Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

Extreme ultraviolet detection using AlGaN-on-Si inverted Schottky photodiodes

We report on the fabrication of aluminum gallium nitride (AlGaN) Schottky diodes for extreme ultraviolet (EUV) detection. AlGaN layers were grown on silicon wafers by molecular beam epitaxy with the conventional and inverted Schottky structure, where the undoped, active layer was grown before or after the n-doped layer, respectively. Different current mechanisms were observed in the two structures. The inverted Schottky diode was designed for the optimized backside sensitivity in the hybrid imagers. A cut-off wavelength of 280 nm was observed with three orders of magnitude intrinsic rejection ratio of the visible radiation. Furthermore, the inverted structure was characterized using a EUV source based on helium discharge and an open electrode design was used to improve the sensitivity. The characteristic He I and He II emission lines were observed at the wavelengths of 58.4 nm and 30.4 nm, respectively, proving the feasibility of using the inverted layer stack for EUV detection

Silicon Photomultipliers (SiPM) as novel photodetectors for PET

Next generation PET scanners should fulfill very high requirements in terms of spatial, energy and timing resolution. Modern scanner performances are inherently limited by the use of standard photomultiplier tubes. The use of Silicon Photomultipliers (SiPMs) is proposed for the construction of a 4D-PET module of 4.8×4.8 cm2 aimed to replace the standard PMT based PET block detector. The module will be based on a LYSO continuous crystal read on two faces by Silicon Photomultipliers. A high granularity detection surface made by SiPM matrices of 1.5 mm pitch will be used for the x–y photon hit position determination with submillimetric accuracy, while a low granularity surface constituted by 16 mm2 SiPM pixels will provide the fast timing information (t) that will be used to implement the Time of Flight technique (TOF). The spatial information collected by the two detector layers will be combined in order to measure the Depth of Interaction (DOI) of each event (z). The use of large area multi-pixel Silicon Photomultiplier (SiPM) detectors requires the development of a multichannel Data Acquisition system (DAQ) as well as of a dedicated front-end in order not to degrade the intrinsic detector capabilities and to manage many channels. The paper describes the progress made on the development of the proof of principle module under construction at the University of Pisa.

Biosensors based on vertically interrogated optofluidic sensing cells

El objetivo de la presente tesis doctoral es el desarrollo de un nuevo concepto de biosensor óptico sin marcado, basado en una combinación de técnicas de caracterización óptica de interrogación vertical y estructuras sub-micrométricas fabricadas sobre chips de silicio. Las características más importantes de dicho dispositivo son su simplicidad, tanto desde el punto de vista de medida óptica como de introducción de las muestras a medir en el área sensible, aspectos que suelen ser críticos en la mayoría de sensores encontrados en la literatura. Cada uno de los aspectos relacionados con el diseño de un biosensor, que son fundamentalmente cuatro (diseño fotónico, caracterización óptica, fabricación y fluídica/inmovilización química) son desarrollados en detalle en los capítulos correspondientes. En la primera parte de la tesis se hace una introducción al concepto de biosensor, en qué consiste, qué tipos hay y cuáles son los parámetros más comunes usados para cuantificar su comportamiento. Posteriormente se realiza un análisis del estado del arte en la materia, enfocado en particular en el área de biosensores ópticos sin marcado. Se introducen también cuáles son las reacciones bioquímicas a estudiar (inmunoensayos). En la segunda parte se describe en primer lugar cuáles son las técnicas ópticas empleadas en la caracterización: Reflectometría, Elipsometría y Espectrometría; además de los motivos que han llevado a su empleo. Posteriormente se introducen diversos diseños de las denominadas "celdas optofluídicas", que son los dispositivos en los que se va a producir la interacción bioquímica. Se presentan cuatro dispositivos diferentes, y junto con ellos, se proponen diversos métodos de cálculo teórico de la respuesta óptica esperada. Posteriormente se procede al cálculo de la sensibilidad esperada para cada una de las celdas, así como al análisis de los procesos de fabricación de cada una de ellas y su comportamiento fluídico. Una vez analizados todos los aspectos críticos del comportamiento del biosensor, se puede realizar un proceso de optimización de su diseño. Esto se realiza usando un modelo de cálculo simplificado (modelo 1.5-D) que permite la obtención de parámetros como la sensibilidad y el límite de detección de un gran número de dispositivos en un tiempo relativamente reducido. Para este proceso se escogen dos de las celdas optofluídicas propuestas. En la parte final de la tesis se muestran los resultados experimentales obtenidos. En primer lugar, se caracteriza una celda basada en agujeros sub-micrométricos como sensor de índice de refracción, usando para ello diferentes líquidos orgánicos; dichos resultados experimentales presentan una buena correlación con los cálculos teóricos previos, lo que permite validar el modelo conceptual presentado. Finalmente, se realiza un inmunoensayo químico sobre otra de las celdas propuestas (pilares nanométricos de polímero SU-8). Para ello se utiliza el inmunoensayo de albumina de suero bovino (BSA) y su anticuerpo (antiBSA). Se detalla el proceso de obtención de la celda, la funcionalización de la superficie con los bioreceptores (en este caso, BSA) y el proceso de biorreconocimiento. Este proceso permite dar una primera estimación de cuál es el límite de detección esperable para este tipo de sensores en un inmunoensayo estándar. En este caso, se alcanza un valor de 2.3 ng/mL, que es competitivo comparado con otros ensayos similares encontrados en la literatura. La principal conclusión de la tesis es que esta tipología de dispositivos puede ser usada como inmunosensor, y presenta ciertas ventajas respecto a los actualmente existentes. Estas ventajas vienen asociadas, de nuevo, a su simplicidad, tanto a la hora de medir ópticamente, como dentro del proceso de introducción de los bioanalitos en el área sensora (depositando simplemente una gota sobre la micro-nano-estructura). Los cálculos teorícos realizados en los procesos de optimización sugieren a su vez que el comportamiento del sensor, medido en magnitudes como límite de detección biológico puede ser ampliamente mejorado con una mayor compactación de pilares, alcanzandose un valor mínimo de 0.59 ng/mL). The objective of this thesis is to develop a new concept of optical label-free biosensor, based on a combination of vertical interrogation optical techniques and submicron structures fabricated over silicon chips. The most important features of this device are its simplicity, both from the point of view of optical measurement and regarding to the introduction of samples to be measured in the sensing area, which are often critical aspects in the majority of sensors found in the literature. Each of the aspects related to the design of biosensors, which are basically four (photonic design, optical characterization, fabrication and fluid / chemical immobilization) are developed in detail in the relevant chapters. The first part of the thesis consists of an introduction to the concept of biosensor: which elements consists of, existing types and the most common parameters used to quantify its behavior. Subsequently, an analysis of the state of the art in this area is presented, focusing in particular in the area of label free optical biosensors. What are also introduced to study biochemical reactions (immunoassays). The second part describes firstly the optical techniques used in the characterization: reflectometry, ellipsometry and spectrometry; in addition to the reasons that have led to their use. Subsequently several examples of the so-called "optofluidic cells" are introduced, which are the devices where the biochemical interactions take place. Four different devices are presented, and their optical response is calculated by using various methods. Then is exposed the calculation of the expected sensitivity for each of the cells, and the analysis of their fabrication processes and fluidic behavior at the sub-micrometric range. After analyzing all the critical aspects of the biosensor, it can be performed a process of optimization of a particular design. This is done using a simplified calculation model (1.5-D model calculation) that allows obtaining parameters such as sensitivity and the detection limit of a large number of devices in a relatively reduced time. For this process are chosen two different optofluidic cells, from the four previously proposed. The final part of the thesis is the exposition of the obtained experimental results. Firstly, a cell based sub-micrometric holes is characterized as refractive index sensor using different organic fluids, and such experimental results show a good correlation with previous theoretical calculations, allowing to validate the conceptual model presented. Finally, an immunoassay is performed on another typology of cell (SU-8 polymer pillars). This immunoassay uses bovine serum albumin (BSA) and its antibody (antiBSA). The processes for obtaining the cell surface functionalization with the bioreceptors (in this case, BSA) and the biorecognition (antiBSA) are detailed. This immunoassay can give a first estimation of which are the expected limit of detection values for this typology of sensors in a standard immunoassay. In this case, it reaches a value of 2.3 ng/mL, which is competitive with other similar assays found in the literature. The main conclusion of the thesis is that this type of device can be used as immunosensor, and has certain advantages over the existing ones. These advantages are associated again with its simplicity, by the simpler coupling of light and in the process of introduction of bioanalytes into the sensing areas (by depositing a droplet over the micro-nano-structure). Theoretical calculations made in optimizing processes suggest that the sensor Limit of detection can be greatly improved with higher compacting of the lattice of pillars, reaching a minimum value of 0.59 ng/mL).

Stopping power dependence of nitrogen sputtering yields in copper nitride films under swift-ion irradiation: Exciton model approach

Nitrogen sputtering yields as high as 104 atoms/ion, are obtained by irradiating N-rich-Cu3N films (N concentration: 33 ± 2 at.%) with Cu ions at energies in the range 10?42 MeV. The kinetics of N sputtering as a function of ion fluence is determined at several energies (stopping powers) for films deposited on both, glass and silicon substrates. The kinetic curves show that the amount of nitrogen release strongly increases with rising irradiation fluence up to reaching a saturation level at a low remaining nitrogen fraction (5?10%), in which no further nitrogen reduction is observed. The sputtering rate for nitrogen depletion is found to be independent of the substrate and to linearly increase with electronic stopping power (Se). A stopping power (Sth) threshold of ?3.5 keV/nm for nitrogen depletion has been estimated from extrapolation of the data. Experimental kinetic data have been analyzed within a bulk molecular recombination model. The microscopic mechanisms of the nitrogen depletion process are discussed in terms of a non-radiative exciton decay model. In particular, the estimated threshold is related to a minimum exciton density which is required to achieve efficient sputtering rates.

Improved GaN-based HEMT performance by nanocrystalline diamond capping

As a wide-bandgap semiconductor, gallium nitride (GaN) is an attractive material for next-generation power devices. To date, the capabilities of GaN-based high electron mobility transistors (HEMTs) have been limited by self-heating effects (drain current decreases due to phonon scattering-induced carrier velocity reductions at high drain fields). Despite awareness of this, attempts to mitigate thermal impairment have been limited due to the difficulties involved with placing high thermal conductivity materials close to heat sources in the device. Heat spreading schemes have involved growth of AIGaN/GaN on single crystal or CVD diamond, or capping of fullyprocessed HEMTs using nanocrystalline diamond (NCD). All approaches have suffered from reduced HEMT performance or limited substrate size. Recently, a "gate after diamond" approach has been successfully demonstrated to improve the thermal budget of the process by depositing NCD before the thermally sensitive Schottky gate and also to enable large-area diamond implementation.

Understanding phosphorus diffusion into silicon in a MOVPE environment for III-V on silicon solar cells

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon bottom cell seem to be attractive candidates to materialize the long sought-for integration of III?V materials on silicon for photovoltaic applications. When manufacturing a multi-junction solar cell on silicon, one of the first processes to be addressed is the development of the bottom subcell and, in particular, the formation of its emitter. In this study, we analyze, both experimentally and by simulations, the formation of the emitter as a result of phosphorus diffusion that takes place during the first stages of the epitaxial growth of the solar cell. Different conditions for the Metal-Organic Vapor Phase Epitaxy (MOVPE) process have been evaluated to understand the impact of each parameter, namely, temperature, phosphine partial pressure, time exposure and memory effects in the final diffusion profiles obtained. A model based on SSupremIV process simulator has been developed and validated against experimental profiles measured by ECV and SIMS to calculate P diffusion profiles in silicon formed in a MOVPE environment taking in consideration all these factors.

Mechanical characterization of multicrystalline silicon wafers

The possibility of using more economical silicon feedstock, i.e. as support for epitaxial solar cells, is of interest when the cost reduction and the properties are attractive. We have investigated the mechanical behavior of two blocks of upgraded metallurgical silicon, which is known to present high content of impurities even after being purified by the directional solidification process. The impurities are mainly metals like Al and silicon compounds. Thus, it is important to characterize their effect in order to improve cell performance and to ensure the survival of the wafers throughout the solar value chain. Microstructure and mechanical properties were studied by means of ring on ring and three point bending tests. Additionally, Young’s modulus, hardness and fracture toughness were measured. These results showed that it is possible to obtain marked improvements in toughness when impurities act as microscopic internal crack arrestors. However, the same impurities can be initiators of damage due to residual thermal stresses introduced during the crystallization process.

Full-Wafer Roller-NIL Processes for Silicon Solar Cell Texturisation

The highest solar cell efficiencies both for c-Si and mc-Si were reached using template based texturing processes. Especially for mc-Si the benefit of a defined texture, the so called honeycomb texture, was demonstrated impressively. However, up until now, no industrially feasible process has been available to pattern the necessary etching masks with the sufficient resolution. Roller-Nanoimprint Lithography (Roller-NIL) has the potential to overcome these limitations and to allow high quality pattern transfers, even in the sub-micron regime, in continuous in-line processes. Therefore, this etch-mask patterning technique is a suitable solution to bring such elaborate features like the honeycomb texture to an industrial realization. Beyond that, this fast printing-like technology opens up new possibilities to introduce promising concepts like photonic structures into solar cells.

On track for solar grade silicon through a siemens process-type laboratory reactor: operating conditions and energy savings

Polysilicon cost impacts significantly on the photovoltaics (PV) cost and on the energy payback time. Nowadays, the besetting production process is the so called Siemens process, polysilicon deposition by chemical vapor deposition (CVD) from Trichlorosilane. Polysilicon purification level for PV is to a certain extent less demanding that for microelectronics. At the Instituto de Energía Solar (IES) research on this subject is performed through a Siemens process-type laboratory reactor. Through the laboratory CVD prototype at the IES laboratories, valuable information about the phenomena involved in the polysilicon deposition process and the operating conditions is obtained. Polysilicon deposition by CVD is a complex process due to the big number of parameters involved. A study on the influence of temperature and inlet gas mixture composition on the polysilicon deposition growth rate, based on experimental experience, is shown. Moreover, CVD process accounts for the largest contribution to the energy consumption of the polysilicon production. In addition, radiation phenomenon is the major responsible for low energetic efficiency of the whole process. This work presents a model of radiation heat loss, and the theoretical calculations are confirmed experimentally through a prototype reactor at our disposal, yielding a valuable know-how for energy consumption reduction at industrial Siemens reactors.

The Influence of Different Surface Treatments on the Mechanical Strength of Silicon Wafers

The implementation of photovoltaic solar energy based on silicon is being slowed down by the shortage of raw material. In this context, the use of thinner wafers arises as a solution reducing the amount of silicon in the photovoltaic modules. On the other hand, the manufacturing process with thinner wafers can become complicated with traditional tools. The high number of damaged wafers reduces the global yield. It’s known that edge and surface cracks and defects determine the mechanical strength of wafers. There are several ways of removing these defects e. g. subjecting wafers to a mechanical polishing or to a chemical etching. This paper shows a comparison between different surface treatments and their influence on the mechanical strength.

A function using cubic splines for the analysis of alpha--particles spectra from silicon detectors

A function based on the characteristics of the alpha-particle lines obtained with silicon semiconductor detectors and modi"ed by using cubic splines is proposed to parametrize the shape of the peaks. A reduction in the number of parameters initially considered in other proposals was carried out in order to improve the stability of the optimization process. It was imposed by the boundary conditions for the cubic splines term. This function was then able to describe peaks with highly anomalous shapes with respect to those expected from this type of detector. Some criteria were implemented to correctly determine the area of the peaks and their errors. Comparisons with other well-established functions revealed excellent agreement in the "nal values obtained from both "ts. Detailed studies on reliability of the "tting results were carried out and the application of the function is proposed. Although the aim was to correct anomalies in peak shapes, the peaks showing the expected shapes were also well "tted. Accordingly, the validity of the proposal is quite general in the analysis of alpha-particle spectrometry with semiconductor detectors.