Characterization

techniques 1
of ZnON Charles Smith

Abstract.
This paper describes the methods used in characterization of Zinc
OxyNitride. We determined several properties such as band gap energy, surface
structure, and crystalline structure of our samples. This overview uses a
noncommercial ultra violet visible spectroscopy machine, a scanning electron
microscope, energy dispersive spectroscopy, and x-ray diffraction. I will give an
overview of how each technique works, and the results of our efforts will be given
by Meagan Parker in senior seminar of spring of 2017.

Introduction
The first part of my talk was about me. Meagan Parker and I received a grant
of $2,499 to do this project from the Office of Undergraduate Research at Weber
State University. The grant was nice to be able to purchase glass cutter, time at the
XRD and $1500 was a stipend for Charles to do the research. Our plan was to be
finished by late August and to most respects we were, but we are still doing research
and will be doing the second half of
our project during the spring semester
of 2017.

UV-VIS
An Ultraviolet-Visible
Spectroscope (UV-VIS) was the most
key part to our research. The series of
lens, chopper, and Si detector gave us
Figure 1a above. The band diagram of metals,
our results. It essentially takes light
semiconductor and insulator.
shines it through a sample and
Figure 1b below. The UV-VIS Machine.
measures the value of where the
electron goes from the valence
band to the conduction band; this
is known as the band gap. We
classify different types of band as
metals, 0 eV, Semiconductors, ~1
eV, and Insulators, ~10 eV
(Figure1a.) We can know where
the band gap is by measuring the
amount of light that gets
transmitted versus light that gets
absorbed. We did this with slides
that had varying amount of
nitrogen and oxygen in them.
Our machine is unique
Characterization techniques 2
of ZnON Charles Smith

(Figure 1b); we made it here at the Weber State Physics Department. It was also the
second that we had tried to use. The first was Ocean Optics Spectrometer. We did a
long series of experiments with a silicon sample. We were able to correctly measure
the band gap of a silicon sample. When we started the Zinc-Oxynitride (ZnON)
samples, something went wrong. We werent able to measure the band gap correctly
because of the noise in the CCD camera. With reluctance, we went with our second
option which turned out to be my favorite part of this whole research journey. Dr.
Rabosky introduced us to a new setup that we eventually were really excited to use.
It started with a monochrometer, a machine able to control what
wavelengths of light that you would want to measure. The wavelengths ranged
from 800-325 nanometers (nm). From there, the light would go through the
cylindrical lens and morph from a narrow slit to a square shape. The light would go
through a chopper. This cut up the light into pulses that the Si detector would be
able to pick out from the ambient light and be able to look only at that signal. It went
into a convex lens that focused the light onto the Si detector. After the convex lens, it
went through our sample. This could have been a blank slide or it could have been a
sample of material we wanted to look at. Finally, the light would be focused onto the
Si detector.
The Si detector had some
limitations that we soon found out.
It could only handle certain
wavelengths of light. If the
wavelengths were below a certain
point or above a different point the
noise of the detector would
overcome the sample signal light.
So we generally know, our
monochrometer and the Si
detector had an effective range of
1000-550 nm (1.24-2.25 eV)
(Figure 2.)
Our ZnON slides have Figure 2. General estimated range of
varying concentrations of nitrogen effective spectrum of light.
and oxygen on our samples. The
we were able to effectively measure the bang gap energy for the nitrogen rich slides
but we were not able to measure the band gap on the oxygen rich slides, because the
band gap fell out of our effective range, 1.24-2.25 eV. The band gap for oxygen is
lower, and the nitrogen band gap is higher. This was a problem and we wont have a
solution to this problem until our new machine is here. We still have more work to
do with our slides before we are done.
The Agilent Cary 60 UV-VIS machine is an all-in-one machine. A black box,
which you put a sample in and get a graph out. There are benefits and drawbacks to
this machine. One drawback is that it works, and we do not have to know a single
thing about it. Here at Weber State we are given a yardstick and told to go measure
the speed of light. This machine just works. The biggest benefit of this machine is
Characterization techniques 3
of ZnON Charles Smith

that it measures the band gap energy
from 6.5-1.2 eV. We can measure more
band gaps of more materials. This
machine has just arrived at WSU and will
be running shortly.
When a ray or light hits an
electron, it can either pass through or get
adsorbed (Figure 3.) If the photon energy
is low enough, the photon will not interact
with the electron or the sample, and it will
simply pass and not get adsorbed.
There is a point to which the photon Figure 3. What light can do when
energy is high enough that the electron interacting with a material.
will absorb the photon and go to a
higher energy state. The higher energy
state is not stable, so the electron
will want to go back down to the
lowest possible energy state. When
it goes back down to the lowest
possible energy state, it emits a
photon in a random direction, not
likely the direction of the Si detector.
The point where the photon has
enough energy is called the band
gap. If the energy of the photon is
above the band gap the extra energy
turns into heat. If there are enough
photons and they excite enough
electrons, there will be a bigger
electric field. The field will eventually Figure 4a (above). An example of raw
even out as electrons are going from a data collected from UV-VIS.
high to low and low to high-energy Figure 4b (below) Shows the band
state. What if you give those high- gap energy with the range of 1.9-2.1
energy state electrons a path to follow eV
while in the conduction band? The
answer is you will get a current out.
This is the fundamental process of all
solar cell operations.
The process to get the band gap
goes as follows: collection of data then
the analysis of data. We would start by
collecting data going through a glass
slide (T0). It calibrates our machine for
the sample slides. Then we went
through all the slides collecting the data
Characterization techniques 4
of ZnON Charles Smith

!
(T). From that raw data we get the transmittance of !!
(Figure 4a.) The only thing
we are missing now is the thickness of the sample. Thickness (Th) we got from Dr.
Rabosky. Then we plot the equation
! !
= !! ln ! (equation 1)
!
on the y axis and the x axis is the energy (eV) of the photon. To find the energy we
use,
!"#$ !" !(!")
= ! !"
, (equation 2)
!
where ! is the measured photon wavelength. When we plot these two axes, we get
a S shaped curve. We want to find where the downward slope interacts with the x-
axis. To do this we draw a hand drawn slope (Figure 4b.) We drew the steepest
slope and the shallowest slope. The range gives us the average band gap and the
uncertainty.

X-Ray Diffraction
When we put X-rays into a
crystal structure, we can prove two
things: that x-rays are waves, and
crystals have a pattern to them. X-rays
are electromagnetic waves with
tremendous energy(124000-124 eV.)
They have a wavelength of .01-10 nm.
The wavelengths are small enough that
they can easily fit in-between atoms.
But when they hit an atom, they can
bounce off and scatter. X-rays like most
light will bounce off with the law of Figure 5a above. XRD in rows of
reflection. When two waves, lets say atoms.
that are (d) apart, come back together in Figure 5b below. Shows the three
phase, the waves are added together different types of crystalline
and make constructive interference materials.
(figure5a.) When the waves do not
come back in phase, then they do not
produce constructive interference, and
you dont get a strong peak. We are
then able to take the peaks where the
constructive interference takes place
and starts to formulate how the
crystalline structure appears. This is
very easy for a row of atoms. But when we take into account that crystals are three-
dimensional objects, the d now becomes the distance between planes of atoms.
The XRD can show different types structures (Figure 5b). The first structure
is crystalline structure where everything is nice and orderly. There is a distinct
Characterization techniques 5
of ZnON Charles Smith

pattern. The second, a polycrystalline structure means you have a multiple of
crystals in your sample. The third type of structure is exactly the absence of
structure, amorphous. This is a type of structure that doesnt have a pattern; its just
in random order.
Knowing that the 3-D
structure is complicated, you can try
to look up your material in a index
rather than figuring out the
construction of the sample. Looking
at our results; however, we knew
what we had. We had amorphous
material, and we didnt go much
further than that (Figure 6.)

Figure 6. Example of XRD of the ZnON. The

Sample is exerting an amorphous behavior.

Scanning Electron
Microscope
We also took pictures of our
samples with the Scanning
Electron Microscope (SEM). The
SEM works by bouncing electrons
off of the surface and then getting
detected. This will give you an
image of your sample that is better
than any optical system by a
thousand times. Since most of our
samples were amorphous, they
didnt really have much pattern to
them. Most of our samples had a
smooth surface with not a lot of
abnormalities. This was good for
us. In solar cells the more Figure 7. An example of SEM picture of our
surface area that the sun can hit, samples. Most pictures looked like this.
the more energy the cell can Notice smooth flat surface.
produce. Our sample had mostly
smooth surfaces with some
acceptable abnormalities to them (Figure 7.)
Characterization techniques 6
of ZnON Charles Smith

EDAX
How can we tell what our samples consist of? Attached to our SEM, there is a
machine called EDAX. It is a technology that uses energy dispersive spectroscopy to
get a normal distribution of what is in your sample. It works by reading the x-rays
coming off of an atom. We consider the atom to have the nucleus, and two different
types of electrons: valence shell electrons and core electrons. The valence shell has
higher energy electrons, and they are also loosely bound to the nucleus. The core
electrons are tightly bound to the nucleus and are low energy. With EDAX we knock
core electrons out of the core shell. Electrons from the valence shell then want to fill
the core electron spot. When the electron goes from a valence to a core shell the
energy state is in also changes. When it changes its energy state, it gives off a
photon. The photons that come off of the change in energy state are x-rays that
range from .01-10 nm in length. These get collected and sorted. EDAX has its own
version of the periodic table. Each
element has its own value associated
with it. When we scanned over a
sample, we got several normal
distributions that are collected. We Figure 8a above. Shows the
determined which peaks are what type penetration depth of EDAX. The black
of element, and the computer did the layer is the sample, the gray layer is
rest. the glass.
When we did this all with our Figure 8b below. Standard calculation
samples, we had a problem. The first of EDAX sample.
problem we had was the oxygen content
was just too high, and there was
silicon in our ZnON samples. We were
able to correct this easily by realizing
the glass sample we had was SiO2
(Figure 8a.) We took the silicon,
doubled it and subtracted it from the
oxygen and took the silicon out. That
gave us the relative abundance of zinc,
oxygen, and nitrogen in our samples
(Figure 8b.)

Conclusion
My talk is a two part series of our characterization techniques. Next semester
Meagan Parker will go over our results. She will show the correlation between
nitrogen and the band gap energy. This project took Meagan to a conference in Las
Cruses, New Mexico. This project wouldnt have happened without the help from
Dr. Rabosky, Dr. Englefield, Nick Allen, Meagan Parker, or Charles Smith. We still
have a long ways to go with this ZnON project. We were only able to do the band gap
energy for half of the samples. We didnt have a detector that worked with the band
gap of the oxygen. When we get our new machine the Cary UV-VIS, we will then be
Characterization techniques 7
of ZnON Charles Smith

able to correlate the band gap to the percent oxygen. Our future goals will be to
correlate the band gap energy to the concentration of oxygen and nitrogen together.
The materials lab here at Weber State is young and is growing. They will be
starting a lot of new research. Getting students interested in this type of research is
key to this programs survival.
The start of this research project was a great learning experience. I was able
to learn the lesson of never give up with my grant. My grant helped me with my
research. I was able to determine the band gap of about half of the samples with the
UV-VIS that we made. We will take the other half of the measurements with the Cary
UV-VIS machine. The XRD and the SEM helped us to know that our samples were
exactly what we wanted: amorphous and relatively smooth. This research has taken
Meagan and I so far, and it will only take us further.

Work Cited
"P/N Junctions and Band Gaps." P/N Junctions and Band Gaps. N.p., n.d. Web. 08
Dec. 2016.
Thor labs inc. PO Box 366, 435 Route 206N, Newton, NJ 07860
Ph (973) 579-7227, Fax (973) 300-3600, http://www.thorlabs.com PDA55 Operating
Manual
http://www.differencebetween.com/difference-between-crystalline-and-vs-
noncrystalline-solids/
Young, Hugh D., Roger A. Freedman, and A. Lewis Ford. University Physics. Boston,
MA: Pearson, 2014. Print.