The Spectroscopic Study of Cr4+ Doped CaOGeO2-Li2O-B2O3(Al2O3) transparent glassceramics

Presentation by: Victor Ortiz

School: M.S./H.S. 141 David A. Stein Riverdale/Kingsbridge Academy
Mentor: Dr. Alexei Bykov, Prof. V. Petricevic
IUSL-Physics Department

Introduction
Study the behavior of Cr-doped Calcium Germanium glass
media during synthesis and devitrification (i.e., heat
treatment)
A number of glass compositions yield transparent glassceramics after heat treatment
Crystallites 1m
Cr doped glass ceramics exhibit a broad band of
fluorescence (1000-1600nm wavelength; peaking at
1280nm).
Optical properties similar to CUNYITE crystals (i.e.,Cr4+:
Ca2GeO4 )
Absorption and Fluorescence Spectra of the samples help
better understand the optical properties of glass-ceramics

Long Term Goal

To create new materials for optical amplifiers and
fiber-lasers to enhance telecommunication systems
and remote LIDAR applications

New Methods
For Analyzing
Summer
Research
Objective
Crystallites

To find
temperature
timeapproach
required
Thethe
use optimal
of the Confocal
Microscopeand
is a new
to afor
better view
and understanding
of the nanoscale
crystallites
mass
crystallization
of nanoscale
crystallites
Cr-doped glass ceramic emits fluorescence in NIR spectrum
Manganese (II) Carbonate emits fluorescence in visible
spectrum

Recipe for Manganese-Doped Calcium Germanium

Glass
[2.0 CaO 1.0 GeO2 1.0 Li2O 0.5 B2O3 0.2 (Al2O3) 0.04
(P2O5)]

Mn-doped Glass Media

Weigh the chemicals

and mix into a Mortar

Powders

CaCO3 Calcium Carbonate

Li2CO3 Lithium Carbonate
GeO2 Germanium Oxide
B2O3 Boron Oxide
Al2O3 Aluminum Oxide
NH4H2PO4 Ammonium Dihydrogen Phosphate
MnCO3 Manganese (II) Carbonate

Place mixture on
crucible and heat at
800C in order to
release carbon gas

Re-heat at 400C in order to

release thermal stress

Checkpoint

Solid
Measure crucible to
see if carbon was
release from the
substance

Heat at 1400C in
order for substance
to become a liquid

Liquid

Remove liquid from furnace

and set into a container to
become a solid

Experimental Protocol
Cut and Polish glass media
into 1-mm thick plates

Measure Absorption
and Fluorescence

Re-measure Absorption
and Fluorescence

Heat at low temperature

for nucleation

Heat at high temperature

for growth of crystallizes

Cr-doped Glass Media

No heat treatment

Few crystallites formed

8 hour in 501C

A large number of nanoscale

crystallites were formed or a
few numbers of large size
crystallites

1 hour in 520C

 All Materials absorb radiation in some

ranges
of
the
electromagnetic
spectrum
The term is used to describe the entire
range of light radiation (gamma rays to
radio waves)
The amount of absorption depends of
the wavelength, the amount of
absorbing material in the radiation
path, and absorption of that material at
that wavelength

Absorption of Cr-Doped Glass Media

1 hour in 520C
The higher the absorption,
the more light will scatter
on crystallites in glass
ceramics. Larger size of
crystallites.

The lower the absorption, the

less light will scatter on
crystallites in glass ceramics.
Smaller size of crystallites.
8 hour in 501C

Measuring Fluorescence Spectrum

Fluorescence spectrum is the amount of electromagnetic radiation the atom
emits when it is excited.
When electrons in the element are excited, they jump to a higher energy level.
Solid mediums tend to absorb light and store it as heat. As the electron falls back
down and leave the excited state, light is re-emitted at longer wavelengths with
less intensity.
680-nm laser

Excited State
Fluorescence

Ground State

Electron

Fluorescence of Cr-Doped Glass Media

Maximum of broad band emission

Mn-doped Glass Media

No heat treatment

Crystallites were formed

within the glass ceramic,
reasons for color changed are
still unknown

45 minutes in 560C

A small number of crystallites

have formed, glass ceramic
still transparent

20 hours in 495C

Absorption of Mn-Doped Glass Media

45 Minutes in 560C

10 Hours in 495C

Fluorescence of Mn-Doped Glass Media

Conclusion
Crystallization in glass media varies according to temperature
and heat treatment time.
Chromium-doped glass ceramics emit fluorescence around
wavelengths of 1200-1300nm, similar to CUNYITE crystals.
Manganese-doped glass ceramics is expected to have a broad
band fluorescence between 550~700nm when excited at
488nm.
The change in color is believed to have to occur due to
crystallization all inside of the Mn-doped Glass Media.
The behavior of this substance is still unsure

Future Plan

Study optical properties of crystallites with

Mn-doped glass media with confocal
microscope
Compare the crystallites within the Mn-doped
media with that of Cr-doped media
Decide another metal to doped depending of
results
Continue running experiments with Cr-doped
glass media and any other metal-doped glass
material
Long term goal is to create a new material for
optical amplifiers and fiber-lasers to enhance
telecommunication systems

Reference
Confocal microscopy of colloids V Prasad, D Semwogerere,
ER Weeks, J. Phys.: Cond. Mat. 19, 113102 (2007)
Synthesis and characterization of Cr4+ -doped CaO-GeO2-LiOB2O3(Al2O3) transparent glass-ceramics by A.B. Bykov, M. Yu
Sharonov, V. Petricevic, I. Popov, L.L. Isaacs, J. Steiner, and
R.R. Alfano
Optical Properties Measurements of Laser Crystals by Dr. A.
Bykov
Guide for Absorption and Fluorescence Spectroscopy by Mr. G.
C. Tang and Prof. R. R. Alfano
Spectroscopic study of chromium-doped transparent calcium
germanate glass-ceramics by M. Yu. Sharonov, A.B. Bykov, T.
Myint, V.Petricevic, R.R Alfano

Acknowledgements
National Aeronautics and Space Administration (NASA)
NASA Goddard Space Flight Center (GSFC)
NASA Goddard Institute for Space Studies (GISS)
NASA New York City Research Initiative (NYCRI)
The City College of New York (CCNY)
Dr. Alexei Bykov, Prof. V. Petricevic
Dr. Frank Scalzo, Dr. Manuel Zevallos, Mr. Daniel Moy
Mr. Jose Lai, Mr. Jorge Franco
Mr. David Deutsch, Ms. Charlene Chan-Lee