09-09-2016

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Solar Photovoltaics : Semiconductor
Fundamentals

Si Solar Photovoltaic Technology:
Semiconductor Fundamentals

Carriers and Energy

Prof. Paresh Kale
Dept. of Electrical Engineering,
NIT Rourkela.

Electrons in atom

Bohr model of hydrogen atom
3

 Atom is made up of a +ve charged
nucleus and –ve charged electrons

4

 Electron while orbiting a nucleus can have only discrete
angular momentum
Electron

 Electrons orbit around the nucleus

-q

? = ??? = ?ℎ

 Posses negative charge =1.6 X 10-19 C

Where,

 Number of e- in an atom is given by its
atomic number

M = mass of an electron
v = velocity
r = the radius of the orbit
h(bar) = Reduced Planck’s constant = h/2π
n = integer constant = 1,2,3….

r

+q
Proton

 Current: Motion of an electron within a
conductor results in a charge transport
from one point to other

Solar Photovoltaics : Semiconductor Fundamentals

Bohr model of hydrogen atom

Solar Photovoltaics : Semiconductor Fundamentals

Bohr model of hydrogen atom
5

6

 If an electron in hydrogen atom is orbiting a proton in an orbit of stable
radius

 As the radius of an orbit increases, the energy requirement of an electron
to exist in that orbit increases

 Force of electronic attraction (between electron and proton) and
centrifugal force must balance each other

 In any orbit, the energy of an electron = PE (due to electrostatic attraction
with proton) + KE (due to its motion)

 Radii of the orbits quantised

 Total energy of the electron in nth orbit

rn 

4 0 n 
mq 2
2

2

En  

ε0 = permittivity of free space
q = charge of an electron

mq 4
13.6
  2 eV
2(4 0n) 2
n

n  1,2,3....

Higher energy orbits will have larger radii
Solar Photovoltaics : Semiconductor Fundamentals

Solar Photovoltaics : Semiconductor Fundamentals

1

…n-1 Within each shell there are different subshell. 3.. For each shell (energy level) there are n subshells. n 1.in an atom is quantized  Atomic number = 14  14 electrons are distributed in 3 energy levels or shells (n=1 to n=3)  Each shell can have 2n2 energy levels (electronic states) which can occupy 2n2 e-  Quantized levels are orbits  Emission: e.f.1…+l Describes the orbital within a subshell.d.depends Solar Photovoltaics : Semiconductor Fundamentals Pauli’s Exclusion Principle and energy bands Many atom 11  When atoms are brought together to form a solid various interaction occurs between the atom 12 • Splitting of energy levels occurs due the Pauli’s Exclusion Principle (no two electrons can have the same quantum numbers) • As the distance between the atom approaches equilibrium inter-atomic distance for a given material. for instance energy level with n=1 will be referred as shell-1. which are described by momentum quantum number. Spin.p. energy bands forms Electron energy One atom Two atoms Many atoms in a crystal Solar Photovoltaics : Semiconductor Fundamentals Solar Photovoltaics : Semiconductor Fundamentals 2 . 1). Momentum. Different m number for a given l describes the orientation of an orbital. 2. Different values of l describe the shape of sub shells referred as s. For instance the shell 2 (n=2) will have two subshells (l=0.can go from lower energy orbit to higher energy orbit by gaining energy 0 eV its orbital location On angular momentum Orientation Spin Solar Photovoltaics : Semiconductor Fundamentals Energy (eV)  Energy of an e. m -l to +l or -l. -½ Describes the spin of electron in an orbital. which precisely describe all possible energy levels in hydrogen atom Representation of hydrogen atom showing nucleus and various possible electron orbits with associated energy Energy levels in hydrogen atom showing absorption and emission of photons Quantum number Principal.. l 0. -l+1. 1. These energy levels are referred as shells.0.… Describes the energy level within an atom. Each shell can have a total of 2n2 electrons. In a given orbital no two electrons should have the same spin Value Description Solar Photovoltaics : Semiconductor Fundamentals Electronic arrangement of Si atom Solar Photovoltaics : Semiconductor Fundamentals Single atom 9 10  Energy of e.09-09-2016 Discretization of energy levels Quantum mechanics 7 8  The solution of wave equation for a hydrogen atoms results in four quantum numbers.can go from higher energy orbit to lower energy orbit by loosing energy  Absorption: e. 2. Magnetic. s +½ . l.

09-09-2016 Elemental Semiconductors Compound semiconductors 13 II III IV B C (6) Al Si (14) Zn Ga Ge (32) Cd In 14  Elemental semiconductors: Si.e. or other physical processes of interest in solar cells  Each atom forms 4 covalent bonds with the 4 surrounding atoms  Therefore. InP  Ternary semiconductors: AlGaAs. HgCdTe  Quaternary semiconductors: InGaAsP. thus appearing to be a positive charge moving through the crystal lattice. a semiconductor has enough free electrons to allow it to conduct current.gain energy to escape from their bonds. InGaAlP V VI P S As Se Elemental IV Compounds Binary III-V Binary II-VI Sb Te Si Ge As SiGe SiC AlP GaAs InP GaP CdTe CdS ZnS CdSe Solar Photovoltaics : Semiconductor Fundamentals Semiconductor structure .  "generation" and recombination of free carriers (electrons or holes) in response to light shining on the material  Hole: empty space is called a "hole".Si Solar Photovoltaics : Semiconductor Fundamentals Conduction in semiconductors 15 16  Bonded electrons cannot move or change energy. between each atom and its 4 surrounding atoms.allows a covalent bond to move from one e.to another. Ge  Compound semiconductors: GaAs. e.surrounding each atom in a semiconductor are part of a covalent bond  Cannot participate in current flow.  Number of free carriers (electrons or holes) available for conduction  The space left behind by the e.  Band gap  At or close to absolute zero a semiconductor behaves like an insulator. e. absorption.are free to move about the crystal lattice and participate in conduction A covalent bond : sharing an e- Solar Photovoltaics : Semiconductor Fundamentals Solar Photovoltaics : Semiconductor Fundamentals Important parameters of a semiconductor material for solar cell operation Conduction in semiconductors 17 18  At room temperature. has a positive charge Solar Photovoltaics : Semiconductor Fundamentals Solar Photovoltaics : Semiconductor Fundamentals 3 . 8 electrons are being shared  At elevated temperatures. not "free" at absolute zero temperature  Each atom is surrounded by 8 e The e. i.

g. Ge High absorption probability Low absorption probability In the indirect band gap semiconductor. k (also know as E-k diagram) a different scenario emerges • Direct bandgap : excitation of carrier requires change in energy • The wave vector is related to the wave function of an electron in an infinite lattice and represents the electron momentum in the lattice. there is still large number of electrons that get excited to occupy conduction band 23  Light to heat conversion  Light to photo-voltage conversion  Separation of opposite charges results in potential difference Continuous band gap Metal Separated band gap Semiconductor Insulator Solar Photovoltaics : Semiconductor Fundamentals Direct and Indirect band gap semiconductors Solar Photovoltaics : Semiconductor Fundamentals Direct and Indirect band gap semiconductors 24 25 • Plot energy ert wave vector or propagation constant.and hole can participate in conduction e-  For an operation of a semiconductor. only valence electrons play role as they can be perturbed easily by small electrical or optical signal. • Eg: GaAs.is bound. is basic to the operation of electronic devices High energy state Ec Eg Low energy state Ev Distance  y-axis of is energy while the x-axis is distance Solar Photovoltaics : Semiconductor Fundamentals Metal – Nonmetal . the conduction band minima does not exist exactly below the valence band maxima in the E-k diagram Solar Photovoltaics : Semiconductor Fundamentals Solar Photovoltaics : Semiconductor Fundamentals 4 . an electron can have 0.Semiconductor Solar Photovoltaics : Semiconductor Fundamentals Principle of Solar Thermal Vs Solar PV 22     Material band gap that determines its conducting properties Metals are re good conductor of electricity Eg for an insulator is quite high e. 5 eV for diamond Due to very large band gap the number of thermally excited electron will be negligible in insulators and therefore insulator materials do not conduct current  Si has a band gap of 1. and cannot participate in conduction Vacuum  Carriers : electron and hole High energy state Ec  The electron cannot attain energy values intermediate to these two levels  Band gap: Minimum energy required for transition from valence band to conduction band 20  both e. while drawing an energy band diagram of a semiconductor only valence band and conduction bands are shown Low energy state Ev  The number and energy of these free eparticipating in conduction.0259 eV energy  Though the band gap of semiconductors is still very high as compared to the electron’s room temperature energy. CdTe • Indirect bandgap : excitation of carrier requires change in energy as well as momentum • Eg: Si. Eg  For this reason.12 eV  At 300K.09-09-2016 Band gap Energy band model Energy 19  Conduction Band: When gains enough energy to participate in conduction (is "free")  Valence Band: When the e.

two particles (photon and phonon) are involved in generation and recombination of electrons  Si solar cell = 200 to 300 µm  GaAs.29 ? 1019 ? 300 2. CdTe = 1 to 3 µm  Due to this both generation and recombination is less probable in indirect band gap semiconductor Solar Photovoltaics : Semiconductor Fundamentals Solar Photovoltaics : Semiconductor Fundamentals Intrinsic Carrier Concentration (ni) 28 29 Solar Photovoltaics : Semiconductor Fundamentals  Intrinsic Semiconductor material: with NO impurities added to it in order to change the carrier concentrations  Intrinsic carriers are the electrons and holes that participate in conduction  No. and how to maximize it Solar Photovoltaics : Semiconductor Fundamentals 31  At 300 K the generally accepted value for the intrinsic carrier concentration of Si is 9.3 x 109 cm-3 Solar Photovoltaics : Semiconductor Fundamentals 5 . which will increase the intrinsic carrier concentration. increasing the temperature makes it more likely that an electron will be excited into the conduction band.  This translates directly to solar cell efficiency  The concentration of these carriers affect conductivity  Knowledge of intrinsic carrier concentration is linked to our understanding of solar cell efficiency. of carriers depends on  band gap of the material  temperature of the material  A large band gap will make it more difficult for a carrier to be thermally excited across the band gap.65 x 109cm-3  A formula for the intrinsic carrier concentration in Si as a function of temperature is given by Misiakos ?? ? = 5.09-09-2016 Direct and Indirect band gap semiconductors Impact of band-gap nature on Solar Cell 26  Since k axis represents electron momentum. instead of one particle (photon). excitation of an electron from valence band to conduction band not only requires 27  Both direct and indirect band gap semiconductors are used for solar cell application  absorption of photon  absorption of phonon  A phonon is particle of low energy and high momentum and is related to lattice vibration  Thicker layer of indirect band gap semiconductor is required to absorb complete solar spectrum as compared to direct band gap semiconductor  Phonon absorption is required from the point of view of conservation of momentum  Typical thickness of commercially available  In indirect semiconductors.54 ??? −6726 ?  For solar cells ni is usually measured at 25 °C and is 8. and therefore the intrinsic carrier concentration is lower in higher band gap materials Carrier Concentration in semiconductors Solar Photovoltaics : Semiconductor Fundamentals Intrinsic Carrier Concentration Intrinsic Carrier Concentration of Si as a Function of Temp 30  Alternatively.

g. Al) Bonds Excess Electrons Missing Electrons (Holes) Majority Carriers Electrons Holes Minority Carriers Holes Electrons Ec Ed Ed Eg Ev T = 0K Donation of e- T  50K from donor level to conduction band Solar Photovoltaics : Semiconductor Fundamentals Solar Photovoltaics : Semiconductor Fundamentals 6 . Boron.g. Technique used to vary the number of electrons and holes in semiconductors Acceptor atom in the covalent bonding model of a Si crystal h+ Al Si Solar Photovoltaics : Semiconductor Fundamentals P-type Si Solar Photovoltaics : Semiconductor Fundamentals N-type Si 34 Ec  N-type materials increase the conductivity of a semiconductor by increasing the number of available electrons Eg Ea 35  Doping creates N-type material when semiconductor materials from group IV are doped with group V atoms (Penta valent) Ea Ev T  50K T = 0K e- P Donor atom in the covalent bonding model of a Si crystal Si Acceptance of a valence band electrons by an acceptor level and the resulting creation of holes Solar Photovoltaics : Semiconductor Fundamentals N-type Si Solar Photovoltaics : Semiconductor Fundamentals Doping 36 37 N-type (negative) P-type (positive) Dopant Group V (e. Phosphorous) Group III (e.09-09-2016 Doping P-type Si 32 33  P-type materials are created when semiconductor materials from group IV are doped with group III atoms (trivalent)  P-type materials increase conductivity by increasing the number of holes present.

09-09-2016 Equilibrium Carrier Concentration Law of mass action 38  Equilibrium carrier concentration: The number of carriers in the conduction and valence band with no externally applied bias 39  Law of Mass Action: At equilibrium. the product of the majority and minority carrier concentration is a constant ???? = ??? ni = intrinsic carrier concentration n0 and p0 = electron and hole equilibrium carrier concentrations  The equilibrium carrier concentration can be increased through doping.0  1016 2 p0  Solar Photovoltaics : Semiconductor Fundamentals 7 .  For majority carriers. What will be the minority hole carrier concentration (po) at room temperature? n0 p0  ni Solar Photovoltaics : Semiconductor Fundamentals 40 2 The electron concentration corresponding to 11016 P atoms/cm3 doping is equal to ND: no= 11016 #/cm3 intrinsic carrier concentration for Si. ni = 1.51010 #/cm3 the minority carrier concentration (po): ni (1. the majority and minority carrier concentrations are given as: ? ????: ?? = ??.  Using the Law of Mass Action above.25  104 # / cm3 n0 1. ?? = ???/?? ?? = ???/?? ND = Concentration of donor atoms NA = Concentration of acceptor atoms Equilibrium carrier concentration = intrinsic carrier concentration + number of free carriers added by doping No.5  1010 )2   2. of minority carriers decreases as the doping level increases Solar Photovoltaics : Semiconductor Fundamentals A Si sample is doped with 11016 P atoms/cm 3. ? ????: ?? = ??.