Rare earths in Sol-gel glasses

Rare earths in sol-gel glasses

Purpose of this website

This website was created as an archive of the sol-gel glass research performed by Dr. Ann Silversmith of Hamilton College and Dr. Dan Boye of Davidson College and their undergraduate research students. It is to be used primarily as a teaching tool for their work. The information presented in professional publications and given at conferences is the product of their best understanding at the time. It should be kept in mind, however, that other ideas and information presented on the website are part of a continual learning process and may not be fully refined or, in a few places, even correct. If a visitor has questions about our research or what is presented on this website, they should contact either Ann Silversmith (asilvers@hamilton.edu) or Dan Boye (daboye@davidson.edu).

Project description and history

While at the 1993 International Conference on Luminescence in Storrs, Connecticut, Ann and Dan heard a talk about sol-gel synthesis of rare earth-doped glass. We thought it sounded like fun - something that could be done at Hamilton and Davidson. Since the summer of 1997, we've been working with Karen Brewer in the Chemistry Department at Hamilton on making glass and doing interesting spectroscopy on our own materials. One of the intriguing aspects is that our students make the samples. They can decide what parameters they want to vary and then can create those samples. We've had grants from the Research Corporation, the American Chemical Society and the National Science Foundation to support the project. There have been many students who have made valuable contributions to the work and they are listed below. In the summer of 2003, Ann and Dan presented two posters of RE-based sol-gels at the Dynamic Processes Conference in Christchurch, NZ and two papers based on this work were published in the Journal of Luminescence. At the 2006 March Meeting of the American Physical Society, Greg Armstrong presented the talk "Enhanced fluorescence in rare earth doped sol-gel glasses containing Al³⁺." In the November issue of the Journal of Luminescence, our latest findings will appear. The publications, posters and presentations listed below are based on the research we have done with our students.

We have observed fluorescence from many of the lanthanide rare earth ions. Most recently, we've found the optical behavior of the rare earth ion Tb³⁺ in sol-gel glasses to be particularly useful. By comparing the fluorescence from the ⁵D₃ and ⁵D₄ levels to the ground state, we have been able to learn a lot about the energy transfer among rare earth ions and between rare earth ions and the glass matrix. Greg Armstrong began the work with a study of the variation in intensity of ⁵D₃ emission with annealing conditions. In the summer of 2005, Yubo Lu '07 and Dan Campbell '08 of Hamilton College, and Rob Correll and Colleen Gillespie of Davidson continued the work with Tb³⁺ by studying the aging of sol-gel samples after annealing. During the academic year '05-'06 we continued to find new information that helps clarify the role of Al³⁺ as a co-dopant in the gels. Al³⁺ increases the fluorescence yield significantly but how it does it is still not clear. This topic continued to be the main focus for the summer of 2006. There were four students working at the two schools and, in July, Dr. Kurt Hoffman from Whitman College and two of his students traveled to Davidson to join in the research effort, thanks to support from the American Chemical Society Petroleum Research Foundation. Silversmith and Thao Nguyen came for two weeks during July as well. The outcome of that summer's work opened up many avenues. Carlos Ortiz '07 of Davidson College investigated upconversion in thulium using pulsed laser excitation. The whole group looked at the nonexponential behavior of the ⁵D₃ emission of Tb³⁺ due to cross relaxation in order to learn more about the rare earth local environment. DPC 2007 was held in Segovia, Spain in June of 2007. It was attended by Boye, Silversmith, Hoffman, and Nguyen who presented 3 posters and an oral presentations. Three manuscripts were submitted and all were accepted for publication in the Journal of Luminescence.

Participants

Ann Silversmith, Physics Department, Hamilton College

Thao Nguyen T. Nguyen, Summer 2006, Summer 2007, AY 2007-08
Dan Campbell, Summer 2005, Summer 2007, AY 2007-08
Tess Olson, Summer 2004, AY 2007-08
Luxue Dang, AY 2006-07
Yuqi Mao, Summer 2006
Yubo Lu, Summer 2005
Greg Armstrong, Summer 2004, AY 2005-06
Brendan Sullivan, Summer 2004, AY 2006-07
Andrew Magyar, AY 2002-03
Stephanie Higgins Summer 2002
Daniel Allen, Summer 2002
David Shaye, AY 2001-02
Jessie McComb, Summer 2001
Rachael Anderman, AY 2000-01, Summer 1999
Bryan Smith, Summer 2000
David Shaye, Summer 2000
Lynwood Rumney, Summer 2000
Brian Lancor, AY 1999-00
Allen Otto, AY 1998-99
Jon Silber, AY 1997-98
Matt Hornbach, Summer 1997

Dan Boye, Physics Department, Davidson College

Abby McKenna, Summer 2007
Carlos Ortiz, Summer 2006, AY 2006-07, Summer 2007
A.J. Hergenroeder, Summer 2006
Jonathan Baker, AY 2006
Robert Correll, Summer 2005, AY 2006-07
Colleen Gillespie, Summer 2005, AY 2005-06
Anders Langworthy, Summer 2004
Kiril Simov, Summer 2004
Sharon Meidt, Summer 2001
Timothy Valdes, Summer 1999
James Nolen, Summer 1999, AY 1999-00

Karen Brewer, Chemistry Department, Hamilton College

Emin Hodzic, AY 2004
Jessica Callahan, AY 2004
Daniel Leonard, AY 2004
Alicia Fucile, AY 2003
Shammi Dowla, AY 2001
Alexis Gletow, AY 2000
Jeffrey Gart, AY 2000
Timothy Reid, AY 2000
Jannett Matthews, AY 1999

Outreach activity: Edible Optical Materials (in developing stages)

Rare earth spectroscopy

Electron Configuration (in development)
Dieke diagram
Extended Dieke diagram
Lanthology_A-L from Molycorp Corporation website
Lanthology_M-Z from Molycorp Corporation website

Sol-gel glasses

Optical Experimental techniques (in development)

Absorption
Fluorescence
Excitation
Fluorescence lifetime
Fluorescence line narrowing
Spectral hole burning
Upconversion

Publications

Ann J Silversmith, Nguyen T Nguyen, Daniel L Campbell, Daniel M Boye, Carlos P Ortiz, "Fluorescence Yield in Rare Earth Doped Sol-gel Silicate Glasses," J. Lumin, submitted July 2008.
D.M. Boye, C.P. Ortiz, A.J. Silversmith, N.T.T.Nguyen, K.R. Hoffman, "Rare-earth ion distribution in sol-gel silicate glasses," J. Lumin. 128, 888 (2008).
A.J. Silversmith, N.T.T.Nguyen, B.W. Sullivan, D.M. Boye, C. Ortiz, K.R. Hoffman, "Rare-earth ion distribution in sol-gel glasses co-doped with Al³⁺," J. Lumin.128, 931 (2008).
C.P. Ortiz, D.M. Boye, "Pulsed upconversion of Tm³⁺ doped sol-gel silicate glasses," J. Lumin.128, 894 (2008).
D.M. Boye, A.J. Silversmith, Thao Nguyen Nguyen, and K.R. Hoffman, "Effects of rehydration on Tb³⁺ spectroscopy in sol-gel glasses," J. Non-crystalline Solids, 353, 2350 (2007).
A.J. Silversmith, D.M. Boye, K.S. Brewer, C.E. Gillespie, Y. Lu and D.L. Campbell, ^"5D₃→⁷F_J emission in terbium-doped sol–gel glasses," J. Lumin 121, 14 (2006).
A.P. Magyar, A.J. Silversmith, K.S. Brewer, and D.M. Boye, "Fluorescence enhancement by Chelation of Eu³⁺ and Tb³⁺ ions in sol-gels", J. Lumin. 108, 43 (2004).
R.E. Anderman, A.J. Silversmith, K.S. Brewer, T.S. Valdes, J.H. Nolen and D.M. Boye, R.S. Meltzer, "Transient and Persistent Spectral Hole Burning in Eu³⁺-doped sol-gel produced SiO₂ glass", J. Lumin. 108, 49 (2004).
A.J. Silversmith, D.M. Boye, R.E. Anderman and K.S. Brewer. "Fluorescence line-narrowing and decay dynamics in sol-gel glasses containing Eu³⁺", J. Lumin 94-94 275-278 (2001).
D.M. Boye, A.J. Silversmith, J. Nolen, L. Rumney, D. Shaye, B.C. Smith, and K.S. Brewer, "Red-to-green upconversion in Er-doped SiO2 and SiO₂/TiO₂ sol-gel silicate glasses", J. Lumin 94-94 279 (2001).
Allen P. Otto, Karen S. Brewer and Ann J. Silversmith, "Red to Blue Upconversion in Tm-doped sol-gel silicate glasses", J. Noncryst. Solids 265, 176-180 (2000).

Recent oral presentations

"Effects of Aluminum and N,N-dimethylformamide additives on Tb³⁺ fluorescence in Sol-Gel glasses," Dwight Swift, Physics 496: Independent Research departmental presentation. Powerpoint presentation (23MB) link.
"Controlling rehydration in sol-gel glasses," C.P Ortiz and D.M. Boye, Southeastern Section of the American Physical Society Meeting, Nashville, November, 2007.
"Rare-earth ion distribution in sol-gel silicate glasses," D.M. Boye, C.P. Ortiz, A.J. Silversmith, N.T.T.Nguyen, K.R. Hoffman, DPC 2007, Segovia , Spain, June, 2007.
"Effective local concentration of terbium ions in sol-gel silicate glass," C.P Ortiz and D.M. Boye, Southeastern Section of the American Physical Society Meeting, Williamsburg, November, 2006.
"Upconversion Spectroscopy of Tm³⁺ Doped Sol-Gel Glasses," C.P. Ortiz & D.M. Boye, Optics in the Southeast, Charlotte, 2006.
"Enhanced fluorescence in rare earth doped sol-gel glasses containing Al^{3+ "} G.L. Armstrong*, A.J. Silversmith, D.M. Boye. American Physical Society Annual Meeting, Baltimore, March, 2006.
"Al³⁺ concentration dependence of Tb³⁺ fluorescence in sol gel glasses," Jonathan Baker, Davidson Physics Student Research Seminar, May, 2006.
"Sol-Gel Glasses, Rare Earths and Phonon Emission,” Rob Correll, Davidson Physics Student Research Seminar, September, 2005.
"Energy transfer from Gd³⁺ to Tb³⁺ in SiO₂ sol-gel glasses," Colleen Gillespie, Davidson Physics Student Research Seminar, September, 2005.

Poster presentations

Pulsed upconversion of Tm³⁺ doped sol-gel silicate glasses, C.P. Ortiz, D.M. Boye, DPC 2007, Segovia , Spain, June, 2007.
Rare-earth ion distribution in sol-gel glasses co-doped with Al³⁺, A.J. Silversmith, N.T.T.Nguyen, B.W. Sullivan, D.M. Boye, C. Ortiz, K.R. Hoffman, DPC 2007, Segovia , Spain, June, 2007.
Effects of Gadolinium co-doping on terbium emission in sol-gel glasses, K.R. Hoffman, J.P. Hutchinson, K.S. Young, A.J. Silversmith, D.M. Boye, C.P. Ortiz, DPC 2007, Segovia , Spain, June, 2007.
Upconversion Spectroscopy of Tm³⁺ Doped Sol-Gel Glasses, Ortiz, C.P. & Boye, D.M., Optics in the Southeast, Charlotte, 2006.
The Effects of Annealing Conditions and Concentration on ⁵D₃ →7F_J Emission in Terbium-Doped Sol-Gel Glasses, Gillespie, C.; Boye, D. M.; Silversmith, A. J. (Davidson College Science and Math Student Research Symposium, 2005).
Fluorescence of Rare Earth Ions in Binary Silica Sol-Gel Glasses, Callahan, J.R.; Brewer, K.S.; Silversmith, A.J. (227th National Meeting of the American Chemical Society, Anaheim, CA, 2004).
Energy Transfer from Chelated Ligands to Rare Earth Cations in a Sol-Gel Matrix, Brewer, K.S.; Magyar, A.P.; Silversmith, A.J.; Boye, D.M. (227th National Meeting of the American Chemical Society, Anaheim, CA, 2004).
Eu³⁺ Doped Y₂O₃ Nanocrystals, Armstrong, Greg; Burke, Peter; Silversmith, A. J.; Brewer, K. S. (Hamilton College Summer Student Research Symposium, 2004).
Spectroscopic Analysis of Tb³⁺ Doped Sol-Gels, Sullivan, B. W.; Silversmith, A. J.; Brewer, K. S. (Hamilton College Summer Student Research Symposium, 2004).
Fluorescence Enhancement by Chelation of Eu³⁺and Tb³⁺ Ions in Sol Gels, Silversmith, A. J.; Magyar, A. P.; Brewer, K. S.; Boye D. M. (Dynamic Processes in the Excited State Conference, Christchurch, NZ, 2003).
Transient and Persistent Spectral Hole Burning in Eu³⁺-Doped Sol-Gel Produced SiO₂ Glass, Boye, D. M.; Valdes, T. S.; Nolen, J. H.; Silversmith, A. J.; Brewer, K. S.; Anderman, R. E; Meltzer, R. S. (Dynamic Processes in the Excited State Conference, Christchurch, NZ, 2003).
Red-to-Green Upconversion in Er-Doped SiO₂ and SiO₂/TiO₂ Sol-Gel Silicate Glasses, Boye, D. M; Silversmith, A. J.; Nolen, J; Rumney, L.; Shaye, D.; Smith, B. C.; Brewer, K. S. (Dynamic Processes in the Excited State Conference, Lyons, France, 2001).
Fluorescence Line Narrowing and Decay Dynamics in Sol-Gel Glasses Containing Eu³⁺, Silversmith, A.J.; Anderman, R. E.; McComb, J.; Brewer, K. S.; Boye, D. M. (Dynamic Processes in the Excited State Conference, Lyons, France, 2001).

Student Theses

Nguyen T.T.Nguyen, Senior Thesis, Hamilton College, 2007 "The Role of Aluminum in Rare Earth-Doped Sol-Gel Silicate Glasses"
Dan Campbell, Senior Thesis, Hamilton College, 2007 "Synthesis and Characterization of Melt Density Sol-Gel Derived Glasses"
Carlos Ortiz, Honors Thesis, Davidson College, 2007. "Spectroscopy of Terbium-doped Sol-gel Glasses"
Brendan Sullivan, Senior Thesis, Hamilton College, 2007
Luxue Dang, Senior Thesis, Hamilton College, 2007
Greg Armstrong, Senior Thesis, Hamilton College, 2006
Andrew Magyar, Senior Thesis, Hamilton College, 2003

Applications

SPC freeware

Other links

Sol-Gel Gateway
International Sol Gel Society
Brinker Nanostructures Research Group

Acknowledgment

This website contains information based upon work supported by the National Science Foundation under Grant No. 0421023. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.

Pdfs

SH (.pdf) 1MB

Branson Thesis (.doc) 17MB

Branson Bricks (.avi) 39MB

Movie (.wmv) 92MB

Drops (.avi) 11MB