Basic Overview Kinetically Controlled Vapor Diffusion Synthesis Of Chromium Doped Indium Hydroxide Thin Films Faculty Advisor:Dr. Dan Morse Faculty Advisor:Dr. Dan Morse Research Mentors: Dr. Birgit Schwenzer, James Neilson Research Mentors: Dr. Birgit Schwenzer, James Neilson RET Advisor: Dr. Martina Michenfelder RET Advisor: Dr. Martina Michenfelder RET Participant: Jason Smith RET Participant: Jason Smith RET research funding made possible by the National Science Foundation (NSF) RET research funding made possible by the National Science Foundation (NSF) Morse Group Funding: The Defense Advanced Research Projects Morse Group Funding: The Defense Advanced Research Projects Agency (DARPA) and The Department of Energy (DOE) Agency (DARPA) and The Department of Energy (DOE)

Purpose To create stable, crystalline films of indium oxide To create stable, crystalline films of indium oxide To attain “tunable levels ” of chromium doping To attain “tunable levels ” of chromium doping Basic research Basic research T.Tomita, K.Yamashita and J.Yasui and Y.Hayafuji, “Electronic Structures of Indium Oxide with Point Defects” and Bull.Soc.Discrete Variational Xα, 16, O-2p09 (2003) (in press).

Potential Applications beyond basic research Memory devices and spin valves in the new frontier of “spintronics” Memory devices and spin valves in the new frontier of “spintronics” Semiconductors Semiconductors Multiferroics Multiferroics The unknown.. The unknown..

What is a chromium doped indium hydroxide thin film? It is just that. A thin film (thickness not yet determined ) It is just that. A thin film (thickness not yet determined ) Forms on surface of aqueous solution given proper precursors and catalysts. Forms on surface of aqueous solution given proper precursors and catalysts. Somewhat resembles a lily leaf (no scientific relevance) in shape, color and location* Somewhat resembles a lily leaf (no scientific relevance) in shape, color and location* ( *floating on aqueous solution). ( *floating on aqueous solution).

Doping Film framework (base material) is indium hydroxide Film framework (base material) is indium hydroxide Doping = substitution Doping = substitution chromium is substituted for indium (see schematic) May result in unique electrical and magnetic properties May result in unique electrical and magnetic properties Annealing (heating) film may result in crystalline structure of indium oxide doped with chromium, the desired result Annealing (heating) film may result in crystalline structure of indium oxide doped with chromium, the desired result Un-doped indium hydroxide Doped

Doping A brief animation A brief animation A brief animation A brief animation

Lingo X-ray diffractionXRD X-ray diffractionXRD Scanning electron microscopySEM Scanning electron microscopySEM Energy dispersive spectroscopy EDS Energy dispersive spectroscopy EDS Inductively coupled plasma spectroscopyICP Inductively coupled plasma spectroscopyICP Carbon, hydrogen, nitrogen, analysis CHN Carbon, hydrogen, nitrogen, analysis CHN Indium nitrate hydrate In(NO 3 ) 3 ·XH 2 O Indium nitrate hydrate In(NO 3 ) 3 ·XH 2 O Chromium III nitrate Cr(NO 3 ) 3 Chromium III nitrate Cr(NO 3 ) 3 Ammonium hydroxide NH 4 OH Ammonium hydroxide NH 4 OH

Materials and Methods General Overview indium nitrate hydrate, and the dopant chromium III nitrate, are added to top and bottom rows of wells of 12 well reaction plate (noted IC) Well plate placed in covered reaction box, over several hours thin films form Remove films from wells, whole films are “washed”, “powders” are filtered Whole films analyzed by SEM/EDS for structure, elemental composition and % chromium incorporation Powders/ film fragments analyzed by XRD for crystallinity CHN analysisICP analysis solution of ammonium hydroxide (noted N), is added to middle wells

Materials and Methods A 2 nd brief animation A 2 nd brief animation A 2 nd brief animation A 2 nd brief animation

X-ray diffraction of thin film nanoparticles with varying Cr doping levels XRD: Utilized as a method for determining crystallinity Peak at (22°[2Ө]) corresponding to d spacing of 4.04 Å, indium hydroxide’s most intensely scattering lattice plane sharp peak indicates crystallinity, higher doping (10%) results in amorphous background signal no sharp crystalline peak 10% 8% 6% 4% 2% 0%

EDS Data Overview In Conjunction With Qualitative Data Low doping ( 2-4%) : macroscopically thin, brittle, films, predictable doping High doping ( 10%) : macroscopically thick, stable films, unpredictable doping 6% Cr doping: consistent film stability and dopant incorporation, averaged 5.17 at% (twelve experiments, forty-four data sets), candidate for further analysis

Lessons Learned I learned that a thorough understanding only comes with thorough and complete analysis I learned that a thorough understanding only comes with thorough and complete analysis I learned the importance of accuracy and attention to detail I learned the importance of accuracy and attention to detail I learned that patience is a virtue necessary for basic research I learned that patience is a virtue necessary for basic research Peer reviews can be painful but enlightening Peer reviews can be painful but enlightening

Special Thank You To Dr. Martina Michenfelder for her endless patience and wisdom To Dr. Martina Michenfelder for her endless patience and wisdom To the staff of the MRL for making and creating such an outstanding opportunity for teachers To the staff of the MRL for making and creating such an outstanding opportunity for teachers To the NSF for continuing its dedication to support science and exploration To the NSF for continuing its dedication to support science and exploration To the Morse Group for a glimpse into biomimetic chemistry To the Morse Group for a glimpse into biomimetic chemistry

Preliminary Conclusion Indium hydroxide thin film chromium doping/ Indium hydroxide thin film chromium doping/ incorporation can be influenced by adjusting chromium levels of starting solution incorporation can be influenced by adjusting chromium levels of starting solution

Resources Indium oxide structure Indium oxide structure (image 1) T.Tomita, K.Yamashita and J.Yasui and Y.Hayafuji, “Electronic Structures of Indium Oxide with Point Defects” and Bull.Soc.Discrete Variational Xα, 16, O-2p09 (2003) (in press). Lily image courtesy of Lily image courtesy of