Rochester Institute of Technology RIT Scholar Works Theses Thesis/Dissertation Collections 2007 The synthesis and characterization of a novel single source beta-barium borate precursor barium (18-crown-6) dimesitylborinate Travis M. Scott Follow this and additional works at: http://scholarworks.rit.edu/theses Recommended Citation Scott, Travis M., "The synthesis and characterization of a novel single source beta-barium borate precursor barium (18-crown-6) dimesitylborinate" (2007). Thesis. Rochester Institute of Technology. Accessed from This Thesis is brought to you for free and open access by the Thesis/Dissertation Collections at RIT Scholar Works. It has been accepted for inclusion in Theses by an authorized administrator of RIT Scholar Works. For more information, please contact [email protected]. The Synthesis and Characterization of a Novel Single Source Beta-Barium Borate Precursor Barium (l8-crown-6) Dimesitylborinate Travis M. Scott Thesis Submitted for Partial Fulfillment of the Requirements for the Degree in Master of Science Approved: M. L. IIlingsworth Thesis Advisor T. C. Morrill Department Head Department of Chemistry Rochester Institute of Technology Rochester, New York February 13 , 2007 Thesis/Dissertation Author Permission Statement Title of thesis or dissertation: ike s'jl)tkes I ~ (tAd C~cJe f' r2(A hOI\ 4- C\. N()ve-l&tGt- B ">I'-I \...lJV\ J3(;1."G1.k- ~ C'e..0- v,.I'5<:"":';----- 1)o.!'I v-MC t~ -tNk".J) .... tD) D 1 Me-s, I-~I bc?('-.I t\o.te .-;. .... <./ . Name of author: 11\\ VI ~ 1'1 . _J( crit Degree: ·scMI McI5/-es'C) eIw'.'16tt\j I §5 H/c)Clv:"-'11lst (\~ Program: LhQ/b Istt-u College: _s_""' -"'c_,e..='1-'-'cc,"-"-_J________________________ _ I understand that I must submit a print copy of my thesis or dissertation to the RIT Archives, per current RIT guidelines for the completion of my degree. I hereby grant to the Rochester Institute of Technology and its agents the non-exclusive license to archive and make accessible my thesis or dissertation in whole or in part in all forms of media in perpetuity. I retain all other ownership rights to the copyright of the thesis or dissertation. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. Print Reproduction Permission Granted: I, ~ V IS fv\ . S'C6ft- , hereby grant permission to the Rochester Institute Technology to reproduce my print thesis or dissertation in whole or in part. Any reproduction will not be for commercial use or profit. Signature of Author: _________________Travis M. Scott Date: qU f-::511- /0/ /'-7 Print Reproduction Permission Denied: I, , hereby deny permission to the RIT Library of the Rochester Institute of Technology to reproduce my print thesis or dissertation in whole or in part. Signature of Author: _________________ Date: _____ Inclusion in the RIT Digital Media Library Electronic Thesis & Dissertation (ETD) Archive I, ~lJlS !vi , SCo4 ,additionally grant to the Rochester Institute of Technology Digital Media Library (RIT DML) the non-exclusive license to archive and provide electronic access to my thesis or dissertation in whole or in part in all forms of media in perpetuity. I understand that my work, in addition to its bibliographic record and abstract, will be available to the world-wide community of scholars and researchers through the RIT DML. I retain all other ownership rights to the copyright of the thesis or dissertation. I also retain the right to use in future works (such as articles or books) all or part of this thesis or dissertation. I am aware that the Rochester Institute of Technology does not require registration of copyright for ETDs. I hereby certify that, if appropriate, I have obtained and attached written permission statements from the owners of each third party copyrighted matter to be included in my thesis or dissertation. I certify that the version I submitted is the same as that approved by my committee. Signature of Author: ___________Travis M. Scott Date: vr? I'")..::J I /07 Table of Contents Page ? Introduction 1 ? Experimental Materials: 14 _ _ Reaction Scheme: 16 Synthesis of Barium ( 1 8-Crown-6) Dimesitylborinate: 1 6 Testing the Reaction by TLC: 19 Isolation of Barium (18-Crown-6) Dimesitylborinate via Recrystalization: 20 Isolation of Barium ( 1 8-crown-6) Dimesitylborate via Column Chromatography: 20 Characterization of Barium ( 1 8-crown-6) Dimesitylborinate: 21 Crystal Growth of Barium (18-crown-6) Dimesitylborainte: Converting Barium (18-crown-6) Dimesitylborinate to Beta-Barium Borate:. 23 Preparation of Thin Films of BBO: 24 ? Results and Discussion o Confirmation of Isolation: 24 Confirmation for Barium and Boron in Barium (18-crown-6) Dimesitylborinate: 24 o Identification of coloration: 25 Single Crystal Structure of Hydrolyzed o Barium (18-crown-6) Dimesitylborinate: Characterization of Barium ( 1 8-crown-6) Dimesitylborinate via Infrared Spectroscopy: 28 Characterization of Barium (18-crown-6) Dimesitylborinate via Nuclear Magnetic Resonance: 34 Characterization of Barium (18-crown-6) Dimesitylborinate via Thermogravimetric Analysis (TGA): 42 Characterization of Barium (18-crown-6) Dimesitylborinate via Characterization of Barium ( 1 8-crown-6) Dimesitylborinate by Elemental Analysis: 44 Characterization of Barium ( 1 8-crown-6) Dimesitylborinate via Mass Spec: 46 X-ray Diffraction of Heated Powders: 49 X-ray Diffraction of Thin Films: 49 ? Conclusions 57 ? Future Work __ 58 ? References 59 List of Figures Figure # Page 4 Figure 1 . (3-BBO Structure Figure 2. Crystal Structure of (enH2)i.5[Ba(hfa)5]C2H5OH 1 Figure 3. Crystal Structure of Bis(hexafluoroacetylacetonate)(crown 12 Barium ether) _ Figure 4. Proposed Single Source Precursor, Barium (18-crown-6) Dimesitylborinate. 14 Figure 5. Design of Reaction Apparatus Figure 6. Crystal Structure of Hydrolysis Product.. 28 of Crystal Structure 28 Figure 7. Molecular View Hydrolyzed Products ._ of Dimesitylborinic Acid Figure 8. IR Spectrum _ _ Figure 9. IR Spectrum of 18-crown-6 32 Figure 10. IR Spectrum of Barium (18-crown-6) Dimesitylborinate.. 33 . of D-chloroform 36 Figure 1 1 NMR Spectrum __ _ of Dimesitylborinic Acid 37 Figure 12. NMR Spectrum _ Figure 13. NMR Spectrum of 18-crown-6 38 Figure 14. NMR Spectrum of Barium (18-crown-6) Dimesitylborinate obtained from Column Chromatography 39 Figure 15. NMR Spectrum of Barium (18-crown-6) Dimesitylborinate obtained from Hexanes 40 Figure 16. TGA Scan of Barium (18-crown-6) Dimesitylborinate 43 m Figure 17. Mass Spectrum of Barium (18-crown-6) Dimesitylborinate Figure 18. Product Crystals Heated to 550C 50 Figure 19. Initial Product Crystals Heated to 800C 51 Figure 20. Second Product Crystals Heated to 800C 52 Figure 21. Second Product Crystals Heated to 800C Figure 22. Product Residue Heated to 550C 54 Figure 23. Washed Product Residue Heated to 800C.___. 55 Figure 24. XRD Thin Films on Sapphire Substrate .... 56 IV List of Tables Table # Page Table I. Physical and chemical properties of NLO crystals 3 Table II. Thin films compared to bulk crystals 5 Table III. Comparison between different thin film techniques 7 Table IV. Notable Research towards the development of BBO Thin Films 9 Table V. Heating cycle for converting precursor to BBO 23 Table VI. X-ray crystallography data for hydrolyzed product C30O8H55B 27 Table VII. NMR data comparing starting materials to product 41 Table VIII. Elemental Analysis of Barium (18-crown-6) Dimesitylborinate 44 List of Abbreviations BBO Barium Borate (BaB208) CE 18-crown-6 DMBA Dimesitylborinic acid DSC Differential Scanning Calorimetry IR Infrared MOCVD Metal Organic Chemical Vapor Dc MOD Metallorganic decomposition MSP Multi-source Precursor NLO Non-linear Optical NMR Nuclear Magnetic Resonance SSP Single Source Precursor SHG Second Harmonic Generation TGA Thermal Gravimetric Analysis THG Third Harmonic Generation TLC Thin Layer Chromatography UV Ultra Violet XRD X-ray Diffraction VI Acknowledgements I would first like to thank Dr. Illingsworth, my research advisor. He was an invaluable help at interpreting and understanding the results of the research. I would like to thank Dr. Gysling for his support and help throughout the research. I would like to thank Dr. Langner for his advice and lessons throughout my education. I would like to thank Dr. Smith for all he has done to help me through the Masters degree program. I would like to thank Krista Fridman for all her advice and ideas while working on this thesis. I would like to thank Tom Blanton from Eastman Kodak Research Laboratories for recording thin film XRD. I would like to thank Thomas lackson and Robert Saccente from Eastman Kodak Research Laboratories for their help obtaining and interpreting mass spectroscopy. I would like to thank Dr. Morrill and Brenda K. Mastrangelo for their help and assistance throughout my education here. I would like to thank all the professors and faculty members who I have met, learned from, and worked with. I would like to thank my family and friends for their support and help. vn Abstract Nonlinear optical materials are a rapidly growing market and are expected to exceed $1.6 billion by 2009. Significant time, energy, and investment have been applied to increasing the efficiency of producing NLO materials. Of these materials beta-barium borate has stood out as an important NLO product. The goal of this research was the development of a novel beta-barium precursor suitable for applications in thin film technology. Special attention was paid towards development of a precursor suitable for metal organic chemical vapor deposition. To that end special attention was paid towards the synthesis of a mononuclear barium compound. The novel BBO precursor obtained was a barium dimesityl borate compound coordinated with 18-crown-6, barium (18-crown-6) dimesitylborinate (BaB2C4g08H68). The apparently water-sensitive precursor has shown conversion to BBO comparable to current industrial processes.