Florian THEUREAUX MAT5 option R&D Polytech Nantes

SOMMAIRE Presentation Introduction

University of Miami Internship

2 3
4 7

Theory
Surface Chemistry Quantum Dots

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9 13

Experiments
6-MPS synthesis Quantum dots capping Quantum dots network

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16 22 26

Conclusion Acknowledgements

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Florian THEUREAUX MAT5 option R&D Polytech Nantes

Presentation
My name is Theureaux Florian, Im an engineer student at Polytech Nantes, in 4th grade of material sciences. Each year, 4th grade students have to make an internship in a foreign country, during a period of 3 months. This internship can be in a university laboratory, in a company or whatever else, but the theme and the subject have to be linked with material sciences. The aim of this internship is to develop an open-minded view in front of a different culture, and way of working. Indeed, future engineers have to be ready to face the internationalization of their job, and thats how the internship is a kind of training for this type of situation. Linked to this need of internationalization, and because I got my TOEIC in English, Ive chosen to focus my research with a country where the main language is English. After two months spent emailing professors around the world, I finally found the internship I wanted in Miami, more precisely at the University of Miami, Chemistry Department. My main research criteria was to found a subject which I didnt study yet, because I wanted something new, something I could work from zero, to prove myself that I can work on any new project in the future, and also, the location was motivating, and thats why I accepted the internship at the University of Miami.

Florian THEUREAUX MAT5 option R&D Polytech Nantes

I. Introduction
My internship was about (CdSe)ZnS quantum dots and Langmuir films. Quantum dots are related with quantum physic, they are special molecules composed of a core and a shell around. In my case, it was quantum dots with a CdSe core, and a ZnS shell, which is a semiconductor whose excitons are confined in all three spatial dimensions. These semiconductors are on the nanometer scale, and they are obeying to quantum mechanical principle of quantum confinement. They are used in three main
Figure 1 LED

fields, such as medical imaging and disease detection, quantum dots LEDs and solar cells. There are other applications that are in development today, for example about counter-espionage and defense applications; we can integrate quantum dots into dust that tracks enemies so it will protect against friendly-fire events. Although, my internship is focused on Langmuir films. Maybe the link between both of them doesnt seem to be very clear, but, if we want to create applications such as LED screen or solar panels with quantum dots, we have to control there placement in 2D: we have to create a quantum dots network. We have to create a thin film of quantum dots in order to create a 2D network, and thats why we use Langmuir films technic. This technic is used to measure the physical and chemistry properties of a
Figure 2 Photovoltaic solar panel

one molecular thickness layer.

During my internship, I had to create a thin layer of quantum dots network using the sol/gel process with a mercapto-silane and it allowed me to create a link between the QDs by polymerization. Thats a brief and general introduction of what I have done during the three months at the University of Miami. Now, I will present with more details where I was working, and all the theory I needed to achieve my internship.

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A. University of Miami The University of Miami (UM) is an 85 years old university, which was founded in 1925 by William Jennings Bryan who first promoted the need and stimulated a community planning effort for a university to serve the growing Miami area. The beginning of UM history wasnt so lucky, the Merrick Building construction started in 1926, but was retarded, and the construction resumed 23 years after, in 1949. Also, in September 1926, just before classes were on the point to begin, the monster hurricane of 1926 caused many damages to the university, and UM managed to open their
Figure 3 UM logo

doors on October. During the next decade, the depression that started in

1929 added further financial problems that brought the survival of UM. Decided to keep UM going the president of the university, Bowman Foster Ashe, and others formed a new corporation, University of Miami, Inc., and the auction started to bring money to the university. The 1940s were a time of big changes the university. President Ashe arranged to have facilities available for U.S. Army training and British Royal Air Force personal. The war gave reasons to expand the university and its facilities. Thats how, in 1947, after the war end, the School of Engineering was founded, and also the beginning of the excavation of Lake Osceola, which is still here today, at Coral Gables campus. Growth of UM continued during 1950s, the School of Medicine was founded in 1952, and was the first in the State of Florida. President After Ashe, the Jay death F. of W.

Pearson was named the second president of UM, and during his tenure, until 1962, the first computer of UM was installed in the Engineering Building, and racial barriers was removed from
Figure 4 Lake Osceola

admission policies. Next, during the tenure of Henry King Stanford, until 1981, UM inaugurated the School of Nursing in 1968 and, also in 1968, with a gift of Rosenstiel Foundation , UM founded what we call now the Rosenstiel School of Marine and Atmospheric Science.

Florian THEUREAUX MAT5 option R&D Polytech Nantes

Edward T. Foote II was inaugurated UMs fourth president in 1981. During his leadership, three new schools were funded: Architecture, Graduate School of International Studies, and School of Communication. He also led a capital campaign that led over $500 million, at the time the third largest campaign in American higher education. Since 2001, Donna E. Shalala is the fifth UM president. She accelerated progress, empower learning, discovery, and UM impact on people in Miami, in the country and around the world by making a billion-dollar effort called Momentum, The Campaign for the University of Miami. In 2007 UM also purchased a 560 bed-facility now known as the University of Miami Hospital just across from the Miller School of Medicine, which is a UM school. Thats a little part of the UM history, just to show you the major events during the last 85 years. Now, its time to speak more about the specification of UM. UM is a private not-for-profit institution and had been classified by the Carnegie Commission as a Very High Research University. 11 colleges and school that offer the following areas of study compose the university: 113 undergraduates, 106 masters and 53 doctorates. Its divided between five UM campuses which incorporate 191 UM owned buildings totaling 10,6 million gross square feet on over 500 acres of land. The campus I was working is in the first and the main campus of UM: Coral Gables Campus.

Figure 5 Coral Gables campus map

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Here, an extract from University of Miami, Fall 2009 fact book that is a great description of the actual campus:
This campus, located on 230-acres in suburban Coral Gables, houses two colleges and seven schools with 134 buildings totaling 5.7 million gross square feet. Since 2005, approximately 560,000 square feet of new facilities have opened on the Coral Gables campus the Martha and Austin Weeks Music Library and Technology Center, the Communication International Building at the Francis L. Wolfson School of Communication, the Jorge M. Perez Architecture Center, the M. Christine Schwartz Center for Nursing and Health Studies, the Basketball Fieldhouse Practice Facility, expansion of the Alex Rodriguez Park at Mark Light Field, the Palley Pavilion at the Lowe Art Museum, the University Village (the first housing project in over 30 years which contains 800 student beds), and sixteen new townhomes for faculty and staff. Future projects include the Robert and Judi Prokop Newman Alumni Center, which is currently under construction, and the new Student Activity Center, the Miguel B. Fernandez Entrepreneurship Building, and the Wellness Center addition.

Coral Gables campus is also directly linked to the Metrorail transportation service, which is a kind of aerial metro, which deserves the main part of Miami Downtown and the beginning of South Miami. It was a big opportunity because Miami transportation system called Miami Dade is far away to be the best of the USA transportation system. Indeed, Miami is known to be a sprawling city and sometimes, it takes two or three buses to go somewhere. With the help of the Metrorail, it allows me to find a housing in a very large area, without any transportation problem.

Florian THEUREAUX MAT5 option R&D Polytech Nantes

B.Internship For the first day of my internship, I had to come first at the secretary of my department, which was in the Cox Science Buildings, in the west part of Coral Gables Campus to meet the secretary who was in charge of my coming at UM, the one who emailed me my visa papers. She introduce me to Dr. Roger M. Leblanc, my internship manager. Dr. Leblanc explained me what I had to do during my internship, and what he expected me to learn. Dr. Leblanc has worked on a process that allows him to create a 2D network of quantum dots, with a 3-carbon length molecule between every quantum dots. What he expected from me was to extend his theory on 6 and 9 carbons length molecule by the same process as 3 carbons length molecule before sending his publication. Also, he told me that if I succeed I would have been noticed in his publication, sure, it motivation. After this first step, I had to make my own University of Miami ID card, a card which
Figure 6 Cox building

and was

for a

proved that I was a UM student, and also, this card allowed me to enter in my laboratory with a swipe system. It was also useful to get this card because I every months, I got 50% off on my monthly transportation card which was $50 instead of $100. I also had to plan an appointment with the international relationship office, a step that every foreign student has to go through. The purpose of this appointment was to explain us all the administrative habits in Florida, such as social security, driving license and healthcare, and it was very useful. After all this administrative procedure, I really could start my internship 3 days later approximately, and as I said, I had to learn a lot of theory before really start my experiments. During all my internship, I had to use many new technics, and also, learn a lot about quantum dots and surface chemistry theory. Indeed, thats why Ive chosen my internship with Dr Leblancs group. Before I went to Miami, I didnt know anything about surface chemistry and quantum dots, and I wanted to test if I was able to adapt myself to a new context and a new subject to study.

Florian THEUREAUX MAT5 option R&D Polytech Nantes

The first weeks were almost only theory, I read many publications on the subject, and also a book about surface chemistry: The Physics and Chemistry Sol-Gel Processing by C.Jeffrey Brinker and George W. Scherer. There were three main fields I had to study: surface chemistry, quantum dots, and synthesis of MPS theory. After that, I had to work with PHD students in my laboratory to get started my own reactions, and experiments on the machinery. A student teached me how to use a Langmuir Films machine by making measurements of surface tension of a one molecule thick layer of stearic acid on water. I also had to learn how to get QDs capped with MPS, the chemical reaction that allowed me to create a QD network and how to synthesize 6 and 9 carbon length MPS. This was how and where my internship began, now lets talk more about what I did during my internship.

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III.Theory
A. Surface Chemistry Surface chemistry is a part of chemistry that dictates the chemical properties of a surface. During my internship, surface chemistry was one of the topics I was working on. Because my goal was to form 2D QDs network at air/water interface, I had to know what were the chemistry properties of that thin layer, and how it will react. To form my 2D network, I used a KSV mini-through (Helsinki, Finland) equipped with computercontrolled movable barriers and fitted with a quartz window suitable for transmission absorption at the air-water interface. This machine was used to measure the surface pressure of a monolayer film monitored by the surface pressure/area isotherm.

Figure 7 KSV mini-through (Langmuir film machine)

The machine was composed by a dipping trough, a dipper, two barriers, a barrier drive which could move from 0,1 to 200 mm/min and a film balance. The film balance was super sensitive, for example it wasnt advised to move close to the machine when we were taking measurement, because the simple air movement near the sensor lead to wrong data. All this device was fully controlled by computer with KSV WINLB software, all I had to do was to configure my experiments in the software such as : sub phase type, material concentration, spreading volume, etc. When I learned how to use it, they told me that it had to be very clean, because dust or other particles inside the measurement area are not advisable because of the surface tension perturbations they could introduce. Also, to control the amount of dust in the room, the machine was placed in a 9

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clean room, with controlled atmosphere. In fact, the major part off high precision measurement devices was installed in this clean room. Indeed, Miami has a tropical weather, very hot, and almost 98% of humidity, so its necessary to work in a clean room ; the one I used was clean room of class 1000 where temperature (20 1C) and humidity (50 1%) were controlled. It also prevent from having dust in the air because it was continuously filtered. The protocol was simple. I used clean water as the sub-phase (obtained with a Modulab 2200 water purification system (San Antonio, TX)) to fill the 225 cm2 area of the Langmuir film machine. The next step was to spray the sample on the water surface with a little syringe. The volume sprayed was about 75 L, and this volume had to be checked with accuracy because the surface tension is dependent from the quantity of material sprayed on the air-water interface. Between the end of this last step, and the moment I had to start the measurements, I had to wait 10 minutes. Indeed, throughout the literature on Langmuir monolayers at the air/water interface, there is a waiting time period to allow the spreading solvent to evaporate. During this waiting time period, the solvent used in the studied solution is supposed to evaporate, and our expectations are that it only remain the amphiphilic molecules under study at the interface. The waiting time period varies between all the research groups and the machines they use, but generally, its about 10-20 minutes. Its commonly accepted that after the waiting period, all the solvent used is evaporated at the air/water interface and therefore doesnt have any influence on interfacial properties. Moreover, it depends on the solvent we use. A recent publication, made by Jhony Orbulescu and Roger M. Leblanc (J. Phys. Chem. C 2009, 113, 5313-5315), both member of the research group I worked with, has shown that using aromatic solvents can interfere in the aggregate formation at the interface, and also can disturb the absorption spectrum of the molecule which is analyzed. The only way to avoid these two effects is to wait for a longer time period, allowing the solvent to evaporate correctly. So, after the 10 minutes waiting period, the software was launched, and the only thing to do was to wait, and check if everything was right during the experiment. All the measurements was performed by a thin plate called Wilhelmy plate. This plate was used to measure equilibrium surface or interfacial tension at the air-liquid interface. This plate was oriented perpendicular to the interface. In my case, the plate I used was a piece of paper attached to a balance via a thin metal wire. The surface of the plate was on the order of a few centimeters square. This system was able to measure the force on the plate via a microbalance, and calculate the surface tension via the Wilhelmy equation : represents the surface tension (mN/m), l is the wetted perimeter and is the contact angle between the liquid phase and the plate.

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Thats how I was measuring the surface tension.

Figure 8 Wilhelmy plate

For the first time I used this machine, I trained myself with a solution of stearic acid C18H36O2 (10-3 mol/L), in chloroform. The solution was prepared by adding 0,77 mg of stearic acid in 2,71 mL of chloroform, and after 5 minutes into the tabletop ultrasonic cleaner (Branson 1510, CT) the solution was ready to use. All I had to do was to follow the protocol, and after about 30 minutes of experiment I got my first graph :

Figure 9 Example of a surface pressure isotherm

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What is shown with this plot is the surface pressure (mN/m) depending from the occupied molecular area. The occupied molecular area is the area that the molecule is using on the interface. Indeed, the molecule have two different parts : hydrophobic and hydrophilic The hydrophilic part stays in the water, and the other one, generally the carbon chain, stays in the air. When the barriers are moving, they reduce the free area available for the molecule, their occupied area is reduced too.

Figure 10 Free area reduction

As you can see, when the barriers are moving to the center, the molecules are organizing themselves on the surface to take the less area possible. We can see on the graph that there is 3 different parts : from 55 to 22 A2, the barriers are moving to the center of the tank, so the free area available for the molecules is decreasing. from 22 to over 15 A2, surface pressure is increasing, because the free area begins to be reduced at its minimum and the molecules start to be well placed on the surface. at 15 A2, the surface pressure reaches its maximum, the carbon chains of all the molecules are oriented in the same way : the surface area occupied by one molecule is at its critical maximum. under 15 A2, the one molecule thick layer starts to break, and to entangled : at this point, we can stop the experiment. The red line on the graph is tangential to the linear part of the graph. The value on the intersection between this tangent and the X-axe is the normal occupied zone of the molecule on the interface. This area allows us to determine what kind of molecule there is on the interface ; thats why I will use this machine to see if the 2D network is working between MPS and QDs.

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B. Quantum Dots Quantum dots are small devices that contains a tiny droplet of free electrons. This devices are made in semiconductor materials, and they have a typical dimension ranged from nanometers to few microns. The shape and the size of these structures and therefore the number of electron they contains can be now precisely controlled, and a quantum dot can have from one electron to a collection of several thousands. Also, the physics of quantum dots shows many parallels between the behavior of naturally occurring quantum systems in atomic and nuclear physics. As in an atom, the energy levels in a quantum dot are quantized, due to the confinement of electrons, but unlike atoms, they can easily be connected to electrodes and are therefore excellent tools for studying atomic-like properties. Because of analogies to real atoms, semiconductor quantum dots are frequently referred as artificial atoms. Here is a schematic plot of a single particle energy band gap, the upper band is the conduction band and the lower one is the valence band. This energy band gap determines the required wavelength of radiation absorption and emission spectra, and requisite absorption and resultant emission wavelengths are depending from the dot size. The importance of semiconductor quantum dots lies primarily in their tunability and sensitivity to external parameters as electrons are confined in all the
Figure 11 Single particle energy band gap

directions. The quantum confinement profoundly affects the way electrons interact with each others and with external parameters, such as magnetic fields for example. Moreover, the effects of the size on the optical properties of the quantum dots is very striking. For example, the smallest CdSe quantum dots with a diameter of less than 2 nm show a blue fluorescence. Larger quantum dots of the same material, but with a diameter of 6 nm show a red fluorescence. In a simple model, this can be understood by the confinement of exciton, the light is generated because of the electronhole pair whose recombination is responsible for the fluorescence emission. Like the classical example of a particle in a box, a stronger confinement leads to a larger separation of energetic levels.
Figure 12 Particle in a box

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In a more detailed analysis, the quantum dots semiconductors can be considered as an intermediate between molecules, or atom on the one hand, and bulk material on the other hand. We can calculate by LCAO (linear combination of atomic orbitals) approach the energetic levels of a molecule. In this model, the orbitals are combined, the outers one from the participating atoms with the new molecular
Figure 13 - LCAO

orbitals. Generally we observe two types of orbitals : ones with lower energy that the atomic orbitals, called binding orbitals, and orbitals of higher energy, called anti-binding orbitals. This model can be extended to a larger number of atoms, that leads to the formation of bands : the binding orbitals form the valence band and the anti-binding orbitals form the conduction band. These bands are separated by a gap, called band gap, the more atoms are added to the molecule, the more the band gap decreases. This trend can be observed when comparing the quantum dots of the same materials, but of different sizes : the larger the quantum dots are, the more the fluorescence emission color is shifted towards the red, that
Figure 14 Bands theory

means lower energies.

Although, optical properties are also shape dependent. Indeed, spherical quantum dots can be considered as zero-dimensional objects due to the fact that confinement is exerted in all the three dimensions. It has been shown that rod-shaped quantum dots, which are called Nano rods emit polarized light. The degree of polarization scales with their aspect ratio. These Nano rods are appealing system for electronic devices because if one axis of the Nano crystal is extended, there is a slightly change in the density of charges as confinement is now exerted in two dimensions. Therefore, the quantized levels are broadened by the absence of confinement in the long axis of the structure, and the position of the electronic levels are still dominated by the size of the smallest axis. In electronic, the long axis facilitates to contact the structure while the short ones preserve the quantized nature of the electronic levels. For CdSe Nano rods, electroluminescence is observed. Their symmetry facilitates the alignment of the quantum dots, that can be very useful in case of 14

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designing a quantum dots network. Furthermore, and as I said before, Nano rods were proven to be an advantage in solar cells.

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Experiments
A. 6-MPS synthesis As I have explained, the aim of my internship was to study a two dimensional QD network made by the polymerization of silane capped quantum dots. The network matrix is composed by quantum dots linked each of them by a carbon chain, and this length characterizes the matrix. In Dr. Leblancs publication, the carbon chain length used was 3 atoms of carbon, so during my internship at UM, I had to create a two dimensional QD network with a matrix of 6 carbons and 9 carbons. Of course, It should have been too easy if these components had been available in store, so I had to synthesize them. The reaction used contained different steps. The first step was to synthesize a bromide component from an alcohol. I tried the 6-MPS synthesis first, thats why the alcohol I used was 5-hexen-1-ol. This alcohol contains a 6 carbons length chain, exactly the same size required for the quantum dots network : in fact, this carbon chain was the one used for the matrix in the quantum dots network. Next, here is a diagram of the first step mechanism :

Figure 15 First step MPS synthesis mecanism

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The components used in this first step are triphenylphosphine, carbon tetra bromide and the alcohol, the solvent used is chloroform. Carbon tetra bromide has to be dry for our reaction, and thats why I had to dry it, with a protocol a professor gave me : dissolve the CBr4 crystals in chloroform (about 1 mg of CBr4 crystals) put some salted water solution (NaCl) and the CBr4 in chloroform solution to settle remove the aqueous phase (bottom) and put the organic phase in an Erlenmeyer put sodium sulfate in the Erlenmeyer put a cap, and let the solution to rest during 24 hours after 24 hours, eliminate the solid parts of the solution with a simple filtration remove the solvent with an under-vacuum filtration After following this protocol, I got a white dry CBr4 powder.

Figure 16 CBr4 powder (Wet/Dry)

Generally, with 1,0 g of CBr4 as starting material, I got about 800 mg of dry CBr4. After this step passed, I was able to start the reaction which allows me to transform an alcohol component into a bromide component. The protocol was easy : I added all the compounds in a round flask with my solvent (chloroform), a magnet, and I let the solution steering during 5 hours. It was the starting protocol, and after many attempts, the reaction failed every time. In order to know how and why the reaction did not happen, I used TLC analysis to check and compare the compounds I had at the beginning and at the end of my reaction.

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With a TLC plate, the solvent is moving upward due to capillarity. When the solvent arrives on the top border of the plate, the plate is removed and putted at room temperature to dry. In fact, the compounds dropped on the bottom of the plate are moving to the top thanks to the moving solvent. Each compound is moving with different speed, and leave different spots on the plate. Knowing where and how are the spots could allow me to know what there was in my solution. I used two different technics to reveal spots: UV and iodine vapors. The last one was the most useful because it was the one able to reveal the bromide compounds, which allows me to know if my reaction failed or not. Next, a picture of a TLC plate after the iodine vapors bath: This is the first TLC analysis made. From the left to the right I had my solution, solution + starting material, starting material. The three big spots at the same level are due to the starting alcohol. The two at the bottom of the plate are due to the formation of a complex. If the bromide compound, the one I wanted to synthesize was in my solution, I should have a spot in the top left border of the plate, and, there is none. In this case, the alcohol, (starting material), was still in the solution, and that means the reaction was not complete, because if it does, the alcohol
Figure 17 TLC plate principle

should be entirely consumed by the bromide synthesis. Also, there is

formation of a complex which means that the reaction started, but stopped in one step of the mechanism. Due to these observations, I had to change the protocol, and find the correct one to synthesize my bromide compound. Ive tried many possible way, such as heating the solution a little bit less than 50C; I couldnt heat with a higher temperature because of the chloroform bolting point. I also tried a longer reaction time, with and without heating: after 4 days spent steering my solution, the results of the TLC analysis was always the same, starting material, complex, but not bromide compound. Thats why I understood that reaction time and heating was not the parameters I had to change.

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The next parameter I changed in the protocol was the solvent. Instead of using chloroform solvent, I used acetonitrile (CH3CN), which is better because its a polar solvent and its liquid domain is very extended.

I first used the normal protocol, and I got a little change after the TLC analysis: the starting material disappeared from my solution. It means the reaction consumed all the starting alcohol. The reaction has three main steps, and the alcohol is used in the second one, it means that the problem came from the last step, bromide ions cannot be capped by our complex to form our last compound, and the one I was looking for. Because the regular protocol did not work, I tried again to change 2 parameters like reaction time and heat, and I changed them in the same proportions as when I was using chloroform as a solvent. I still got only the complex and no starting material in my solution, but not bromide compound. Increasing of the reaction time, and heating had no effects on the reaction, I had to find another parameter to change. Because the bromide ions didnt seem to be capped by the complex, I decided to add more of bromide ions, and thats why I added a few of lithium bromide. Again the reaction did not work. During the entire period of my internship, I was blocked on this step. Ive never obtained what I should obtain due to the fact that the bromide component wasnt synthesized by the intermediate components. Furthermore, the person who was in charge to teach me this reaction was a searcher/teacher extern from UM. He used to teach at Nova university, at the north of Miami, and he was coming to the UM campus only a few times in a week, that mean I only had few moments with him during the week to talk about the reaction. I couldnt go further than this first step, which means that I didnt get the compounds to realize the capping of the CdSe/ZnS quantum dots with 6-MPS or 9-MPS. Ive also searched on the Internet and books of chemistry companies to know if these compounds (6-MPS and 9-MPS) were commercially available but they were not, the only way to get them was to synthesize them. On the next page, there is a little summary of the experiments I made in order to synthesize the compounds I need. It shows the main steps of my experiments. Of course I made more that 10 experiments, but these represent the main ones :

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I tested many experiments possible, and more than there is in this table, but none of them was working. Eduardo told me he knew other solutions to make this reaction possible, but they were more difficult to use, and it was the end of my internship. I didnt find the solution during my internship, but thats research: I had to search in order to get my solution, even if the solution seems to take time to come, I had to keep searching, and thats what I did during my internship.

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B. Quantum dots capping

The second goal of my internship was to make the quantum dots capped by the silane compound. The quantum dots used in this step was ones form the laboratory I worked. A PHD student named Sheba who also works in Dr. Leblancs group made them. She began her PHD 2 months before I came in Miami, she decided to work on quantum dots synthesis and analysis. She showed me how to synthesize quantum dots, and which parameters have to be modified to modify the optical properties of the quantum dots. The ones I used for my studies were quantum dots made with cadmium selenium for the core and zinc sulfide for the shell, or by abbreviation: CdSe(ZnS) quantum dots. The size of the quantum dots I used was approximately about 4 nanometers and due to this typical size, the quantum dots got an orange color.

Figure 18 TLC plate

As Ive explained before, the quantum dots network is created by polymerization between the Nano particles. The polymerization is made by hydrolyze and condensation with mercapto compounds, and these compounds need to be fixed to the quantum dots to map the network. This fixation to the quantum dots will be made thanks to a silane. For this reaction, I followed the protocol that Dr. Leblanc was using in his publication.

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The protocol was the following:

Figure 19 Different sizes of quantum dots under UV light

The quantum dots used were diluted in hexane, and they were capped by TOPO. The TOPO capping is made to protect the quantum dots from aggregation, and because quantum dots are capped with TOPO, I need to first uncap them ; if I dont, it wont be possible to do the MPS capping. Thats why, in the first step of the reaction, quantum dots have to be washed three times with anhydrous methanol. Anhydrous methanol and hexane are miscible together, and TOPO has more affinities with hexane than methanol, so the only thing I got to do was to put anhydrous methanol in my quantum dots solution, and to centrifuge. After doing this step three times, TOPO was in hexane, and the quantum dots were in methanol. This step was very crucial, because if the quantum dots were not correctly uncapped, the MPS capping was not possible due to the fact that the quantum dots surface was not free. Also, if TOPO was not correctly removed from the surface of the quantum dots, it could disrupt the network created by the MPS. After this first crucial step, I had to add the MPS. I used first a 3-MPS compound because I had to be familiar with the method, and 3-MPS is a commercial compound which was in stock in the lab, and it was not the case for 6-MPS and 9-MPS which have to be prepared. 50L of MPS was added 23

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to the solution, and stirred. After stirring, a solution of TMAOH (tetramethylammonium hydroxide) was added, approximately 500L, with also a solution of 10mL of basified methanol (pH10, with TMAOH) to dissolve the QD/MPS solution. The next step was about stirring the solution under argon (Ar) protection during one hour. No heat was needed. At the end of this stirring, the solution was centrifuged in 50K Amicon filter, in order to separate our capped quantum dots from the solution, and eliminate the TOPO left in the solution. Here is a basic schema of an Amicon filter :

Figure 20 MPS capping protocol

I used the Amicon 50K filter because it was the one that was the faster to filtrate the volume of QD/MPS solution I needed, and also because I was the one indicated on the notes.

Figure 21 Amicon filter schema

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After the filtration, I added a little bit of anhydrous methanol to dissolve my capped quantum dots. At this moment, the solution obtained should have been colorless, but each time I realized the capping, I obtained a colored solution, which means that my capping was not fully realized. Maybe some of TOPO capped quantum dots was left in the final solution, or the amount of MPS was not enough to make the capping of all the quantum dots. What Ive tried during my internship was to change the initial protocol, in order to get the colorless solution needed at the end. I tried to increase the amount of TOPO, but each time the result was the same. I also tried to lower the concentration of quantum dots, but again the result was the same. I tried to centrifuge with a 100K Amicon filter and again no positive results. I also changed the filtering time, I made it longer, and no positive results were observed. At the end of my internship, I received quantum dots from a company based in the U.S. and specialized in quantum dots synthesis. I tried the initial protocol with them, and again no positive results. Because it was the end of my internship, I did not go further in my researches on these quantum dots. With all these experiments, I can say now what it is to do research on a subject. Even if I didnt find the solution about this quantum dots capping, its very instructive to discover the method on how to make researches, and how to go further on our researches.

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C. Quantum dots network As I told you before, the purpose of my internship was to create a quantum dots network. Quantum dots can be very useful Nano particles, and the amount of studies on these particles is increasing each years. In fact, in the last few years the development of colloidal Nano crystals has been extended from the pure adjustment of the size of the particles to the control of more sophisticated properties as their shape and composition. The hope is that through these features different fields of applications might be opened for the use of Nano crystals. Once prepared, however, quantum dots in general have a strong tendency to agglomerate owing to the presence of a great deal of highly active surface atoms, which dramatically deteriorates their physicochemical properties. Stabilization of quantum dots is necessitated for both exploring their intrinsic size-related properties and exploiting their technical applicability. Up to now numerous approaches have been developed to stabilize semiconductor NCs by surface charges, functionalized alkanes, silica, and polymers. The stability of a quantum dot is determined by the thermodynamic balance between repulsive interactions (mainly electrostatic repulsion and steric repulsion) and attractive interactions (mainly van der Waals and hydrophobic interaction) the quantum dot is stable when the repulsive interactions are dominant Because the electrostatic repulsion is rather sensitive to the size of quantum dots and the variation of the surrounding media, steric repulsion is envisioned ideal for stabilization of quantum dots. Among all materials used to stabilize quantum dots, polymers, by far, usually provide an excellent steric hindrance effect on the quantum dots, and this give to quantum dots a robust stability against the environmental variation. In addition of stabilization, hybridizing quantum dots with polymers can also bring out a number of merits. First of all, quantum dots are envisaged to inherit the good compatibility, the excellent processing capability, and the high-engineering performance from the polymer stabilizers, which are sought in most technical applications of quantum dot. In case of biomedical applications, the proper choice of hydrophilic polymer stabilizers such as polyethylene glycol (PEG) based (co-)polymers also render semiconductor quantum dots biocompatibility and reduce the cytotoxicity of the quantum dots. The merits of using polymers to stabilize quantum dots can be also foreseen from the intelligent response of polymers to a vast variety of external stimuli and their rich phase separation properties. Using polymers for directing the self-assembly of semiconductor quantum dots allows for the construction of tailor-made sophisticated arrays of the quantum dots with the desired properties. The stimuli-response of polymer stabilization matrices allows a fine control of

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the interaction of neighboring semiconductor quantum dots and thus the collective properties of quantum dots. As a result, enormous effort has been devoted to the development of different methods to stabilize semiconductor quantum dots with polymers, including synthesis of quantum dots within polymer stabilizers, polymerization of monomers in the presence of quantum dots, (co-)polymerization of quantum dots capped with monomers, coating quantum dots with polymers, exchange of the original ligands on quantum dots with polymers, growth of polymer brushes from quantum dots, layer-by-layer (LbL) consecutive deposition of quantum dots and polymers via non-covalent bonding, and blending of quantum dots with polymers. All these methods can be classified into two categories: chemical synthesis and physical blending. Ones of the main possible use of quantum dots in the future will be solar panels and LED screens, but these two kind of electronic devices need quantum dots which are not aggregated, but which are clearly positioned in space : thats why creating quantum dots network is important. For example, here is a possible use of a quantum dots conjugated polymer network : solar panel.

Figure 22 Filtrate volume vs. spin time for Amicon filter

The quantum dots network is encapsulated in a polymer, in order to create the network. Quantum dots have to be fixed in order to stop their aggregation so the solution is to catch them in a polymer. Indeed, if the quantum dots are not able to move, it wont be possible for them to aggregate, and quantum dots will be fixed in 3D space. This solution is an outline of the real solution, because if quantum dots are fixed, and they cannot aggregate, their position is not clearly determined in space: in fact, they have a random position in all the 3 dimensions. The random position isnt helpful if industrials have to create solar panels for example, because quantum dots have to be placed with a lot of precision if they want to guarantee the productivity of their solar panel.

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An example of an undefined quantum dots network in a solar panel:

Figure 23 Example of quantum dots solar panel

The amount of light have to be maximal for each quantum dots because it will guarantee the maximal output for electricity production, that means each quantum dots have to received the more photons possible, in order to convert them into electrons to product electricity. To do that, we have to place the quantum dots into a network that will maximize their disposition and by the way the output of our solar panel. To create the network, the process I had to use was to synthesize polymer links between all the quantum dots. In order to, it was the 3-MPS (or 6-MPS/9-MPS) used to create these polymer links. Here is a presentation of the reaction happening between the polymer molecules :

Figure 24 Undefined quantum dots network in a solar panel

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As you can see, the OCH3 group is reacting with water by hydrolyze/condensation in order to create links between polymer molecules with oxygen bridges. These bridges will manage the quantum dots network, because each molecules of polymer are linked to a quantum dots, due to the silane group (-SH). It will characterize the exact space it has to be between all of the quantum dots, and it will remove the possibility for quantum dots to aggregate. During my internship, I should do this reaction, but the previous reaction needed (MPS/QD capping) did not work, thats why I was not able to experiment on this. The protocol I should use was the same I used for studying stearic acid with the Langmuir film machine.

As you can observe, the capped quantum dots is dropped at the Air/Water interface. Like I explained before, due to evaporation/condensation, there is a polymerization happening between all the quantum dots : that will create a thin film of quantum dots at the interface. After the creation of the thin film, the barrier of the KSV mini-through were moving, in order to lower the free area and get our surface pressure-area isotherms graph of the MPS-QDs Langmuir monolayer. The graph gave the surface pressure related to the free area for a nanoparticle, and its linked to the sub phase pH and the time after spreading the MPS-QDs on the sub phase. This graph can give us information about the network we synthesized, and I should use it to compare the graph between a 3-MPS network and a 6-MPS (and 9-MPS) network to see if they were working.

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All this part is only theory because the previous ones did not work, that mean I did not try to create and analyze a thin film of polymerized quantum dots.

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Conclusion
To conclude, this internship has been very helpful for me. First, because as I was waiting for, it really improve to increase my English level. Even if Dr. Roger Leblanc comes from Quebec, and he can speak French, I asked him to speak English with. All the other peoples I worked with during my internship were speaking English, so I had to speak English too. The most difficult part was when I had to speak with a very technic vocabulary, and especially the chemistry vocabulary. Its very different from the French one, and sometimes it can lead to misunderstanding, thats why I was very careful about the professors, and the PHD students were telling me. Although, according Dr. Roger Leblanc, my English has increased during the three months I spent in Miami, so the first objective was completed. Next, the fact I worked on a laboratory was also very helpful. I always asked me if I was interested in research. Now I have the answer at this question: I really dont think that I will be a searcher one day. In fact, I realized all the good things research can bring to us: never give up, always try to find a solution, and be very strict on what you are doing everyday. Even if I wont be a searcher, I think I will always be able to re-use these three things in all the jobs I will have. I also realized that even if I like science, Im more attracted by design and business jobs. Maybe I will be able to work on both of them, but design and business was more attractive for me, and thanks to this internship, I am now sure about it This internship was very instructive, and I dont regret the choice I made. I dont have any proposition to make this 4th year internship better, except maybe having more help from the school about all the visa things, and all the administrative part. Except that, its perfect, and I think the next one will be perfect again.

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Acknowledgements
I would thank first Polytech Nantes, to allow us travelling around the world and discovering new cultures and new way of work, and the Envoleo service for the work they did on my visa. I would also thank Dr. Roger Leblanc, for allowing me in his laboratory and giving me his trust. Thanks to him, I spent 3 great months studying and working in Miami. I would thank all the lab staff that helped me, especially the PHD students Sheba Johnson and Garima Thakur. Also Eduardo Veliz, for helping me a lot when I tried to synthesize my MPS compound, and Lydia Maria Gonzalez for helping me in all the administrative parts of my stay in Miami. Thanks a lot!

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Bibliography
Quantum Dots: Research, Technology and Applications, Randolf W. Knoss, New York, Nova Science Publishers, 2009. Semiconductor Nanocrystal Quantum Dots: Synthesis, Assembly, Spectroscopy and Applications, Andrey L Rojach, Wien, SpringerWienNewYork, 2008. Importance of the Spreading Solvent Evaporation Time in Langmuir Monolayers, Jhony Orbulescu, Roger M. Leblanc, J. Phys. Chem. C 2009, 113, 53135315. Self-Assembly of Liquid Crystal Semiconductor Molecules at the Air/Water Interface, Guodong Sui, Jhony Orbulescu, Mustapha Mabrouki, Miodrag Micic, Roger M. Leblanc, Shenggao Liu, Russell A. Cormier, and Brian A. Gregg, J. Phys. Chem. B 2002, 106, 93359340 Quantum Dots: Science and Applications, James McDaniel, Physics 3500 Nanochemistry

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