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KELVIN PROBE EXAMINATION OF ORGANIC/METALLIC SEMICONDUCTORS ______________________________________ A Thesis Presented to The Honors Tutorial College Ohio University ______________________________________ In Partial Fulfillment of the Requirements for Graduation from the Honors Tutorial College with the degree of Bachelor of Science in Physics ______________________________________ By Vincent Roberts June 2012 Table of Contents I. Introduction 4 A. An Energy Crisis 4 B. The Advent of the Solar Cell 6 II. Background and Theory 8 A. Solar Cell Technology: The Photoelectric . 8 B. Work Function and Charge Transfer . 11 C. Background on Kelvin Probe 15 D. “Seeing” at the Quantum Level 18 E. Principles of the Kelvin Method 19 III. Molecules and Preparation 25 A. Organic Molecule F4-TCNQ 25 B. Zinc Oxide 29 C. Sample Substrate Preparation 32 D. F4-TCNQ Preparation 34 IV. Data Collection 35 A. Kelvin Probe Preparation 35 B. Sample Probing 37 --2-- C. Data Collection Parameters 41 D. Discerning Between Good and Bad Data 42 V. Results and Conclusions 45 A. Discussion 45 B. Conclusions 50 C. Suggestion for Further Experimentation 54 Acknowledgements 56 References 57 --3-- I. Introduction An Energy Crisis Nano- and quantum technology are terms often used in science- fiction during the past several decades. They have become very much akin to “buzz” words of modern-day companies and technologies. The world is in the midst of a technological boom, yet it is also in a severe energy crisis. It’s no exaggeration to say that fossil fuels will be running short in the foreseeable future, and the call by environmentalists to save the planet have only added flames to the proverbial fire regarding the question of humanity’s sustainable energy dilemma. Green technology is now the hot field in the energy market, and solar power seems to be the next logical step in the crisis, but current solar panels operate at only less than 30% efficiency [1]. Traditionally, silicon has been the main source of solar cells. However, silicon semiconductors seem to have reached their limit in the field, and now there is a push to examine new unique materials, utilizing the contemporary concept of charge transfer between organic and metallic semiconductor materials to perhaps find a more efficient solar cell candidate. A prominent semiconducting-like organic material has come to the forefront: 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane, or, --4-- simply, F4-TNCQ. Since it is a novel organic molecule, not much research has been conducted on it in combination with metallic semiconductors. There have been a few instances of work function being [2] increased on ITO samples, increases of at least 0.6 eV . Since F4-TCNQ can cause an increase in work function in semiconductors, a preferable condition in solar cells, it is being tested on many other materials. The focus of this paper is on the new organic material F4-TNCQ and its bonding properties to metallic semiconducting substrate, Zinc Oxide (ZnO). F4-TNCQ has had interesting reactions with ITO in previous studies, successfully bonding and altering the work function of the materials; therefore, it can be postulated that it will have a similar effect with another metallic oxide such as ZnO. In order to make accurate measurements of the material work functions in an applicable setting, the sample was measured inside of a Kelvin Probe, which is able to make work function measurements at room temperature and at atmospheric pressure. Real solar cells must function in such conditions, so all data taken is done at a directly applicable level. --5-- The Advent of the Solar Cell While solar cells may seem like a relatively new innovation, specific to the green technology era, the photovoltaic effect (the working principle of the solar cell) was first discovered nearly 200 years ago by physicist Edmond Becquerel [1]. Extensive work on the photovoltaic effect was later done at the turn of the 20th Century by Albert Einstein, whose connection of quantum mechanics to work function of the photoelectric effect won him his only Nobel Prize. Much later, in the 1950’s, silicon became the most popular semiconducting material. Silicon became the main source of diodes in electronics, most specifically in the form of photovoltaic (PV) diodes [1]. Ecological crisis of the 1990’ss and 2000’s, especially CO2-based global warming, have pushed sustainable energy science back towards solar power. Since the 1990’s, there has been continuing progress in the field of solar energy. Commercial prices in solar modules have shown a sustained average reduction of 7.5% per year, while global production of modules has increased on average 18% per year, with both expected to rise in the future [1]. However, despite trends of increases in production and lowering of manufacturing prices, the cost of installation of solar generating modules has remained high, approximately an order of magnitude higher than current prices of non-solar energies, e.g. hydro, nuclear, and fossil fuels [1]. --6-- Importantly, current solar cell technology is not a sufficient producer of energy. Lower-end solar modules used today are only efficient in energy conversion at about 15% [1]. As a result, more area, wiring, supports, and substrates are needed to provide enough energy for the modern energy driven way of life. Beyond the issue of low energy efficiency, there is a problematic artifact of production. While the use of solar cells does not produce CO2 or other pollutants, their production generates pollutants and requires large amounts of energy during their manufacture [1]. This begs the question of how well the benefits of solar technology balance with their manufacturing on an ecological basis. --7-- II. Background and Theory Solar Cell Technology: The Photoelectric Effect The foundation of solar cell technology began at the turn of the 20th century with physicist Albert Einstein. In his Nobel Prize winning research, he revealed the basis of the photoelectric effect using newly founded principles of quantum physics developed by Planck [3]. The photoelectric effect is the observation that when a metal surface is bombarded with incident light, electrons from the metal may be ejected [3]. In order to explain this effect, Einstein focused on the localized packets of light energy, called photons, and their interactions with the metal. In this case, the photon packets were directly interacting with the electrons in the metal, giving them energy and causing them to be ejected from the metal surface [3]. In such a metal, electrons with energy to escape this well can be disassociated from the parent atom. This “escape energy” is known as the work function ϕ [3]. Energy must be conserved in this process, therefore the energy of an ejected electron by a photon must be: E = hν – ϕ [3]. Whenever an electron is ejected by a photon, a positively charged “hole” is left where the electron formerly was [3]. In a solar cell, the free electrons are captured via a voltage source, and the positive holes are --8-- moved to the other side of the cell. This separation of charge creates a capacitor type structure in the solar material, with positive holes opposing the negatively charged electrons [1][4]. Such a capacitor builds up charge continuously as photons strike the surface, and thus energy is stored. Once the separation of holes and electrons is removed, there is a flow of charge, i.e. current, creating the wanted electricity [1][4]. Therefore, the basic solar cell is simply a semiconducting diode, a photovoltaic silicon diode being a common example [1]. A semiconducting material absorbs incident photons from a light source and then converts it to an electron-hole pair [1]. The main energy parameter comes from the work function of the solar material, specifically in the energy between band gaps, i.e. the valence and conduction bands [1][2]. Due to quantum mechanics, a photon with energy less than the band gap will not contribute to the photogeneration, but a photon with energy of the band gap or higher will contribute, with any extra energy rapidly lost [1]. Therefore, the maximum current density J is given by the flux of photons with energy greater than the band gap [1]. Similarly, current density J will decrease with an increasing energy gap. However, not every photon that strikes the cell surface will contribute to charge separation of the electron-hole pairs. Solar cell efficiency is characterized by how many photons contribute to charge separation divided by the total number of incident photons. In theory --9-- there can only be a maximum efficiency related to band gap and electron charge [1][4], yet nice solar films that have good quality can greatly enhance the efficiency. With many current models of solar cells, there are only efficiencies up to and approaching 30%, and most materials such as gallium arsenide, indium phosphide, Fig. 1: The standard solar cell uses and cadmium telluride are common silicon in order to reach energy efficiency 15-20%. much too costly for widespread application [1][4]. Some crystalline silicon cells reach an efficiency of 25%, but they are too sophisticated and too expensive for widespread industrial use [4]. Cheap modules that can be produced in large quantities rarely exceed an efficiency of 15% [1]. Therefore, there is a quest to find better materials to increase efficiencies. Research and use of silicon seems to have reached a limit, and more work is being done on other semiconductors. Organic semiconductors are also under scrutiny due to their easy availability and low cost [1][5]. --10-- Work Function and Charge Transfer in Organic Semiconductors By measuring the current over changes in voltage, dI/dV curves, energy spectra of the sample can be measured around its Fermi level at low temperatures [5].