Investigation of refractory dielectrics for integrated circuits

Pyrolytic silicon nitride dielectric for integrated circuit

An investigation of electrical and optical properties of sputtered amorphous silicon nitride and germanium thin films

Low temperature preparation of thin amorphous Silicon Nitride and Germanium Films by direct RF sputter deposition was investigated. Influence of various sputtering parameters on film properties was studied. Infrared transmission spectrophotometry was used to evaluate optical properties of the films whereas electrical characteristics of the films were determined from current-voltage measurements of MIS structures. For Silicon Nitride films it was observed that the stoichiometry, as indicated by the IR transmission, dielectric constant and current density versus square root of electric field measurements, was a strong function of the sputtering gas composition and particularly the Ar/N ratio in the sputtering gas. It was established from the current-voltage relationship that the dominant conduction mechanism in these films is of PooleFrenkel type. The current-voltage characteristics of the MIS devices were observed to be independent of the electrode material, device area and the film thickness. It is concluded that the insulating films thus deposited were comparable to those deposited using any other deposition method and is anticipated that due to the low deposition temperatures, sputtering may emerge as a highly potential process for optoelectronic device passivation. Germanium Gamma-ray p-n junction detectors coated with 30 nm thick sputtered amorphous germanium exhibited improved surface stability. Hydrogenated amorphous germanium was also used and the result indicated that this material would have superior passivating properties than amorphous Germanium

Process techniques study of integrated circuits Final scientific report

Surface impurity and structural defect analysis on thermally grown silicon oxide integrated circui

Oxidation as Key Mechanism for Efficient Interface Passivation in Cu (In,Ga)Se2 Thin-Film Solar Cells

Copper-indium-gallium-diselenide (CIGS) thin-film solar cells suffer from high recombination losses at the back contact and parasitic absorption in the front-contact layers. Dielectric passivation layers overcome these limitations and enable an efficient control over interface recombination, which becomes increasingly relevant as thin-film solar cells increase in efficiency and become thinner to reduce the consumption of precious resources. We present the optoelectronic and chemical interface properties of oxide-based passivation layers deposited by atomic layer deposition on CIGS. A suitable postdeposition annealing removes detrimental interface defects and leads to restructuring and oxidation of the CIGS surface. The optoelectronic interface properties are very similar for different passivation approaches, demonstrating that an efficient suppression of interface states is possible independent of the metal used in the passivating oxide. If aluminum oxide (Al2O3) is used as the passivation layer we confirm an additional field-effect passivation due to interface charges, resulting in an efficient interface passivation superior to that of a state-of-the-art cadmium-sulfide (CdS) buffer layer. Based on this chemical interface model we present a full-area rear-interface passivation layer without any contact patterning, resulting in a 1% absolute efficiency gain compared to a standard molybdenum back contact. © 2020 authors. Published by the American Physical Society

Characterization of alternative carrier selective materials and their application to heterojunction solar cells

Crystalline silicon (c-Si) solar cells can be considered a highly industrialized and mature product with a record conversion efficiency of 26.6%, not far from the practical limit of 29.4% (for single p/n junction devices). Accordingly, current research and development are addressing some remaining efficiency and cost limitations, including the reduction of (1) carrier recombination in highly doped materials, (2) parasitic absorption by narrow band gap films and (3) high temperature energy-intensive processing (especially critical for wafer thicknesses below 100 µm). In parallel, thin-film PV (e.g. organics and perovskites) have introduced a large number of dopant-free, hole- or electron-selective materials with optoelectronic properties that are comparable or superior to standard p- and n-doped layers in c-Si. Consequently, this thesis work explores novel heterojunctions between c-Si and these carrier-selective contact materials, putting special emphasis on TMO thin films whose wide energy band gap (>3 eV), surface passivation and large work function (>5 eV) characteristics permit their utilization as transparent/passivating/hole-selective front contacts in n-type c-Si (n-Si) solar cells. To this purpose, a comparative study among three thermally evaporated TMOs (V2O5, MoO3 and WO3) allowed correlating their chemical composition with thin film conductivity, optical transmittance, passivation potential and contact resistance on n-Si substrates. The variation of these properties with film thickness, air exposure or temperature annealings was also studied. Overall, V2Ox outperformed the other oxides by obtaining higher implied open-circuit voltages and lower contact resistances, translating into higher selectivities. Next, a thorough study of the TMO/c-Si interface was performed by electron microscopy, secondary ion-mass spectrometry and x-ray photoelectron spectroscopy, identifying two separate contributions to the observed passivation: (1) a chemical component, as evidenced by a thin SiOx interlayer naturally-grown by chemical reaction during TMO evaporation; and (2) a "field-effect" component, a result of a strong inversion (p+) of the n-Si surface, induced by the large work function difference between both materials. Considering all this, an energy band diagram for the TMO/SiOx/n-Si heterojunction was proposed, reflecting the possible physicochemical mechanisms behind c-Si passivation and carrier transport. Then, the characterized TMO/n-Si heterojunctions were implemented as front hole contacts in complete solar cell devices, using thin TMO films (15 nm) contacted by an indium-tin oxide (ITO) anti-reflection/conductive electrode and a silver finger grid. As rear electron contacts, n-type a-SiCx:H thin films (20 nm) were used in localized (laser-doped) and full-area configurations, the former contacted by titanium/aluminum while the latter by ITO/silver electrodes. The best performance solar cells were obtained for V2Ox/n-Si heterojunctions, characterized by an open-circuit voltage (VOC) close to 660 mV and a maximum conversion efficiency of 16.5%. Additional characterization confirmed the good quality of the induced p+/n-Si junction, with ideality factors close to 1 and built-in potentials above 700 mV. Moreover, a photocurrent gain of ~1 mA/cm2 (300-550 nm wavelength range) was directly attributed to the difference in energy band gaps between TMOs (>2.5 eV) and the a-SiCx:H reference (~1.7 eV). On a sideline, hole-selective contacts based on PEDOT:PSS polymer solutions were also characterized, resulting in a moderate conversion efficiency of 11.6% in ITO-free devices. Finally, it is worth emphasizing the high degree of innovation in this thesis project, reporting for the first time the properties of these alternative contact materials in the context of c-Si photovoltaics and contributing to a more generic understanding of solar cell operation and design.Las celdas solares de silicio cristalino (c-Si) pueden ser consideradas un producto maduro y altamente industrializado, con eficiencias de conversión record de 26.6% muy cercanas al límite práctico de 29.4%. En consecuencia, la investigación y desarrollo actuales están abordando las limitantes restantes en eficiencia y costes, incluyendo la reducción de (1) la recombinación de portadores en materiales altamente dopados, (2) la absorción parásita debido a energías de banda prohibida insuficientes y (3) los procesos térmicos (un factor crítico para obleas delgadas de 100 micras o menos). En paralelo, tecnologías de capa delgada (e.g. orgánicos y perovskitas) han introducido un gran número de materiales selectivos a electrones o huecos, libres de dopantes y cuyas propiedades optoelectrónicas son comparables o superiores a las capas dopadas tipo-n o tipo-p usadas de manera estándar en c-Si. Es así que esta tesis explora heterouniones novedosas entre c-Si y dichos materiales de contacto selectivos, poniendo especial énfasis en capas delgadas de TMOs cuya energía de band prohibida (>3 eV), pasivación superficial y alta función de trabajo (>5 eV) permiten su utilización como contactos frontales, transparentes, pasivantes y selectivos a huecos en celdas con substrato tipo-n (n-Si). Con este propósito, se realizó un estudio comparativo entre tres TMOs evaporados térmicamente (V2O5, MoO3 and WO3) que permitió correlacionar su composición química con la conductividad, transmitancia óptica, pasivación y resistencia de contacto de capas delgadas sobre sustratos de n-Si. La variabilidad de estas propiedades con el grosor de las capas, su exposición al aire o a recocidos de alta temperatura también fue estudiada. En general, V2Ox tuvo un mejor desempeño que el resto de los óxidos al obtener mayores pseudo-voltajes de circuito abierto y menores resistencias de contacto, traduciéndose en una mayor selectividad. En seguida, un estudio detallado de la interface TMO/c-Si fue llevado a cabo mediante microscopia de electrones, espectrometría de masas de iones secundarios y espectroscopia fotoelectrónica de rayos-x, identificando dos contribuciones a la pasivación superficial: (1) un componente químico, demostrado por la presencia de una inter-capa de SiOx formada mediante reacción química durante el depósito del TMO; y (2) un componente de "efecto de campo", que es resultado de la fuerte inversión de la superficie (p+/n-Si) inducida por la gran disparidad en funciones de trabajo entre ambos materiales. Bajo esta consideración, se propuso un diagrama de bandas para la heterounión TMO/SiOx/n-Si que refleja los posibles mecanismos de pasivación y transporte de cargas. Acto seguido, se implementaron dichas heterouniones como contactos tipo-p frontales en celdas solares finalizadas, con la estructura Ag/ITO(80 nm)/TMO (15 nm)/n-Si, donde el ITO "óxido de indio y estaño" sirve de capa antirreflejo conductora y la plata como electrodo. Para el contacto tipo-n trasero, capas de a-SiCx:H dopado (20 nm) fueron utilizadas en dos configuraciones (dopado puntual por láser y contacto en área completa). El mejor desempeño se obtuvo para las celdas de V2Ox/n-Si, caracterizadas por voltajes de circuito abierto (Voc) cercanos a 660 mV y una eficiencia máxima de 16.5%. La caracterización adicional de estos dispositivos reveló factores de idealidad cercanos a 1 y una barrera interna de potencial mayor a 700 mV, comprobando la buena calidad de la unión p+/n-Si inducida. Además, ganancias en fotocorriente de ~1 mA/cm2 (para el rango de longitudes de onda de 300-550 nm) fueron directamente atribuidas a las diferencias en energías de banda prohibida entre el TMO (>2.5 eV) y la capa referencia de a-SiCx:H (~1.7 eV). Finalmente, vale la pena enfatizar el alto grado de innovación en este proyecto de tesis, reportando por primera vez las propiedades de estos materiales de contacto alternativos en el contexto de la fotovoltaica de silicio

Characterization of alternative carrier selective materials and their application to heterojunction solar cells

Crystalline silicon (c-Si) solar cells can be considered a highly industrialized and mature product with a record conversion efficiency of 26.6%, not far from the practical limit of 29.4% (for single p/n junction devices). Accordingly, current research and development are addressing some remaining efficiency and cost limitations, including the reduction of (1) carrier recombination in highly doped materials, (2) parasitic absorption by narrow band gap films and (3) high temperature energy-intensive processing (especially critical for wafer thicknesses below 100 µm). In parallel, thin-film PV (e.g. organics and perovskites) have introduced a large number of dopant-free, hole- or electron-selective materials with optoelectronic properties that are comparable or superior to standard p- and n-doped layers in c-Si. Consequently, this thesis work explores novel heterojunctions between c-Si and these carrier-selective contact materials, putting special emphasis on TMO thin films whose wide energy band gap (>3 eV), surface passivation and large work function (>5 eV) characteristics permit their utilization as transparent/passivating/hole-selective front contacts in n-type c-Si (n-Si) solar cells. To this purpose, a comparative study among three thermally evaporated TMOs (V2O5, MoO3 and WO3) allowed correlating their chemical composition with thin film conductivity, optical transmittance, passivation potential and contact resistance on n-Si substrates. The variation of these properties with film thickness, air exposure or temperature annealings was also studied. Overall, V2Ox outperformed the other oxides by obtaining higher implied open-circuit voltages and lower contact resistances, translating into higher selectivities. Next, a thorough study of the TMO/c-Si interface was performed by electron microscopy, secondary ion-mass spectrometry and x-ray photoelectron spectroscopy, identifying two separate contributions to the observed passivation: (1) a chemical component, as evidenced by a thin SiOx interlayer naturally-grown by chemical reaction during TMO evaporation; and (2) a "field-effect" component, a result of a strong inversion (p+) of the n-Si surface, induced by the large work function difference between both materials. Considering all this, an energy band diagram for the TMO/SiOx/n-Si heterojunction was proposed, reflecting the possible physicochemical mechanisms behind c-Si passivation and carrier transport. Then, the characterized TMO/n-Si heterojunctions were implemented as front hole contacts in complete solar cell devices, using thin TMO films (15 nm) contacted by an indium-tin oxide (ITO) anti-reflection/conductive electrode and a silver finger grid. As rear electron contacts, n-type a-SiCx:H thin films (20 nm) were used in localized (laser-doped) and full-area configurations, the former contacted by titanium/aluminum while the latter by ITO/silver electrodes. The best performance solar cells were obtained for V2Ox/n-Si heterojunctions, characterized by an open-circuit voltage (VOC) close to 660 mV and a maximum conversion efficiency of 16.5%. Additional characterization confirmed the good quality of the induced p+/n-Si junction, with ideality factors close to 1 and built-in potentials above 700 mV. Moreover, a photocurrent gain of ~1 mA/cm2 (300-550 nm wavelength range) was directly attributed to the difference in energy band gaps between TMOs (>2.5 eV) and the a-SiCx:H reference (~1.7 eV). On a sideline, hole-selective contacts based on PEDOT:PSS polymer solutions were also characterized, resulting in a moderate conversion efficiency of 11.6% in ITO-free devices. Finally, it is worth emphasizing the high degree of innovation in this thesis project, reporting for the first time the properties of these alternative contact materials in the context of c-Si photovoltaics and contributing to a more generic understanding of solar cell operation and design.Las celdas solares de silicio cristalino (c-Si) pueden ser consideradas un producto maduro y altamente industrializado, con eficiencias de conversión record de 26.6% muy cercanas al límite práctico de 29.4%. En consecuencia, la investigación y desarrollo actuales están abordando las limitantes restantes en eficiencia y costes, incluyendo la reducción de (1) la recombinación de portadores en materiales altamente dopados, (2) la absorción parásita debido a energías de banda prohibida insuficientes y (3) los procesos térmicos (un factor crítico para obleas delgadas de 100 micras o menos). En paralelo, tecnologías de capa delgada (e.g. orgánicos y perovskitas) han introducido un gran número de materiales selectivos a electrones o huecos, libres de dopantes y cuyas propiedades optoelectrónicas son comparables o superiores a las capas dopadas tipo-n o tipo-p usadas de manera estándar en c-Si. Es así que esta tesis explora heterouniones novedosas entre c-Si y dichos materiales de contacto selectivos, poniendo especial énfasis en capas delgadas de TMOs cuya energía de band prohibida (>3 eV), pasivación superficial y alta función de trabajo (>5 eV) permiten su utilización como contactos frontales, transparentes, pasivantes y selectivos a huecos en celdas con substrato tipo-n (n-Si). Con este propósito, se realizó un estudio comparativo entre tres TMOs evaporados térmicamente (V2O5, MoO3 and WO3) que permitió correlacionar su composición química con la conductividad, transmitancia óptica, pasivación y resistencia de contacto de capas delgadas sobre sustratos de n-Si. La variabilidad de estas propiedades con el grosor de las capas, su exposición al aire o a recocidos de alta temperatura también fue estudiada. En general, V2Ox tuvo un mejor desempeño que el resto de los óxidos al obtener mayores pseudo-voltajes de circuito abierto y menores resistencias de contacto, traduciéndose en una mayor selectividad. En seguida, un estudio detallado de la interface TMO/c-Si fue llevado a cabo mediante microscopia de electrones, espectrometría de masas de iones secundarios y espectroscopia fotoelectrónica de rayos-x, identificando dos contribuciones a la pasivación superficial: (1) un componente químico, demostrado por la presencia de una inter-capa de SiOx formada mediante reacción química durante el depósito del TMO; y (2) un componente de "efecto de campo", que es resultado de la fuerte inversión de la superficie (p+/n-Si) inducida por la gran disparidad en funciones de trabajo entre ambos materiales. Bajo esta consideración, se propuso un diagrama de bandas para la heterounión TMO/SiOx/n-Si que refleja los posibles mecanismos de pasivación y transporte de cargas. Acto seguido, se implementaron dichas heterouniones como contactos tipo-p frontales en celdas solares finalizadas, con la estructura Ag/ITO(80 nm)/TMO (15 nm)/n-Si, donde el ITO "óxido de indio y estaño" sirve de capa antirreflejo conductora y la plata como electrodo. Para el contacto tipo-n trasero, capas de a-SiCx:H dopado (20 nm) fueron utilizadas en dos configuraciones (dopado puntual por láser y contacto en área completa). El mejor desempeño se obtuvo para las celdas de V2Ox/n-Si, caracterizadas por voltajes de circuito abierto (Voc) cercanos a 660 mV y una eficiencia máxima de 16.5%. La caracterización adicional de estos dispositivos reveló factores de idealidad cercanos a 1 y una barrera interna de potencial mayor a 700 mV, comprobando la buena calidad de la unión p+/n-Si inducida. Además, ganancias en fotocorriente de ~1 mA/cm2 (para el rango de longitudes de onda de 300-550 nm) fueron directamente atribuidas a las diferencias en energías de banda prohibida entre el TMO (>2.5 eV) y la capa referencia de a-SiCx:H (~1.7 eV). Finalmente, vale la pena enfatizar el alto grado de innovación en este proyecto de tesis, reportando por primera vez las propiedades de estos materiales de contacto alternativos en el contexto de la fotovoltaica de silicio.Postprint (published version

Chalcogenide Nanocrystal Assembly: Controlling Heterogeneity And Modulating Heterointerfaces

This dissertation work is focused on developing methods to facilitate charge transport in heterostructured materials that comprise a nanoscale component. Multicomponent semiconductor materials were prepared by (1) spin coating of discrete nanomaterials onto porous silicon (pSi) or (2) self-assembly. Spin-coating of colloidal quantum dot (QD) PbS solutions was employed to create prototype PbS QD based radiation detection devices using porous silicon (pSi) as an n-type support and charge transport material. These devices were initially tested as a photodetector to ascertain the possibility of their use in high energy radiation detection. Short chain thiolate ligands (4-fluorothiophenolate) and anion passivation at the particle interface were evaluated to augment interparticle transport. However, the samples showed minimum interaction with the light source possibly due to poor infiltration into the pSi. The second project was also driven by the potential synergistic properties that can be achieved in multicomponent metal chalcogenide nanostructures, potentially useful in optoelectronic devices. Working with well-established methods for single component metal chalcogenide (MQ) particle gels this dissertation research sought to develop practical methods for co-gelation of different component particles with complimentary functionalities. By monitoring the kinetics of aggregation using time resolved dynamic light scattering and NMR spectroscopy the kinetics of aggregation of the two most common crystal structures for CdQ nanocrystals was studied and it was determined that the hexagonal (wurtzite) crystal structure aggregated faster than the cubic (zinc blende) crystal structure. For gel coupling of nanoparticles with differing Q (Q=S, Se and Te), once we accounted for the crystal structure effects, it was dtermined that the relative redox characteristics of Q govern the reaction rate. The oxidative sol-gel assembly routes were also employed to fabricate metal chalcogenide NC gels with different NC components with control over the degree of mixing. In order to control the degree of mixing, the factors that underscore sol-gel oxidative assembly were elucidated and the aggregation and gelation kinetics of metal chalcogenide QDs were monitored through time-resolved dynamic light scattering (TR-DLS), and nuclear magnetic resonance spectroscopy (NMR). Through these kinetic studies of the surface speciation of metal chalcogenides, control over heterogeneity in dual component CdSe-ZnS system, was achieved through adjustment of the capping ligand, the native crystal structure and the chalcogenide, thereby changing the relative rates of assembly for each component independently

Numerical Simulation of Solar Cells and Solar Cell Characterization Methods: the Open-Source on Demand Program AFORS-HET

Within this chapter, the principles of numerical solar cell simulation are described, usingAFORS HET automat for simulation of heterostructures . AFORS HET is a onedimensional numerical computer program for modelling multi layer homo orheterojunction solar cells as well as some common solar cell characterization methods.Solar cell simulation subdivides into two parts optical and electrical simulation. By opticalsimulation the local generation rate G x, t within the solar cell is calculated, that is thenumber of excess carriers electrons and holes that are created per second and per unitvolume at the time t at the position x within the solar cell due to light absorption.Depending on the optical model chosen for the simulation, effects like external or internalreflections, coherent superposition of the propagating light or light scattering at internalsurfaces can be considered. By electrical simulation the local electron and hole particledensities n x, t , p x, t and the local electric potential amp; 981; x, t within the solar cell arecalculated, while the solar cell is operated under a specified condition for example operatedunder open circuit conditions or at a specified external cell voltage . From that, all otherinternal cell quantities, such like band diagrams, local recombination rates, local cellcurrents and local phase shifts can be calculated. In order to perform an electricalsimulation, 1 the local generation rate G x, t has to be specified, that is, an opticalsimulation has to be done, 2 the local recombination rate R x, t has to be explicitly statedin terms of the unknown variables n, p, amp; 981; , R x, t f n, p, amp; 981; . This is a recombination modelhas to be chosen. Depending on the recombination model chosen for the simulation, effectslike direct band to band recombination radiative recombination , indirect band to bandrecombination Auger recombination or recombination via defects Shockley Read Hallrecombination, dangling bond recombination can be considere