Joseph Weiner Physics 556 Fall 2013 Dr.

Gayen Measuring Electron Transport in the Bechgaard Salt (TMTSF)2PF6 A remarkable diversity of phenomena is observed in the quasi-two dimensional organic conductor (TMTSF)2PF6 known as a Bechgaard salt. An extensive phase diagram study shows that a single crystal of (TMTSF)2PF6 exhibits metallic, semi-conducting, semimetallic, antiferromagnetic, spin wave density (SDW), and super-conducting phases as pressure, temperature, and magnetic field are varied. Since the discovery of the Bechgaard salts over thirty years ago, there have not been any experimental results displaying the super-conducting nature of the salt on a nano-level. The Dean NanoElectronics Laboratory at City College of New York is attempting to experimentally test this salt for a particular super-conducting phenomenon known as the proximity effect by reducing the size of the crystals to the nano-scale. We are at a pinnacle point in our research with details results on the horizon. To understand super-conductivity, we must first understand conductivity. This starts by learning what a band gap is for an atom. What is a band gap? It is a system that consists of a “gap” and “bands”. The gap is considered a “forbidden zone” for electrons; this zone is better known as the “Band Gap”. It is the energy gap between the valence band (the band consisting of electrons) and conduction band (Consisting of possible energy states for the electrons to occupy), represented as Eg; Eg=Ev-Ec. In order for an electron in the valence band to be excited to the conduction band, the electron must be provided with and energy greater than or equal to that of the band gap energy.

we see an increase in energy states that the electron can occupy not only at the ground state but also we see multiple states that the electron can occupy in the excited state. We also see a larger gap has formed between the multiple states of the ground and excited states. we will need to take a closer look at what is happening. Eventually we will reach a point where the individual energy levels in the ground state and excited state will start to blend together. Let’s take the hydrogen atom which consists of one proton and one electron. it will fall back down to the ground state and the energy lost will be ejected as a photon. starting on the atomic scale. And this time we are not talking about Hydrogen atoms.In order to understand how this diagram is formed. it will do so by releasing its lost energy as a photon. And like the diagram for the atom. If an electron gains energy (say by absorption of a photon) it will become excited and “jump” energy states according to E= hf= hc/λ. There are potential energy states the electron can occupy. this blending produces two important parabolic shaped bands of interest: The Valence band and the Conduction band. it must be supplied with enough energy to overcome the gap. Now as we keep increasing the amount of atoms in this system we will approach Avogadro’s number and now we are embarking into solid state material. These parabolic curves . we will become more concerned with arbitrary atoms that will start to form solids as we add more atoms into our system. if an electron drops energy levels. Of course in order for the electron to leave the ground state and enter the excited state. As the number of electrons increase in the system. So what happens as we add more atoms to the system? We start to form molecules. Now if the electron loses energy equal to the energy gained from the photon.

0eV . is filled with electrons. let’s take a look at how they help us determine the makeup of materials.take their shape from the energy vs. Here are the 3 most common classifications of solids: 1 Conductor: 2 Semiconductors: 3 Insulator: Examples of each are: Conductor: Copper Semiconductor: Silicon Insulator: Sulfer And here are their band structures: A conductor has no band gap and its band gap energy is Eg= 0 A semiconductor has a very small band gap. The Conduction Band. named for the electrons in the outer most energy state or shell form the atoms core. This type of graph is also known as “Phase Diagram”. Once again in order for electrons to produce conductivity. The Valence Band. no electrons are in this band (so long as they are not excited). its Eg <= 3. Eg. Now that we have a little background on band gaps. named for (in the event electrons are excited into this band) conductivity. momentum diagram. they must be excited by photons and/or phonons with enough energy to overcome the band gap energy.

called superconductivity. This phenomenon. often a temperature in the liquid helium range. Bechgaard salts are any one of a number of organic charge-transfer complexes that exhibit superconductivity at low temperatures. 35-40 ml of the solvent 1. So what makes a conductor a superconductor? The electrical resistivity of many metals and alloys drops suddenly to zero when the specimen is cooled to a sufficiently low temperature. can give rise to superconductivity in organic conductors. 2 TMTSF donate one e. . 80-100 mg of the donor TMTSF is places in the anode compartment. This brings us to the Bechgaard salts. 200-300 mg of the tetrabutylammonium derivative of the desired anion (PF for us) is placed in the cathode compartments. Little proposed: exciton induced from highly polarizable medium instead of phonons.2-trichloroethane (TCE) is placed in both sides.0eV.1. The H-cells are fitted with frits in the middle to chemically isolate the two adjoining compartments. Before the electro-crystallization is initiated.And an insulator has a very large band gap. In addition. resulting in excess holes in TMTSF stacks. Paul Chaikin of New York University. was observed first by Kamerlingh Onnes in Leideli in 1911.9K. High quality single crystals of TMTSF can be produced using a simple electrochemical oxidation technique in an H-cell. its Eg is > 3. A. At a critical temperature Tc the specimen undergoes a phase transition from a state of normal electrical resistivity to a superconducting a monovalent anion. Our TMTSF samples were grown in the labs of Dr. 1979. W. Finally. which was found to superconduct under pressure at 0. Klaus Bechgaard of University of Copenhagen synthesized (TMTSF)2PF6 (TetraMethylTetraSelenaFulvalene). three years after he first liquefied helium. The conduction comes from overlap of -orbits of Se.

The cells are kept in the dark in a temperature controlled environment. we needed to find a way to deposit them onto a substrate of silicondioxide so that we may probe them.The H-cell is then sealed with glass stoppers containing platinum electrodes. needle-shaped crystals.6V. The group worked with several different solvents. The growth period lasts for a little more than a week. They worked with suspending BN. The solutions are allowed to come to equilibrium (for about 30 minutes) before being connected to a power supply. The solvents were chosen based on the strength of their surface tension. A large surface tension (and density) would be able to suspend the crystals. • • • • • Mix crystals into a 40 mL beaker with 20 mL of IPA Sonicate for 1 hour Let sit for about 24 hours Top ¾ of dispersion to be collected by pipette Centrifuge at 1500 rpm for 45 minutes . This is when we discovered a method called “liquid exfoliation” from the Dr. Higher voltage tends to give higher yield composed mainly of thinner samples. and WS2 among other materials.4V to 1. A constant voltage is used to obtain shiny. The Coleman group published a paper with Science Mag in 2011 pertaining to Liquid Exfoliation. The applied voltage ranges from 1. MoS2. This is the exact recipe that the Coleman group used to find monolayer samples of their materials. With these crystals. Coleman group of Trinity College in Dublin. Lower voltages tends to give lower yield but with bulkier samples. The growth period may last from two weeks to a month for the lower voltage growth.

• Decant the supernant and take spectroscopy This is my personal recipe for the first attempt. Right now we are still attempting to properly probe the crystals. References: . This has not been tested for organics yet. • • • • • • 15 crystals in 15 mL of IPA Sonicate for 1 hour Let sit for about 17 hours Pipette from dispersion closest to the bottom of the beaker Drop-cast and heat at 90° for 5 minutes Let cool 2 minutes Now our lab is attempting to probe these crystals for the proximity effect. The Proximity Effect is an interesting phenomenon in superconductors that are in a series with non-superconducting metals. There are many different tests to be done at this point. This method worked perfectly for Sample 14 but 16 came out quite differently. When a current passes through a series of non-superconductor – superconductor – non-superconductor (N-S-N) there will be superconducting through all of the metals. The metals used never exhibit superconductivity but they do act as conductors. This “quantum leakage” still requires further research.

• Introduction to Solid State 8th ed by C.CELEBONOVIC Institute of Physics. Kang. Woowon ProQuest Dissertations and Theses. Kittel 2005 Chapters 9 and 10 • Superconductivity.. Pregrevica . quantum Hall effect.. Foury-Leylekiana et al 2013 • The Properties of Five Highly Conducting Salts Derived From TeteraMethylTetraSelenaFulvalene K Bechgaard Solid State Communications 1979 • Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials Coleman Science 2011 • Some results and open problems in research on low dimensional organic conductors V. 1992 • Magnetic Field Induced Commensurability and Correlation Effects in Low Dimensional Organic Conductors by Weida Wu 2004 • Low temperature structural effects in the (TMTSF)2PF6 and AsF6 Bechgaard salts P. and magnetic field induced .