Lawrence Woody Tomas Mullins Ayoub Ali

Explanation of DSSC (Dye-Sensitized Solar Cells) Abstract

A solar cell, or Photovoltaic Device, is a way to convert photons given by the sun directly into usable electricity. We were assigned to choose a certain photovoltaic device and explain it in this document. The type of solar cell we decided to study were Dye-Sensitized Solar Cells, or DSSC. We liked the idea of a solar cell that anyone with technological know-how could produce them. Its also a bonus that they are both flexible and transparent. This paper will explain how normal photovoltaic devices work, how DSSC are different, how DSSC work exactly, and finally current and future properties of DSSC.

Photovoltaic Devices
A solar cell (also called photovoltaic cell or photoelectric cell) is a solid state electrical device that converts the energy of light directly into electricity by the photovoltaic effect.

Semiconductor behave as insulators, however; at high temperatures , some of the electron from the top of completely filled valence band can make a shift across the energy gap and occupy states in the bottom of the conduction band. As a result, electrons and holes are created in a semiconductor that refers to as charge carriers which called electrons and holes. When two pieces of semiconductors, differing in their conductivity type they formed what calls p n junctions. Solar cells are one kind of the semiconductor. It converts solar energy into electrical energy. It is a simple device consisting of a p-n junction that is illuminated by solar radiation. In the solar cells, when two materials contain different concentrations of the two types of charge carriers that is called electrons and holes. The p-type semiconductor has many mobile holes and ionized acceptors and few electrons. The n-type semiconductor has many mobile electrons and ionized donors and few holes. Where the two types of materials meet, the carriers diffuse across the junction because of the large concentration gradients in the carrier concentrations. Holes diffuse from the p-side into the n-side, and electrons diffuse from the n-side into the p-side. This diffusion process leaves some uncompensated donors and acceptors in the area of the junction. And as a result, an electric field is set up across the junction. This electric field creates drift components of currents. At equilibrium, no net current flows across the junction because drift current cancel the diffusion current. High-efficiency solar cells are of interest to decrease the cost of solar energy. Many of the costs of a solar power plant are related to the area of the plant; a higher efficiency cell may reduce area and plant cost, even if the cells themselves are more costly. Efficiencies of basic cells, to be useful in evaluating solar power plant economics, must be evaluated under accurate conditions. The basic parameters that need to be evaluated are the short circuit current, open circuit voltage. Dye-sensitized solar cells (DSSCs) are made of low-cost materials and do not need elaborate equipment to manufacture, so they can be made in a DIY fashion, possibly allowing players to produce more of this type of solar cell than others. A solar cell is made from two doped crystals, one doped with n-type impurities (n-type semiconductor), which add additional free conduction band electrons, and the other doped with p-type impurities (p-type semiconductor), which add additional electron holes. When placed in contact, some of the electrons in the n-type part flow into the p-type to "fill in" the missing electrons, and that is known as electron holes. Eventually enough electrons will flow across the

edge to match the Fermi levels of the two materials. The result is a region at the line, the p-n junction, where charge carriers are depleted and/or added on each side of the line. In silicon, this transfer of electrons produces a potential barrier of about 0.6 to 0.7 V. [6]. Dye-sensitized solar cells separate the two functions provided by silicon in a traditional cell design. Normally the silicon acts as both the source of photoelectrons, as well as providing the electric field to separate the charges and create a current. In the dye-sensitized solar cell, the bulk of the semiconductor is used only for charge transport, the photoelectrons are provided from a separate photosensitive dye. Charge separation occurs at the surfaces between the dye, semiconductor and electrolyte. Different materials display different efficiencies and have different costs. Materials for efficient solar cells must have features matched to the spectrum of available light. Some cells are designed to efficiently convert wavelengths of solar light that reach the Earth surface. However, some solar cells are optimized for light absorption beyond Earth's atmosphere as well. Light absorbing materials can often be used in multiple physical configurations to take advantage of different light absorption and charge separation mechanisms. Solar cells are often electrically connected and summarized as a module. Photovoltaic modules often have a sheet of glass on the front (sun up) side, allowing light to pass while protecting the semiconductor wafers from cut and impact due to wind-driven debris, rain, storm, etc. Solar cells are also usually connected in series in modules, creating an additive voltage. Connecting cells in parallel will produce a higher current; however, very significant problems exist with parallel connections. The solar cell works in three steps: - Photons in sunlight hit the solar panel and are absorbed by semiconducting materials, such as silicon. - Electrons (negatively charged) are knocked loose from their atoms, causing an electric potential difference. Current starts flowing through the material to cancel the potential and this electricity is captured. Due to the special composition of solar cells, the electrons are only allowed to move in a single direction.

- An array of solar cells converts solar energy into a usable amount of direct current (DC) electricity. The dye-sensitized solar cells (DSC) deliver a technically and economically reliable different concept to present day pn junction photovoltaic devices. In contrast to the conventional systems where the semiconductor assume both the task of light absorption and charge carrier transport the two functions are separated here. Light is absorbed by a sensitizer, which is attached to the surface of a wide band semiconductor. Charge separation takes place at the interface via photo-induced electron injection from the dye into the conduction band of the solid. Carriers are transported in the conduction band of the semiconductor to the charge collector. The use of sensitizers having a broad absorption band in conjunction with oxide films of nanocrstalline morphology permits to harvest a large fraction of sunlight. There are good prospects to produce these cells at lower cost than conventional devices.

Silicon Solar cell structure and mechanism

Polycrystalline photovoltaic cells laminated to backing material in a module http://www.fotosearch.com/FSD106/x16830578/

http://www.123rf.com/stock-photo/solar_cell.html

Solar Cells

DSSC
In a normal photovoltaic device, a single semiconductor is responsible for both light intake and carrier transmission. Not so in the case of a Light Absorbing Dye, also called a Dye Sensitized Solar Cell (DSSC). These terminologies will be used interchangeably in the rest of this document. There are two separate parts of a DSSC device; specifically a Sensitizer which

absorbs light, and a wide band semiconductor. Why these are used will be discussed later. Whats particularly useful about these devices is that they do not require extensive fabrication techniques, meaning anyone with any knowledge and ability can produce these solar cells, combined with efficiencies beyond 10%, make them particularly useful as a cheap alternative for current, expensive solar cells. The dye is grown on glass which makes it easy to produce, with the expectation that they could be grown on flexible materials. (JD Sorge) The best explanation for what a DSSC is has been described by one author as, The basic element of a DSC is a nanostructured material, an assembly of titanium dioxide nanoparticles about 20 nm diameter, well connected to their neighbors.TiO2 is the preferred material since its surface is highly resistant to the continued electron transfer. However, TiO2 only absorbs a small fraction of the solar photons (those in the UV). Molecular sensitizers (dye molecules) attached to the semiconductor surface, are used to harvest a great portion of the solar light. The main dye molecules consist on one Ru metal atom and a large organic structure that provides the required properties (wide absorption range, fast electron injection, and stability) (J. Bisquert) A DSSC is made of 4 parts, a conducting substrate, the sensitizer, the electrode, and the cathode. The conducting substrate is the glass part of the cell, which takes in light. The sensitizer is made of 2 materials, generally Ti02 as a high eV absorber, and then one or more layers of dyes, which can be organic (one example is raspberries) or inorganic to absorb the rest of the photons. As the light comes in, the sensitizer injects an electron into the semiconductor. The injected carriers move through the semiconductor with relative ease due to a large band gap and indirect band gap materials and finally transfers current to the cathode.

Figure showing relative makeup of cell (Michael Grtzel)

The cell is made in such a way that the Ti02 layer is grown as the large bandgap semiconductor, and then the dye is injected into the Ti02 layer. The most common and accessable forms that Titanium Dioxide take are Anatase, Rutile, and Brookite. Because the Titanium Dioxide is nanocrystalline and mesoporous, the dye gets absorbed into the layer and mixes throughout. The dyes are either organic or inorganic, with organic being the most common. The electrolyte is then grown onto the sensitizer, which is a redox electrolyte (usually an organic solvent containing a redox system, such as iodide/triiodide couple) (Jihuai) many times a liquid electrolyte. The cathode is then applied which is typically graphite or carbon which acts as a collector for the electrons produced by the cell. Organic dyes utilized in (a) 9% efficient indoline, (b) 6.5% efficient coumarin, (c) 5.2% efficient hemicyanine, (d) 4.5% efficient squarine, (e) 7.1% efficient porphyrin, and (f) 3.5% efficient phthalocyanine-based DSSCs. (Hamann)

An example of a DSSC in full use (Michael Grtzel)

As per a physical description of how the Cell works: Photons come through the glass and pass through the semiconductor, as the semiconductors band gap is too large to collect any photons. The electrons pass directly into the sensitizer. The dyes collect the photons and emit an

electron to the anode or conducting substrate through the semiconductor. Dye sensitizer absorbs the incident sunlight and exploits the light energy to induce vectorial electron transfer reaction. (Wei) Immediately, because the dyes have given up an electron, they begin to decompose, which is why the electrolytes are necessary. The electrolytes transfer an electron back to the dye, thereby reconstructing it. The cathode responds with the electrolytes to refuel the electrolytic material. Although the DSSC is not quite as efficient as other currently used types of solar cells, they are very cost effective. This is not to say that peak proposed efficiency has been met, however. In a related note, 11% current efficiency of a DSSC is not bad compared to solar cells of the past.

Characteristics of DSSC
Efficiency=8-12%, with a theoretical peak efficiency higher than that (possibly another 10 %) Types of TiO2 Bandgap (Eg) (eV) Conductivity (S/cm) Density (g/cm3) Anatase 3.2 10-12 3.69 Rutile 3.0 10-12 4.25 Brookite 2.96 10-12 3.92

Lattice Constant () All values at 300K

3.78

4.59

5.45

Common Semiconductor Bandgap (Eg): (Anatase most common) (ensuring the semiconductor doesnt do any light absorption, rather the dyes) No doping Many semiconductor values are not necessary in this type of semiconductor. Since the semiconductor does not actually absorb photons, the only relevant information about the semiconductor is its band gap and whether its direct or indirect, and the conductivity.

A Dye Sensitized Solar Cell ***A***

Future Of Dyes
In order for Dye Sensitized Solar Cells to become more widely used the efficiency will have to be increased and the cost decreased. Currently the biggest problem with DSSC is that they have very low efficiencies.***C*** The most promising way to increase the efficiency of these devices is to use multiple dyes, or what is called a system of multiple dyes. Each

individual dye has unique photon absorption characteristics. This means that a specific dye will absorb light differently at different wavelengths. An ideal device will cause one electron to move into the conduction band for every photon that strikes the device. However, because light is made up of a vast amount of photons with a wide range of wavelengths, creating a device that is able to efficiently absorb all photons is very unlikely. Researchers have discovered that the best way to increase the number of photons that the device absorbs is to use a system of multiple dyes.***B*** When multiple dyes are used that each absorb different wavelengths, then the entire system will absorb a wider range of photons, and thus become more efficient.

A DSSC using a system of multiple dyes. ***B***

As seen in figure 2, the two different dyes are able to absorb photons of different energy levels. Intuitively, a device that is able to convert more photons will be able to produce more free moving electrons in the conduction band and will in turn become more efficient. As seen in figure 3, the two dyes acting together do create a device that performs better over a wider range of wavelengths.

Incident photon to current efficiency ***B***

CURRENT DYES
The dye used to make Dye Sensitized Solar Cells is probably the most important part of the whole device. There are many different dyes being used and a multitude of methods being used to create them. The dyes are named with a code, which is a combination of numbers and letters. These dyes are a unique substance that has a complex chemical makeup as seen in figure 4.

[a] is Santalin [b] is Santarubin, which are two dyes currently being used to create DSSC.***C*** The two dyes seen in figure 4 are actually two pigments found in sandalwood. ***C***Sandalwood is the wood from Santalum trees, which are found in southeastern asia and islands in the south pacific.***D*** The dyes are able to be extracted from the sandalwood by the following method. Pulverized red sandalwood was digested in petroleum ether for 24 h to extract lipids. Digestion in dichloromethane for further 24 h remove several other mildly

polar compounds and a large portion of santarubin (some santalin is also lost). The residue is washed with warm water to remove tannin and digested in acetone containing 25% water and the solution is evaporated to dryness in a rotaryevaporator. The dark red solid containing mostly santalin with some santarubin and tannin was washed with dichloromethane and warm water to reduce the santarubin and the tannin content. Further purification is achieved by chromatography using a silica gel column and elution with dichloromethane and methanol mixture. ***C*** This is just one method to extract only two of the many possible dyes that are being used in the creation of a DSSC. Now that a dye has been extracted the next step is to deposit it onto a semiconductor. This step turns out to be far more inexpensive than one would think. A Titanium Oxide plate is boiled in a substance made up of the dye and acetone. Dyes are also attached to the TiO2 using acids, such as carboxylic acid.***F*** Titanium Oxide is a commonly used material for DSSC because it has an extremely porous surface area as seen in figure 5. This porosity allows the dye to penetrate deeply into the TiO2 film and also results in increased bond strength. The porosity of the TiO2 gives it a greater surface area, which allows more of the dye molecules to attach. As the device has more dye molecules the chances that an incoming photon will strike the dye will also increase. This increase will result in a higher efficiency.

A cross sectional view of a TiO2 film ***C***

An Assembled DSSC. ***C*** As previously stated, there are a vast number of different dyes that can be used in a DSSC. The dyes used for DSSC have many requirements in order to function in an efficient manner. First, the dye must be able to strongly bind to the inorganic semiconductor, usually TiO2. The dye must also pass electrons from the dye into the semiconductor quickly so as to minimize the number of electrons that the dye reabsorbs.***F****

Conclusion
Dye-Sensitized Solar Cells definitely have a future in this world. After understanding how they work, and that the technology is in its initial stages, its clear that the potential of DSSC is huge. Most likely, it will be used more as public demand for green energy increases. Its easy to imagine that buying DSSC solar cells could be common place for the average consumer and sold en masse and inexpensively. Potentially, DSSC solar cells could be sold in home improvement stores and similar retailers as a means for the public to reduce their dependence on energy companies and make it a viable option to save money in energy consumption.

Works Cited
1) Di Wei Dye Sensitized Solar Cells Int J Mol Sci. 2010; 11(3): 11031113. (2010) 2) JD Sorge Dye-Sensitized Solar Cells, Rutgers November 22, 2004 3) J. Bisquert, D. Cahen, G. Hodes, S. Ruhle, A. Zaban Physical chemical principles of photovoltaic conversion with nanoparticulate, mesoporous dye-sensitized solar cells Journal of Physical Chemistry B, 108, 8106-8118 (2004) 4) Michael Grtzel Dye-sensitized solar cells Laboratory for Photonics and Interfaces, Swiss Federal Institute of Technology, CH-1015 Lausanne, Switzerland (2003)

5) Hamann, T.W., Jensen, R. A., Martinson, A. B. F., Van Ryswyk, H and Hupp, J. T., Advancing beyond current generation dye-sensitized solar cells, Energy Environ. Sci., 1, 66 78. (2008)

6) David Martineau Dye Solar Cells for Real: The Assembly Guide for Making Your Own Solar Cells Solaronix (2011)

7) Jihuai Wu, Zhang Lan, Sanchun Hao, Pingjiang Li, Jianming Lin, Miaoliang Huang, Leqing Fang, and Yunfang Huan Progress on the electrolytes for dye-sensitized solar cells IUPAC, Pure and Applied Chemistry 80, 2241225(2008)

8) NCLT Nanotechnology Center for Learning and Teaching http://www.community.nsee.us/concepts_apps/dssc/DSSC.html

9) R. Zallen, M.P. Moret The optical absorption edge of brookite TiO2 Department of Physics, Virginia Tech (2005)

10) S. Banerjee, Judy Gopal, P. Muraleedharan, A.K. Tyagi, Baldev Raj Physics and chemistry of photocatalytic titanium dioxide: Visualization of bactericidal activity using atomic force microscopy Current Science, Vol. 90 (2006) 11) webmineral.com