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Material Analysis of Amorphous Silicon Solar Cells 11/17/11 John Majzner Levi Weiss Andrew Kom Class of Vikram Dalal, EE 332, Iowa State University, Ames, Iowa 50010 Abstract Amorphous silicon (a-Si), is one of the many new technologies that might have Another way to reduce the number of dangling bonds is to pre-bake the transparent film substrate. the ability to dominate the solar cell market. Amorphous silicon is an attractive material The temperature dependence of a-Si because it is relatively cheap, light weight, is very unique. For most solar cell and durable. However, at the same time, it materials, as temperature increases, the is much less efficient than other forms of Si efficiency decreases. However, for a-Si, as based solar cells. This paper is an analysis temperature increases, the efficiency will of the physical properties, manipulation, and also increase. This makes amorphous implementation of a-Si. silicon more useful in hotter environments, which is common for real world applications The thickness of the a-Si cell is much of solar cells. thinner than crystalline silicon. This smaller thickness causes a decrease in the absorption Beyond being able to efficiently of incident solar rays. This can be remedied work in hot environments, it is also very by putting multiple layers of junctions on useful for harsh environments due to its top of each other. durability. Amorphous silicon is also used in many space program related projects since If the annealing temperature of a-Si goes above 250°C, then the the film will its light weight makes it ideal for many space related needs. begin to lose conductivity as well as increase the initial dangling bond density. These Another way to boost a-Si is to use dangling bonds make the material less graded doping and help increase the electric efficient, but can be filled by adding field in a a-Si cell. This electric field hydrogen to them, through a process call boosted by the graded doping will increase hydrogenation. The hydrogen seals the gap and leaves the Si molecule completed. the flow of electrons, and help improve the characteristics of the cell. As for the future of amorphous Benefits of Amorphous Si There are a number of particularly silicon, outside of solar cell technology, is that it will be largely used in LEDs for both important characteristics that make the less lighting and television sets. The a-Si is efficient amorphous silicon solar cells made into dots that will, depending on the size, give a maximum photoluminescence at valuable and useful. The first of these is cost [3]. short wavelengths that crystalline silicon cannot emit. This makes it so the LED can flash in different colors and be highly efficient. Amorphous silicon can be produced at a much lower cost than any crystalline or polycrystalline solar cell available. The materials used to produce a-Si solar cells Introduction Due to the number of different materials that can be used for solar cells, a clear identification of each material’s unique cost significantly less money than either of the more efficient models. Also, the ability to be produce a-Si in a large roll and in mass quantities contributes to this lower cost [3]. properties must be analyzed. This paper will discuss basic information about physical properties of a-Si and widely used manipulation methods used to increase efficiency. The reason it can be produced rollto-roll is directly related to the material’s flexible nature. Since amorphous silicon has no orderly structure, it can be disturbed by flexing it. This property can be utilized for A general understanding of what makes a-Si a unique in the solar cell market many projects that include irregularly shaped structures [3]. is that it is a low cost, light weight, durable, and low efficiency material [1]. It is generally not used alone, but in layers or in combination with other materials, to increase its effectiveness [2]. Arguably the most important attribute when considering the benefits of aSi is weight. In many cases, weight is a very important factor on whether solar power is a feasible option. For many space related projects, light weight solar power is light will bend and scatter as it travels ideal, since it reduces the weight that has to though the cell. The Image clearly shows its be propelled [3]. interaction of light with the different layers and its eventually be absorbed in the i-layer The flexibility and lightweight of a- [4]. The p and n layers induce an electric Si leads to another useful trait of being able field in the intrinsic layer which allows to put the cell on a large range of surfaces. movement of carriers as seen in figure B. What is meant by this is that it can be put The intrinsic layer acts as the depletion onto fabrics, textiles, magnetic backing, and region between the n and p doped layers [5]. almost any other material one would want. This allows for more flexibility in what it can be used for [3]. Finally, its ruggedness is another very good quality of a-Si. Amorphous silicon is very rugged, because of how it is made. The fact that a single amorphous silicon panel includes many interconnected cells allows a different path for electrons to travel if the panel were to be punctured. In most cases, any crystalline or polycrystalline Figure A, The different layers of a solar cell and how panel would significantly decrease in its light interacts with them [6] . ability to produce, or lose it entirely if punctured or damaged in any way [3]. a-Si Design Figure A shows the basic design of a typical a-Si cell. In addition, it shows how other word, each cell is its own structure and is separate from the others in the panel. In aSi however, no such requirement exists. This means that you may have multiple cells that are built connected together. The reason that this is good, is that it allows one to have a cell get damaged, but still have all the others work around the bad cell, which means the output is not affected as much as Figure B, The energy band diagram for an amorphous silicon solar setup. if you were to damage a crystalline cell in a crystalline based panel. Differences Between Crystalline and Amorphous Si Solar Technology Beyond the simple aesthetic differences between the two, such as look and weight, there exist important differences between the two technologies. To begin with, if one were to examine a crystalline panel and an amorphous silicon panel sideby-side, one would notice something right away. In many amorphous silicon based panels, the “fingers” extend a short ways, but do not extend across the panel as they do in crystalline. This is because crystalline Figure (?), Crystalline Silicon Based Solar http://www.monocrystallinesolarpanels.com/china156mmx156mm_high_efficiency_monocryst alline_solar_cells-118314.html Figure (?), Amorphous Silicon Based Solar Energy Bands in Amorphous Silicon panel require crystalline structure, which means that the material must be clearly transitioned from one cell to another. In According to [5], what is perhaps the most important characteristic of amorphous silicon is the band gap change. In crystalline silicon, the band gap can be represented by figure D. Figure D is the indirect band gap with a much larger direct band gap energy. The indirect gap for Silicon is 1.1eV, while direct band gap can be on the range of 2.2eV [7]. The disorder found in amorphous silicon causes it to develop a direct band gap (Figure C) that can range from 1.6-1.8eV. Having a direct band gap allows the amorphous silicon to have a much higher absorption coefficient. This results in an improved ability to produce energy in lower light conditions. Figure D, Inderect Energy Band [8] . Hydrogenating the a-Si Effectively, when amorphous silicon is made, it has a large number of defects that come from the disorder of the silicon atoms. These defects, referred to as dangling bonds, are silicon atoms that have bonded with 3 other silicon atoms, but not with a 4th [9]. This defect significantly decreases the efficiency of solar conversion [10]. To counteract this result, hydrogen is introduced into the material. The hydrogen, Figure C, Direct Energy Band [8] . to fill its outer state, is attracted to the open silicon bond. This attraction leads to the silicon bond being filled. This process significantly cuts down on the number of defect states as can be seen in Figure E, but cannot delete them entirely [3]. the dangling bond density. Figure F shows a example of the plasma deposition system used for adding the hydrogen to a-Si to transform it into a-Si:H. Figure E, Diagram of the hydrogenated amorphous silicon [11] . Figure F, Diagram of a plasma deposition system [1] reports that hydrogenated [1] . amorphous silicon (a-Si :H) is a useful photovoltaic material based on the easiness in which it is manufactured, as well as some Physics Manipulation Using hydrogen to remove dangling attractive properties; a high absorption bonds was first reported by Anderson and coefficient, high photoconductivity, and p-n Spear [12]. This single change from a-Si to controllablility. a-Si:H has made amorphous silicon one of the top contenders in the material war of the These a-Si:H films are produced solar cells. Further manipulation of a-Si through plasma deposition from monosilane allows for a more efficient solar cell and (SiH4), which is diluted by hydrogen to 10 making it a better material. Generally, as mol%. The films are heated to improve the you add more H into the cell, the bandgap photoconductivity and doping efficiency, increases [13]. To get more H into the cell, with a cap of 250°C. If the temperature of you can raise the pressure and or lower the the anneal goes over 250°C, the film will temperature during deposition. begin to lose conductivity as well as increase The electric field E in the i-layer will greatly affect the cell performance through not require new equipment, but can improve the solar cell. the fill factor. Having control over E within the i-layer will allow for a more efficient design. If the i-layer becomes too thick, the E is deformed and reduced [14]. Thickness [18] states that a-Si films can be much thinner than crystalline Si devices, with a thickness of 500 nm compared to tens Creating a buffer of a-SiC:H between of hundreds of microns. However, there are the p-layer, pc-Si, and the i-layer, a-Si:H, a large amount of defects in a-Si:H films improves the performance due to the that limit the minority carrier diffusion repelling of AEc [15]. lengths to 100 nm. Since a-Si:H cells are fabricated even thinner than regular a-Si, the Having a higher open circuit voltage (Voc) in the top layer of a triple-junction a- incident absorption of solar radiation is reduced even further. Si solar cell is better then having a higher band gap with a-SiC alloys [16]. The [2] states that multi-junction solar highest Voc that could be obtained was cells are used in a-Si cells to obtain higher 1.04V when it was deposited at 150°C [16]. efficiencies. However, a major roadblock for this is that it is has not been possible to When we pre-bake the transparent film substrate, the impurity content of the aSi will be reduced [17]. This process will reduce the number of dangling bonds for hydrogen and make it a more effective solar cell. This manipulation is a low cost example of how to better create a-Si. These types of changes are incredibly useful because it will not increase the cost and do make a cell with a bandgap lower than 1.5 eV. With microcrystalline silicon technology combined with a-Si technology, however, thin film materials with 1.12 eV bandgaps can be made. Temperature Photovoltaic (PV) modules are very dependent of temperature and irradiance. In humid environments, such as Thailand, the efficiency of a-Si changes to 103.86% of Figure G, Data points showing the relation of normal [19]. This shows that the hotter the temperature and Output of an a-Si solar cell [19] . temperature, the more effective the solar cell can be. From this we can deduce that within colder environments, the effective efficiency of the cell will drop. The IV curve for a-Si keeps the same shape as most solar cell materials. Figure H shows the IV curve of the 11 segmented Si:H. The optimum points are shown as X One thing that sets a-Si apart from other materials is that the PV module shows marks on the graph. The optimum open circuit voltage for this module is ~.8V. much better performance at higher temperatures relative to other types of PV modules [20]. The efficiency of most materials decreases as temperature increases, but the efficiency of a-Si increases as temperature increases [19]. The material a-Si has little temperature dependence when it is operating in a equilibrium state, but it will have a large temperature dependence in short periods of time [20]. Figure G shows a real world relationship between temperature and power Figure H, IV curve of a 11 segmented a-Si [21] . output. Light Spectrum Effects According to [22], a 550 nm wavelength is the most intensive part of the solar spectrum, as seen in figure I. Because this is the most intensive part of the spectrum, it will be the least reflective wavelength by %, as seen in figure J. From figure J, we can also see that reflection is segmented a-Si:H single junction module not a simple function of decay vs has an efficiency of 8.7% [21]. wavelength, but will increase and decay at a specific spectrum. Light trapping is essential for increasing efficiency of a-Si thin film cells. While using the light trapping material Zinc Oxide (ZnO), a stable efficiency of 9.47% could be obtained with an 11 segmented aSi:H [21]. To compare this to the highest confirmed efficiency of other materials see Figure I, Light spectrum to amount adsorbed [22] . figure K. Some ways to increase the light trapping is using graded doping, using a high reflection substrate, and multi-junction a-Si cells [13]. Figure J, Light spectrum to reflection % [22] . Efficiencies Using a glass substrate, a single a-Si cell has a efficiency of 5.54 % with a fill factor of 0.54 and a open circuit voltage of 0.9 [23]. Efficiency for flexible solar cells is 4.03% with a fill factor of 0.5 and a open circuit voltage of 0.82 [23]. An 11 situations. Figure L shows 3 different types of junctions. Figure L, The physical difference of junctions [25] . Graded Doping Graded doping can be used to Figure K, highest confirmed efficiency of solar cell increase the electric field, which will help for multiple materials taken at 1000W/m^2 at 25C surface recombination and electron [24] . collection. Graded doping also increases the amount of light trapped [13]. Since there is Device design The design of a-Si is highly dependent on the application of use. Since a-Si is easy to manipulate, it is an attractive material because there are many types of manipulations that can apply to different more doping on one side of the cell then the other, a larger variation of charge will take place, therefore increasing the electric field. However, this increased electric field will be non-continuous because it is an a-Si material and the doping is graded [22]. Figure N IV curve of graded doping a-Si cell [26] . An example of a graded doping cell is shown below in figure M. It is possible to put a light grading on the junction as well as Plastics Using a method of plasma enhanced the substrate, which could lead to an 18% chemical vapor deposition (PECVD), increase in the max current density (Jmax) amorphous silicon can be deposited at low [26]. The IV curve for the graded bandgap temperatures of 100°C [23]. Using low is shown below in figure N. It gives a fill temperatures for depositing can lower costs factor of .68 V, an open circuit voltage and allow the solar cells to be deposited on (Voc) of .8 V, which are good values for a high temperature deposition. materials that cannot normally be used due to temperature constraints, such as plastics. The thickness of plastic substrates can be much thinner then glass substrates while keeping their integrity [23]. Using plastics can lead to thinner and more light weight products. These thin-film plastics allow for non-planar shaping and greatly increases their ability to be applied in the real world [27]. Figure M, Graded doping of a-Si cell [26] . LED technology [28] shows that a likely material to be used for full-color flat panel displays in the future is silicon based light emitting diodes (LEDs). Silicon LEDs have fullcolor emission, complementary metal oxide semiconductor compatibility, as well as cheap fabrication and system feasibility. The major issue with using silicon LEDs is E(eV) = Ebulk + C/d^2. the tuning of short wavelength emission colors. To remedy the situation, a-Si is where Ebulk is the a-Si bandgap, d is the used. a-Si’s luminescence efficiency is size of the dot, and C is the confinement larger than crystalline silicon because of its parameter. If you adjust the dot size to structural disorder. It also has a band gap of certain values, the intensity of the 1.6 eV, which is larger than the 1.1 eV of photoluminescence will be at a maximum at crystalline silicon. the short wavelengths that are the issue, as shown in figure P. The a-Si is made into a quantum dot. As the quantum dot size increases, the photoluminescence energy decreases, as shown by figure O. Figure O, Varying photoluminescence with change in dot size [28] . Assuming that the potential barrier is infinite, the energy gap E of the a-Si quantum dot is Figure P, Varying wavelengths due to varying dot sizes [28] . High temperature anneal technology Another new idea has recently New methods of implementation are sprung up for improving the efficiency of created every day. Placing this new amorphous silicon based solar cells. In a technology in places it will not be noticed recent experiment conducted in Colorado, but still work effectively has become a large annealing was conducted in temperatures part of the challenge to using solar cells. ranging from 300-400 degrees Celsius. In One example of implementation is current situation, annealing is done well below 300 degrees C. In the case where it is using a semitransparent insulated laminated glass and placing a solar cell of a-Si on it so well below 300, the initial efficiency starts that will not be normal noticed and can out high, but quickly degrades, settling at an generated a power of 42W/m^2 as seen in efficiency of about 6%. The reason this figure Q [6] . happens is because there are light-induced dangling bonds that form due to hydrogen atoms separating from the silicon after light is introduced [29]. The effect of having a higher annealing temperature is that it decreases the number of light-induced dangling bonds, but at the same time also decreases the initial efficiency. What this results in is a higher efficiency after its sun soaking period. The main draw back of amorphous silicon based Figure Q, Application of a-Si solar cell in Germany [6] . solar is its low efficiency, so this could be a very significant discovery for the future [29]. Weight of a-Si A power to weight ration of 275 mW/g can be obtained from integrated type Glass solar cell technology a-Si solar cells [17]. This light weight property is something that makes a-Si a highly desirable material. The average without buying very expensive temperature house hold uses around 1000 watts of power resilient equipment. New technologies are [6]. To give you a idea of how much weight still coming out that are focusing on of solar cells would be needed for each increasing the efficiency and lowering the house 1000 [W] / 257 [W/kg]=3.64 [Kg] (~8 cost of a-Si cells, with a goal of making pounds) of a-Si solar cells to make a them more competitive with respect to other household run during the day at peak energy materials. demand hours. This shows that it is not only possible for people to functionally live with cells on their roof, but practical. Two simple, and cheap, changes to make a-Si more effective is to annealing at around 250°C and pre-bake the transparent In Iowa the average cost of energy is film substrate. Both of these will lower the .0729 [$/kWh] [30]. For each hour the solar number of dangling bonds and lessen the cell is active the amount of money people need to add hydrogen to the material. save is .0729 [$/kWh] * .257 [kW/kg] = .018735 [$/h]. This may seem small for each hour, but the savings will build up for each hour the solar cell is working. The money saved will also increase as energy costs go up. When humans move to the stars the cost of going to space is coming from from weight. Having a weight to power officiant of 275 mW/g on earth, that will only go up in space. The future of the human race is space and the cost to get items into space is Conclusion With its ability to gain efficiency in due to weight of each item. Then a-Si is the best material for solar cells in space travel. heat and its wide use in the world today, aSi may be the best choice of solar cell Development for a-Si is not just for materials. New technology allowing a-Si to solar cells, but also LED lighting. The be created at temperatures as low as 100°C research into LED lights will only build on can make it even cheaper to produce and the understanding of a-Si making it a more allow new companies to create solar cells viable matiral for practical uses. silicon more useful in hotter environments, The future of solar cells is not necessarily based on the efficiency of the which is common for real world applications of solar cells. cell, but its cost to power output. If people begin to buy a-Si solar cells and use them in Beyond being able to efficiently the public sector, (e.g. a-Si cells on roofs), work in hot environments, it is also very a-Si could shine. However, for this to useful for harsh environments due to its become a reality, a-Si would have to either durability. Amorphous silicon is also used in become cheaper, or become much more many space program related projects since efficient. its light weight makes it ideal for many space related needs. Another way to boost a-Si is to use graded doping and help increase the electric field in a a-Si cell. This electric field boosted by the graded doping will increase The thickness of the a-Si cell is much thinner than crystalline silicon. This smaller the flow of electrons, and help improve the characteristics of the cell. thickness causes a decrease in the absorption of incident solar rays. This can be remedied As for the future of amorphous by putting multiple layers of junctions on silicon, outside of solar cell technology, is top of each other. that it will be largely used in LEDs for both lighting and television sets. The a-Si is The temperature dependence of a-Si is very unique. For most solar cell made into dots that will, depending on the size, give a maximum photoluminescence at materials, as temperature increases, the short wavelengths that crystalline silicon efficiency decreases. However, for a-Si, as cannot emit. 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