Brigham Young University BYU ScholarsArchive All Theses and Dissertations 2017-08-01 Miniaturization of Linear Ion Traps and Ion Motion Study in a Toroidal Ion Trap Mass Analyzer Ailin Li Brigham Young University Follow this and additional works at: https://scholarsarchive.byu.edu/etd Part of the Chemistry Commons BYU ScholarsArchive Citation Li, Ailin, "Miniaturization of Linear Ion Traps and Ion Motion Study in a Toroidal Ion Trap Mass Analyzer" (2017). All Theses and Dissertations. 6503. https://scholarsarchive.byu.edu/etd/6503 This Dissertation is brought to you for free and open access by BYU ScholarsArchive. It has been accepted for inclusion in All Theses and Dissertations by an authorized administrator of BYU ScholarsArchive. For more information, please contact [email protected], [email protected]. Miniaturization of Linear Ion Traps and Ion Motion Study in a Toroidal Ion Trap Mass Analyzer Ailin Li A dissertation submitted to the faculty of Brigham Young University in partial fulfillment of the requirements for the degree of Doctor of Philosophy Daniel E. Austin, Chair Matthew C. Asplund David V. Dearden Steven R. Goates Jaron C. Hansen Department of Chemistry and Biochemistry Brigham Young University Copyright © 2017 Ailin Li All Rights Reserved ABSTRACT Miniaturization of Linear Ion Traps and Ion Motion Study in a Toroidal Ion Trap Mass Analyzer Ailin Li Department of Chemistry and Biochemistry, BYU Doctor of Philosophy I describe the miniaturization of a linear-type ion trap mass spectrometer for possible applications in portable chemical analysis, and demonstrate the advantages of using lithographically patterned electrode plates in realizing an ion trap with dimension r0 less than 1 mm. The focus of the work was to demonstrate the viability and feasibility of the patterned electrode approach to trap miniaturization, and also to discover potential obstacles to its use. Planar ceramic substrates were patterned with metal electrodes using photolithography. Plates that were originally used in a linear trap with a half-spacing (r0) of 2.19 mm were positioned much closer together such that r0 = 0.95 mm. A capacitive voltage divider provided different radiofrequency (RF) amplitudes to each electrode, and the capacitor values were adjusted to provide the correct electric field at this closer spacing. Electron ionization mass spectra of toluene and dichloromethane demonstrate instrument performance with better than unit mass resolution. Compared with the larger plate spacing, the signal intensity is reduced, corresponding to the reduced trapping capacity of the smaller device, but the mass resolution of the larger device is retained. A further miniaturized linear ion trap with a half-spacing of 362 μm was designed and tested. A series of obstacles and troubleshooting on ion source, analytical method, and electronics were present. These experiments show promise for further miniaturization using patterned ceramic plates and provide a guide for the ion trap miniaturization. The feasibility of a wire linear ion trap was also demonstrated. Unit mass resolution was obtained, indicating a promise for further optimization and miniaturization of the wire linear ion trap. In addition to the practical experiments on the miniaturized linear ion traps, I theoretically studied ion motion in the toroidal ion trap using SIMION simulations, which show classical chaotic behavior of single ions. The chaotic motion is a result of the non-linear components of the electric fields as established by the trap electrodes, and not by Coulombic interaction from other ions. The chaotic behavior was observed specifically in the ejection direction of ions located in non-linear resonance bands within and adjacent to the region of stable trapping. The non-linear bands crossing through the stability regions correspond to hexapole resonance conditions, while the chaotic ejection observed immediately adjacent to the stable trapping region corresponds to a “fuzzy” ejection boundary. Fractal-like patterns were obtained in a series of zoomed-in regions of the stability diagram. Keywords: linear ion trap, miniaturization, toroidal ion trap, non-linear field, chaotic motion, ion trajectory simulation ACKNOWLEDGEMENTS I would like to express gratitude to those that have been instrumental to the success in my study and career. In particular, I am grateful for the support of my advisor, Dr. Daniel E. Austin. It has been a precious opportunity for me to be advised by him as an excellent and knowledgeable scientist. His mentorship and advice have been vital in guiding me through my career as a student and researcher. I also would like to express thanks to my graduate committee members, Dr. Matthew C. Asplund, Dr. David V. Dearden, Dr. Steven R. Goates and Dr. Jaron C. Hansen, for their critical evaluation and high standards during my research and study. They have all aided my education and progress. I am grateful for their willingness to provide assistance to me. I would like to thank Dr. Aaron R. Hawkins and Dr. Stephen A. Lammert for their enlightened instruction to my research. Dr. Hawkins has helped guide me in learning all I know about ion trap microfabrication. Dr. Lammert provided appreciated consultation and support to my research on ion trap instrumentation and mechanisms. I am grateful for the opportunities for learning and growth that they provided me. They have given me invaluable support and guidance as I have progressed in my career. I have been fortunate to work with several valued colleagues in this endeavor. These include Dr. Brett J. Hansen, Dr. Qinghao Wu, Dr. Brandon L. Barney, Jessica M. Higgs, Yuan Tian, Sara Pratt, Junting Wang, Andrew T. Powell, Justin Sorensen, Derek Andrew, Trevor Decker, and other friends in both Dr. Austin’s group and other groups. Working with these individuals has given me valuable team experience and friendship that always encourage me during my work and study. I also would like to thank the staff in the instrument shop in the Department of Chemistry and Biochemistry at Brigham Young University for helping me repair the electric circuits and accessories in the ion trap system. Thanks also to the department for giving me this precious opportunity and support. Finally, I am particularly grateful for my parents and my husband Zhe Yang. They have been constantly supportive and encouraging during this important time of my life. Their help gives me the focus and motivation to finish this work. This dissertation is dedicated to my parents and my husband. TABLE OF CONTENTS List of Figures ...............................................................................................................................vii List of Tables ................................................................................................................................ xi 1 THEORY, DEVELOPMENT AND MINIATURIZATION OF ION TRAPS ....................... 1 Quadrupole Ion Traps ....................................................................................................... 1 1.1.1 Theory of Quadrupole Ion Trap ................................................................................ 1 1.1.2 Ion Trap Development .............................................................................................. 7 Ion Trap Miniaturization ................................................................................................ 11 1.2.1 Significance of Ion Trap Miniaturization ............................................................... 11 1.2.2 Methods for Ion Trap Miniaturization .................................................................... 12 1.2.3 Obstacles to Ion Trap Miniaturization .................................................................... 12 1.2.4 Microfabrication Approaches to Ion Trap Miniaturization .................................... 15 1.2.5 Miniaturized Ion Traps ........................................................................................... 16 Conclusion ...................................................................................................................... 21 Dissertation Overview .................................................................................................... 23 References ...................................................................................................................... 24 2 MINIATURIZED PLANAR LINEAR ION TRAP MASS ANALYZER ............................ 32 Introduction .................................................................................................................... 32 Miniaturized Linear Ion Trap ......................................................................................... 35 2.2.1 Fabrication and Assembly of Planar Linear Ion Trap ............................................. 35 2.2.2 Germanium Coating Study ..................................................................................... 38 2.2.3 Further Miniaturization ........................................................................................... 41 2.2.4 Calculating and Optimizing Electric Fields ............................................................ 46 Sub-mm Linear Ion Trap ................................................................................................ 49 2.3.1 Instrumentation ....................................................................................................... 49 2.3.2 Electric Field Determination ..................................................................................