

Childhood maltreatment increases risk for Posttraumatic Stress Disorder (PTSD). Maladaptive patterns of attention to threat-related stimuli warrant examination as possible contributing risk factors. It remains unclear whether persistent threat-processing biases are differentially apparent in adults who were maltreated as children and either did, or did not, develop later PTSD. The present study examined associations among attention bias, childhood maltreatment, and PTSD in adults. We hypothesized that attentional bias toward threat significantly mediates associations between childhood maltreatment and adult PTSD symptoms. 183 adults with and without childhood maltreatment histories participated in this study, which involved completion of a range of clinical measures; attention bias was measured by the Dot Probe task. We found that attention bias toward happy faces partially mediated the relationship between childhood maltreatment and PTSD avoidance and numbing symptoms. Childhood maltreatment, happy face attention bias, and perceived racially discriminative experiences all accounted for significant variance in PTSD symptoms.

In this study silicon-germanium quantum dots grown on silicon have been investigated. The aim of the work was to find quantum dots suitable for use as a thermistor material. The quantum dots were produced at KTH, Stockholm, using a RPCVD reactor that is designed for industrial production. The techniques used to study the quantum dots were: HRSEM, AFM, HRXRD, FTPL, and Raman spectroscopy. Quantum dots have been produced in single and multilayer structures. As a result of this work a multilayer structure with 5 layers of quantum dots was produced with a theoretical temperature coefficient of resistance of 4.1 %/K.

<p>Quantum Dot Infrared Photodetectors (QDIPs) are important alternatives to conventional infrared photodetectors with high potential to provide required detector performance, such as higher temperature operation and multispectral response, due to the 3-D quantum confinement of electrons, discrete energy levels, and intrinsic response to perpendicular incident light due to selection rules. However, excessive dark current density, which causes QDIPs to underperform theoretical predictions, is a limiting factor for the advancement of QDIP technologies. The purpose of this dissertation research is to achieve a better understanding of dopant incorporation into the active region of QDIPs, which is directly related to dark current control and spectral response. From this dissertation research, doping related dipole fields are found to be responsible for excessive dark current in QDIPs. </p><p>InAs/GaAs QDIPs were grown using solid source molecular beam epitaxy (MBE) with different doping conditions. The QDIPs were optically characterized using photoluminescence and Fourier transform infrared (FT-IR) spectroscopy. Devices were fabricated using standard cleanroom fabrication procedures. Dark current and capacitance measurements were performed under different temperature to reveal electronic properties of the materials and devices. A novel scanning capacitance microscopy (SCM) technique was used to study the band structure and carrier concentration on the cross section of a quantum dot (QD) heterostructure. In addition, dark current modeling and bandstructure calculations were performed to verify and better understand experimental results.</p><p>Two widely used QDIP doping methods with different doping concentrations have been studied in this dissertation research, namely direct doping in InAs QD layer, and modulation doping in the GaAs barrier above InAs QD layer. In the SCM experiment, electron redistribution has been observed due to band-bending in the modulation-doping region, while there is no band-bending observed in directly doped samples. A good agreement between the calculated bandstructure and experimental results leads to better understanding of doping in QD structures. The charge filling process in QDs has been observed by an innovative polarization-dependent FT-IR spectroscopy. The red-shift of QD absorbance peaks with increasing electron occupation supports a miniband electronic configuration for high-density QD ensembles. In addition, the FT-IR measurement indicates the existence of donor-complex (DX) defect centers in Si-doped QDIPs. The existence of DX centers and related dipole fields have been confirmed by dark current measurements to extract activation energies and by photocapacitance quenching measurements. </p><p>With the understanding achieved from experimental results, a further improved dark current model has been developed based on the previous model originally established by Ryzhii and improved by Stiff-Roberts. In the model described in this dissertation, two new factors have been considered. The inclusion of background drift current originating from Si shallow donors in the low bias region results in excellent agreement between calculated and measured dark currents at different temperatures, which has not been achieved by previous models. A very significant effect has been observed in that dark current leakage occurs due to the dipole field caused by doping induced charge distribution and impact-ionized DX centers. </p><p>Last but not least, QDIPs featuring the dipole interface doping (DID) method have been designed to reduce the dark current density without changing the activation energy (thus detection wavelength) of QDIPs. The DID samples involve an InAs QD layer directly-doped by Si, as well as Be doping in the GaAs barrier on both sides of the QD layer. The experimental result shows the dark current density has been significantly reduced by 104 times without any significant change to the corresponding activation energy. However, the high p-type doping in the GaAs barrier poses a challenge in that the Fermi level is reduced to be well below the QD energy states. High p-type doping is reported to reduce the dark current, photocurrent and the responsivity of the devices. </p><p>To conclude, it is significant to identify to effect of Si-induced defect centers on QDIP dark currents. The subsequent study reveals doping induced dipole fields can have significant effects on QDIP device performance, for example, causing charge leakage from QDs and reducing activation energy, thereby increasing dark current density. The DID approach developed in this work is a promising approach that could help address these issues by using controlled dipole fields to reduce dark current density without changing the minimum detectable energy of QDIPs.</p> / Dissertation