SemiconductorsAndBandTheoryH tcm4-658243

NATIONAL QUALIFICATIONS CURRICULUM SUPPORT
Physics
Semiconductors and Band Theory
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SEMICONDUCTORS AND BAND THEORY (H, PHYSICS)
Learning and Teaching Scotland 2011
Contents
Electrical conductivity and band theory Summary of band theory Intrinsic semiconductors Extrinsic semiconductors Student Activity 1 Thermistor investigation Summary of intrinsic and extrinsic semiconductors pn junctions Photovoltaic cells Student Activity 2 Photovoltaic cells Light emitting diodes Student Activity 3 LED threshold voltage Why use LEDs? Summary of pn junctions, LEDs and photovoltaic cells References and further reading 4 8 9 11 13 14 15 17 18 18 20 21 21 22
SEMICONDUCTORS AND BAND THEORY (H, PHYSICS) Learning and Teaching Scotland 2011
SEMICONDUCTORS AND BAND THEORY
Semiconductors and band theory

The purpose of this document is to introduce the new approach that is being brought to the Higher Physics course, in teaching about semiconductors from the perspective of band theory.
Electrical conductivity and band theory

All solids can be classified as conductors, semiconductors or insulators according to the availability of conduction electrons in their structures. Band theory gives an explanation for these differences in electrical properties and accounts for the availability, or not, of those conduction electrons. Although individual atoms have certain permitted energy levels for their electrons, as defined by quantum theory, when large groups of atoms are incorporated into a solid mass those energy levels become reorganised in such a way as to result in bands of possible energy levels (Figure 1). This is known as the tight binding approximation.
Permitted energy levels
Permitted energy bands
Figure 1 Discrete energy levels within an individual atom (left) and bands of permitted energy levels within a solid (right)
There are such enormous numbers of electrons in a solid mass that although the bands actually consist of very large numbers of closely packed discrete energy levels, the bands become essentially continuous. There may be several permitted energy level bands, but in particular we consider the two uppermost bands. These are known as the valence band and the conduction band (Figure 2).
Conduction band (empty)
Valence band (full)
Figure 2 Conduction and valence bands in an insulator. These bands contain the only permitted energy levels, and since the valence band is full and the conduction band is empty, no net movement of electrons can occur within the material. Note the gap separating the bands.
The electrons with lower energy levels are described as occupying the valence band. The innermost electrons in an atom are much less influenced by neighbouring atoms, and occupy discrete energy levels. They are sometimes considered to be bound. At higher levels in the valence band electrons can, in fact, move from atom to atom, but only up to the top of the valence band. Since they are permitted only to swap places with other valence electrons in neighbouring atoms, they are effectively unavailable for conduction. Electrons fill the valence band from the lowest level to the highest. The top of the valence band for a material is the highest level, which would, in theory, be filled by all the available electrons within an atom of that material at a temperature of 0 K. In insulators and semiconductors, the valence band is completely filled with electrons. The conduction band is empty (Figure 2).
The electrons fill energy levels in order because, as fermions, they must obey the Pauli exclusion principle and cannot occupy identical energy levels. The only way that an electron could move from one atom to another in an insulator or semiconductor would be to occupy a slightly different energy level in a neighbouring atom. However, all those energy levels are already full. As discussed above, the electrons may effectively swap places, but in order to facilitate conduction, they must leap up to the conduction band. An energy level band must have some space within it (some vacant energy levels) in order for there to be any net movement of electrons within the material. For a material to be able to conduct electricity it must have electrons in its conduction band or spaces in its valence band. There must be spaces for charges to move into: a partially filled band. http://phet.colorado.edu/en/simulation/conductivity The simulation demonstrates how energy levels differ in conductors, semiconductors and insulators, and the impact the energy levels have on conductivity. Again, as a result of the wavelike behaviour of electrons within atoms, materials may exhibit a certain range of forbidden energy levels (Figure 3). It is simply not possible for an electron to exist with an energy level that would place it in this range. This leaves insulators and semiconductors with a gap between the two bands.
Gap of forbidden energies
Conduc tor Insulat or Semicondu ctor
Figure 3 : Conduction bands (blue) and valence bands (yellow) for insulators, semiconductors and conductors. Note the energy gaps in insulators and semiconductors, and how in a conductor there is no gap, simply a continuous, partially filled conduction band.
In insulators this zone of forbidden energy levels is very substantial, and separates the valence band and the conduction band significantly. The forbidden zone is of the order of a few electron volts, and is therefore so large that it is not normally practicable for there to be sufficient energy to move electrons across it from the valence band to the conduction band. For example, thermal excitations and conventional electric circuit voltages within a material provide energies that are smaller than 1 eV on an atomic scale. It would be necessary to expose an insulator to electric fields of the order of 1010 V m 1 in order to give the valence electrons enough energy to jump across the gap to the conduction band, since this could provide energy in the order of a few electron volts on an atomic scale. This is what happens when there is dielectric breakdown. Contrastingly, conductors only have one band, and the top of this band is only partially filled, permitting electrical conduction. This means that there are plenty of nearby energy levels available for electrons to move into. They can flow easily from one atom to another when a potential difference is applied across the conducting material. Like insulators, semiconductors have a completely full valence band and so electrons are not able to facilitate conduction at low temperatures. However, for semiconductors, the forbidden energy level zone between the two bands is sufficiently small to make it much easier for significant numbers of electrons to move across this gap and go from the valence band to the conduction band. This can happen if sufficient energy is supplied, for example if there is some thermal excitation. As a result, semiconductors exhibit increased conductivity with increasing temperatures. In many semiconductors, a temperature increase of 10 K will permit a doubling of the numbers of electrons in the conduction band. In order to increase the conductivity of semiconductors, small amounts of doping material can be used. This results in significant increases in conductivity as a result of the narrowing of the gap between the conduction and valence bands.
Summary of band theory

In solids, permitted electron energy levels are organised as bands. The valence band contains electrons that can be considered to be bound to the atom. In insulators and semiconductors the valence band is full. The conduction band is a region of permitted energy levels that is empty in insulators and semiconductors, but partially filled in conductors. Only partially filled bands may permit conduction. There is a forbidden zone that forms an energy gap between the valence and conduction bands in insulators and semiconductors. That energy gap must be jumped if an electron is to move to the conduction band, and this is not normally possible in insulators because the gap is too large. In semiconductors, the forbidden zone is much smaller and electrons can jump the gap to the conduction zone as a result of thermal excitation. Doping of semiconductors can significantly reduce the width of the energy gap. For further information on this topic, try this high-level simulation: http://phet.colorado.edu/en/simulation/band-structure There is also further information from the Hyperphysics website: http://hyperphysics.phy-astr.gsu.edu/hbase/solids/band.html Many links lead from this, although it should be noted that some (otherwise very useful) resources describe an overlap between valence and conduction bands in metals. This is misleading and should be treated with caution.
Intrinsic semiconductors
Pure, undoped silicon and germanium are two simple examples of intrinsic semiconductors (Figure 4). They are both in Group IV of the Periodic Table, and form a tetrahedral crystalline structure, similar to diamond. Each atom of silicon and germanium has four electrons in its outermost electron shell, and each of these electrons is used in a covalent bond with one of the atoms four neighbours.
Figure 4 Two-dimensional illustration of a crystal of pure undoped Si. If any individual atom of silicon is considered, it can be seen that each of its four valence electrons is used in maintaining covalent bonds with the atoms neighbours. These electrons are therefore unavailable for conduction.
Since all valence electrons are involved in bonding, pure silicon and germanium may be expected to be good insulators. However, relatively small energies are required to move a valence electron across the energy gap to the conduction band. This is 1.1 eV for silicon, and only 0.7 eV for germanium. This means that a significant number of electrons are available in the conduction band, even at room temperature (Figure 5).
Silic on
Germaniu m
Conduction band Electrons moving across energy gap due to thermal excitation
Valence band
Figure 5 It is possible for significant numbers of electrons to cross the energy gap in semiconductors.
It must be noted at this stage that although most thermal excitation involves energies much less than even 0.7 eV, quantum mechanics clearly shows that there is a small but significant probability of an electron being able to jump the energy level gap, even at relatively low temperatures. As previously discussed, this probability increases rapidly with temperature. Once an electron jumps up to the conduction band in the crystal lattice, it leaves behind a hole in the covalent bond. This hole can enable another neighbouring valence band electron to move into it. As such, a hole behaves rather like a positive charge carrier, even though it is actually a vacancy for an electron. A hole can travel through the crystal lattice of the semiconductor. A helpful analogy might be to consider a queue of cars on a road. If a space appears at the front of the queue, cars may move forward in turn. Each time a car moves forward, it leaves a space behind it, into which the next car may now move. An observer from above might consider that the cars are moving forwards or that the space is moving backwards. Some semiconductors, like pure silicon or germanium, are known as intrinsic semiconductors. Intrinsic semiconductors must always contain equal numbers of conduction electrons and holes. If an electron can move from its place then it must leave behind a hole (Figure 6).
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electro ns hole s
Figure 6 In intrinsic semiconductors like pure silicon or germanium, every electron that moves up to the conduction band must leave a hole in the valence band. Electrons and holes exist in equal numbers and both contribute to conduction. There are no majority charge carriers in intrinsic semiconductors.
Extrinsic semiconductors
Often, it is more useful to control the properties of a Group IV semiconductor by deliberately introducing very small proportions of a Group III or Group V element. This is known as doping and results in what is known as an extrinsic semiconductor. Extrinsic semiconductors have majority charge carriers that may be either electrons or holes. Consider a semiconductor that is doped with a Group III element (Figure 7). Each atom of the doping agent will have only three electrons in its outer shell. This is insufficient to form the four covalent bonds with its Group IV neighbours and therefore results in a hole. Countless holes are now built into the semiconductors crystal lattice. It may be referred to as a p-type semiconductor as the majority charge carriers are positively charged holes. As a result of the doping process, it will require much less energy to allow charge to flow through the semiconductor and so its conductivity is greatly enhanced. Unlike metals, a p-type semiconductors conduction occurs in the valence band. In effect, the doping agent adds an extra energy level just above the valence band, sometimes called an acceptor band.
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Electro n Hole
Silicon
Group III
Figure 7 Introducing small quantities of Group III atoms into a silicon lattice (in practice only around one part in a million) leaves holes built into the valence band.
Technically, there will also still be a small degree of intrinsic behaviour, as electrons leave behind holes, but this is not considered to be significant in comparison with the overwhelming number of majority charge carriers. A similar process is involved if a Group V element is used for doping. This gives an extra electron, surplus to covalent bonding requirements, for each atom of the doping agent. These electrons are negatively charged and so an n-type semiconductor has been produced. In an n-type semiconductor, the majority charge carriers are electrons. The conductivity has been greatly enhanced as before, but this time conduction occurs in an extra energy level just below the conduction band, which is sometimes called the donor band. Therefore, in p-type and n-type semiconductors conduction can occur easily because there is effectively unfilled space within either the valence or the conduction band, respectively. Semiconductors are crucial to modern life. According to estimates (Sheffield University) 43% of all semiconductor production goes into computers, 23% into consumer products, 13% into communication and 12% into manufacturing.
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In Scotland, Silicon Glen (which is a large proportion of the central belt) has been pioneering electronics production since the 1940s, employing around 50 000 people at its peak in 2000. The name Silicon Glen reflects the importance of semiconductors to this sector of Scottish industry, whilst making comparisons with Californias Silicon Valley. One specialist application for semiconductors is the detection of magnetic fields using the Hall effect. You may be lucky enough to have a Hall effect probe in your school. If not, here are some simulations of the effect: http://www.youtube.com/watch?v=_ATDraCQtpQ&feature=related http://www.youtube.com/watch?v=FUNnziMmgSQ&feature=related
Student Activity 1 Thermistor investigation

Thermistors use semiconductors in order to vary resistance as a function of temperature. Negative temperature coefficient (NTC) thermistors use thermal energy to free up more charge carriers, so an increase in temperature results in a reduction in resistance. Students can investigate the resistance variation with temperature for an NTC thermistor:
The thermistor can be immersed in a small beaker of hot water (with a thermometer) and the meter readings used to calculate resistance at 5C intervals as it cools. A plot of resistance versus temperature can then be produced by the students. A similar procedure could be used for an Light Dependent Resistor.
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Summary of intrinsic and extrinsic semiconductors

Semiconductors allow conduction by means of negative charge carriers, which are electrons, or positive charge carriers, which are holes. The energy band gap in semiconductors is small enough that thermal excitation is sufficient for significant numbers of electrons to be able to move up from the valence to the conduction band. Intrinsic semiconductors, such as pure silicon, will always have equal numbers of holes and electrons since each conduction electron will leave behind a hole. Semiconductors may be doped with impurities that add either extra electrons or holes to the lattice. These doped semiconductors now have a majority charge carrier present and are known as extrinsic semiconductors. Group III doping agents result in p-type extrinsic semiconductors, which contain extra holes. Group V doping agents result in n-type extrinsic semiconductors, which contain extra electrons. This link gives you a simulation for a semiconductor that you can adjust yourself: http://phet.colorado.edu/en/simulation/semiconductor
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pn junctions
If a single semiconducting crystal is doped in such a way that one end is p-type and the other n-type, then some very useful properties come into play. The interface between the p-type and n-type sections is known as a pn junction. In this boundary region, electrons from the n-type material may diffuse across the boundary and combine with holes from the p-type material, and vice versa. This results in a lack of majority charge carriers in the immediate vicinity of the junction and as such the region is known as the depletion zone. The pn junction greatly affects the conductivity of the semiconductor as a whole. When electrons from the n-type material diffuse into the p-type material, they form negative ions as they combine with holes. Positive ions are also left behind in the n-type material. Eventually, this process results in there being no further diffusion of electrons or holes as a result of Coulomb attraction and repulsion (Figures 8a and 8b).
Depletion zone
--ptype ---------
++ + ++ ++
ntype
Junctio ++ n +
Figure 8a In a pn junction a depletion zone is formed by the diffusion of electrons from the n-type material into the p-type material. As the electrons combine with holes, ions are formed in the depletion zone.
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p-type
n-type
Conduction band
Depletion zone Valence band
Figure 8b Band theory gives us a model for explaining what happens at a pn junction. Holes and electrons diffuse towards the junction in their different bands. At the junction they combine, producing the depletion zone. This pn junction is forward biased.
The pn junction may only allow current to flow if it is forward biased. By connecting the negative terminal of a power supply to the n-type material, the junction becomes forward biased. Electrons may be pushed across the depletion zone if the supply has a sufficient potential difference to overcome the Coulomb repulsion discussed above. This is typically of the order of 0.7 V. Once the depletion zone is crossed, conduction is easily facilitated by the majority charge carriers in each of the semiconducting materials. If the pn junction is reverse biased, ie the n-type material is connected to the positive terminal of a power supply, the depletion zone effectively becomes a greater and greater barrier to conduction. One can imagine the depletion zone illustrated in Figures 8a and 8b becoming a higher and higher barrier to conduction as electrons are driven further and further back from the depletion zone. The junction can only allow a tiny leakage current to flow because of the intrinsic semiconductors electrons and holes. Since this is usually undesirable, silicon is preferable to germanium because its leakage current is so much smaller as a result of it having a larger energy gap between its valence and conduction bands (Figure 5). Eventually, if the reverse voltage continues to increase, the semiconductor will break down and may result in damage to the junction.
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Photovoltaic cells
A photovoltaic cell consists of a very thin layer of p-type semiconductor that is in contact with a layer of n-type material. The conduction electrons are freed through the action of photons of light. The photons provide sufficient energy to the electrons to enable them to jump up across the energy gap to the conduction band, leaving behind a hole. The band gap energy for silicon is of the order of 1.1 eV, and so only photons with at least 1.1 eV of energy can cause the release of conduction electrons. The wafer of semiconductor is very thin and so there is a good chance that this process will happen at or very close to the pn junction. The electric field produced by the depletion layer at this junction forces the electron and hole apart, creating a potential difference, and so a current can flow if the cell is connected to a circuit. The p-type layer must be very thin, perhaps 1 m thick, to prevent conduction electrons from being captured and immobilised by holes. This animation is useful: http://solarhorizon.com.au/Flash/LightCurrent.html
Photons interact with electrons close to pn junction
n-type
Contac ts
Figure 9 Simplified photovoltaic cell in cross-section.
ptype
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A solar cell must also have a layer of antireflective coating (not shown in Figure 9) to improve efficiency because a silicon crystal is so shiny that without this layer many of the photons would be reflected before they could cause the release of an electron. Even so, typical efficiencies of solar cells stand close to 15% and the greatest efficiencies rarely exceed 25%. Finally, the cell must be coated in glass to reduce damage from the elements. A compromise must be reached in the choice of materials used to optimise the performance of the solar cell. By reducing the band gap energy in the semiconducting material, photons with longer wavelengths and lower frequencies may be harnessed to free electrons and holes. Although this may seem desirable and will release more charges, it has the effect of reducing the strength of the electric field across the junction. It turns out that a band gap energy of about 1.4 eV is close to ideal, maximising the current and voltage, and therefore the power, of the cell.
Student Activity 2 Photovoltaic cells

Students can do investigations into the voltage produced by a photovoltaic cell as a function of one of the following: Irradiance . This investigation may be better suited to a qualitative rather than quantitative approach because of difficulties in measuring irradiance accurately. One approach could involve a dimmable light source, another could be to vary the distance from source to cell. Angle of incidence on the solar cell . Use one light source keep the distance constant at, say, 1.0 m in order to keep the test as fair as possible, then vary the angle. Frequency of radiation . This could employ a range of high-powered lightemitting diodes (LEDs) or filters on a white light source. Again, distance and power must be kept constant. Turning this investigation into a look at the inverse square law is another possibility. Best results will be achieved if the laboratory can be blacked out for this investigation.
Light-emitting diodes
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When a diode is forward biased, electrons from the n-type semiconductor may move across the junction and combine with holes in the p-type material. The electrons in the n-type semiconductor move within the higher energy
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conduction band, and as they cross the junction they move briefly into the empty conduction band of the p-type material. Since the lower energy p-type valence band is only partially filled, however, the electrons rapidly fall into an energy level within that valence band. In effect, electrons fall into holes, and as this happens energy is released in the form of emitted photons (Figure 10). For ordinary diodes, these photons have a relatively low frequency and long wavelength, which means that they fall outside the visible spectrum. However, in the construction of LEDs the semiconducting materials may be engineered in such a way as to result in the photons having sufficiently high frequency that they fall within the range of visible light. The frequency of the light emitted from LEDs is controlled by the size of the energy gap between the conduction and valence bands. A bigger gap will result in a larger energy change and, in accordance with the relationship E = hf , a higher frequency of light will be emitted. So, a small energy gap will result in red light and a much larger energy gap is required for green or blue light.
ntype Conduction band (partially filled)
Junctio n
ptype Photons emitted as electrons drop down to valence band
Valence band (partially filled)

Figure 10 In an LED electrons cross the junction from n to p in the conduction band. Once on the p side of the junction, they fall back across the energy gap to the valence band. This releases photons of light.
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Since electrons usually drop from the bottom of the conduction band into the top of the valence band, light from LEDs tends to be nearly (although not completely) monochromatic, with a narrow emission spectrum. To alter the energy gap in an LED, different doping agents are used. They may typically include indium, gallium and nitrogen to produce blue light, gallium and phosphorous for green light, and gallium, phosphorous and arsenic for red light. By using combinations of red, green and blue it is possible to produce any colour of light and this has led to the advent of LED televisions. Furthermore, by varying the proportions of the doping agents, single intermediate colours may also be produced.
Student Activity 3 LED threshold voltage

There is an approximate correlation between the threshold voltage for an LED and its colour, since the energy returned in the form of an emitted photon is approximately the same as the energy required to raise an electron across the energy gap of the material. This can be investigated in a practical, as illustrated in Figure 11.
+ Supply
Figure 11 A practical investigation into the correlation between energy band gaps and colours of LEDs can be carried out. Different colours of LEDs can be put into the circuit and the potential difference required to illuminate them noted. A graph of frequency of light versus potential difference may be plotted.
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Organic light emitting diodes (OLEDs) use organic polymer layers sandwiched between two electrodes. When a voltage is applied across the layers, electrons and holes are generated, which then recombine to emit photons. The layers may be put into a composite of red-, green- and blueemitting sections so as to produce full-colour displays. Further information on this topic can be found here: http://www.chemistry.wustl.edu/~courses/genchem/Tutorials/LED/bands_06.h tm
Why use LEDs?

LEDs have many advantages over other light sources. An LED typically has an efficiency of around 80%. This is far superior even to energy-saving compact lights because of the way in which light is produced. This clearly has major implications for reducing carbon dioxide emissions and fuel bills. Because of the very low levels of undesirable thermal energy produced, LEDs may also be expected to have much greater longevity than conventional light sources. LED and OLED TVs are expensive but with low power usage and high reliability they are set to become more common in future. Infrared LEDs are used in remote controls because of their reliability and low power consumption. Ultraviolet LEDs can be used for detecting counterfeit notes and even for sterilisation procedures. LEDs have extremely fast switching speeds, which means that they are particularly useful for applications where light sources must be pulsed, strobed or simply switched on and off rapidly with reliability. Additionally, they work well at low temperatures, are shock resistant and contain fewer hazardous materials than energy-saving light bulbs.
Summary of pn junctions, LEDs and photovoltaic cells

The interface between p-type and n-type material is called the pn junction. Majority charge carriers diffuse towards the junction and electrons combine with holes, forming ions. This lack of charge carriers results in a depletion zone across the pn junction, with positive ions on the n-type side and negative ions on the ptype side. If the p-type material is connected to the positive terminal of a supply and the n-type to the negative terminal, then the junction is forward biased .
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If the potential difference across the junction is sufficient to force electrons to cross the depletion zone, then the junction will conduct. If the terminals are reversed, the junction is reverse biased and cannot conduct. LEDs emit photons of light as electrons fall from the conduction band of the n-type material into holes in the valence band of the p-type material. The bigger the energy gap between the bands, the greater the energy, and therefore the frequency, of the emitted photons. Photovoltaic cells use the energy of absorbed photons to separate electrons and holes and thus produce a potential difference.
References and further reading

You will find a great deal of further reading on the internet and in specialist electronics books. The following sources are recommended: http://www.chemistryexplained.com/Ru-Sp/Semiconductors.html http://hyperphysics.phy-astr.gsu.edu/hbase/solids/band.html http://www.educypedia.be/education/solarcellanimations.htm and many other linked pages associated with this topic from Hyperphysics. http://en.wikipedia.org/wiki/P-n_junction In addition, for those with a sense of humour, the somewhat eccentric http://britneyspears.ac/physics/basics/basics.htm
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NATIONAL QUALIFICATIONS CURRICULUM SUPPORT

SEMICONDUCTORS AND BAND THEORY (H, PHYSICS)

Learning and Teaching Scotland 2011