Mesoscopic study regarding density of states of

a MoS2 monolayer
Eric Helgemo
Niles North High School

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 Acknowledgement

Mr. Richard Theisen for his guidance and support throughout this entire project

Dr. Venkat Chandrasekhar for giving me the opportunity to join a team in his lab working
on this project.

Mr. Patrick Kratz for teaching me and for working with me to better my understanding of
the project.

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 Table of Contents
Title Page 1
Acknowledgements 2
Table of Contents 3
Purpose, Hypothesis, and Rational 4
Review of Literature 5-11
Materials 12
Procedure 13
Safety 14
Citations 15-17

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 Purpose
The purpose of this experiment is to determine the density of states of a MoS 2
monolayer at various different energy states. Determining this will lead to increased
knowledge of electrical properties of MoS2.

Hypothesis/Rational
If an Atomic Force Microscope modified to have electric potential at the tip, then it
will be possible to test the local densities of states of a MoS2 monolayer through
gate voltage. This is possible due to the presence of a potential on the tip of the
AFM’s cantilever, allowing for a voltage only locally. By scanning the surface with
the cantilever, it is then possible to get the data needed to determine the density of
states as a function of position and the gate voltage.

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 Review of Literature

In any experiment, invention or innovation, it is key to know all that is available

about as many different materials that can be used for the same application. This is

vital, because it allows for the desired tests to be done in the best way possible with

current technology. There is no need for some innovation to a system that could have

easily been done the first time. This is why it is important to build a large database of

properties for different materials, minerals, and compounds. For this project, the goal is

to probe local densities of states of a MoS2 monolayer using a modified atomic force

microscope at room temperature.

Electron Beam Lithography, also known as e-beam lithography, is a technique

used in nanofabrication to make 2D structures down to scales of 10’s of nanometers

and upwards to thousands of nanometers. This is achieved by using a beam of

electrons aimed at an electron-sensitive film, called a resist, to make a pattern on a

desired substrate. Resists can be positive or negative. A resist is considered negative

when the developer leaves the part of the resist exposed to the electron beam. The

resist is considered positive when the developer has not dissolved only the part of the

resist that was not exposed to the electron beam.(See image 1) (Physical principles of

electron beam lithography, 1986) The resists used in the project are Poly(methyl

methacrylate) (PMMA)((C5O2H8)n), and Methyl methacrylate

(MMA)(CH2=C(CH3)COOCH3).

Image 1 (LNF Wiki, 2012)

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The substrates that are usually used for e-beam lithography range from only a few

micrometers to a couple hundred micrometers in thickness, and can be made up of

many different materials. Silicon wafers are some of the cheapest examples of

substrates used for e-beam lithography, as materials like silicon dioxide wafers can be

made through processes involving melting sand. Therefore, by rapidly rotating a

substrate, usually around 1000 to 6000 rpm, and pouring resist on top of it, a thin, even

coat can be applied.(AZoNano, 2005) After being cleaned and properly coated, the

substrate is moved into a device for electron-beam lithography, where a line-by-line

preprogrammed path to engrave wanted pattern is taken by a high-energy beam of

electrons, which is usually between 3-50 kilovolts, exposing each area to a dosage of

between 3-30 microcoulombs/cm2, dependant on the sensitivity of the resist. (google

patents, James Robert Kitcher, 1978). When the electron beam is fired at the resist and

substrate, the parts of the resist hit by the electron beam become more soluble and a

developer, a chemical solution which remove the resist that was exposed to the electron

beam, is used, leaving a positive image of the desired design on the substrate. Some

developers are organic solvents and others require aqueous alkaline solutions. This

creates chips with nanostructures on the surface.(see Image 2)(google patents, James

Robert Kitcher, 1978) After this i finished, the substrate will have gaps in the layer of

resist that are desired for the experient. Now, a process called Electron Beam

Evaporation is used to coat the substrate with the material desired for the experiment. In

this experiment, titanium and gold will be coated to around 50 nm in thickness. Electron

Beam Evaporation is a form of Physical Vapor Deposition in which the target material to

be used as a coating is bombarded with an electron beam from a charged tungsten

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filament to evaporate and convert it to a gaseous state for deposition on the material to

be coated. Taking place in a high vacuum chamber, these atoms or molecules in a

vapor phase then precipitate and form a thin film coating on the substrate. (Semicore,

June 15, 2016) Once this process is finished, the substrate is placed in a solvent that

removes the rest of the resist, and the titanium and gold layer on top of it, leaving only

the precise nanostructure needed for the experiment.

Image 2 (sciencedirect, 2014)

After this, the next step is to apply a 1 layer thick sheet of Molybdenum Disulfide,

a mineral forms in layers of 3 atomic layers, over the lithographed nanostructure. This

changes electrical properties in the system, which will be explain further later in the

review of literature. Applying one layer can be done by using polydimethylsiloxane

(PDMS) stamp on a MoS2 seed crystal. (Image 3) Then using a microscope, single

layered stamps can be identified and baked off the PDMS stamp, and attached with

leeds through E-beam Lithography.

Image 3 (Two-dimensional Graphene, 2017)

In a second part of the experiment, all of this will be done

a second time, however the chip will be encapsulated in Boron

Nitride (BN). This has some interesting effects on the system,

which does many things. It helps protect the system from the atmosphere and improves

the stability of states between the MoS2 and BN, which will be discussed in detail later.

Another key piece of equipment is the Scanning Electron Microscope(SEM),

which is a system used to get high resolution images of surfaces at micro and

nanoscales. Optical microscopes have useful resolutions up to

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1,000-2,000x, but SEM have useful resolution up to 2,000,000x. Electron microscopes

are able to achieve this massive gap in the resolution because they have a much

smaller wavelength than photons used for optical microscopes. As shown in image 4,

because the 2 particles on the left are far enough away, we can see a gap in the center

which provides us with our ability to tell that the 2 particles are separate. However, on

the right, because the wavelength is too long, the Image 4

(Microbehunter, 2016) particles are seen to be connected. However,

supposing these 2 particles really are not connected, and it is just

that the photons used to detect it were of too high a wavelength, an

electron microscope would likely be able to see that gap, because

the waves would have interfered as we saw in the first set of particles. This change is

resolution has some stunning effects, as are shown in images 5 and 6. In images 5 and

6, the same nanofiber structure was photographed, however Image 4 was taken with a

strong optical microscope, and Image 5 was taken with a strong electron microscope.

<= Optical Microscope

Images 5 (Microbehunter, 2016)

Electron Microscope =>

Image 6 (Microbehunter, 2016)

The next important piece of

equipment to be used in the

project, is an Atomic Force

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Microscope(AFM). Atomic Force Microscopes are used to look at the topology of a

surface with resolutions down to fractions of a nanometer. This is achieved by using

measurable force interactions, such as, Temperature, magnetic, electrical, or Van der

Waal. Van der Waal forces are atomic forces, such as dipole-dipole interactions and

london dispersion forces. This is accomplished by reflecting a laser off of the back of a

cantilever, a probe that has an extremely sharp tip of only a few nanometers to around

10 nanometers in width that interacts with the surface, changing its height to experience

the same forces while moving over the surface, to hit a photodetector. By using this

data, the topology of the surface can be determined down to subnanometer scales.

(See image 7)

Image 7 (nanoscience.com, 2017)

This mechanism can be modified to perform

many different functions. In this experiment,

the AFM will be modified so that the tip of

the cantilever have a potential on it. This

makes the AFM effectively have a scanning

gate voltage. The gate voltage is the

minimum gate-to-source voltage differential that is needed to create a conducting path

between the source and drain terminals. (Gate Voltage, July 11, 2017) This is useful for

the subject of the study, which is to probe the local density of states of a molybdenum

disulphide(MoS2) monolayer as a function of gate voltage and position by use of the

aforementioned modified AFM. The density of states (DOS) is essentially the number of

different states at a particular energy level that electrons are allowed to occupy, i.e. the

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number of electron states per unit volume per unit energy. Bulk properties such as

specific heat, paramagnetic susceptibility, and other transport phenomena of conductive

solids depend on this function. (electrons.wikidots, 2017) Quantum wells are potential

energy wells with quantized values. One example of a potential energy well can be seen

by looking at the graph of the kinetic and potential energy in an oscillating spring

system. (See image 8)

Image 8 (schoolphysics, 2011) This system is an example of a potential well, because

as time goes on, the potential energy is converted to kinetic energy then back to

potential. This causes a ‘well’ that is the most simply visible in graphic form. A quantum

well does this, however it is in quantized amounts. This means that the potential well

has bandgaps- an energy range where no electrons can occupy. This is easiest to

understand in the context of electrons orbiting a nucleus. What is found when observing

these systems is that seem to stay it these electron orbitals, or areas where the electron

has any chance of being while in orbit of a nucleus. These orbitals are also quantized

and have bandgaps, which has some interesting implications for the particle's position.

Like how certain energies in the quantum well can not be occupied, parts of the area

surrounding the nucleus can not be occupied, forming the shape of this ‘probability

cloud’ around the nucleus. Interestingly enough,

there are even bandgaps in the position of the

orbitals. Famously, an example of the bandgap in a

semiconductor is between the valence and

conduction band, where no electrons will ever be

found orbiting there, in spite of the fact that this

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would completely separate the 2 bands, forcing electrons to ‘teleport’ in order to be in

either band. This seems to state that this probability cloud doesn’t need to be

continuous, and in fact has many possible separate sections. Electrons enter these

different orbitals by absorbing photons, particles of light that are discrete packets of

energy. This ‘excites’ the electrons, allowing them to jump between parts in the cloud if

they absorb certain frequencies of light. This is precisely how the electrons move in a

quantum well: they gain energy in the discrete need amounts to jump to the next energy

level. Quantum wells are achieved by confining a material between another material

with a wider bandgap. Quantum wells are 2D systems when viewed through DOS. This

allows for the determination of properties of the material in non-bulk systems.

Materials

● Electron microscope/Lithography mechanism

● Class 1,000 clean room
● Bright/Dark field microscope
● Electron-gun evaporator
● MoS2 see and PDMS stamps
● Acetone
● Isopropanol

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● MMA/PMMA
● Silicon-based waffers
● Oven
● Rotational Mechanism
● Pipet
● Atomic Force Microscope

Procedure

1. Take a 295 micrometer thick silicon wafer and break it into pieces 1cm by 1cm
2. Clean silicon substrate in this order(Steps 2 and 3 done in class 1000 clean room
to avoid particulates):
a. Submerge in Isopropanol and place in ultrasonicator for 5 minutes
b. Submerge in Acetone and place in ultrasonicator for 5 minutes
c. Submerge in Deionized Water and place in ultrasonicator for 5 minutes
d. Repeat part a

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 e. Dry by blowing with compressed nitrogen stream
3. Apply MMA/PMMA
a. Place the cleaned substrate on rotational mechanism with a vacuum seal
to hold while rotating
b. Using a pipet, play 2-3 drops of MMA on the surface of the substrate
c. Rotate substrate at 3000 rotations/minute for 1 minute.
d. Place substrate in oven set to 170 degrees celsius for 30 minutes
e. Repeat step 2
f. Repeat parts 3 a-c with PMMA instead of MMA
g. Place substrate in oven set to 140 degrees celsius for 30 minutes
4. Lithography
a. Use E-beam lithography to make a grid on surface of substrate
5. PDMS Stamping
a. Use PDMS stamp to get layers off the surface of a MoS2 seed crystal
b. Use microscope to determine if the stamped layer is a monolayer
c. Bake off the monolayer of MoS2
6. Lithograph MoS2 to substrate
a. Lithograph leads to attach MoS2 to the substrate
7. AFM
a. Use AFM with potential on the tip to change local gate voltage on the
surface to measure electrical properties as a function of gate voltage.

Safety
Hazards Procausion

High temperatures Avoid placing body in high temperature

areas

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Chemicals Do not drink chemicals in lab
Do not mix chemicals in lab that are not
known
Do not take deep breaths of the
chemicals
Thoroughly clean/sterilize equipment
before use to avoid mixing chemicals
accidently

Citations:

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Ahmed, H. (1986). Physical principles of electron beam lithography. Science Progress

(1933- ), 70(4 (280)), 473-487. Retrieved from http://www.jstor.org/stable/43420653

Density of states. (n.d.). Retrieved from Wikidot website:

http://electrons.wikidot.com/density-of-states

Electron beam heating evaporation [Fact sheet]. (n.d.). Retrieved from

http://www.icmm.csic.es/fis/english/evaporacion_electrones.html

Electron beam lithography [Fact sheet]. (2017, March 10). Retrieved from LNF Wiki

website: http://lnf-wiki.eecs.umich.edu/wiki/Electron_beam_lithography

Electron beam lithography (EBL) - overview of systems, processes and potential industry

applications. (2005, April 27). Retrieved from AZO nano website:

https://www.azonano.com/article.aspx?ArticleID=1208

Electron-beam lithography of gold nanostructures for surface-enhanced raman scattering.

(n.d.). Journal of Micromechanics and Microengineering. Retrieved from

http://iopscience.iop.org/article/10.1088/0960-1317/22/12/125007

Gibbs, K. (2011). Energy in simple harmonic motion. Retrieved from School physics

website: http://www.schoolphysics.org/age16-

19/Mechanics/Simple%20harmonic%20motion/text/Energy_in_shm/index.html

Gomez, A. C., Buscema, M., Molenaar, R., Singh, V., Janssen, L., Van-der-Zant, H. S. J.,

& Steele, G. A. (2017). Deterministic transfer of two-dimensional materials by all-dry

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viscoelastic stamping. Retrieved from Gelpak website: http://www.gelpak.com/--two-

dimensional-graphene

Hughes, M. (2016, June 15). What is e-beam evaporation? Retrieved from Semicore

website: http://www.semicore.com/news/89-what-is-e-beam-evaporation

Kalhor, N., Boden, S. A., & Mizutaab, H. (2013, September 18). Sub-10 nm patterning

by focused he-ion beam milling for fabrication of downscaled graphene nano devices.

Retrieved from Science Direct website:

http://www.sciencedirect.com/science/article/pii/S0167931713006229

King, C. R., Jr. (2005, December 17). Density of states: 2d, 1d, 0d [Lecture notes].

Retrieved from Georgia Institure of Technology website:

http://alan.ece.gatech.edu/ECE6451/Lectures/StudentLectures/King_Notes_Density_of_S

tates_2D1D0D.pdf

Kitcher, J. R. (1976). U.S. Patent No. US4099062 A. Washington, DC: U.S. Patent and

Trademark Office.

Nanoscience instruments. (2017). Retrieved from Nanoscience website:

http://www.nanoscience.com/technology/sem-technology/

Quantum well. (2017, September 13). Retrieved from Wikipedia website:

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

Threshold voltage. (2017, July 11). Retrieved from Wikipedia website:

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

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Yue, W., Wang, Z., Yang, Y., Chen, L., Syed, A., Wong, K., & Wang, X. (2012). Electron-beam

lithography of gold nanostructures for surface-enhanced raman scattering. Journal of

Micromechanics and Microengineering. Retrieved from IOPScience database.

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