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Spectroscopy of Ruby Fluorescence

Physics 3600 - Advanced Physics Lab - Summer 2021
Don Heiman, Northeastern University, 6/8/2021

I. INTRODUCTION

The laser was invented in May 1960 by Theodor Maiman while working at the Hughes Research Lab in
Malibu, California. This first laser was constructed of a cylindrical ruby crystal surrounded by a
photographic flash lamp, all contained in a polished aluminum cylinder (shown on the left). The flash
lamp was used to excite the chromium ions in the sapphire host crystal. As the excited Cr(3+) ions
de-excite they emit light as individual photons. Then as these photons travel back and forth in the
optical cavity between the mirror-coated ends of the crystal, they induce other excited Cr ions to
de-excite causing "stimulated emission." Rapidly, all of the ions become de-excited and generate a
lasing light pulse. The light beam is coherent in the sense that the photons all travel in the same
direction and have the same electromagnetic phase. LASER is an acronym for Light Amplification by
Stimulated Emission of Radiation.

This type of laser requires three energy levels, as shown in the diagram on the right. Absorbed pump
light excites the Cr3+ ion into excited states. The lifetime of these levels is short (50 ns), so that the
excited ion quickly relaxes by making a transition to the long-lived metastable state. The energy which is
lost in this process is nonradiative and goes into heating the crystal by generating phonons that are
vibrational excitations of the crystal atoms. The metastable energy level must have a lifetime which is
long enough to enable the Cr ions to remain excited until a photon having the precise energy comes
along to de-excite it. The lasing line in ruby is the so-called "R-line" having a wavelength of ~0.7 μm. The
fluorescence lifetime of the R-line is several ms. Fluorescence of the R-line can be excited by light in any
of three absorption bands, at 250, 410, and 550 nm.

This lab experiment does not produce lasing in ruby, but it investigates the excited states via the
absorption spectrum and spontaneous fluorescence. A green laser is used here for exciting the R-line
fluorescence.
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– CAUTION –
Never look directly into any laser beam.
Also, make sure there are no reflections that exit the bench top.
Place unnecessary optical components to block stray beams from exiting the bench top.
This green laser has a power of approximately 5 mW. Compare this to the 1 mW of sunlight that
would enter your 1 mm diameter pupil if you looked directly at the sun.

This experiment also introduces the widely used tool – the spectrometer – for optical spectroscopy. A
spectrometer is an instrument used for measuring the intensity of light as a function of wavelength.
Spectrometers usually contain a diffraction grating (or prism) to disperse the light, thereby spreading
out the light of differing wavelengths into different positions. The spectrometer unit used here has an
internal CCD (charged coupled device) silicon detector, essentially a digital camera detector, to measure
the light intensity at various positions along its length. In the figure, light from an optical fiber enters at
position #1; reflects off the collimating mirror #4; is diffracted by the grating #5; reflects from focusing
mirror #6; then finally is read out by the CCD detector #9. For more information on Ocean Optics
spectrometers see their website, https://www.oceaninsight.com/.

II. APPARATUS

aluminum breadboard with 1/4-20 tapped holes

green laser diode, ~5 mW @ 532 nm
USB2000-FLG or USB4000FL Ocean Optics spectrometer, OceanView software, USB cable
lens, 25 mm focal length, 25 mm diameter, for collecting and focusing fluorescence
lens, 200 mm focal length, 12.5 mm diameter, for focusing the laser beam
mirror, in x-y adjustable mount
photodiode (PD) detector
neutral-density (ND) optical filter (black)
long-pass optical filter (red-orange)
optical fibers, 50 and 600 micron core
white light illuminator
ruby crystal, Al2O3:Cr, approximately 0.05% Cr, length L=2.00±0.05 mm
EasyPlot software
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III. PROCEDURE

A. Room Light Spectrum

1. Start the OceanView software. Note the following: adjust Integration Time to keep the peaks below
saturation; check the Electric Dark box to remove the background; if the data looks noise then increase
the Scans to Average; use Copy to Clipboard then save the clipboard.

2. Insert one end of the 50 μm core fiber optic (FO) into the spectrometer input. Adjust the collection
(integration) time so that the highest spectral peak is near but not above saturation. Store data in
tab-delimited format after you click on the storage disk icon.
a. Calibrate the spectrometer – use the green laser to determine the shift in the wavelength.
b. If the shift is >1 nm from the expected value, correct the wavelength of all subsequent spectra.

3. Now, point the open end of the FO at the wall or ceiling to collect stray room light. You should see
many spectral peaks from the fluorescent room lights.
a. Store the spectrum and include in report.
b. What is the characteristic linewidth (full-width at half-maximum) of the narrowest spectral line?
c. List in table form the wavelengths and intensities of the 5 or 6 strongest lines in counts/sec.
d. Why are there separate spectral peaks?
e. What are the colors of the strongest peaks.

B. Absorption Spectrum
The light intensity after passing through a material of length L is given by I = Io (1-R)2 exp(-αL), where Io is
the initial light intensity (see Appendix). The factor (1-R)2 corrects for reflection losses from the two
surfaces, where R = (n-1)2/(n+1)2 is the reflectivity.

Here, the absorption spectrum α(λ) of the ruby crystal will be measured. Make a new setup where a
white light illuminates one end of the 600 μm core optical fiber, but leave a space large enough (10-20
cm) to slide in the ruby crystal just in front of the FO. Cover apparatus with black cloth to shield the
room light. As before, adjust the collection time and the lamp/FO such that the spectrometer intensity is
just below saturation.

1. Collect and store spectra Io (λ) without the ruby crystal, then collect I (λ) with the ruby crystal
directly in front of the input end of the FO.

2. Roughly compute the transmission T=I / Io at a wavelength of λ~700 nm.

Retake the measurements until T is in the range 80 % to 90 %.
a. Assuming that α=0 at λ~700 nm and the accepted value for n, what is the expected T at λ~700
nm. Discuss.
b. Plot I(λ) and Io(λ) on the same graph (after you subtract a constant background from each).
c. Compute and plot the transmission spectrum, T(λ) = I(λ) / Io(λ).
d. Plot the spectrum of the absorption coefficient as a function of wavelength, α(λ).
e. For the absorption maxima, what is the “absorption length,” 1/α, and uncertainty.
f. Smooth out the noise and discuss the absorption peaks.
g. What is wavelength and width of the main absorption peak?

You must show the TA your plots at the end of each section before proceeding to the next
section.
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C. Optical Fluorescence Setup

Mount the optical components on the breadboard approximately as shown in the diagram and
photograph. Before aligning the beam, you must place the black neutral-density (ND) optical filter in
front of the laser to reduce the beam intensity.

D. Ruby Fluorescence Spectrum

Collect laser-excited fluorescence from the ruby crystal and plot its spectrum.

Optical Setup – Before beginning, slide the black neutral-density (ND) filter in front of the laser to
reduce the beam intensity. First, set all of the optical components to equal heights above the plate.
Now the collection optics must be finely aligned. Insert one end of the 600 μm FO into the mount that
points at the collection lens, and shine a white light source into the other end. Using the “thin lens
formula,” compute the image and object distances for the f=25 mm focal length collection lens. While
holding a white piece of paper at the front face of the ruby crystal, adjust the position of the lens and FO
so that the white spot image is focused at the front face of the ruby crystal. Now adjust the mirror to
overlap the green laser beam and the white spot image on the ruby crystal.

Measurement – Insert one end of the FO into the holder pointing at the collection lens and the other
end into the spectrometer. Look for the R-line fluorescence in the spectrum. Maximize the intensity of
the R-line emission by turning the adjusting screws on the mirror mount. Cover the breadboard with the
black cloth.

a. Store the spectrum and include in the report.

b. Record the wavelength of the R-line. Discuss.

E. Fluorescence Lifetime of Ruby R-line

This section describes measurement of the lifetime of the ruby R-line fluorescence.

1. Laser setup – Insert the 200 mm focusing lens in the laser beam, in order to produce a smaller laser
spot on the ruby crystal. Turn the diode laser power switch OFF (down). Connect a BNC cable from the
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TTL output of the function generator to the diode laser power supply. Connect another BNC cable from
the “Output” of the function generator to channel-1 of the oscilloscope. Adjust the function generator
to output a square wave having a period of 30 to 50 ms (select the 10 Hz pushbutton). Trigger the scope
on the edge of the square wave.

2. Collection setup – Use the FO to collect the fluorescence from the collection lens, and attach the
other end of the FO to the photodiode (PD). Connect the BNC output of the PD to channel-2 of the
scope. Turn the PD switch on (up). Next, remove the ND filter from the laser beam. Place the long-pass
(red-orange) filter between the collection lens and the FO. This blocks (absorbs) the green laser light,
while transmitting the red R-line. On the oscilloscope you should see a signal from the PD which is
synchronous with the function generator.

a. Capture one complete period of the PD output and the function generator for your report.
b. Curve fit the decay of the PD signal to an exponential function.
In the region of interest, plot the data as points and the curve fit as a solid line.
c. What is the exponential decay time of the fluorescence? What is the uncertainty?

IV. SUMMARY

a. Discuss how you used the “thin lens formula” to optimize the collection of the fluorescence.

b. Compute the photon energies (E) of the green laser line, the absorption peak, and the R-line.
[E(eV)=1239.513/λ(nm)].

c. Make a TABLE listing the important values (with uncertainties) and reference the expected
values. Always discuss the origin of the uncertainties.

V. OPTIONAL

Measure the index of refraction of the ruby crystal using a reflection from the surface.
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V. APPENDIX

A. Thin Lens Formula

The “thin lens formula” is used here to determine the parameters for focusing the image of the ruby
fluorescence into the optical fiber.

Convex focusing lens are useful for projecting an image of an object

from one side of a lens onto the other side. See the diagrams. The
distance of an image from the lens is related to the distance of the
object from the lens by the thin lens formula,
O i
1/i + 1/o = 1/f,
where i is the image distance, o the object distance, and f the focal
length of the lens. The magnification of the lens is M=i/o. A special case
of this formula is the focusing of a collimated laser beam. There the
object distance is infinite, so the laser beam is focused to a small f
diameter spot at a distance i=f from the lens, shown in the lower
diagram.

B. Light Absorption

Materials which absorb light, such as the ruby crystal used here, have an absorption coefficient α which
characterizes the depth to which light penetrates into the crystal. The light power P (or intensity I )
decreases as a function of increasing distance x into the material given by
P(x) = Po exp(-αx),
where Po is the initial power at x=0. The absorption length, 1/α, characterizes the penetration depth of
the light. Light energy absorbed in the ruby crystal is converted into energy stored in the excited Cr ions
(plus some energy lost which goes into heating the crystal). Note that light intensity is the light power
divided by the cross sectional area of the light beam, I = P / A.

C. Optical Excitation

Each photon of green light absorbed by the ruby crystal raises the energy of a Cr ion to an excited state.
This state rapidly relaxes to the long-lived metastable state having a lifetime t. Before the light is turned
on, all the Cr ions are in the ground state. After turning on an excitation source, the number of excited
ions increases. After time t of weak excitation, the number of excited ions is given by
N (t) = No [1- exp(- t / τ)],
where No is the number of ions which are excited after the crystal has been weakly illuminated for a long
time t >> τ. Neglecting stimulated emission, the excitation process comes to equilibrium when the rate
of excitation equals the rate of decay from the metastable state. The rate at which Cr ions are excited is
P / hν, where hν = hc/λ is the photon energy. The rate of decay is 1/τ. At equilibrium, the number of
excited Cr ions per unit volume is given by no = α I τ/hν. After the exciting light is removed, the number
of excited Cr ions decreases exponentially for increasing time as
N (t) = No exp (- t/τ).
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D. Chromaticity Diagram

All the possible colors of light which the human eye can distinguish can be made by adding relative
amounts of the three additive primary colors: red, green and blue. These are related to the three
wavelength-dependent photoreceptors in the human eye. The relative response of the three
photoreceptors is shown below. Note that the spectrum for each color is fairly broad, covering 100 to
200 nm, compared to the total 300 nm width of the visible spectrum 400-700 nm. These three colors are
also used in TV and computer color monitors.

Left: Spectra of the three colors.

Below: CIE 1931 Color

Matching Functions.

In the mid-19th century, J.C. Maxwell first described a

diagram, the Maxwell triangle, to quantitatively
represent all possible colors using the three primary
colors. The Maxwell triangle has been updated into the
universally accepted CIE chromaticity diagram, shown
on the right. In this diagram, the x- and y-axis are the
relative amounts of red and green light, respectively,
and the amount of blue is 1-x-y. The outer rim of the
“tongue” shape represents pure or saturated colors
(hues), and is light of a single wavelength. Going inward
from the edge towards the center is equivalent to
adding white light, referred to as changing the tint.
Pure white light is composed of an equal mixture of the
three primary colors, x=y=z=0.33. Note that the light
from the green laser used in the experiment (532 nm)
lies on the upper, outer edge at x=0.17 and y=0.79. It is
interesting that after dark you can see many variations
of “white” lights that are distinguishable.

https://en.wikipedia.org/wiki/CIE_1931_color_space