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# Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Electronic Properties of a semiconductor heterojunction determined by: Energy Gaps Electron Affinities Doping Types & levels. Straddling Gap Broken Gap

Offset Gap

Egap,1

C Bands EC EV V Bands

C Bands EC

C Bands EC

Egap,2

Egap,1

Egap,2

Egap,2
EV

EV V Bands

Egap,1

V Bands

(a)
CB & VB edges of one lies within the energy gap of the other. Eg1>Eg2. Electron affinity of the small gap material slightly larger than the wider gap material. Eg1-Eg2>2- 1>0 E.g.: AlAs-GaAs

Eg1~Eg2. Electron affinities different, and the difference is less than either band gap. 2> 1>0 Both Band Edges of one SC lies above both Band Edges of the other. Portion of band Gap over lap at the interface. E.g.: InSb-InP

(b)

(c)
Extreme difference in Electron affinity . Band gaps do not overlap. VBE of one lies above the CBE of Other. One SC has narrow band gap. E.g.: InAs-GaSb

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Important consideration is the Energy of the Band Edges. Some simple rules: Linearity: The intrinsic energy gap and band edge positions do not change on joining 2 semiconductors. On joining, the band edge discontinuity can be determined. Mathematically the linearity principle is: Ev=Ev(A)-Ev(B) Valence Band Offset EC=EC(A)-EC(B) Conduction Band Offset Transitivity: If you know the discontinuity between any two semiconductors and a third one, the discontinuity between the first two can be inferred. Ev(A:B) + Ev(B:C) + Ev(C:A) = 0 Common Anion Rule: When the anion is common, the change in CBE is greater than the change in VBE across the semiconductor heterojunction. EV < EC Common Cation Rule: When the cation is common, the VBE scales with the anion electronegativities. E.g., VBE of Phosphides will be below Arsenides which will be below Antimonides. EV(CA1)<EV(CA2))<EV(CA2) where C is cation, A1, A2 & A3 designate 3 anions

## Semiconductor Heterojunctions Electron Transport

Data used in drawing the figure Compound n-AlAs P-GaAs Electron Affinity 3.56 eV 4.07 eV NA(GaAs)~ND(AlAs) Energy Gap 2.16 eV 1.42 eV

## Sketch a Band edge diagram

1) 2) 3)

Mark a vertical line on a page to indicate the junction & a horizontal line to indicate flat-band vacuum level. Mark the band edge positions on the vertical line using electron affinity & energy band gap values for the 2 semiconductors. These are doping independent & fix the band edges. Draw a horizontal dashed line indicating the Fermi level at equilibrium tricky & important determines how band bending is distributed. Far from the junction, mark the band edges relative to the Fermi level depending on doping. Connect the band edges far from the junction to the band edges in Step 2. Requirements for this are: Slopes of the connecting segments must match where they intercept the points in Step 2 satisfy electron continuity. Energy gaps must be constant on each side of the junction. Depletion widths are fixed by the doping levels.

D is the potential energy difference associated with band bending. DA + DB = EF or the contact potential which is the difference in Fermi energies of the semiconductors before contact.

## Semi-conducting & Magnetic Materials

Diffusion & Drift of Carriers
Carrier motion in a chemical potential gradient Thermodynamics deals with driving force for particle movement the potential energy of a particle at a given position.

Real particles move to lower their chemical potential. Charged particles in an electrical field move according to their electrostatic potential. Large particles in a gravitational field move to the center of mass. Particles placed in a concentration gradient move from high concentration to low concentration (diffuse).
Once the chemical potential of a particle is known, its motion can be easily described. When 2 systems interact exchange matter or energy equalization of chemical potential equilibrium. Fermi level gives a measure of the chemical potential of the lowest energy free electron or the highest energy free hole.

## Semi-conducting & Magnetic Materials

Diffusion & Drift of Carriers
The force, F, on a particle is through the corresponding gradient in the chemical potential, :

F = C

d dx

(1)

Where C is a constant. Let us consider a specific particle the electron. The force on a electron due to the chemical potential gradient produces a current density, J:

d J = qn n dx

(2)

n is the electron mobility & is the chemical potential of the electron. Let us consider the electron chemical potential gradient due to electric fields & concentration gradients. The general chemical potential gradient in the system is given by:

d k BT dn dV = dx qn dx dx

(3)

## Semi-conducting & Magnetic Materials

Diffusion & Drift of Carriers
The general chemical potential gradient in the system is given by:

d k BT dn dV = dx qn dx dx
Change in concentration, n, in the absence of an electric field

(3)

## Substituting into (2):

k T dn d dn B J = qn n = qn n + E = n k T + qn nE dx qn dx B dx
Using Einstein relation between diffusivity & mobility:

}
D=

k T
n B

}
Voltage (potential) gradient at constant concentration of electrons electric field.

(4)

(5)

## Semi-conducting & Magnetic Materials

Diffusion & Drift of Carriers
The standard form for the current density:

J = qD

dn + q nE n dx

(6)

## Current due to concentration.

Diffusion Current

## Both related to the chemical potential gradient

}
Current due to the electric field.

Drift Current

## Semi-conducting & Magnetic Materials

pn junction

N-type there is higher concentration of electrons energies close to CBE (high chemical potential) P-type there is empty states near the VBE & having low chemical potential for electrons. On contact, electrons are free to flow - Electrons drift and diffuse across a junction between unlike materials. Large concentration gradient across the junction electrons diffuse from n-type to p-type, leaving positively-charged donor dopants atoms behind. The residual electric potential resulting from carrier diffusion presents a barrier to further electron motion in one direction fundamental of diode behavior.

## Semi-conducting & Magnetic Materials

Energy Bands in Crystalscontd. pn junction C.B.

V.B.

C.B.

V.B.

Difference in Fermi Energies before contact establishes a band bending edge and a contact potential Vbi after contact.

## Semi-conducting & Magnetic Materials

Energy Bands in Crystalscontd. pn junction

Band diagrams for (a) n-type whose surface is negatively charged (b) p-type whose surface is positively charged. Assume that the surface of an n-type SC has somehow been negatively charged will repel the free electrons near the surface leaving +vely charged holes behind. Any electron that drifts towards the surface feels this repelling force. Far fewer free electrons at surface compared to the interior depletion region is a potential barrier for electrons.

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
The Junction Contact Potential
Diffusion of charged species build up of electrostatic potential opposes further diffusion of electrons. Initial difference in chemical potential of the electrons on the 2 sides of the junction decreases goes to zero diffusion stops. Result is: Accumulation of positive charge on the n-side & negative charge on the p-side gives rise to electric field at the junction whose magnitude is given when J=0

k T dn d dn B J = q n n = qn n + E = n k T + q n nE dx qn dx B dx
dn J = qD + q nE n dx
Solving for E:

ln n / n E= qn n p
B

k T

(7)

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Integrating across all x in the electric field:

V =
bi

k T
B

ln n / n n p q

(8)

Vbi is the built-in voltage or the contact potential across the junction, nn & np are the electron concentrations on the n & p sides of the junction respectively. For a shallow dopant at high temperature, nn~ND where ND is the donor concentration on the n-side. Likewise, np=ni2/pp or

n =
p

N N
C

E gap / k BT

A
(9)

N N E gap / k BT E N N gap = ln n = ln A D e + ln A D n NC NV k BT NC NV p n

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Putting (9) in the expression for Vbi (8):

N N qV = E + k T ln A D bi gap B NC NV
Vbi is zero if both sides are undoped and increases with NA and ND.

(10)

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Heterojunctions as Diodes P-type N-type

Forward Bias: A forward applied bias will reduce the potential between the layers, narrow the depletion region & lower the barrier for carrier injection (by diffusion) across the junction. The band-gap discontinuities have opposite sign -one is step upward, other is step downward, -electrons emitted into the GaAs will have a much lower barrier to overcome than holes injected from GaAs into the AlAs. Most of the forward diffusion current will be carried by electrons. Reverse Bias: Current is from thermally generated carriers reach depletion region swept into the AlAs. Larger energy gap of AlAs relatively few minority carriers & drift from AlAs to GaAs.

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Bipolar Junction Transistor
Began the microelectronics revolution. Consists of 2 diodes joined back to back by a thin semiconductor layer (the base). p-n-p or n-p-n depending whether the common base is n-type or p-type. Consider a n-p-n bipolar junction transistor (BJT): The 1st n-p junction is Emitter-Base. The 2nd p-n junction is Base-Collector. On turning it on, the emitter junction is forward biased. Electrons are injected into the Base & holes into the Emitter. The holes in the base recombine & have no function. The electrons emitted into the base can recombine or travel. If base is thin, most of the electrons pass through it - reach the reverse biased collector junction & accelerated into the collector. As long as the time required for the injected electrons to diffuse through the base is < minority carrier lifetime, the transistor will permit more current to flow E C than E B

Gain, =

i i

icollector

ibase

b t If base is wider than mfp between collisions, carrier must diffuse across the base. Minority Carrier Devices. High gain by high n & low t ie high carrier mobility. This requires high quality materials, low doping & no defects. GaAs has higher electron mobility than Si high n-p-n speeds.

## Semi-conducting & Magnetic Materials

Semiconductor Heterojunctions
Field Effect Transistor
Different from BJT. Current flow by majority carriers. Continuous current path of one conductivity type. E.g., 2 heavily doped n-type regions in a lightly doped p-type substrate. Short p-type region between the n-type regions. The heavily doped n-type regions are called: (a) Source (from where the electron flow) (b) Drain (into which the electrons drain). (c) Gate controls the current. Device is normally off. Conduction is enhanced by applying a negative gate bias relative to the source creates a n-type channel. Source-drain voltage adds to it. Increasing bias voltage provides a wider channel lowers resistance. Speed of FET - depends on time it takes for electrons or holes to transit the channel. Smaller channels shrinking devices faster PC!

MISFET or MOSFET

## Semi-conducting & Magnetic Materials Photovoltaics

Concept of converting light to electricity possible by the discovery of The Photoelectric Effect in 1839 by Edmond Becquerel First commercial solar cell crystalline Si in 1954 of 4%. Over the next 50 years, has gone to 25% close to the theoretical of 31%. Typical commercially available PV cell is at of 17%. Photovoltaic Devices - conversion of radiant Solar Energy into Electrical Energy. Amount of Electrical Energy consumed annually ~ 1,000 GW Terrestrial installed capacity ~ 1GW i.e. 0.1% - growing 40% per year. Each PV module can produce 1 kW. Total Solar energy falling on the Earths surface annually is huge 10,000 times the annual consumption. Objective of a PV cell capture as much of solar energy & convert into Electrical Energy.

## Semi-conducting & Magnetic Materials

Photovoltaics
Si ribbon 3.0% Amorphous Si 4.0% CdTe 2.7% CIGS 0.3% Other Crystalline Products 6.0%

## Single Crystal Si 38.0%

Poly-Crystalline Si 46.0%

## Semi-conducting & Magnetic Materials

Photovoltaics
Solar radiation wide spectrum of wavelengths. Atmospheric gases will absorb certain wavelengths. Shift in the spectral distribution will effect the efficiency of absorption of solar radiation. Additionally, all semiconductors will display cut-off wavelength dictated by its energy band gap. Need to specify the atmospheric absorption when quoting efficiency as: Depth of atmosphere that solar radiation has passed through will affect: Spectral distribution & Total amount of energy.

Atmospheric absorption measurement is Air Mass (AM) which is: Zero for solar radiation outside the atmosphere AM 0 & One for radiation reaching the ground when sun has reached its zenith AM 1
For space application (e.g. satellites), AM 0 1353 W/m2 & for terrestrial application AM 1.5 925 W/m2 - solar angle of 45

## Semi-conducting & Magnetic Materials

Photovoltaics
Si is not the ideal PV semiconducting material Indirect Band-Gap. Optical absorption is not efficient since we have Phonon scattering & emission With Photons. Therefore thickness of Si required to absorb 90% of sunlight (photons above the band-gap) is ~ 125 m, while for a Direct Band-Gap Semiconductor, GaAs, it is 0.9 m. So, why Si? it is the 2nd most abundant element cost is the issue. And? Since PV cell is a Semiconductor Device & Si technology is mature manufacturing integration is well established again cost! In 2008, PV is estimated to be a \$17B industry & growing 30-40% annually. Most importantly, clean energy with Free input source Sunlight.

## Semi-conducting & Magnetic Materials

Photovoltaics
Thermodynamic calculations show that solar energy conversion efficiency can be maximum 85%, while single band-gap thermodynamic efficiency is ~ 44% assuming blackbody radiation; PV cell limits are ~ 31% due to a number of factors: Refractive index, shape of solar cell, realistic solar spectrum, concentration and recombination effects. The main reason Single junction PV cell limits are around 31% is that they do not absorb a significant fraction (~ 20%) of the photons in the solar Spectrum below the band-gap the photons are simply lost.

## Significance of Eg for PV application.

Semiconductor is assumed to be opague for Photon energies > Eg & transparent for Photon energies < Eg

## Semi-conducting & Magnetic Materials

Photovoltaics
For space application (e.g. satellites), AM 0 1353 W/m2 & for terrestrial application AM 1.5 925 W/m2 - solar angle of 45
Simple PV cells are homojunction diodes convert light to electricity. Electron- Hole pairs are created by absorption of light & they are separated by the built-in voltage of the junction. They are similar to and opposite in functionality of Light-Emitting Diodes.

## Semi-conducting & Magnetic Materials

Photovoltaics

Absorption of light can occur on both sides of the junction creating minority carriers that can diffuse towards the junction. -If there is no recombination, a photocurrent can be generated. -The junction is shallow & absorption will occur on one side -where there is greater depth of absorbing material. - In the dark, no current is created. -When light impinges on the PV device, current flows through the wire from the -p-type side to the n-type side as in conventional current.

Photovoltaics

## Heterojunction p-n devices

Two semiconductors different Band-Gaps. Wider Eg - less absorption. Why?

Photovoltaics

## Heterojunction p-n devices

Two semiconductors different Band-Gaps. Wider Eg - less absorption. Why? Narrower Eg absorption layer Absorption characteristics of this layer determines the maximum absorption possible.

## Semi-conducting & Magnetic Materials

Photovoltaics Heterojunction p-n devices

## Semi-conducting & Magnetic Materials

Photovoltaics

Ideal J-V characteristics for a PV cell with Js = 30 mA/cm2. Shaded area = Maximum extracted power. JS is saturation current reverse bias qV / k T zero illumination. B q is charge on carrier s L V is applied voltage kB is Boltzmanns constant T is temperature of cell JL is photogenerated current.

J = J e

1 J

## Semi-conducting & Magnetic Materials

Photovoltaics

qV / kBT 1 J L J = Jse

Ideal J-V characteristics for a PV cell with Js = 30 mA/cm2. Shaded area = Maximum extracted power. In the ideal cell, JL is the short-circuit current shown as JSC. Power extracted (JV) lies in shaded area ie, (+V J) quadrant. Load determines operating point. Maximum Power at the operating point is given by the largest JV area.

## Semi-conducting & Magnetic Materials

Photovoltaics qV / k T

J = Jse

1 J L

Ideal J-V characteristics for a PV cell with Js = 30 mA/cm2. Shaded area = Max extracted power.

## k BT qVm k BT Em ln1 + Pm = I L VOC = IL q k BT q q

Em is max energy that can be extracted / photon depends on band parameter of absorber layer this determines VOC and Vm.

## Semi-conducting & Magnetic Materials

Photovoltaics qV / k T

J = Jse

1 J L

## k BT qVm k BT Em Pm = I L VOC ln1 + = IL q k BT q q

2 Fundamental parameters that will limit the Efficiency of the PV cell:

Fraction of Solar photons absorbed by the PV cell. Electrical energy created by the photon.

Photovoltaics

## Fraction of Solar photons

Calculate by integrating over the solar spectrum for the appropriate AM number - include the cut-off wavelength of semiconductor absorber layer.

abs =

n ( E ) dE
g

n ( E ) dE
0

Photovoltaics

## Fraction of Solar photons absorbed by the PV cell.

Calculate by integrating over the solar spectrum for the appropriate AM number - include the cut-off wavelength of semiconductor absorber layer.

abs =

n ( E ) dE
g

n ( E ) dE
0

Photons with Energy < Band-Gap will not be absorbed & will not contribute to the Photocurrent. Maximum energy that can be extracted with a CdTe solar cell with a band-gap of 1.45 eV.

## Electrical energy created by the photon.

Units?

Photovoltaics

Implies that not all of the photon energy will be converted into electrical energy even if one photon absorbed constitutes one minority carrier crossing the junction. Electrical energy per carrier is given by Em, so the maximum power of the device = absorption rate of photons x mean electrical energy created per photon. This is shown by the inner shaded area. Ideal value of Em will track the band-gap. Narrower Eg materials larger proportion of photons absorbed, but less electrical energy per photon.

## Semi-conducting & Magnetic Materials

Photovoltaics
Efficiency versus Eg Optimum Efficiency for semiconductors in the near-infrared region, around 1.5 eV. Compromise between (1) Absorption of solar radiation & (2) Transfer of optimum amount of energy/photon to electrical energy. Max Efficiency (~30%) for Si, InP, GaAs & CdTe. Reality much less: Optical reflections, poor junctions, carrier recombination. Ideal efficiency against band-gap energy for single-junction cell for AM 1.5 radiation.

## Semi-conducting & Magnetic Materials

Photovoltaics
Materials issues: Single crystal vs polycrystalline films Multiple junctions better costly. Absorber coefficient Contact resistance Raw materials costs Toxicity of process gases? Stability of materials & junctions. We shall discuss only terrestrial applications.

Ideal efficiency against band-gap energy for single-junction cell for AM 1.5 radiation.

Photovoltaics

Photovoltaics

## Semi-conducting & Magnetic Materials

Energy Bands in Crystalscontd. Table 1. Chemical Composition of Commercial LEDs. Color Blue Green Yellow Orange Red Infrared Wavelength (nm) 470 556 578 635 660 or >700 Composition In0.06Ga0.94N GaP GaP0.85As0.15 GaP0.65As0.35 GaP0.40As0.60 Al0.25Ga0.75As GaAs

## Semi-conducting & Magnetic Materials

Photovoltaics Si PV

>80% of PV is Single Crystal or polycrystal Si drawback is that it is an Indirect Band-Gap Semiconductor lower absorption. Si absorption coefficient ~ 2 x 103 /cm, for CdTe it is 1 x 105 /cm ~ 17% Need thicker material to absorb Photon Energy > Eg Polycrystal Si random grains of size 1 cm loss of photogenerated charge at the g.b - ~ 15%

Photovoltaics

Si PV

CdTe PV

## Semi-conducting & Magnetic Materials

Photovoltaics

III-V Multi-junction PV

## Semi-conducting & Magnetic Materials

Photovoltaics
Anti-reflection Coating, eg, ZnO:Al GaInP2, Eg1 = 1.9-2 eV visible light GaAs, Eg2 = 1.42 eV red to infrared Ge substrate, Eg3 = 0.67 eV Metal contact Eg1 > Eg2 > Eg3 Triple junction PV cell Ge substrate, Narrow bandgap absorber to capture the radiation that passes through the GaInP2/GaAs cell.

## Semi-conducting & Magnetic Materials

Photovoltaics

III-V Multi-junction PV

CuInxGa1-xSe2 PV

Photovoltaics

Photovoltaics

Photovoltaics

## Semi-conducting & Magnetic Materials

Photovoltaics
Anti-reflection Coating, eg, ZnO:Al Eg1= 2.583 eV

## Semi-conducting & Magnetic Materials

Photovoltaics
Band-Gap Engineering InxAl1-xN
y = 0.0532x + 0.7 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 0.0 0

## Energy Band-Gap (eV)

15% Al
20 40 % Al 60 80 100

## Semi-conducting & Magnetic Materials

Photovoltaics
Band-Gap Engineering GaAsxP1-x
2.5 Energy Band-Gap (eV) 2 1.5 y = 0.0084x + 1.42

9.524% P
1 0.5 0 0 20 40 %P 60 80 100

## Semi-conducting & Magnetic Materials

Photovoltaics
Band-Gap Engineering GaxIn1-xP
2.5 Energy Band-Gap (eV) 2 1.5 1 0.5 0 0 20 40 % Ga 60 80 100 y = 0.0092x + 1.34

17.4% Ga

Photovoltaics

Photovoltaics

Photovoltaics

Photovoltaics

Photovoltaics

## Semi-conducting & Magnetic Materials

Misfit Dislocations

## Semi-conducting & Magnetic Materials

Misfit Dislocations

## Semi-conducting & Magnetic Materials

Energy Bands in Crystalscontd.