You are on page 1of 77

Solar Cells

Basic Device Physics- Fonash Summary important

Lifetime

Flow mechanism

Diffusion

At time t=0

At time t= t1

Forward bias p-n junction


Drift current -no change

Diffusion current- Increases

Equilibrium

Reverse biased p-n junction

Energy band diagram

Definitions
Photovoltaic Energy Conversion: Direct

production of electrical energy in the form of current and voltage in the form of current and voltage from electromagnetic(i.e.,light) energy Electrode: electrical conductor used to make contact with the non-metallic part ( i.e., semiconductor) of the circuit.

Basic Steps
Light absorption process which causes the transition in a material(the absorber) from ground state to an excited state The conversion of the excited state into a free negative and positive charge carrier pair A discriminating transport mechanism which moves the resulting charge carriers in opposite directions The negative charge carrier arriving at the cathode result in electrons which travel through the external electric circuit At anode combining with the arriving positive charge carriers thereby returning absorber to the ground state

Five Basic steps needed for Photovoltaic Energy Conversion

Excited State
Electron hole pair- Step 1 and 2 coalesce

Exciton- Step 1 and 2 are different

Input Energy for Solar cell- Photons coming from

the sun. Input is distributed based on dependent parameters(latitude, time of day, and atmospheric conditions), over different wavelengths. Distribution patterns are called Solar Spectra o()expressed as photons/time/area/bandwidth Standard spectra are needed in solar cell research.

Total Input power PIN per area impinging on a cell

for a given o() is PIN =


Where, h- Plancks Constant c- speed of light Output power POUT = J*V Where, J- Current density V- Operating Voltage

Cross section of Solar Cell

Current density- Voltage characteristic under illumination

Terminologies
Best thermodynamic efficiency of the

photovoltaic energy conversion is given by= Where, As= Solar cell area generating current AC= Area collecting the photons Jmp = Current density at maximum power point Vmp= Voltage at maximum power point Fill factor(FF)= =

Solar Cell Applications


Space energy Terrestrial energy generation generation To increase the use of solar cells we need to increase the figure of merit defined as, = Energy conversion efficiency* lifetime True Costs

Material Properties
Materials used can be solid or liquid

Can be organic or inorganic


Solids can be metals, insulators, semiconductors

and solid electrolytes

Structures of Solids
1.Crystalline- Single crystal materials 2.Polycrystalline- materials with crystallites separated by disordered regions (grain boundaries) Represented by a mathematical construct lattice and a basic building block unit cell. In (2.) grain boundaries influence physical properties like getter dopants, store charge in localized states

Structures of Solids
3.Amorphous- completely lack long-range order Disordered materials containing large number of structural and bonding defects No unit cell and lattice

Phonon Spectra of Solids


Photon- Quantum of electromagnetic radiation

Phonon- Quantum of lattice vibration energy


In thermodynamic equilibrium(TE), the distribution

of phonons among allowed modes of vibration(phonon energy levels, Epn) is dictated by Bose- Einstein statistics Phonons are involved in carrier generation and recombination process Behave like particles Epn= Epn(k), relates the phonon energy Epn to the wave vector k of the vibration modes

Single, micro and multi crystalline solids


In these solids, both energy and momentum must

be conserved in electron- phonon interaction K-selection rule- The change in k- vector will conserve the energy and momentum Only specific values of k are allowed and can be used in Epn= Epn(k) relation gpn(E) dE- density of allowed phonon states in kspace(reciprocal space) per volume between E and E+dE

All the information on the dispersion relation Epn=

Epn(k) is contained in the unit cell of the reciprocal lattice, called Brillouin Zone Phonon energies are of the order of 10^-1 eV compared to photon energies of the order 1 eV

Nanoparticles and Nanocrystalline solids


Surface-volume ratio increases, hence surface

phonon modes become more important doubts

Amorphous Solids
Vibrational modes can extend only over a few

nanometers xk= 2**, implies that phonons in disordered material are not characterized by a well-defined wave vector k and there is no phonon selection rule The concept of gpn(E) is still valid in amorphous solids

Electron energy levels in solids


Born Oppenheimer or adiabatic principle-

Solving Schrodinger equation for single electron problem gives rise to single electron energy levels

Single, micro and multi crystalline solids


As the unit cell in the direct lattice completely

defines the structure, it completely determines the environment of an electron in a crystalline solid The periodicity of the direct lattice ensures that the dispersion relation E=E(k) is periodic in reciprocal space. Only certain k-vectors are permitted to electrons in a crystal ge(E)- density of allowed single particle states per energy per volume

Allowed electron energies versus kvectors


(a)Silicon-indirect gap (b)Gallium Arsenidedirect gap

The highest allowed energy in the valence band is

called valence band edge (Ev) The lowest energy in the conduction band is called conduction band edge (Ec) The energy levels in these bands are single particle states and are de-localized (i.e. extend throughout the crystal) At absolute zero, VB is completely filled and CB is empty

Holes- When electrons gain energy by heat or

photon absorption in VB and move to CB ,the remaining acts like positive particles called holes The number of holes equals the number of vacated states The holes in VB are free carriers and can move in an electric field or diffuse In intrinsic semiconductor, n=p, where n and p are number of electrons and holes per volume in respective bands

If intrinsic material is in TE, n=p=ni , where ni is

intrinsic carries population in TE Electron Affinity()- Energy required to promote an electron from the bottom of conduction band to vacuum at some position x

Energy bands in semiconductor Vs Position

Where, EvL= vacuum energy level Eg = Energy forbidden gap

Localized states
A localized state is represented in the above

energy band diagram by introducing a short horizontal line drawn at its position in energy and space Localized gap states are produced due toSurface in real materials Defects and impurities in bulk Structural and bonding defects in grain boundary regions

Localized states have energies that lie in the

range of the bands and energy gap. Carrier in these states cannot move unless they are moved to delocalized states Drift and diffusion are not possible for carries in these states unless the gap state density is extremely high Gap states can be present to dope a material, supports generation and recombination and can store charge affecting the electric field in a device

Gap states are classified as-

1. Acceptor States- Neutral when unoccupied by an e- and ve when occupied by an e- (ionized) 2. Donor states- Neutral when occupied and +ve when unoccupied by an e3. Amphoteric States- one e- neutral, 0 +ve and 2 ve charged situation

The charge per volume resulting from acceptor-

like states at energy E in the gap depends on whether they have captured an electron and is given by -enT where nT is the number of acceptor states per volume at the energy E that have been successful in capturing an electron. Extrinsic semiconductor- due to doping n =/ p in semiconductor Intermediate band(IB)- Band with energy gap formed by localized states

Excitons* wiki
Multi-particle phenomenon involved in light

absorption process in solar cells Multi-electron solutions i.e. electron bound to a hole via coulombic attraction Binding energy is the energy required to dissociate an exciton in its ground state into an free electron in the CB and a free hole in the VB They are created by photon absorption and can be mobile in a solid When they move energy, and not net charge moves They are not charged so they can move only by diffusion

Nanoparticles and Nanocrystalline solids


doubts

Amorphous Solids
It can contain large number of localized gap

states which are of 2 types1.Intrinsic- arising from distribution of bond angles and interatomic distances These localized states are seen principally near the band edges 2.Extrinsic- arising from defects and impurities These localized states are found in large density in the remaining gap

Since the localized states density is large -

Doping will have little effect on dislodging the

fermi level position Recombination and trapping a severe problem* Transport via gap states is possible but its extent will be less as compared to delocalised states

Comparison of density of states(a)amorphous and (b)crystalline solid

Organic Solids
These are either small -molecule or polymeric

solids The molecular orbital picture is similar to nano crystalline solids Density of the delocalized states is parabolic in single and nanocrystalline whereas for organic materials is expected to have levels within a Gaussian-like envelope

Optical phenomenon in Solids


Absorption process

Free carrier absorption- arises from photoninduced, electron(or hole) transitions within a band from one single-particle state to other It is forbidden in crystalline solids due to kconservation 2. Phonon absorption- Light is absorbed by exciting phonon modes in a material, no electrons involved Occurs in the infrared region of the light spectrum because of low energy absorbed by phonons
1.

3. Photon- induced transitions between states in the gap as well as between gap states and a band 4. Exciton producing absorption- found in organic materials and nanoparticles 5. Band-band transitions 6. Loss observed in some amorphous materials due to electrons hopping from localized state to localized state

Range of optical absorption processes in solids

The absorption coefficient () is critical to solar

performance

G(,x)- function determining the number of

process 3,4 and 5 taking place at x per volume per time per bandwidth where, (,x) is electric field of light of wavelength at point x Ignoring reflection and interference effects, the monochromatic light entering the cell at x=0 with intensity I0 (photons per area per time per bandwidth) is expected to have intensity I(,x)-

I(,x)= I0 () - Beer Lambert Law => - gives the amount of photons lost In direct gap, an electron can be excited from the top of the VB to the bottom of the CB with no change in k-vector Since a photon has k 0 , there is no difficulty in k-vector conservation in electron-photon interaction

In indirect gap material, electrons excited across the gap will change its k-vector. The photon cannot provide the required change so phonon involvement is required. This will be a three body interaction which will the require the conservation of energy and momentum and decreases the absorption coefficient () at and above the fundamental absorption edge This issue for conserving k-vector disappears in nano crystalline solids for 2 reasonsThe constraint of well-defined k vector can disappear for phonons and electrons with confinement. Because of this, nanocrystalline silicon exhibits stronger absorption than its single crystal Amorphous solids contain large densities of localized gap states at the delocalized state band edge. As a result, the absorption edge broadens. Also , due to relaxation of k-vector conservation rule , absorption can be stronger than the crystalline material.

Franz Keldysh effect- A strong electric field can shift the fundamental absorption edges. It allows band-band absorption for h< Eg Due to which the delocalized wave functions leak into the forbidden gap in the presence of a strong electric field Therefore, there is a probability P that a photon can promote an electron at the valence band edge at point x to the conduction band edge at point x The electric field dependence of this probability goes as-

where

and m* is the effective mass

No excitons are involved in this process.

Franz Keldysh effect Photonic structures can be used to exploit the wave behavior of light to shape the (,x)^2 distribution within a solar cell absorber. Only specific values of follows Beer Lambert law for a given structure and undergoes absorption whereas other values of wavelength undergoes reflection and interference

Photonic Structures
Texturing at contacts of a cell with features on the

order of a micron can also lead to light trapping and reduced reflection from the cell This will lead to larger path lengths and hence more absorption The approach becomes problematic for nano particles since their absorber thickness can be of the order of or smaller than, the texturing features required

Plasmonics*
Phenomenon for improving the absorption

process in nano crystalline materials It refers to the cooperative electron oscillations that can be set off by light impinging on nanoscale metal features and re-radiation of light from these features Plasmonic effects can give rise to very strong near fields in the immediate vicinity of the metal features, resulting in greatly enhanced absorption in these volumes Consequently, plasmon scattering can be designed to create an advantageous (,x)^2 distribution and thereby to enhance absorption

Carrier Recombination and Trapping


Excited electrons can come back to its ground

energy level or drop in energy into some gap state without doing any useful work 1.Radiative Recombination- involves emission of photons, no involvement of gap states 2.Schokley- Read- Hall or gap state assisted recombination- involves emission of phonons which involve gap states 3.Auger Recombination- involves transfer of energy to another electron or hole

In thermal equilibrium, there is no applied or

developed voltage, illumination, nor temperature gradient present When additional(excess) carriers are created in a material, as occurs under light or carrier injection (due to biasing), the material is no longer in the state of TE and there is net recombination, where net recombination is defined as recombination minus thermal generation.

Trapping
1. To mean capture by a gap state as part of a series of processes in localized state assisted recombination 2. To mean the act of an electron or hole getting stuck at a localized state Carriers in gap states, whether there due to trapping or passing through in a recombination process, give rise to charge according to the state occupation and to whether the states are acceptor-like, donor-like, or amphoteric

Recombination Modeling
(A) Radiative Recombination

Net radiative recombination traffic(number of free

holes or electrons annihilated per volume per time)or or

In TE,

=0 If a material is p-type and if, even under illumination, p is still essentially po

Where

- electron radiative recombination

lifetime =

(b) Schokley-Read-Hall recombination


The trapping of an electron and trapping of a hole

completes the recombination The net recombination through gap states at energy E can be expressed in a steady state as

If a material is p-type and if, even under illumination,

p is still essentially po, then

is the called the electron S-R-H recombination lifetime or simply the electron lifetime.

(C)Auger Combination
Many types of Auger processes1. Electron falling from CB to VB giving its energy to another electron in CB. 2. Hole forming the electron hole pair and generating another energetic hole in VB counts the single electron states per volume at energy E that are missing an electron and counts the single electron states per volume at energy E that are occupied by an electron

Net Recombination for process 1

Net Recombination for process 2

The strong dependence of the above expressions

on n or p means Auger recombination can become dominant in solar cells at high carrier concentrations

Auger transition processes in solids

Linearized modelsFor p-type materials-

For n- type materials-

Transport
Transport processes in bulk solids

The drift-diffusion model is valid for single crystal

solids In cases of multicrystalline and microcrystalline inorganic solids, the drift-diffusion model is strictly valid within crystals so long as the scattering length is less than the characteristic dimension of the crystal. In polycrystalline materials, intragrain driftdiffusion transport may be in series with injection, recombination, or tunneling processes at grain boundaries.

For nanocrystalline materials, a drift-diffusion

model can suffice by using an effective mobility, which depends on grain size The drift-diffusion approach also works well for amorphous inorganic and amorphous and crystalline organic materials the general expression for n(x), the free electron population per volume in the conduction band at some point in a material system, which is valid even when out of TE, is given by


Where Ac(E-Ec)^(1/2) is a model for the

conduction band density of states ge(E) Current density per volume at some point x,
or

Electron effective force field

Transport in Amorphous solids


Transport in amorphous solids is complex because

current can be carried not only by electrons and holes in the conduction and valence bands, respectively, but also by carriers in gap states; i.e., the gap states may be of a high enough density that they too can support transport in some amorphous materials

The motion of electrons in gap states may often be

best described in terms of their hopping from one site to another

Transport processes at interfaces


(a)- (e)- majority charge carriers,(f)- minority and

majority carriers and (g)- minority carriers

(a) Thermionic emission is a classical process (no tunneling) by which a carrier transfers from an allowed state in one material to an allowed state in another material with ideally no change in total energy. (b) Thermally enhanced field emission is a direct tunneling process by which an electron is transferred from an allowed state in one material to an allowed state in another (c) Multistep tunneling- indirect tunneling. Analogue of hopping in bulk transfer. Since this path does not involve direct tunneling but rather tunneling from one defect to another in the barrier region, it can involve

(d) Field emission- direct tunneling.The field emission current density JFE has a very strong dependence on any changes that take place in the semiconductor band bending, since this modifies the barrier shape and therefore the tunneling probability. (e)Trapping and subsequent emission- an electron in the conduction band at x = 0 is trapped by a localized state at or near the interface and then be subsequently emitted into the metal (f)Interface Recombination- trap-assisted interface recombination (g) Minority carrier injection-

Surface recombination speed model


All transport interfaces are modeled using a linear

model
and Sn and Sp- surface recombination speeds

Coninuity concept
The free electron conventional current density J,(x1)

at some point x1 and the free electron conventional current density at some point x2 (where x2 > x1) must be equal in steady state unless free electrons are (1) gained by photogeneration or (2) lost to net recombination in the region x1 to x2

Mathematical model
J= Jn+ Jp The terminal voltage V produced by the cell at

some operating point while delivering the current density J is given as-

It is valid regardless of whether the cell has an

exciton producing absorber or free electron hole producing absorber. It is valid for all types of cells The sign convention is cathode is assumed to be left hand contact

5 equations and 4 boundary conditions

The quantity Gph(, x) in this set is the

photogeneration function In the case of free electron-hole pair-caused absorption, it is modeled in the numerical simulations by using the Beer Lambert Law