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Characterization of Cu2ZnSnSe4 kesterite thin film solar cells : understanding of the fundamental material properties and quality control for process optimization and monitoring / Caractérisation des cellules solaires à base de couches minces kesterite Cu2ZnSnSe4 : compréhension des propriétés fondamentales des matériaux et contrôle de la qualité pour l'optimisation et le suivi des procédés de fabricationRisch, Lisa Carina Mareike 12 December 2016 (has links)
Cette thèse porte sur la caractérisation des cellules solaires à base de couches minces de kesterite Cu2ZnSnSe4 (CZTSe). Au cours des dernières années, une attention croissante a été portée aux cellules solaires kesterite. En effet, Cu, Sn et Zn étant abondants dans la croûte terrestre, les technologies photovoltaïques à base de couches minces absorbantes de kesterite apparaissent comme un candidat prometteur pour la production à grande échelle et à faible coût de cellules solaires. Cependant, les cellules solaires kesterite souffrent d'un sévère déficit de la tension en circuit ouvert (Voc) par rapport aux autres technologies PV, résultant en un écart de performance significatif avec la technologie cousine à base de chalcopyrite (CIGS). Les meilleurs rendements reportés pour la technologie à base de couches minces CIGS sont 22,6%, alors que les cellules solaires kesterite restent en dessous de 13% de rendement. Comprendre les propriétés fondamentales des matériaux et cellules solaires kesterite et résoudre les difficultés liées à leur fabrication sont des points cruciaux pour améliorer les performances de cette technologie.Dans le cadre de cette thèse, différents mécanismes responsables des faibles valeurs de Voc des cellules kesterite ont été identifiés et caractérisés. Deux facteurs principaux y contribuent de manière significative: la recombinaison non radiative et le bandtailing. Ces phénomènes sont liés à la présence de phases secondaires et de défauts impactant l'hétérojonction p-n. Par conséquent, cette thèse se concentre sur la détection des phases secondaires et des défauts et le rôle de la couche tampon de type n. / The present thesis deals with the characterization of Cu2ZnSnSe4 (CZTSe) kesterite thin film solar cells. Over the last years, kesterite based devices have attracted growing attention. As Cu, Sn and Zn are earth-abundant metals, the kesterite compounds are promising candidates as absorber materials for the mass production of low-cost photovoltaic devices. However, kesterite solar cells suffer from a severe open circuit voltage (Voc) deficit in comparison with other PV technologies, resulting in a significant performance gap between thin film kesterite and chalcopyrite (CIGS) based devices. Best reported efficiencies for the related CIGS thin film technology are 22.6% at cell size and 17.9% for a commercial module – very close to the performance of Si solar cells – while kesterite solar cells remain below 13% power conversion efficiency. Understanding the fundamental properties of kesterite materials and devices and solving challenges associated with their fabrication are the key to improve device performances.In the framework of this thesis, different loss mechanisms related to the low Voc values of kesterite solar cells have been identified and characterized. Two major factors are thereby observed to be responsible for the significant Voc deficit: non-radiative recombination and band tailing. These aspects are related to the presence of secondary phases and defects that have a significant impact on the pn-heterojunction. Therefore, this thesis focuses on the detection of secondary phases and defects and the role of the n-type buffer layer.
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Optimisation d'un procédé hybride de co-pulvérisation/évaporation pour l'obtention de cellules solaires à base de Cu(In,Ga)Se2 / Optimization of a hybrid co-sputtering/evaporation process for Cu(In,Ga)Se2 thin film solar cells applicationsPosada Parra, Jorge Ivan 17 March 2015 (has links)
Les cellules solaires en couches minces à base d'absorbeurs de type Cu(In,Ga)Se2 (CIGS) représentent une technologie d'avenir à haut rendement de conversion d'énergie. Plusieurs techniques sont utilisées pour synthétiser le CIGS. La pulvérisation cathodique réactive est une technique de dépôt adaptée aux grandes surfaces offrant la possibilité d'effectuer un scale-up industriel. L'objectif de ce travail est de développer et d'optimiser un procédé alternatif hybride de co-pulvérisation/évaporation pour la synthèse du composé CIGS. Pour répondre à cet objectif, différentes études ont été réalisées afin d'assurer le contrôle des différents paramètres de dépôt. Dans un premier temps, la phase plasma a été étudiée à l'aide de la spectroscopie d'émission optique pour pouvoir établir des corrélations entre la composition des couches déposées et les espèces présentes dans le plasma. Ceci a permis d'établir des courbes d'étalonnage et de suivi in-situ de la composition et l'homogénéité de l'épaisseur des couches déposées, ainsi que de déterminer l'existence de différentes modes de pulvérisation, reliés à la température appliquée pour l'évaporation du sélénium. Dans un deuxième temps, différents absorbeurs de CIGS ont été synthétisés à partir du procédé hybride développé. Ces absorbeurs ont été déposés en une et en trois étapes pour analyser l'influence des gradients de composition sur leurs propriétés morphologiques, structurales et optoélectroniques. Un absorbeur de CIGS avec un rendement de conversion maximum de 10,4 % a été fabriqué à partir d'une séquence de dépôt en une étape. Un rendement de 9,4 % a été obtenu avec une séquence dépôt en trois étapes. / Cu(In,Ga)Se2 (CIGS) thin film solar cells are a very promising technology for high efficiency energy conversion. Several techniques are used to synthesize CIGS absorbers. Magnetron reactive sputtering is an attractive deposition technique for depositing CIGS absorbers because of its potential for providing uniform coatings over large areas, thus offering the possibility for more competitive industrial scale-up. The objective of this work is to develop and optimize a hybrid alternative co-sputtering/evaporation CIGS deposition process. To meet this goal, various studies have been conducted to ensure control of the various deposition parameters. Initially, plasma was studied with Optical Emission Spectroscopy in order to establish correlations between plasma species and thin film composition, structure and morphology. This has allowed to establish in-situ calibration curves for monitoring the deposited layers composition and their homogeneity, and to determine the existence of different sputtering modes, linked to the selenium evaporation temperature. Then, different CIGS absorbers were synthesized with the stabilized hybrid process. These absorbers were deposited in one and three stages to analyze the influence of composition gradients on their morphological, structural and optoelectronic properties. A CIGS absorber giving a maximum conversion efficiency of 10.4 % was fabricated with a one step process. A 9.3 % efficiency solar cell was obtained with a three-stage deposition process.
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Developing a Combinatorial Synthesis Database ToolQuaglia Casal, Luciano January 2018 (has links)
Thin-film solar cell research is central to the electricity production of the near future. Photovoltaic technologies based on silicon have a significant portion of the global market and installed capacity. Thin-film solar cells are port of the emerging photovoltaic technologies that are challenging silicon for a part of the electricity production based on solar power. These thin-film technologies, such as copper indium gallium selenide (CIGS) and cadmium telluride (CdTe), are lower cost and require less energy to produce, but also require rare materials. An alternative to these technologies are thin-film solar cells based on more abundant materials. To develop these new materials at Uppsala University, combinatorial synthesis is used. This method produces a significant amount of data across different measurement methods. The data needs to be analysed and combined to gather information about the characteristics of the materials being developed. To facilitate the analysis and combination of data, a database tool was created in MATLAB. The result is a program that allows its User to combine energy-dispersive X-ray spectroscopy (EDS), Raman spectroscopy and Photoluminescence spectroscopy measurements done on solar cell absorber layers. Absorber layers are the section of solar cells where sun lighet is absorbed, and electron-hole pairs are created. The program provides multiple figures and graphs combining the different data collected, enabling the User to draw conclusions about the characteristics of the sample and its suitability as an absorber layer. The combinatorial synthesis database tool created could be user for combinatorial synthesis analysis of other material samples that are not necessarily absorber layers for thin-film solar cells. This report describes both the development of the tool and the code itself.
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Study in analytical glow discharge spectrometry and its application in materials scienceEfimova, Varvara 28 September 2011 (has links) (PDF)
Glow Discharge Optical Emission Spectrometry (GD OES) has proved to be a versatile analytical technique for the direct analysis of solid samples. The application of a pulsed power supply to the glow discharge (GD) has a number of advantages in comparison with a continuous one and thereby broadens the analytical potential of the GD. However, because the pulsed GD (PGD) is a relatively new operation mode, the pulsing and plasma parameters as well as their influence on the analytical performance of the GD are not yet comprehensively studied.
The aim of this dissertation consists in the investigation of the PGD features, which are crucial for both understanding the discharge plasma processes and analytical applications. The influence of the pulsing parameters on the PGD is ascertained and compared for direct current (dc) and radio frequency (rf) discharges. In the research attention is firstly paid on the electrical parameters of PGD, then on the sputtered crater shapes, sputtering rates and finally on the light emission. It is found that the sputtered crater shape is strongly affected by the duration of the applied pulses even when the duty cycle is fixed. The pulse length influences the intensity of the light emission as well (at constant duty cycle). Moreover this influence is different for emission lines of atoms and ions in the plasma. This phenomenon can be seen at the comparison of atomic and ionic lines of different elements.
The voltage–current plots of the PGD are found to indicate heating of the discharge gas when operating at high duty cycles. Using this feature a new method for the estimation of the discharge gas temperature from the voltage-current characteristics of the PGD is developed. The calculated temperature values are compared with another temperature measurement technique. Different temperature estimation procedures have shown that the discharge gas temperature can be reduced by around 100 K when PGD is applied. The temperature measurements have also confirmed that the gas heating can be adjusted by variation of the pulsing parameters.
The effect of sputtering on the Cu(In,Ga)Se2 (CIGSe) layer surface of the solar cells is described for the first time. SEM investigations of the CIGSe layer of the solar cells have shown that sputter induced effects can be reduced by variation of the pulsing parameters.
With regard to the question whether dc and rf pulsed discharges behave similarly: nearly all phenomena found with dc discharges also appear in the rf case. Hence it is concluded that the pulsed rf and dc discharges are very similar in terms of the electrical properties, sputtered crater formation, light emission and temperature.
It is concluded that matrix specific, as well as matrix independent quantification principles and the intensity correction developed by Arne Bengtson can be applied for the pulsed mode, if special conditions are fulfilled. CIGSe solar cell samples and thin layered electrode metallizations of SAW devices are measured and quantified with application of PGD. The proposed quantification procedures are performed at commercial GD OES devices and can be used for the analysis with application of pulsed rf discharge.
The studies of the PGD performed in this dissertation are relevant for the application of the GD OES analysis in materials science. During the collaborative work with Helmholtz-Zentrum Berlin für Materialien und Energie and with the research group of Dr. Thomas Gemming at IFW Dresden the optimized pulsed GD OES measurements could be successfully applied at the investigation of thin film solar cells with CIGSe light absorbing layer and electrode matallizations of SAW devices. In case of solar cell samples pulsed GD OES depth profiling along with SIMS measurements reveal the role of the Al2O3 barrier layer in high efficiency solar cells consisting of a CIGSe/Mo/Al2O3/steel substrate layer stack (the barrier layer is to prevent the Fe diffusion into the CIGSe). The features of the CIGSe films growth are studied with help of pulsed GD OES and in situ synchrotron XRD measurements. The diffusion coefficient of Zn into the CuInS2 layer is determined for the first time from the measured GD OES depth profiles of the corresponding solar cell samples. In case of SAW samples, pulsed GD OES measurements helped to evaluate the different SAW electrode preparation procedures and to select the most suitable one. In addition pulsed GD OES depth profiling along with XPS, TEM-EDX and electrode lifetime measurements indicate the possible mechanism of power durability and lifetime improvement of the SAW devices when a small amount of Al is added to the Cu-based electrodes. / Die optische Glimmentladungsspektroskopie (engl. Glow Discharge Optical Emission Spectrometry - GD OES) hat sich als eine vielfältige und schnelle Methode für die direkte Analyse von festen Materialien erwiesen. Die Anwendung von gepulsten Glimmentladungen (GD) bietet eine Reihe von Vorteilen im Vergleich zu einer kontinuierlichen Entladung und erweitert dadurch das analytische Potential der Methode. Die praktische Anwendung von gepulsten GD erfordert jedoch ein tiefes Verständnis der Prozesse, die in der Entladung und im elektrischen System ablaufen. Der Einfluss der Puls- und Plasmaparameter auf die analytische Leistung der gepulsten GD ist bislang noch nicht umfassend erforscht worden.
Die Zielstellung dieser Arbeit besteht in der Untersuchung der Eigenschaften der gepulsten GD, welche von besonderer Bedeutung sowohl für das Verständnis des Entladungsprozesses als auch für analytische Anwendungen ist. Die Auswirkungen der Pulsparameter auf die gepulste GD wurde für den Gleichstrom-(DC) und Hochfrequenz- (HF) Modus untersucht und verglichen. Die Reihenfolge der Untersuchungen wurde in dieser Arbeit wie folgt gewählt: elektrische Parameter, Sputterkraterformen, Sputterraten und Lichtemission. Die Form des Sputterkraters korreliert stark mit der Pulsdauer, selbst wenn das Tastverhältnis konstant ist. Die Pulsdauer beeinflusst nicht nur die Kraterform, sondern auch die Intensität der Emissionslinien (bei konstantem Tastverhältnis). Darüber hinaus ist dieser Einfluss unterschiedlich für Atome und Ionen. Dieses Verhalten wurde an mehreren Emissionslinien (atomar bzw. ionisch) nachgewiesen.
Aus der Analyse der U-I-Kennlinien der gepulsten GD ergab sich, dass es zu einer Erhitzung des Plasmas bei höherem Tastverhältnis kommt. Dieser Effekt wurde zur Bestimmung der Plasma-Gastemperatur ausgenutzt. Die ermittelten Temperaturen wurden mit einer andere Methode verglichen. Aus der Abschätzung ergab sich, dass die Plasmatemperatur bei gepulsten GD um bis zu 100 K gesenkt werden und durch die Pulsparameter genauer eingestellt werden kann.
Der Einfluss des Sputterns auf Cu(In,Ga)Se2 (CIGSe) Dünnschichten von Solarzellen wurde erstmals beschrieben. REM-Untersuchungen an GD-gesputterten CIGSe Schichten haben gezeigt, dass die Sputtereffekte durch die Variation der Pulsparameter reduziert werden können.
Es konnte gezeigt werden, dass HF- und DC-Entladungen dieselben Effekte aufweisen und sich nur geringfügig voneinander unterscheiden. Daraus kann geschlussfolgert werden, dass DC- und HF-Entladungen in Bezug auf elektrische Eigenschaften, Kraterformen, Lichtemission und Temperatur sehr ähnlich sind.
Die Quantifizierung der mit gepulsten GD gemessenen Tiefenprofile ergab ferner, dass die Anwendung der Quantifizierungsmethoden für den kontinuierlichen Modus unter den gegebenen Bedingungen zulässig ist. Die Tiefenprofile von Solarzellen-Schichten sowie SAW-Metallisierungen wurden anhand gepulster GD gemessen und quantifiziert. Die empfohlenen Quantifizierungsmethoden können mit kommerziellen GD OES-Geräten durchgeführt werden.
Die Untersuchungen an gepulsten GD sind insbesondere relevant für GD OES-Anwendungen im Bereich der Werkstoffwissenschaft. Während der Zusammenarbeit mit dem Helmholtz-Zentrum Berlin für Materialien und Energie und der Arbeitsgruppe von Dr. Thomas Gemming (IFW Dresden) konnten optimierte, gepulste GD OES Messungen erfolgreich zur Untersuchung von Dünnschicht-Solarzellen bzw. hochleistungsbeständigen SAW-Metallisierungen angewendet werden. Für die Solarzellen haben GD OES und SIMS Messungen geholfen, die Rolle der Al2O3-Barriere in CIGSe/Mo/Al2O3 Schichtstapeln auf flexiblem Stahlsubstrat besser zu verstehen (Al2O3 soll die Diffusion der Fe-Atome in CIGSe verhindern). Die gemeinsame Untersuchung getemperter CIGSe-Schichten mit gepulster GD OES und in-situ Synchrotron-XRD ergab neue Erkenntnisse zum Schichtwachstum. Der Diffusionskoeffizient von Zn in CuInS2 wurde erstmals aus GD OES-Tiefenprofilen bestimmt. Im Fall der SAW-Metallisierungen konnte die GD OES zur Bestimmung des geeignetsten Herstellungsverfahrens einen wichtigen Beitrag leisten. Die gepulste GD OES hat neben anderen Untersuchungsmethoden wie TEM-EDX, XPS und Lebensdauermessungen die Verbesserung der Leistungsbeständigkeit von Cu-Metallisierungen durch geringen Al-Zusatz aufklären können.
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Studies On Fabrication And Characterisation Of TiO2 Based Dye-Sensitised Solar CellsSharmila, S January 2015 (has links) (PDF)
Photovoltaic cells are a promising solution to the current energy crisis. Among the different photovoltaic cell technologies developed, dye-sensitised solar cells (DSSC) are emerging as viable low-cost alternatives to Si PV technology. This thesis presents studies on fabrication and characterisation of TiO2 based dye-sensitised solar cells. Chapter 1 gives an overview of different photovoltaic cell technologies and a review of the state-of-the art DSSC technology. Chapter 2 describes the techniques used for characterisation of DSSCs. Chapter 3 describes the fabrication of TiO2 based dye-sensitised solar cells. Chapter 4 presents the analysis of measurements obtained by the characterisation techniques. Finally chapter 5 summarises the work done and suggests directions for future work.
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Study in analytical glow discharge spectrometry and its application in materials scienceEfimova, Varvara 18 August 2011 (has links)
Glow Discharge Optical Emission Spectrometry (GD OES) has proved to be a versatile analytical technique for the direct analysis of solid samples. The application of a pulsed power supply to the glow discharge (GD) has a number of advantages in comparison with a continuous one and thereby broadens the analytical potential of the GD. However, because the pulsed GD (PGD) is a relatively new operation mode, the pulsing and plasma parameters as well as their influence on the analytical performance of the GD are not yet comprehensively studied.
The aim of this dissertation consists in the investigation of the PGD features, which are crucial for both understanding the discharge plasma processes and analytical applications. The influence of the pulsing parameters on the PGD is ascertained and compared for direct current (dc) and radio frequency (rf) discharges. In the research attention is firstly paid on the electrical parameters of PGD, then on the sputtered crater shapes, sputtering rates and finally on the light emission. It is found that the sputtered crater shape is strongly affected by the duration of the applied pulses even when the duty cycle is fixed. The pulse length influences the intensity of the light emission as well (at constant duty cycle). Moreover this influence is different for emission lines of atoms and ions in the plasma. This phenomenon can be seen at the comparison of atomic and ionic lines of different elements.
The voltage–current plots of the PGD are found to indicate heating of the discharge gas when operating at high duty cycles. Using this feature a new method for the estimation of the discharge gas temperature from the voltage-current characteristics of the PGD is developed. The calculated temperature values are compared with another temperature measurement technique. Different temperature estimation procedures have shown that the discharge gas temperature can be reduced by around 100 K when PGD is applied. The temperature measurements have also confirmed that the gas heating can be adjusted by variation of the pulsing parameters.
The effect of sputtering on the Cu(In,Ga)Se2 (CIGSe) layer surface of the solar cells is described for the first time. SEM investigations of the CIGSe layer of the solar cells have shown that sputter induced effects can be reduced by variation of the pulsing parameters.
With regard to the question whether dc and rf pulsed discharges behave similarly: nearly all phenomena found with dc discharges also appear in the rf case. Hence it is concluded that the pulsed rf and dc discharges are very similar in terms of the electrical properties, sputtered crater formation, light emission and temperature.
It is concluded that matrix specific, as well as matrix independent quantification principles and the intensity correction developed by Arne Bengtson can be applied for the pulsed mode, if special conditions are fulfilled. CIGSe solar cell samples and thin layered electrode metallizations of SAW devices are measured and quantified with application of PGD. The proposed quantification procedures are performed at commercial GD OES devices and can be used for the analysis with application of pulsed rf discharge.
The studies of the PGD performed in this dissertation are relevant for the application of the GD OES analysis in materials science. During the collaborative work with Helmholtz-Zentrum Berlin für Materialien und Energie and with the research group of Dr. Thomas Gemming at IFW Dresden the optimized pulsed GD OES measurements could be successfully applied at the investigation of thin film solar cells with CIGSe light absorbing layer and electrode matallizations of SAW devices. In case of solar cell samples pulsed GD OES depth profiling along with SIMS measurements reveal the role of the Al2O3 barrier layer in high efficiency solar cells consisting of a CIGSe/Mo/Al2O3/steel substrate layer stack (the barrier layer is to prevent the Fe diffusion into the CIGSe). The features of the CIGSe films growth are studied with help of pulsed GD OES and in situ synchrotron XRD measurements. The diffusion coefficient of Zn into the CuInS2 layer is determined for the first time from the measured GD OES depth profiles of the corresponding solar cell samples. In case of SAW samples, pulsed GD OES measurements helped to evaluate the different SAW electrode preparation procedures and to select the most suitable one. In addition pulsed GD OES depth profiling along with XPS, TEM-EDX and electrode lifetime measurements indicate the possible mechanism of power durability and lifetime improvement of the SAW devices when a small amount of Al is added to the Cu-based electrodes. / Die optische Glimmentladungsspektroskopie (engl. Glow Discharge Optical Emission Spectrometry - GD OES) hat sich als eine vielfältige und schnelle Methode für die direkte Analyse von festen Materialien erwiesen. Die Anwendung von gepulsten Glimmentladungen (GD) bietet eine Reihe von Vorteilen im Vergleich zu einer kontinuierlichen Entladung und erweitert dadurch das analytische Potential der Methode. Die praktische Anwendung von gepulsten GD erfordert jedoch ein tiefes Verständnis der Prozesse, die in der Entladung und im elektrischen System ablaufen. Der Einfluss der Puls- und Plasmaparameter auf die analytische Leistung der gepulsten GD ist bislang noch nicht umfassend erforscht worden.
Die Zielstellung dieser Arbeit besteht in der Untersuchung der Eigenschaften der gepulsten GD, welche von besonderer Bedeutung sowohl für das Verständnis des Entladungsprozesses als auch für analytische Anwendungen ist. Die Auswirkungen der Pulsparameter auf die gepulste GD wurde für den Gleichstrom-(DC) und Hochfrequenz- (HF) Modus untersucht und verglichen. Die Reihenfolge der Untersuchungen wurde in dieser Arbeit wie folgt gewählt: elektrische Parameter, Sputterkraterformen, Sputterraten und Lichtemission. Die Form des Sputterkraters korreliert stark mit der Pulsdauer, selbst wenn das Tastverhältnis konstant ist. Die Pulsdauer beeinflusst nicht nur die Kraterform, sondern auch die Intensität der Emissionslinien (bei konstantem Tastverhältnis). Darüber hinaus ist dieser Einfluss unterschiedlich für Atome und Ionen. Dieses Verhalten wurde an mehreren Emissionslinien (atomar bzw. ionisch) nachgewiesen.
Aus der Analyse der U-I-Kennlinien der gepulsten GD ergab sich, dass es zu einer Erhitzung des Plasmas bei höherem Tastverhältnis kommt. Dieser Effekt wurde zur Bestimmung der Plasma-Gastemperatur ausgenutzt. Die ermittelten Temperaturen wurden mit einer andere Methode verglichen. Aus der Abschätzung ergab sich, dass die Plasmatemperatur bei gepulsten GD um bis zu 100 K gesenkt werden und durch die Pulsparameter genauer eingestellt werden kann.
Der Einfluss des Sputterns auf Cu(In,Ga)Se2 (CIGSe) Dünnschichten von Solarzellen wurde erstmals beschrieben. REM-Untersuchungen an GD-gesputterten CIGSe Schichten haben gezeigt, dass die Sputtereffekte durch die Variation der Pulsparameter reduziert werden können.
Es konnte gezeigt werden, dass HF- und DC-Entladungen dieselben Effekte aufweisen und sich nur geringfügig voneinander unterscheiden. Daraus kann geschlussfolgert werden, dass DC- und HF-Entladungen in Bezug auf elektrische Eigenschaften, Kraterformen, Lichtemission und Temperatur sehr ähnlich sind.
Die Quantifizierung der mit gepulsten GD gemessenen Tiefenprofile ergab ferner, dass die Anwendung der Quantifizierungsmethoden für den kontinuierlichen Modus unter den gegebenen Bedingungen zulässig ist. Die Tiefenprofile von Solarzellen-Schichten sowie SAW-Metallisierungen wurden anhand gepulster GD gemessen und quantifiziert. Die empfohlenen Quantifizierungsmethoden können mit kommerziellen GD OES-Geräten durchgeführt werden.
Die Untersuchungen an gepulsten GD sind insbesondere relevant für GD OES-Anwendungen im Bereich der Werkstoffwissenschaft. Während der Zusammenarbeit mit dem Helmholtz-Zentrum Berlin für Materialien und Energie und der Arbeitsgruppe von Dr. Thomas Gemming (IFW Dresden) konnten optimierte, gepulste GD OES Messungen erfolgreich zur Untersuchung von Dünnschicht-Solarzellen bzw. hochleistungsbeständigen SAW-Metallisierungen angewendet werden. Für die Solarzellen haben GD OES und SIMS Messungen geholfen, die Rolle der Al2O3-Barriere in CIGSe/Mo/Al2O3 Schichtstapeln auf flexiblem Stahlsubstrat besser zu verstehen (Al2O3 soll die Diffusion der Fe-Atome in CIGSe verhindern). Die gemeinsame Untersuchung getemperter CIGSe-Schichten mit gepulster GD OES und in-situ Synchrotron-XRD ergab neue Erkenntnisse zum Schichtwachstum. Der Diffusionskoeffizient von Zn in CuInS2 wurde erstmals aus GD OES-Tiefenprofilen bestimmt. Im Fall der SAW-Metallisierungen konnte die GD OES zur Bestimmung des geeignetsten Herstellungsverfahrens einen wichtigen Beitrag leisten. Die gepulste GD OES hat neben anderen Untersuchungsmethoden wie TEM-EDX, XPS und Lebensdauermessungen die Verbesserung der Leistungsbeständigkeit von Cu-Metallisierungen durch geringen Al-Zusatz aufklären können.
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Earth Abundant Alternate Energy Materials for Thin Film PhotovoltaicsBanavoth, Murali January 2013 (has links) (PDF)
Inexhaustible solar energy, which provides a clean, economic and green energy, seems to be an alternative solution, for current and future energy demands. Harvesting solar energy presents a challenge in using eco-friendly, earth abundant and inexpensive materials. Although present CdTe and Cu (In, Ga)Se2 (CIGS) technologies, provide light-to-electricity comparable to silicon technology, toxicity of Cd and scarcity of In limits the widespread utilization. Future tera-watt level module capacity would then be feasible by the low-cost technologies. The chalcogenide thin film technology would therefore provide the exceptional utilization in the large-area module monolithic integrations benefitting from the low material consumption owing to the direct band gap. The current thesis presents the results obtained from the quest of other thin film materials and their utilization to an unconventional Cd-free buffer layer. The films suitability for the future applications was assessed through photovoltaics device studies in a comparative manner.
Chapter-1 deals with the motivation for the solar energy and the importance of thin film photovoltaics. Alternative materials which are abundantly available would help to reach the future tera watt level production, where the conventional silicon technology alone cannot satisfy the global energy demand. The utilization of non-conventional thin film based solar cells and their working principles were elucidated. The histories of the copper based alternative materials were introduced.
Chapter-2 deals with the versatile thin film growth technique that has been designed fabricated and installed further which can handle the growth of the absorber and the top TCO layers with insitu sulphurisation. The methodology of the absorber deposition was discussed in detail. The experimental details for the co-sputtering of CuInAl alloy were presented. A novel selenization method, assisted by the combination of inert gases was developed for the annealing of CuInAl alloyed precursor films.
Chapter-3 deals with the presentation of the results obtained on buffer and window layers. Chemical Bath deposition technique was employed for the growth and optimization of the conventional CdS and non-toxic buffer ZnS buffer layers. A) Cadmium sulphide thin films suitable for the utilization of high efficiency solar cells were optimized. Optimization of the buffer involved the effects of cadmium precursors, ammonia concentration and buffer capsule effect. A green route was presented so as to consume the precursors to the maximum extent possible. B) The alternative non-toxic buffer Zinc Sulphide (ZnS) thin films were successfully grown using the above optimized conditions.
Moreover the window layer was also optimized for better device partner. Zinc Oxide was used as a n-type partner for the p-type CIS films. The ZnO films were grown by the RF-sputtering from the single cathode exhibited good crystallinity with Zincite structure (hexagonal ZnS, a= 3.249A0 and c= 5.205A0). All the grown films showed high resistivity. Al: ZnO thin films were optimized in two methods 1) by dc co-sputtering from the elemental cathodes, Zinc and Aluminum, 2) dc-sputtering from the single 2% Al-doped ZnO cathode. Low resistivity Al:ZnO thin films were deposited in both the cases. Effect of Aluminum doping into ZnO crystal lattice upon the optical and electrical properties were discussed.
Chapter-4 deals with the synthesis of various absorber materials, characterizations and some properties. Briefly the A) Optimization of the CuIn1-xAlxSe2 phase with better adhesion and better crystallinity. Aluminum doping into the crystal lattice of CuInSe2 aided the wide band gap tuning of CIAS thin films. Morphological investigations were carried out for the different set of thin films before and after selenization. Effects of copper and Aluminum concentrations on the lattice parameter of the selenized thin films were addressed. The present chapter deals with the A) electrical properties of CIAS films and its heterojunction partners. Resistivity measurements and effects of Cu/In ratio and the effect of Al doping were described in detail. The CIAS/ZnO heterostructure, CIAS/Al:ZnO heterostructure junction properties as a function of different sun illuminations were discussed.
B) The alternative earth abundant, eco-friendly, non-toxic elements Cu2ZnSnS4, absorber thin films synthesis and characterizations. Photo conductive photo measurements showed CZTS a potential candidate for near infra-red photodectection. C) Cu2CoSnS4 (CCTS) nanostructures and quantum dots were synthesized via simple chemical routes. CCTS quantum dots were tuned to exhibit the red edge effect and cold white phosphors. D) Cu3BiS3 nano rods were synthesized and characterized structurally and optically. The transport properties of Cu3BiS3 nanorods were tailored for showing the metallic to semiconducting transitions.
Chapter-5 Discusses the A) Efforts made in understanding the CIAS based solar cells through interfaces such as CIAS/ZnO, Mo/CIAS, CIAS/CdS/i-ZnO/Al:ZnO and improving the open circuit voltage VOC upon a rotating substrate, involving the inline and in situ processes, for fabricating the cell/ module were discussed. The device statistics for various set of cells were analyzed. B) Solar cells of CTS absorber with the non-toxic buffer ZnS were fabricated and device properties were analyzed. C) CCTS quantum dots embedded in the polymer matrix were utilized for making the inverted hybrid solar devices in combination of ITO/AZnO bilayered contact replacing the acidic PEDOT: PSS. D) The solar cells made of CCTS hollow spheres by spin coating the absorber in the configuration SLG/Mo/CCTS/CdS/ iZno-AZnO/Ni-Al-Al showed a lower efficiency of 0.02%.
Chapter-6 concludes with the summary of present investigations and the scope for future work.
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Development Of Cu2ZnSnS4/ZnS Thin Film Heterojunction Solar Cells By Ultrasonic Spray PyrolysisPrabhakar, Tejas 12 1900 (has links) (PDF)
Semiconductors such as CuInGaSe2 and CdTe have been investigated as absorber layer materials for thin film solar cells since their band gap matches with the solar spectrum. Films as thin as 2m are sufficient for the absorption of the visible part of solar radiation, because they are characterized by a high absorption coefficient. However, the scarcity and high costs of Indium, Gallium and Tellurium have led to concerns on the sustainability of these technologies. The semiconductor Cu2ZnSnS4 (Copper Zinc Tin Sulphide) consisting of abundantly available elements promises to be an excellent photovoltaic absorber material. The present study is focused on the growth and characterization of CZTS/ZnS thin film heterostructure suitable for PV applications. Ultrasonic Spray Pyrolysis (USP), a variation of Spray Pyrolysis is a thin film deposition technique where the solution to be sprayed is atomized by ultrasonic frequencies. The details of the USP experimental set up and the deposition principle are presented in the thesis. The active layers of the solar cell, viz. the CZTS absorber layer and ZnS emitter layer were grown by this technique. The metal top contact was deposited using e-beam evaporation. The effects of copper concentration and sodium diffusion on the Cu2ZnSnS4 film properties were investigated. The films have shown preferred orientation along (112) direction confirming kesterite structure. The optical studies revealed that a reduction of copper in the films will bring the band gap energy to 1.5eV, which will match with the solar spectrum. Sodium diffusion in the CZTS films is found to passivate the grain boundaries and enhance the electrical conductivity. These properties render CZTS films as good photovoltaic absorber layers. ZnS has a high band gap and is non toxic unlike CdS. The influences of variation in substrate temperature and spray duration on the ZnS film properties were examined. The optical studies conducted on ZnS films revealed that they are highly transparent in the visible region of the solar spectrum. The films were found to possess a band gap of 3.5 eV. These properties make them potential candidates as solar cell emitter layers. The CZTS/ZnS heterojunction solar cell was fabricated and subjected to electrical characterization in dark and illuminated conditions. A conversion efficiency of 1.16% was achieved for the device.
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Studies on AgInS2 Films as Absorber Layer for Heterojunction Solar CellsSunil, Maligi Anantha January 2016 (has links) (PDF)
Currently conventional sources like coal, petroleum and natural gas meet the energy requirements of developing and undeveloped countries. Over a period of time there is high risk of these energy sources getting depleted. Hence an alternate source of energy i.e. renewable energy is the need of the hour. The advantages of renewable energy like higher sustainability, lesser maintenance, low cost of operation, and minimal impact on the environment make the role of renewable energy sources significant. Out of the various renewable energy sources like solar energy, wind energy, hydropower, biogas, tidal and geothermal, usage of solar energy is gradually increasing. Among various solar energy sources, Photovoltaics has dominated over the past two decades since it is free clean energy and availability of abundant sunlight on earth.
Over the past few decades, thin film solar cells (TFSC) have gained considerable interest as an economically feasible alternative to conventional silicon (Si) photovoltaic devices. TFSCs have the potential to be as efficient as Si solar cells both in terms of conversion efficiency as well as cost. The advantages of TFSC are that they are easy to prepare, lesser thickness, requires lesser materials, light weight, low cost and opto-electronic properties can be tuned by varying the process parameters. The present study is focused on the fabrication of AgInS2/ZnS heterojunction thin film solar cell. AgInS2 absorber layer is deposited using both vacuum (sputtering/sulfurization) and non-vacuum (ultrasonic spray pyrolysis) techniques. ZnS window layer is prepared using thermal evaporation technique, detailed experimental investigation has been conducted and the results have been reported in this work. The thesis is divided into 6 chapters.
Chapter 1 gives general introduction about solar cells and working principle of solar cell. It also discusses thin film solar cell technology and its advantages. Layers of thin film solar cell structure, Significance of each layers and possible materials to be used are emphasized. A detailed overview of the available literature on both AgInS2 absorber layer and ZnS window layer has been presented. Based on the literature review, objectives of the present work are defined.
Chapter 2 explains the theory and experimental details of deposition techniques used for the growth of AgInS2 and ZnS films. Details of characterization techniques to study film properties are described in detail.
Chapter 3 presents a systematic study of AgInS2 thin films deposited by sulfurization of sputtered Ag-In metallic precursors. Initially, AgInS2 films are deposited by varying the substrate temperature and properties of as-deposited films are characterized. Structural, morphological, electrical and optical properties of AgInS2 films are explained. From these studies, samples with better properties at particular substrate temperature are optimized. By fixing the substrate temperature, deposition time of silver is varied by keeping other deposition conditions same and the properties of films are discussed. It was observed that deposition time of silver doesn’t have much impact on structural properties of AgInS2 films. However, opto-electric properties of AgInS2 films are enhanced. Based on characterization studies, deposition time of silver is optimized. Deposition time of indium is varied by keeping substrate temperature and silver deposition to optimized value. The properties of as-deposited films are discussed. Based on the above studies, the optimized p type films have a band gap of 1.64 eV, carrier concentration of 1013 ions/cm3 and Resistivity of order 103 Ω-cm.
Chapter 4 presents a systematic study of AgInS2 thin films deposited by ultrasonic spray pyrolysis. AgInS2 films are deposited by varying the substrate temperature and properties of as deposited films are characterized. Structural, morphological, electrical and optical properties of AgInS2 films are explained. From these studies, samples with better properties at particular substrate temperature are optimized. By fixing the substrate temperature, concentration of silver molarity in the precursor solution is varied by keeping other deposition conditions same and the properties of films are discussed. Structural, optical and electrical properties of AgInS2 films are
enhanced with the increase in silver concentration. Based on characterization studies, concentration of silver is optimized. Similarly concentration of indium molarity in the precursor solution is varied and the properties of as-deposited films are discussed. Finally, sulfur molarity in the precursor solution is varied and properties of films are discussed. It was observed that increasing sulfur after certain limit does not have any effect on the properties of the films. Based
on the above studies, this method resulted in the films with resistivity of 103 Ω-cm and band gap of 1.64 eV. These films showed a carrier concentration of 1013 ions/cm3.
Chapter 5 describes the growth of ZnS films using thermal evaporation technique. Influence of thickness on the properties of ZnS films is explained. Samples with good crystallinity, high transmission, and wider gap are selected for device fabrication. This p type layer showed a band gap of 3.52 eV. Solar cells have been fabricated using the AgInS2 films developed by both sputtering and ultrasonic spray pyrolysis techniques. A maximum cell efficiency of 0.92 percent has been achieved for the cell with 0.950 µm thick sputtered AgInS2 layer and thermally evaporated 42 nm thick ZnS layer. In comparison, the ultrasonic spray pyrolysis deposited films gave an efficiency of 0.54 percent. These values are comparable to those mentioned in a couple of reports earlier.
Chapter 6 summarizes the conclusions drawn from the present investigations and scope of future work is suggested.
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