In Situ Process Monitoring Using Raman Spectroscopy PDF Download

Author: Javier A. Falcon
Publisher:
ISBN:
Category : Biomolecules
Languages : en
Pages : 336

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Author:
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Category :
Languages : en
Pages :

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The theoretical and experimental applications of Raman spectroscopic techniques to the study of battery electrode processes are described. In particular, the potential of Raman spectroscopy as an in-situ analytical tool for the characterization of the structure and composition of electrode surface layers at electrode-electrolyte interfaces during electrolysis is examined. It is anticipated that this understanding of the battery electrode processes will be helpful in designing battery active material with improved performance. The applications of Raman spectroscopy to the in-situ study of electrode processes has been demonstrated in a few selected areas, including: (1) the anodic corrosion of lead in sulfuric acid and (2) the anodization and sulfation of tetrabasicleadsulfate in sulfuric acid. Preliminary results on the anodization of iron and on the electrochemical behavior of nickel positive-electrode active material in potassium hydroxide electrolytes are presented in the Appendix.

Author: Ravi Varma
Publisher:
ISBN:
Category :
Languages : en
Pages : 47

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Author: Van Duren, Stephan
Publisher: Universitätsverlag der TU Berlin
ISBN: 3798330646
Category : Technology & Engineering
Languages : en
Pages : 188

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In recent years, kesterite Cu2ZnSnS4 (CZTS) has become an interesting alternative to copper indium gallium (di)selenide (CIGS) due to its non-toxic and earth abundant constituents. A variety of methods is being used to fabricate kesterite thin films, such as coevaporation, sputtering, electrodeposition, spray pyrolysis and others. Most of them include an annealing step to stimulate elemental mixing and interdiffusion. Although conversion efficiencies of kesterite solar cells have increased among different research groups, the record value of 12.6% set by IBM in 2014 has not been broken yet. Therefore, experimental and theoretical studies are needed to predict the effect of the secondary phases and detrimental defects on the electronical properties of the CZTS based solar devices. The work presented here studies non-destructive techniques for in situ process control and monitoring. With the aim to detect phases and phase transitions to optimize crucial processing steps such as pre-annealing of metal precursors, high temperature annealing and vacuum deposition of Cu-Sn-Zn-S based thin films. The research consists of three parts in which Raman spectroscopy, X-ray diffraction (XRD) and reflectometry are used to explore this objective. In the first part Raman spectroscopy is investigated as an in situ monitoring technique during high temperature annealing of thin films. It investigates whether the occurrence of CZTS can be monitored when it is created from annealing a Mo/CTS/ZnS layered thin film. CuS, SnS, ZnS and CTS (Cu-Sn-S) films are prepared by physical vapor deposition. The Raman scattering intensity was compared to investigate whether their specific vibrational modes can be distinguished from each other at room temperature. Then, the CTS film is annealed between 50 and 550 °C in order to investigate whether CTS vibrational modes can be identified at elevated temperatures and to see which transitions take place within the thin film. Also, a CZTS reference film is annealed between 50 and 550 °C for reference purposes. The temperature dependence of the main CZTS modes is examined to investigate whether it can be used for in situ temperature control. Finally, a ZnS layer is deposited on the unannealed CTS film to obtain a Mo/CTS/ZnS layered film. This film is used to study the conversion of CTS/ZnS into CZTS at elevated temperatures. It was found that Raman spectroscopy can successfully be used to monitor formation of CZTS by identifying its main vibrational mode during the annealing process. The intensity of the CTS modes reduces at elevated temperatures. At 450 °C, the main CZTS mode at 338 cm-1 can be clearly identified. The second part also focuses on high temperature annealing. However, in this part the focus lies on annealing of the metal precursor films. It is explored whether specific alloys benefit or hinder the formation of secondary phases during formation of the CZTS absorber films. Also, to what extent this influences solar cell performance. In situ XRD was investigated for in situ monitoring of the pre-annealing process. Cu-poor metal precursor films are prepared by sputtering deposition. The precursors are annealed at 150 °C, 200 °C, 300 °C and 450 °C in a three zone tube furnace. The effect on the structural properties is analysed by XRD to study the formation mechanism of alloys. The precursor films are then sulfurized in a three zone tube furnace. The structural properties of the absorber are analysed and correlated with structures in the precursor. It is found that formation of SnS2 in the absorber is proportional to the remaining Sn in the pre-annealed precursor. Also, electron micrographs showed that pre-annealing temperature influences grain growth and surface precipitation of Sn-S and Zn-S. Pre-annealed absorbers at 450 °C did not exhibit these phases on the surface. Solar devices are fabricated from the absorber films and best performing devices were obtained from pre-annealed absorbers at 450 °C. They showed absence of Sn and SnS2 in, respectively, the precursor and absorber. It could be concluded that SnS2 phases are detrimental to device efficiency and that SnS2 XRD peak intensity follows an inverse proportionality with device efficiency. The third part explores reflectometry as a method to monitor a growing film during thermal evaporation in a physical vapor deposition (PVD) system. A set of six CZTS absorbers is examined by ex situ Raman spectroscopy and reflectometry to study the influence of secondary phases CuS and ZnS on reflection spectra. Composition strongly influences reflection spectra and CuS leaves a characteristic dip in the reflection spectrum at about 600 nm. An integration method was used to analyze this phenomenon quantitatively. Subsequently, a reflectometry setup is designed, developed and integrated in the PVD system. Four different CZTS co-evaporated and multi-layered films are deposited. Structural, morphological and vibrational properties are investigated. The reflection spectra are monitored during deposition and time-dependent reflection spectra are analyzed for characteristic aspects related to properties such as thickness, band gap and phase formation. CuS could not be detected in the films by the integration method due to the superposition of the CuS dip with developing interference fringes during film growth. However, in multilayered CTS/ZnS film it is found that the onset of ZnS deposition can be detected by increased reflection intensity due to reduced surface roughness. Additionally, the shifting onset of the interference fringes to lower photon energies can be used as a characteristic fingerprint during the deposition process. In conclusion, this work showed that Raman spectroscopy, XRD and reflectometry could be successfully implemented for in situ process control and monitoring of high temperature annealing and vacuum deposition of Cu-Sn-Zn-S based precursors and absorbers. The application of these in situ techniques can lead to the optimization of thin film material properties and solar cells. As such, this study has paved the way for further improvement of Cu-Sn-Zn-S based precursors and thin film absorbers. Innerhalb der letzten Jahre hat sich Kesterit Cu2ZnSnS4 (CZTS) aufgrund seiner ungiftigen Bestandteile und deren hoher Verfügbarkeit zu einer interessanten Alternative zu Kupfer Indium Gallium (di-)Selenid (CIGS) entwickelt. Zur Herstellung von Kesterit Dünnschichten wird eine Vielzahl von Methoden verwendet wie Ko-Verdampfung, Sputtern, Elektrodeposition, Spray Pyrolyse und andere. Die meisten davon beinhalten einen Temper-Schritt um die Durchmischung und Interdiffusion der Elemente zu stimulieren. Obwohl der Wirkungsgrad der Kersterit Solarzellen von verschiedenen Forschungsgruppen erhöht wurde, ist der Rekordwert von IBM von 12,6 % noch nicht gebrochen worden. Daher werden experimentelle und theoretische Studien benötigt, die den Einfluss von Fremdphasen und schädlichen Defekten auf die elektronischen Eigenschaften der CZTS Solarzellen vorhersagen. Die vorliegende Arbeit untersucht zerstörungsfreie Methoden für die in situ Prozesskontrolle und -überwachung. Dabei ist das Ziel, entscheidende Prozessschritte wie das Vortempern der Metall-Vorläufer sowie das Hochtemperatur-Tempern und die Vakuum-Abscheidung von Cu-Sn-Zn-S basierten Schichten zu optimieren. Die Untersuchung besteht aus drei Teilen, in denen Raman-Spektroskopie, Röntgendiffraktion (XRD) und Reflektometrie benutzt werden um dieses Ziel zu erreichen. Im ersten Teil wird die Ramanspektroskopie als in situ Methode zur Überwachung des Hochtemperatur-Temperns von Dünnschichten betrachtet. Es wird untersucht, ob das Entstehen von CZTS beim Tempern von gestapelten Mo/CTS/ZnS Dünnschichten beobachtet werden kann. CuS, SnS, ZnS und CTS (Cu-Sn-S) Schichten werden durch physikalische Gasabscheidung hergestellt. Die Intensität der Raman Streuung wurde vergleichen um zu untersuchen, ob die spezifischen Vibrations-Moden bei Raumtemperatur voneinander unterschieden werden können. Dann werden die CTS Schichten zwischen 50 °C und 550 °C getempert um zu untersuchen, ob die CTS Vibrations-Moden bei höheren Temperaturen identifiziert werden können und um festzustellen, welche Übergänge innerhalb der Schicht auftreten. Außerdem wurde eine CZTS Referenzschicht zwischen 50 °C und 550 °C für Referenzzwecke getempert worden. Die Temperaturabhängigkeit der CZTS Haupt-Moden werden betrachtet, um zu untersuche, ob sie für die in situ Temperaturüberwachung verwendet werden können. Abschließend wurde eine ZnS Schicht auf einem nicht getemperten CTS Film abgeschieden, um eine gestapelte Mo/CTS/ZnS Schicht zu erhalten. Diese Schicht wird verwendet, um die Umwandlung von CTS/ZnS zu CZTS bei erhöhten Temperaturen zu untersuchen. Es wurde festgestellt, dass Raman Spektroskopie erfolgreich verwendet werden kann, um die Bildung von CZTS zu überwachen, indem die Haupt-Vibrations-Moden während des Temperns identifiziert werden. Die Intensität der CTS Moden verringert sich bei höheren Temperaturen. Bei 450 °C kann die CZTS Hauptmode bei 338 cm-1 klar identifiziert werden. Der zweite Teil konzentriert sich ebenfalls auf das Hochtemperatur-Tempern. In diesem Teil liegt der Fokus allerdings auf dem Tempern der Metal-Vorläufer-Schichten. Es wird erforscht, ob bestimmte Legierungen die Entstehung von Fremdphasen während der Entstehung der CZTS Absorberschichten begünstigen oder hemmen und welchen Einfluss dies auf die Leistung der Solarzelle hat. In situ XRD wird verwendet, um die Prozesse des Vortemperns zu überwachen. Kupfer arme Metall-Vorläufer-Schichten werden durch Sputtern aufgetragen. Die Vorläufer werden bei 150 °C, 200 °C, 300 °C und 450 °C in einem Drei-Zonen-Röhren-Ofen getempert. Die Auswirkungen auf die strukturellen Eigenschaften werden mit XRD analysiert, um den Entstehungsmechanismus der Legierungen zu untersuchen. Die Vorläuferschichten werden dann in einem Drei-Zonen-Röhren-Ofen sulfurisiert. Die strukturellen Eigenschaften des Absorbers werden analysiert und mit der Struktur der Vorläufer korreliert. Es wurde festgestellt, dass die Entstehung von SnS2 im Absorber proportional zum verbleibenden Sn im vorgetemperten Vorläufer ist. Außerdem zeigen Bilder des Rasterelektronenmikroskops, dass die Temperatur des Vortemperns das Kornwachstum und das Abschieden von Sn-S und Zn-S an der Oberfläche beeinflusst. Bei 450 °C vorgetemperte Absorber weisen keine dieser Phasen an der Oberfläche auf. Solarzellen werden aus diesen Absorber-Schichten hergestellt und die besten Zellen entstanden aus den bei 450 °C vorgetemperten Absorbern. Bei diesen traten Sn und SnS2 weder im Vorläufer noch im Absorber auf. Es konnte geschlussfolgert werden, dass SnS2 Phasen schädlich für den Wirkungsgrad der Zellen sind und dass die Intensität der SnS2 XRD Peaks invers proportional zum Wirkungsgrad der Zellen ist. Der dritte Teil erforscht die Reflektometrie als Methode zur Überwachung des Schichtwachstums während des thermischen Verdampfens in einer Anlage zur physikalischen Gasabscheidung (PVD). Ein Satz aus sechs CZTS Absorbern wird mittels ex situ Raman-Spektroskopie und Reflektometrie vermessen, um den Einfluss der Fremdphasen CuS und ZnS auf die Reflexionsspektren zu untersuchen. Die Zusammensetzung beeinflusst die Reflexionsspektren stark und CuS hinterlässt eine charakteristische Senkung bei 600 nm im Reflexionsspektrum. Eine Integrationsmethode wurde verwendet um dieses Phänomen quantitativ zu analysieren. Anschließend wurde ein Reflektometrieaufbau entworfen, entwickelt und in die PVD-Anlage integriert. Vier verschiedene CZTS koverdampfte und Mehrschicht-Filme wurden abgeschieden. Strukturelle, morphologische und Vibrationseigenschaften werden untersucht. Die Reflexionsspektren werden während des Abscheidens aufgenommen und zeitabhängige Reflexionsspektren werden auf charakteristische Aspekte im Zusammenhang mit Eigenschaften wie Dicke, Bandlücke und Entstehung von Phasen untersucht. CuS konnte in den Schichten mit der Integrations-Methode wegen der Überlagerung der CuS Senkung mit dem entstehenden Interferenzmuster nicht detektiert werden. Allerdings wurde in gestapelten CTS/ZnS Schichten beobachtet werden, dass der Beginn der ZnS Abscheidung durch eine ansteigende Intensität der Reflektion aufgrund der verringerten Oberflächenrauigkeit detektiert werden kann. Zusätzlich kann die Verschiebung des Startpunkts der Interferenzen zu niedrigeren Photonenenergien als charakteristischer Fingerabdruck während des Abscheidungsprozesses verwendet werden. Zusammenfassend zeigt diese Arbeit, dass Raman-Spektroskopie, XRD und Reflektrometrie erfolgreich als in situ Prozesskontrolle und –überwachung bei Hochtemperatur-Tempern und Vakuum-Abscheidung von Cu-Sn-Zn-S basierten Vorläufern und Absorbern realisiert werden konnten. Die Anwendung dieser in situ Techniken kann zu einer Optimierung der Eigenschaften von Dünnschicht-Materialien und von Solarzellen führen. Als solche hat diese Untersuchung den Weg für weitere Verbesserung von Cu-Sn-Zn-S basierte Vorläufer und Dünnschicht-Absorber geebnet.

Author: Angelo Chianese
Publisher: John Wiley & Sons
ISBN: 3527645179
Category : Science
Languages : en
Pages : 253

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Crystallization is an important technique for separation and purification of substances as well as for product design in chemical, pharmaceutical and biotechnological process industries. This ready reference and handbook draws on research work and industrial practice of a large group of experts in the various areas of industrial crystallization processes, capturing the essence of current trends, the markets, design tools and technologies in this key field. Along the way, it outlines trouble free production, provides laboratory controls, analyses case studies and discusses new challenges. First the instrumentation and techniques used to measure the crystal size distribution, the nucleation and solubility points, and the chemical composition of the solid and liquid phase are outlined. Then the main techniques adopted to control industrial crystallizers, starting from fundamental approaches to the most advanced ones, including the multivariable predictive control are described. An overview of the main crystallizer types is given with details of the main control schemes adopted in industry as well as the more suitable sensors and actuators.

Author: Katherine A. Bakeev
Publisher: John Wiley & Sons
ISBN: 0470689609
Category : Science
Languages : en
Pages : 576

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Process Analytical Technology explores the concepts of PAT and its application in the chemical and pharmaceutical industry from the point of view of the analytical chemist. In this new edition all of the original chapters have been updated and revised, and new chapters covering the important topics of sampling, NMR, fluorescence, and acoustic chemometrics have been added. Coverage includes: Implementation of Process Analytical Technologies UV-Visible Spectroscopy for On-line Analysis Infrared Spectroscopy for Process Analytical Applications Process Raman Spectroscopy Process NMR Spectrscopy: Technology and On-line Applications Fluorescent Sensing and Process Analytical Applications Chemometrics in Process Analytical Technology (PAT) On-Line PAT Applications of Spectroscopy in the Pharmaceutical Industry Future Trends for PAT for Increased Process Understanding and Growing Applications in Biomanufacturing NIR Chemical Imaging This volume is an important starting point for anyone wanting to implement PAT and is intended not only to assist a newcomer to the field but also to provide up-to-date information for those who practice process analytical chemistry and PAT. It is relevant for chemists, chemical and process engineers, and analytical chemists working on process development, scale-up and production in the pharmaceutical, fine and specialty chemicals industries, as well as for academic chemistry, chemical engineering, chemometrics and pharmaceutical science research groups focussing on PAT. Review from the First Edition “The book provides an excellent first port of call for anyone seeking material and discussions to understand the area better. It deserves to be found in every library that serves those who are active in the field of Process Analytical Technology.”—Current Engineering Practice

Author: Dennis P. Strommen
Publisher: Wiley-Interscience
ISBN:
Category : Science
Languages : en
Pages : 160

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This book presents a nuts and bolts approach to using Raman spectroscopy and recording Raman data. It serves as a laboratory reference manual for both novice and expert chemists, with procedures and appropriate cautions carefully explained. It includes tables of laser frequency, plasma lines and calibration procedures as well as a listing of sampling techniques.

Author: Andreas Braeuer
Publisher: Elsevier
ISBN: 0444634207
Category : Science
Languages : en
Pages : 396

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In situ Spectroscopic Techniques at High Pressure provides a comprehensive treatment of in-situ applications of spectroscopic techniques at high pressure and their working principles, allowing the reader to develop a deep understanding of which measurements are accessible with each technique, what their limitations are, and for which application each technique is best suited. Coverage is also given to the instrumental requirements for these applications, with respect to the high pressure instrumentation and the spectroscopic components of the equipment. The pedagogical style of the book is supplemented by the inclusion of "study questions" which aim to make it useful for graduate-level courses. - Bridges the gap between supercritical fluid science/technology and in-situ spectroscopic techniques - Provides a powerful guide to applying spectroscopic techniques as gainful sensors at high pressure - Highlights the influence of a high pressure environment and high pressure equipment on spectroscopic techniques - Presents a deep understanding of which measurements are accessible with each technique, what their limitations are, and for which application each technique is best suited

Author: Lars T. Kuhn
Publisher: Springer
ISBN: 364239728X
Category : Science
Languages : en
Pages : 311

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Elucidating Organic Reaction Mechanisms using photo-CIDNP Spectroscopy, by Martin Goez. Parahydrogen Induced Polarization by Homogeneous Catalysis: Theory and Applications, by Kerstin Münnemann et al. Improving NMR and MRI Sensitivity with Parahydrogen, by R. Mewis & Simon Duckett. The Solid-state Photo-CIDNP Effect, by Jörg Matysik et al. Parahydrogen-induced Polarization in Heterogeneous Catalytic Processes, by Igor Koptyug et al. Dynamic Nuclear Polarization Enhanced NMR Spectroscopy, by U. Akbey & H. Oschkinat. Photo-CIDNP NMR Spectroscopy of Amino Acids and Proteins, by Lars T. Kuhn.

Author: Judit E. Puskas
Publisher: Springer Science & Business Media
ISBN: 9780306474101
Category : Science
Languages : en
Pages : 234

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This book is a collection of selected papers presented at the symposium titled "In situ Spectroscopy in Monomer and Polymer Synthesis," held at the April, 2001 ACS National Meeting in San Diego, California, USA. The co-organizers of this symposium were Timothy Long, Judit E. Puskas, Robson F. Storey, and J. Andrews. In situ spectroscopic monitoring is gaining popularity both in academia and industry. FfIR monitoring is used most frequently, but UV-visible, raman, and NMR spectroscopy are also important. This book concentrates mostly on FfIR monitoring, both in the near and mid-infrared ranges. The first chapter is a short general overview of FfIR spectroscopy, followed by the symposium contribu tions. We thought that this would be especially useful for student readers. We hope that the book will present a state-of-the-art overview of research related to in situ spectroscopic monitoring. -Judit E. Puskas ix Acknowledgments This book would not have been possible without the dedicated effort of the chapter contributors and the symposium committee: Professor Judit E. Puskas Professor Timothy Long Professor Robson F. Storey Professor J. Andrews The symposium was financially supported by: ACS-Petroleum Research Fund REMSPEC Co. Wyatt Technology Co.