SYNTHESIS AND CHARACTERIZATION OF RUBY (IEF T3)

Authors: (PL2 G4)

Denisa Lapuste NM:107820
Francisco Silva NM:114495
Oliwia Wdowiak NM:116652

Summary:
With this experiment, our goal was to produce rubies using a method similar to Verneuil method
but using a CO2 laser exposure and then characterize these resulting crystals. We started by
preparing a mixture of aluminum oxide and chromium oxide, then exposing it to the laser in order
to grow the rubies. Afterwards, proceeded to analyze its fluorescence using an UV flashlight and
performed spectral analysis of the rubies emission at 694nm under various excitation
wavelengths using a monochromator and spectrometer, and by this examine the wavelengths
that excite rubies the most. It resulted that the primary exciters for ruby were the wavelengths
around 400nm (UV) and around 560nm, violet and green. As the results obtained agree with the
expected, despite some errors, it is deemed that the experiment was a success.

Experimental procedure:
Materials:
- Aluminum oxide (Al2O3)
- Chromium oxide (Cr2O3)
- Digital scale (±0,01g)
- Lab tongs and spatula
- Molybdenum crucible
- Laser with CO2 beam (machine) Figure 1 – Used machine of laser with CO2 beam.

- UV flashlight
- Light source Sarspec A

- Monochromator Sarspec B
D

C
- Optic fiber
- Spectrometer Sarspec Flex RES+ UV/Vis/NIR-IS E

- Computer with software LightScan D

Figure 2 – Material and setup to study the ruby’s fluorescence.

(A)Light source; (B)Monochromator; (C)Spectrometer; (D)Optic
fiber; (E)Sample holder.
PART 1: SYNTHESIS OF RUBY
At the beginning of our experimental procedure, we had to create the proper mixture of
aluminum oxide (Al203) as well as chromium oxide (Cr2O3) in the proper ratio, that is 97% of the
first chemical compound and 3% of the other one. After this we put the mixture inside a
molybdenum crucible (Fig.3) and irradiated it with a laser CO2 beam of a laser machine (Fig.1). It
is crucial to mention that in order to obtain proper results we had to follow the rule that we start
with the power of laser of 7% first to check whether the mixture is well aligned with the laser
beam and then to melt a small surface layer of the mix to avoid dispersion of the chemical
compound outside the molybdenum crucible when increasing the percentage. After some time
in the 7%, form the formation of the mentioned layer, we were able to increase the power of the
laser from 7% to 80% consequently and hold it for 30 seconds. After this process, we obtained
beautiful small rubies (Fig.4), which we later used for the second part of the experiment.

Figure 4 – Synthetized rubies exposed to daylight.

Figure 3 – Mixture inside the molybdenum crucible.

PART 2: RUBY’S FLUORESCENCE ANALYSIS

In the second part of the experiment, we conducted the fluorescence analysis with the use of UV
flashlight from laboratory room to check whether they indeed emit the light as they are supposed
to. Fortunately, they did exhibit fluorescence when exposed to UV light (Fig.5). Afterwards, we
properly connected the source of light, monochromator and spectrometer (Fig.2), having the
rubies inside the sample holder, in a black background, in the position to reflect the light coming
from the monochromator to the spectrometer. With this setup, then, we started taking values
for the intensity of the 694 nm (wavelength characteristic from rubies fluorescence), detected
on the spectrometer, in function of different monochromatic beam. Additionally, we recorded
the intensity values of various wavelengths emitted by the monochromator, without the
presence of rubies but with a white material to reflect the light into the spectrometer, with the
purpose to make corrections to the previous data. Lastly, we observed the spectrum of the ruby
irradiated with the UV light.
Results and discussion:
It is known that ruby is mostly aluminum oxide (Al203), but some aluminum is replaced by Cr3+,
and we got it surrounded by 6 oxide ligands, leading to a resulting structure that may absorb
green and violet lights and emit red light. This emission, in simple terms, is due to the fact that
before the emission of light from the ruby, there is a non-radiative transition (thermal relaxation)
from the pumped levels to a metastable state (“particular excited state of an atom, nucleus, or
other system that has a longer lifetime than the ordinary excited states and that generally has a
shorter lifetime than the lowest, often stable, energy state, called the ground state.”) and just
then happens the emission of the red light we see, at 694nm. [1] [2]
So, in our experiment we synthesized rubies with a mixture of aluminum oxide (Al203) and
chromium oxide (Cr2O3), remembering that the chromium present is the element responsible for
the fluorescence of ruby, resulting on reddish rubies that exhibited a bright red fluorescent color
in the presence of UV light (Fig.5). As stated above, ruby absorbs violet and green light, which
makes ruby already red, because we know that the color we see on a material is the one it
reflects, and since ruby absorbs violet and green, we get that the red color is reflected, on top of
that, as ruby also emits red light, it makes ruby even more red and shiny. Seeing our resulting
rubies, we concluded then that we indeed created ruby, knowing that it typically emits a red
fluorescence under UV light [3].

Figure 5 – Rubies exposed to UV light.

Also, we observed a clear difference of the bright light emitted from the rubies when excited with
UV light and when only exposed to the daylight, noticing that our resulted rubies in the presence
of natural light didn’t exhibit a purely red color (Fig.4), but more like a reddish-purple color, this
is probably because part of the blue color is also reflected, which mixed up with the red results
on that color, and actually, this idea agrees with the results we will see on the study we did next,
where we proceeded to the characterization of the rubies, examining the emitted light and
studying its spectrum across various wavelengths.

First, with the rubies inside the sample holder, we got values for the intensity of emission at the
wavelength of 694nm in function of different wavelengths coming out of the monochromator
 into the rubies, exciting them. We did it at 694nm because it is the wavelength characteristic of
ruby, so to see if we successfully created good rubies, we could do the study mentioned above.

In Fig.6 we have the graph with the values we got in function of the excitation wavelengths,
where we see that the wavelengths around 560nm excite more the ruby, having two other local
maximums, one around 440nm and then a very small one around 670nm. Yet it’s very important
to mention that these results need some corrections, since the intensity of the monochromatic
light coming out of the monochromator may vary depending on the wavelength, then influencing
the intensity resulted from the data we got, for it is obvious that a wavelength that goes with a
higher intensity will excite more the ruby then if the intensity was lower.

Figure 6 – Graph of the intensity of emission at 694 nm as a function of Figure 7 – Graph with the relative intensity of emission at 694 nm as a
the excitation wavelength coming out if the monochromator. function of the excitation wavelength with the correction.

For the proper correction, we had to take the rubies out of the sample holder and only get the
intensity for every different wavelength from the monochromator, that was being reflected to
the spectrometer. By employing this approach, we divided the previously obtained values (used
in Fig. 6) by the values obtained through this method, and then we plotted the result on function
of the wavelengths. Fig. 7 shows the resulting graph with the necessary corrections. This graph
gives us a better and more accurate representation of how the different wavelengths/colors
excite the rubies.

Between the two figures, the main difference we see is that the peak around 400nm became
more prominent after the correction, showing how light around those wavelengths, violet color,
excite pretty much ruby.

Unfortunately, we don’t have a completely accurate correction, given that the values we
obtained for the intensity of each wavelength reflected on the empty sample holder, used for
the correction, are not accurate for values in between the 480nm and 620nm, for we can see in
Fig.8 that the graph is saturated on that interval of values.
 Figure 8 – Graph with the intensity of each wavelength reflected on the
white tape inside the sample holder.

Based on the graph in Fig.8, we can infer that most values on the saturated part correspond to
higher intensities and, if we got those proper values, it is very likely that this would result in a
visually noticeable reduction of the peak around the 560nm seen in Fig.7.

However, despite this issue, we still believe it is reasonable to compare the obtained results
(Fig.7) with the shape of the theoretical graph presented in Fig.9, since we anticipate that any
potential reduction mentioned should not be too significant, jeopardizing the results, or at least
it’s what we believe.

Figure 9 – Theoretical intensity of emission at 694 nm as a

function of the excitation wavelength. [4]

Comparing then the two graphs we can see how similar they look, both having three local
maximums and around the same wavelengths (400nm, 560nm and 670nm), being the most
noticeable one the one in the middle and then the one at 400nm, although the one in 560nm
would be smaller in Fig.7 with the proper correction than it currently is.

So, from the resulted graph we can see which are the wavelengths that excite the rubies the most
that is around 400nm, corresponding to the violet color, and around 560nm, green-yellow color,
as well as the ones that are not that good at exciting it, that is around 470nm (blue) and around
650nm (red). It makes sense that the red color hardly excites the rubies, as this wavelength is
mostly reflected by them, since it is the characteristic color of ruby. As for blue, although we
notice that both wavelengths are bad at exciting rubies, the blue color excites more than red,
which tells us that there must be some blue light being absorbed, from which we infer that it is
not reflected as much as the red color is. This relates to what was previously stated when
examining the possible reason why our rubies, when exposed to daylight, exhibited a reddish-
purple color.

At last, in Fig.10, we see the graph showing the spectrum from our rubies when exposed to UV
light, together with the UV wavelength peak (UV light centered on 400nm), and we see a
noticeable peak in the 694nm wavelength, which is within the range associated with the
characteristic color of a ruby. In addition, together with the obtained graph on Fig.7, we deduce
that the UV light, 400nm, is indeed good to excite ruby; reason why we could actually see the
fluorescent of the rubies when directing the UV flashlight at them (Fig.5), for the absorption of
these crystals at this wavelength is strong and so is the fluorescence.

Figure 10 – Spectrum from ruby when exposed to UV light.

Despite the problems, we can conclude that we got satisfying results in getting ruby synthesized
and got that the wavelengths that excite our rubies the most agree with the ones that were
supposed to (Fig.9).
Conclusion:
In this experiment, we synthesized some small rubies proceeding then to the study of their
fluorescence and emission spectrum. It was observed that the resulted rubies exhibit
fluorescence when exposed to UV light, and from our analysis, we were able to study and see
which wavelength excite the rubies the most and, by doing this, also correlate with the absorbed
and reflected wavelengths done by these crystals.
The primary exciters for ruby, according to our results, appear to be the wavelengths around
400nm (UV light) and 560nm, which correspond to the colors violet and green, respectively, and
so, it can be inferred that ruby absorbs these colors the most, followed by a deexcitation resulting
in the fluorescence emitted by this crystal. Also, we can mention the wavelengths that less
excited the rubies, being these mainly around 650nm (red color). Around 470nm we can also see
that the wavelengths excite less and, correlating it with the color we see on our rubies when
exposed to simple daylight, it makes sense that our rubies’ color appeared as a blend of red with
some blue.
After all the analysis, we see that our results agree with what was expected, but we believe that
there are some things that probably could be improved in the experiment. It was difficult to
create bigger rubies, so maybe a different amount (percentage of each) of the components of
ruby or a bigger crucible would possibly diminish this issue. Another thing we think we should
have done to improve the results was to use an integration time, in the software LightScan, a
little bit smaller than the used one, so that our graph for the correction (Fig.8) wouldn’t saturate
and that way get accurately all the actual values, for a better correction.
References:
[1] “20 7 Luminescence - Why Ruby Is Red”, YouTube, uploaded on November 2020, Available:
https://www.youtube.com/watch?v=9zpCLNrl2v0&ab_channel=PhysicalChemistryTutorial,
Accessed in May 2023.
[2] “Pumping Levels for Ruby Laser”, hyperphysics, published on unknown date, Available:
http://hyperphysics.phy-astr.gsu.edu/hbase/optmod/lassol.html#c3, Accessed in May 2023.
[3] “Ruby Description”, GIA, published on unknown date, Available: https://www.gia.edu/ruby-
description#:~:text=In%20addition%2C%20rubies%20found%20in,be%20found%20in%20basalt
%20rocks, Accessed in May 2023.
[4] “Introdução à Engenharia Física, Guião”, Universidade de Aveiro, 2023.