Photovoltaics: basics and Recent Advances

Prof. Abdelkader OUTZOURHIT

Prof. Cadi Ayyad University
Affiliated Prof., MSN, UM6P

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 Outline
• Basics Photovoltaic
• P-N junction

 I-V characteristic of a P-N junction in the dark

 Processes in a solar cell and I-V characteristics

• Classification of solar cell technologies
• State of the art
 1st generation technologies
 2nd generation technologies
 3rd generation
• Losses in Single Junction Solar cells and the SQ limit
• Tandem/Multi-junctions
• Recent developments
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 Let’s make a solar cell together!!!
1. What is solar energy? (Specify the various forms of Energy)

2. How is solar energy measured? Irradiance and Irradiation

3. What is the spectral range of solar light?

4. What is the relationship between Photon energy and light wavelength l in vacuum? ( Planck constant h = 6.63 x
10-34 [J•s]; speed of light c = 2.998 x 108 [m/s];

5. What is the relationship between Photon flux Fp(photons/m2/s) and irradiance Gi ?

6. What is the photon stream/flux hitting a material receiving monochromatic light of 1 W/m2

7. What is the total Photon flux Fp(photons/m2/s) incident on the surface in the case of wite light (assume a
spectral irradiance Gl(l) of the light ?

8. To what forms can Solar energy be converted to? How?

9. What happens to the light when it is incident on a material? (specify the processes..)
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 Let’s make a solar cell together!!!
8. What is the Difference between internal and external photoelectric effect?
9. Among these materials, in which the process the photo generation of free carriers by solar light can take place and
why? Compare energy of photons with binding energies of valence electrons in the solids(energy needed to eject an
electron from a bond)
Metal? (estimate the concentration of free electrons..), Insulator? Semiconductor?
10. Illustrate this using the bonding picture in Silicon (group IV) and the band diagram picture
11. What would happen to the photo-generated free carriers in the semiconductors? (state some eventualities)
12. How will the photo-generated carrier will move in the semiconductor? (driving force?)
13. How can we separate specially the photo-generated carriers?
14. Propose an Architecture of Solar cell
15. What will be the Thickness of the absorber/and the other layers? Why?
16. Why do we need metallic contacts?

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 Photovoltaics Basics
Photovoltaics: Direct energy conversion of light (solar radiation, artificial light) into electricity
Structure of a photovoltaic cell: absorber (semiconductor) + functional layers
Active layer: Absorber Exciton
Absorber (Active layer)
ETL Functional layers(carrier selective layer)
HTL
• HTL: Hole transport layer
FSF BSF • ETL= Electron Transport
hn > Eg P-type Si
N+ P+ FSF: Front surface electric field
BSF: back surface field
Contacts
Front Contact Bak Contact Photo energy
hn > Eg
- +
Iph
V
Load

Basic steps in PV conversion

 Absorption of Photons in the absorber (hn >Eg )
 Photo-generation of electron/hole (bound) pairs (excitons) and their dissociation
(Exciton binding energy in Si: Eb=10 meV while kT=25 meV at 300 K)
 Diffusion (or drift) of photo-generated electrons and holes(Driving force?)
 Separation and collection of the charge carriers Green BEE SAP+D UM6P 5
 p-type and n-type Silicon

N-type
p-type Silicon Electrons are majority charge carriers
Holes are majority charge carriers Intrinsic Silicon

Free Free
e- e-

Phosphorous (Donor,
Boron ND)
Aceptor

pi=ni=1010 cm-3
n=ND=1016 à 1017 cm-3
pn=n2i/n=103 à 105 cm-3
- Why do we intentionally dope
p=NA=1016 à 1017 cm-3 • n+, n++ (1019 cm-3)
np=n2i/p=103 à 105 cm-3 semiconductor?
• p+, p++ : doping level 1019 cm-3
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 Origin of the FSF and BSF: P-N junction
Contact between a p-type
Free Free
Free and n-type Silicon e- e-
h
Boron Phosphorous
Aceptor (Donor, ND)

Diffusion of majority carriers

near the junction
Progressive appearance fixed charges and of an internal E-field:
Progressively blocks diffusion of majority carriers (electrons
from N to P and holes from P to N
• Internal Electric field doesn't block
At equilibrium
the minority carriers
 Drift current (minority carriers) = diffusion current of
• Electrons can cross from P to N
majority carriers
and holes from N to P (drift))
 Internal electric field near the junction Ei from N to P
 Or a potential barrier (about 0.6 V to 0.7 V for Si) for
• Use Poisson’s equation?? and
majority carriers
charge neutrality to get the Width
 Space charge (Depletion) region: 100 nm (compare to
of the Space charge region and the
thickness of absorber 150 to 200 mm
width of each region
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7
 I-V characteristic of a P-N junction in the dark
Biased PN Junction in the dark +
• When the junction is reverse-biased (V=VP-VN <0): only minority
carriers can cross the junction  saturation current (Io) IDiode V

60
• For forward-bias, V=VP-VN >0, the potential barrier is lowered 

Current(mA)
40
_
injection of majority carriers (electrons from N to P and homes from P
to N)

20
• Current flows from P to N and increases exponentially with voltage

-0.5 0.5
Voltage(V)

-20
-40
V

-60
𝑞⋅𝑉 Ideal diode equation
𝐼𝑑 = 𝐼0 ⋅ (exp −1
𝑘𝑇 𝐼0 (𝐼s ): Saturation current)

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 2 4,003

He

1
Groupe
1A
1.008
Semiconductors for photovoltaics 5
3A
10,81 6
4A
12,01 7
5A
14,01 8
6A
15,99 9
7A
18,99 10
Hélium
20,18
1s2

H B C N O F Ne
1s 22s 22p1 1s 2 2s 22p2 1s 2 2s 2 2p3 1s 22s 22p4 1s 22s 22p5 1s 22s 22p6
1s 1

1 Hydrogène 2A numéro atomique masse atomique Bore Carbone Azote Oxygène Fluor Néon
3 6,939 4 9,012 4 9,012 13 26,98 14 28,09 15 30,97 16 32,06 17 36,45 18 39,95

Li Be Be Al Si P S Cl Ar
1s 22s 1 1s 22s 2 structure électronique 1s 22s 2 symbole solide artificiel (Ne)3s 23p1 (Ne)3s 2 3p2 (Ne)3s 23p3 (Ne)3s 23p4 (Ne)3s 23p5 (Ne)3s 23p6

Lithium Beryllium Beryllium liquide 2B Aluminium Silicium Phosphore Soufre Chlore Argon
2 11 23,00 12 24,31 nom gaz 30 65,38 31 69,72 32 72,59 33 74,92 34 78,96 35 79,91 36 83,80

Na Mg Zn Ga Ge As Se Br Kr
(Ne)3s 1 (Ne)3s 2 (A r)3d104s 2 (A r)3d104s 24p1 (A r)3d104s 24p2 (A r)3d104s 24p3 (A r)3d10 4s 24p4 (A r)3d10 4s 2 4p5 (A r)3d104s 24p6
3 Sodium Magnésium 3B 4B 5B 6B 7B /------------------------8------------------------\ 1B Zinc Gallium Germanium Arsenic Sélénium Brome Krypton
19 39,10 20 40,08 21 44,96 22 47,90 23 50,94 24 52,00 25 54,94 26 55,85 27 58,93 28 58,71 29 63,55 48 112,4 49 114,8 50 118,7 51 121,8 52 127,6 53 126,9 54 131,3

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Cd In Sn Sb Te I Xe
(A r)4s 1 (A r)4s 2 (A r)3d14s 2 (A r)3d2 4s 2 (A r)3d34s 2 (A r)3d54s 1 (A r)3d54s 2 (A r)3d64s 2 (A r)3d7 4s 2 (A r)3d84s 2 (A r)3d104s 1
(Kr)4d105s 2 (Kr)4d105s 25p1 (Kr)4d105s 25p2 (Kr)4d105s 25p3 (Kr)4d10 5s 25p4 (Kr)4d10 5s 2 5p5 (Kr)4d10 5s 25p6
4 Potassium Calcium Scandium Titane Vanadium Chrome Maganèse Fer Cobalt Nickel Cuivre Cadmium Indium Étain Antimoine Tellure Iode Xénon
37 85,47 38 87,62 39 88,91 40 91,22 41 92,91 42 95,94 43 98,91 44 101,1 45 102,9 46 106,4 47 107,9
80 200,6 81 204,4 82 207,2 83 209,0 84 210 85 210 86 222

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Hg Tl Pb Bi Po At Rn
(Kr)5s 1 (Kr)5s 2 (Kr)4d15s 2 (Kr)4d25s 2 (Kr)4d45s 1 (Kr)4d55s 1 (Kr)4d55s 2 (Kr)4d75s 1 (Kr)4d8 5s 1 (Kr)4d105s 0 (Kr)4d105s 1
(Xe)4f 14 5d10 6s 2 (Xe)4f 145d10 6s 26p1 (Xe)4f 14 5d10 6s 2 6p2 (Xe)4f 14 5d10 6s 26p3 (Xe)4f 145d106s 26p4 (Xe)4f 145d106s 26p5 (Xe)4f 145d106s 26p6
5 Rubidium Strontium Yttrium Zirconium Niobium Molybdène Technétium Ruthénium Rhodium Palladium Argent
Mercure Thalium Plomb Bismuth Polonium Astate Radon
55 132,9 56 137,3 57 198,9 72 178,5 73 180,9 74 183,9 75 186,2 76 190,2 77 192,2 78 195,1 79 197,0

Cs Ba La* Hf Ta W Re Os Ir Pt Au
(Xe)6s 1 (Xe)6s 2 (Xe)5d16s 2 (Xe)4f 145d26s 2 (Xe)4f 145d36s 2 (Xe)4f 14 5d46s 2 (Xe)4f 145d5 6s 2 (Xe)4f 145d66s 2 (Xe)4f 145d76s 2 (Xe)4f 145d106s 0 (Xe)4f 14 5d106s 1

6 Césium Barium Lanthane Tantale Tungstène Rhénium Osmium Iridium Platine Or

87 223 88 226 89 227
65 158,9 66 162,5 67 164,9 68 167,3 69 168,9 70 173,0 71 175,0
Fr Ra Ac** Tb Dy Ho Er Tm Yb Lu
(Rn)7s 1 (Rn)7s 2 (Rn)6d17s 2

7 Francium Radium Actinium (Xe)4f 95d0 6s 2 (Xe)4f 105d06s 2 (Xe)4f 115d06s 2 (Xe)4f 125d06s 2 (Xe)4f 13 5d06s 2 (Xe)4f 14 5d0 6s 2 (Xe)4f 14 5d16s 2

* 58 140,1 59 140,9 60 144,24 61 145 62 150,35 63 152,0 64 157,3

97
Terbium Dysprosium
247 98 251 99
Holmium Erbium
254 100
Thulium
257 101
Ytterbium
256 102
Lutétium
254 103 257
Ce Pr Nd Pm Sm Eu Gd
Lanthanides (Xe)4f 25d06s 2 (Xe)4f 3 5d06s 2 (Xe)4f 45d0 6s 2 (Xe)4f 55d06s 2 (Xe)4f 65d06s 2 (Xe)4f 75d06s 2 (Xe)4f 7 5d16s 2 Bk Cf Es Fm Md No (Lw)
6 Cérium Praséodyme Néodyme Prométhium Samarium Europium Gadolinium (Rn)5f 76d2 7s 2 (Rn)5f 96d17s 2

** 90 232,0 91 231 92 238,0 93 237,1 94 244 95 243 96 247 Berkélium Californium Einsteinium Fermium Mendéléviuml Nobélium Laurencium
SC Eg(eV) Th Pa U Np Pu Am Cm
Actinides (Rn)5f 06d27s 2 (Rn)5f 2 6d17s 2 (Rn)5f 36d1 7s 2 (Rn)5f 56d07s 2 (Rn)5f 66d07s 2 (Rn)5f 76d07s 2 (Rn)5f 7 6d17s 2

Si 1.11 7 Thorium Protactinium Uranium Neptunium Plutonium Américium Curium

 IV: Si, Ge
Ge 0.67  II-VI: CdTe, ZnS, ZnTe
GaAs 1.43  III-V: GaAs, GaN, InAs, InP;
CdS 2.42  I-III-VI2: CIS, CIGS ( chalcogenides )
,
CdTe 1.48  Ternary and quaternary compounds
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 Processes in a solar cell 𝐺i (W/m2) (irradiance)
1. Photons flux entering the cell (monochromatic light) 𝐺i
+
Reflection losses (R) (anti-reflect coating) 𝛷𝑝 (x = 0 ) = (1 − 𝑅)
h𝜈
2. Absorption of photons of suitable energy (> absorption edge):
At a depth x from the surface:
Φ𝑝 = Φ𝑝 (x = 0+ )exp−𝛼𝑎𝑥
• Exponential decrease (Attenuation) of the photon-flux due to absorption as
light propagates in the semi-conductor
What is the physical meaning of this law? How about (aa?)
• aais the absorption coefficient of the semiconductor(in cm-1)
• aa probability density (/unit depth) for a photon to be absorbed
• 1/aais the absorption depth: photon flux is reduced by a factor of e=2.7
(36% of its value at x=0).
• aa can be easily measured from transmission/reflection using
spectrophotometers
• Thickness of the absorber > absorption depth (near absorption edge,
Why??) otherwise Incomplete absorption(loss)
Near the Absorption edge:
• 1/aSi=0.01 cm=100mm (indirect band-gap!!)
• 1/aCdTe= 10-4cm=1mm (Thin film Solar cells)

• Where the are the various photons absorbed?

• What happens to the excess energy of carriers produced high energy
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photons?
• dF/dx=-a F => -dF/F=adx

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3. Photo generation

• Photo-Generation rate at x; G= -dFp/dx (carriers/cm3/s)

• Photo-current is proportional to the irradiance/illuminance
 Give the expression of Iph Assuming mono-chromatic light, quantum yield of 1
and that all the photogenerated electrons are generated, CB

Iph=A*q*Fp  Jph=q Auger

Radiative Trap
 What is the maximum voltage that can be generated by a solar cell?

4. Recombination (bulk and surface)

VB
Annihilation of an electron-hole pair (inverse of photo generation)
• Radiative recombination (band-to-band): dominant in direct band-gap SC!! Shockley-Read-Hall (SRH)
More likely in direct gap SCs  Photoluminescence, electroluminescence(LED) recombination
• Non-radiative recombination(Auger, SRH, surface..)
Surface passivation: reduces recombination at the surface

Minority carriers are more affected by recombination!!! (minority!!)

 Minority carrier life-time t: “survival” time before recombination!!
 1/ t =Probability :unit time of recombination (overall t for the differ paths?)
 t can be measured from PL decay experiments
 Recombination Rate of Minority carriers (carrier/cm3/s: R=excess
concentration/lifetime
 Minority carrier diffusion length L: “mean travel” distance before recombination
𝑳 = 𝝉𝑫
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• Diffusion coefficient, Remember!!, on of the carrier transport mechanisms in SC, Jnd=qDn*dn/dx
• Carrier concentration gradient (light)through random motion, net movement from areas of high carrier concentration
to areas of low concentration
• D/m =kT/q : Einstein’s relationship  diffusion and drift currents at equilibrium equal in magnitude..

• Long Diffusion lengths is necessary for efficient collection of minority carriers (at
short circuit and from the large neutral base region ) and thereby, high
performance of solar cells
• Diffusion rather than drift is the dominant mode, given that the electric field is
negligibly low outside of the small SCR.

Order of Magnitude

 Organic semiconductor, the diffusion length of electrons and holes is about 100 nm
 Single crystalline silicon solar cell, it is typically 100-300 µm (depends on doping
level)

Thickness of the absorber should be less than L of the corresponding minority carriers

Thickness of the ETL and HTL?? (What happens to the minority carriers generated in
these layers? Are photons absorbed there useful in creating a current?

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I-V characteristic of a photovoltaic cell

I +
Iph

60
Id V

Current(mA)
40
_
Voc

20
-1 -0.5 0.5 1
Voltage(V)

q V

-20
I = I 0  (exp  1)  I ph

-40
kT (Vmp,Imp)
Isc
-60

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 Ideal cell vs. real Cell
• Non-ideal diode (ideality factor n)
• Add resistive losses(Shunt and
Iph Series resitances)
• Two diode model some times
used

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 Electrical parameters of Cells and Modules
𝐼𝑛𝑐𝑖𝑑𝑒𝑛𝑡 𝐼𝑟𝑟𝑎𝑑𝑖𝑎𝑛𝑐𝑒 𝐺𝑖 (W/m2)
HTL Absorber ETL

hn > Eg 𝐼𝑚𝑝𝑝
N-type
P+ N+

Optimal load
- R=Vmp/Imp
Bak Contact
Front Contact
+ -
V I 𝑉𝑚𝑝𝑝

Efficiency
Load
𝑃𝑜𝑢𝑡 𝑉𝑚𝑝𝑝 𝐼𝑚𝑝𝑝 𝐼𝑠𝑐 𝑉𝑜𝑐
𝜂= = = 𝐹𝐹
𝑃𝑖𝑛 𝐴𝐺𝑖 𝐴𝐺𝑖

FF=Fill factor=??
𝐴: surface area

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 Effets of Irradiance and Temperature

E=Gi=GPOA
(W/m2)

V (Tc ) = V (Tref ) 1  a v (Tc  Tref ) 

kT  I ph  kT  I ph 
V oc = Ln   1  Ln   Ratings of commercial PV modules/PV
q  Is  q  Is  plants are reported at STC I (Tc ) = I (Tref ) 1  a I (Tc  Tref ) 
𝐺𝑖 • Irradiance GSTC= 1 000 W/m²,
𝐼(𝑇𝑟𝑒𝑓) = 𝐼(𝑇𝑟𝑒𝑓 )
𝐺𝑟𝑒𝑓 • Cell/Module temperature: Tref=: 25 °C, a : temperature coefficent of
• Spectrum Air Mass 1.5 Voltage or of current
For Si:
Cell /module Temperature • av = -0,45% /°C
Tc (°C)= Ta(°C)+[NOCT-20]*Gi(W/m2)/GNOCT • aI =0,1% /°C
GNOCT=800 W/m2
NOCT=Normal operating cell temperature Green BEE SAP+D UM6P 17
 Effects on Power and efficiency

P = P (Tref ) 1  a p (Tc  Tref ) 

 =  (Tref ) 1  a p (Tc  Tref ) 

(ap=-0,4%/°C pour c-Si)

See the technical specifications of the modules at the reference conditions: GSTC=1000 W/m2, Tref=Tc=25°C, Spectrum AM1.5
If (ref) =22%, if Tc=60°C(corresponds to an ambient temperature of 35° and an irradiance of 1000 W/m2)
=22% (1-0.4*35/100)=17%!!!
Under other operation conditions (other than STC) Gi and Ta
𝐺𝑖
𝑃 = 𝑃(𝑇𝑟𝑒𝑓 ) 1 + 𝛼𝑝 (𝑇𝑐 − 𝑇𝑟𝑒𝑓
𝐺𝑆𝑇𝐶

Since the maximum power point varies with temperature and irradiance, a maximum power
point tracking (MPPT) system must be used to extract the maximum power from a PV cell or
module or set of PV module

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 Classification of solar cell technologies
Solar cells

1st Generation 2nd generation: 3rd generation: emerging

Crystalline Si solar cell Thin film solar cell technologies

 Organic PV
a-Si:H  DSSC (Gratzel)
 Perovskites
CdTe  Tandem/multi-junction cells
 Nanostructured cells,
CuInSe2, CIGS.  Quantum dot
 Hot-carrier cells,
 Intermediate band solar cells
CZTS, CFTS.  Photon up-conversion and down
Single crystalline Si Polycrystalline Si
conversion technologies,
• Cost-effective  Thermo-radiative-PV
• 95% of the Market • Efficient
• “Light-weight”
• Flexible
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 State of the art: 1st generation
• Crystalline Silicon ( Eg=1.1 eV) • Absorption Coefficient a:102cm-1
• Mono-crystalline
• Polycrystalline • Diffusion length 100 à 200mm

Junction Types:
• p+/n
• n+/p

p+

• Surface texturing
For standard cells (Al BSF) at STC
BSF repels minority carriers and avoids
• Anti-reflective layer • Voc : 620 to 650-mV
their recombination of at the surface of
the Waferprovides field passivation
• Jsc= 37- to 38 mA/cm2
• Cell thickness 150 to 200mm • FF: 77%–80%
• Typical surface 15.6x15.6 cm2 • Efficiency: up to 22%
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 State of the art: PERC, PERT and PERL cells (25%)

• Purity of (bulk) Si is no longer the limit!!! Surface sates (dangling bonds,...)

• The Front and the back surface of the Si wafer are passivated
• Objective reduce defects that behave as carrier traps (recombination
centers)

PERC: Passivated Emitter and Rear Cell PERT: Passivated Emitter and PERL: Passivated emitter with rear locally
Or Passivated Emitter and Rear Contact Rear Totally diffused diffused (boron as dopant)

Boron (for type p Si)

Al-BSF
PERL
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 State of the art……
• Interdigited Back Contact technology (IBC)
• Contacts on the rear surface to reduce grid shadow

Heterojunction with Intrinsic Thin layer (HIT)

• Passivation layers : a-Si:H (~ 5 nm)

on both faces of the wafer. Heterojunction Back-contact(HBC)
• Heterojunction: P+ a-Si:H layer/n-
type crystalline Si.
• η = 24% (100 cm2)
• η = 25.6% with (Panasonic)
• VOC = 0.74 V, JSC = 41.8 mA/cm2
• FF = 82.7%

Sanyo

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 State of the art: N-type TOPCon (Tunnel Oxide Passivated Contact) technology

n-TOPCON

n-PERT

(poly-Si, deposited)
Why N-type cells??.
• An additional ultra thin SiO2 layer and a doped poly-Si layer
• Phosphorus degrades less than boron when exposed to • Ultrathin SiO2 acts as surface passivation layer between
oxygen. the rear Si surface and the rear “contact”
• N-type based modules can achieve higher efficiencies • TOPCON can be upgraded from the existing
PERC or PERT lines
Pb: N-type silicon manufacturing process is still more
expensive.

https://www.alternergy.co.uk/blog/post/topcon-solar-cells
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Bifacial cells

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 Record efficiencies in c-Si technologies
Record efficiency c-of Si solar cells
Silicon heterojunction back-contact (HBC) solar
cells designed by LONGi efficiency of 27.30%
under laboratory conditions.
• Certified by Germany’s Institute for Solar
Energy Research Hamelin (ISFH),

Record efficiency c-Si Modules

LONGi: Hi-MO 9, 660Wp Module
• Passivated Back Contact (HPBC)
• Conversion efficiency up to 24.43%, built to excel in a range of tough environments
(including lakes, mountains, and deserts according to LONGi!!).

Record efficiency of Tandem solar cells

LONGi
World record efficiency c-Si-perovskite tandem solar cells of 33.9%.

https://www.longi.com/en/news/longi-hi-mo9-bc-world-record/
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 C-Si based PV value Chaine

Réduction (Si
métallurgique)
+purification (Si-
grade PV)

Silice Feedstock;
SiO2 +C  Si+CO2 (1200°C) Costs 14%
Ingot
Si+HCl  SiClH3 Module growth;
assembly 8%
; 40%
Wafering;
11%

Cell
processing;
27%

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 Energy consumption/emissions of PV

Why emission factors are low for PV despite

high emission of PV-grade fabrication???

Energy Consumption
• Electronic Grade Silicon (99.99999)~ 200 kWh/kg
• PV Grade Silicon ~ 50kWh/kg
• Metallurgical Grade Silicon~ 20kWh/kg

Energy Recovery Time

• Monocrystalline Si ~ 4 years
• Polycrystalline Si: 1.6 to 2.7 years
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• Amorphous Si: 0.9 to 1.6 years
 Videos

Wafer poly-Si
• https://www.youtube.com/watch?v=4T3KIz15-GA

Cells
• https://www.youtube.com/watch?v=hs9hTCdvcOg

Modules
• https://www.youtube.com/watch?v=r0mC_X0WrDM

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ITRPV 2023

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State of the art: Second Generation

D. Sajitha et al. Progress in Solid State Chemistry 76 (2024) 100490

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 Multi-junctions

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 CdTe and CIGS Solar Cells
glass ZnO, ITO 250 nm
0.2 -0.5 mm CdS 70 nm
60 -200 nm

CIGS
2 -8 mm 1-2.5µm

Mo 0.5-1 µm

Glass,
Metal Foil,
Source NREL Plastics

CdTe: Direct bandgap, Eg=1.45eV CuInxGa1-xSe2 (CIGS): Band gap can be

• Optimal band gap for single-junction devices adjusted between 1.1 to 1.7 eV
•Large absorption coefficient (10x that of Si)
•Thin films (2mm) required
•Inexpensive
• 20.4 % efficiency

Green BEE SAP+D UM6P 32

 a-Si:H solar cell: the pin junction
• Direct bandgap 1.7 eV, Eg>Eg(c-Si)
• Electron affinity: 4.0 eV
• absorption coefficient ~ 10-100 times higher tan that of Si
• Absorption length 3.3 X 10-5 cm

p-i-n a-Si:H solar cell

Window
a-SiC:H
Drift-limited Solar cell

Record efficiency: 10.22%

Back contact reflection + Textured TCO Light trapping/confinement

Green BEE SAP+D UM6P 33
 a-Si:H thin films solar cells (GEP/LaMEE-UCA) 0.016
Single Junction p-i-n
Cell 6

Current density (mA/cm )

2
0.012
Deposition technique PECVD
Glass Cell 1
0.008

SnO2:F 0.004

P-Type a-SiC:H
0.0 0.2 0.4 0.6 0.8 1.0
Voltage(V)
Intrinsic a:Si:H
Efficiency Cell area Voc (V) Jsc FF(%)
(%) (cm2) (
mA/m2)

N-Type a-Si:H
GEP/UCA 8.83 1 0.86 15.6 66.07
Al
Ref. [6] 10.3 1 0.891 17.20 67.0
Ref. [5] 10.09 1.036 0.876 18.098 66.58
Ref. [7] 10.22 1.001 0.896 16.36 69.8

Green BEE SAP+D UM6P 34

 Third Generation: Organic Photovoltaics
 CT
CC
ED Bilayer PV cell
Single-layer PV cell
A

Anode
cathode
+ Anode Donor
cathode P3HT: electron donor
PCBM: electron acceptor
High exciton binding energy (0.5 eV, small dielectric constant) Acceptor
Pheny-C61-butyric acid methyl ester
Low bipolar mobility (h+ & e-): μh (polymer) ≈ 0.1 cm2/Vs
μn (c-Si) > 1000 cm2/Vs
Exciton diffusion length in OPV is ~10 to 20 nm
Absorption lengths around 100 nm
Not all excitons are dissociated in bilayer devices!!!
Efficiency depends on:
 Photon absorption (A): Exciton generation by absorption of light
 Exciton diffusion (ED): Exciton diffusion over LD (~20 nm) PEDOT:PSS
 Charge-transfer reaction (CT): Exciton dissociation by rapid and • Poly(3,4-ethylenedioxythiophenePEDOT
efficient charge transfer at the interface between D and A • P-type
 Collection of the carriers (CC): Charge extraction by the internal • PSS: polystyrene sulfonate (counterion)
electric field • Improve the water solubility and processability of PEDOT

Green BEE SAP+D UM6P 35

 Ca/Al
Bulk hetero-junction PV cell

~200 nm thick
• Ingenious solution to the limited exciton diffusion lengths
• Photoactive polymer (Donor, P3HT) is intimately mixed
acceptor of electrons (ex. PCBM)
• Distribution of active interfaces(heterojunction) throughout
the bulk
• Excitons are created within diffusion length from the PEDOT (buffer layer)
interfaces..
• Solves the exciton diffusion length and absorption depth ITO/Glass
(imbalance) problem…

• Hybrid nanostructured
organic/inorganic cells ( nanowires,
nanorods..) or inorganic BHJ

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 Dye-Sensitized Solar cells, DSSC (Gratzel) Band Diagram
Structure

- Dye-sensitized photo-anode: photo-

generation/excitaion in the dye
- Injection in the CB of the oxide, and transport
- Oxidation of the dye
- Counter electrode (CE): redox pair reduction,
- Redox electrolyte (or hole transporting material): Dye
reduction

Advantages:
• Low-cost thin film solar cells
• Easy fabrication
• Environmental friendly (Natural dye extracts
Challenges:
• High cost platinum counter electrode: Metal nitrides and carbides as advanced
counter electrodes
• Corrosive liquid electrolyte (leaks): Solid electrolyte, conducting polymers and
poly-electrolytes Facade of the SwissTech Congress Center of Ecole
• Use MOF structures as photo-anodes Polytechnique Fédérale in Lausanne (Gratzel)
37
Green BEE SAP+D UM6P
 Perovskite Solar cells
 Inorganic oxide perovskites,
 Alkali metal halides perovskites,
 Organo-metal halides perovskites.
 Chalcogenide perovskites AB(S or Se)3 : A=Ba, Sr, Ca and B=Zr, Ti..

Advantages:
• Direct band gap
• Tunable band gap: directly controlled by the composition and the
choices of the metal, halogens, and organic cations (1.1 eV to 2.
eV)
• Excellent optoelectronic properties(long diffusion lengths, long
charge carrier lifetime and high dielectric constant)
• Diffusion length: exceeds 5 mm for thin films and 170 mm under 1
sun (1000 W m−2) illumination (single crystal)
• Solution-processing.

Lead-Free Perovskites:
• B= Ge2+, Sn2+, Sb3+, Bi3+, and Cu2+
• Double perovskites
• Chalcogenides Green BEE SAP+D UM6P Zhumekenov et al, CS Energy Lett. 2016,38
1, 1, 32–37
 Perovskite solar cell architectures
• Meso-pourous n-i-p
• Planar heterojunction n-i-p
4
2 AF
AR

Current density (mA/cm2)

0
-2 BF
K. Ildrissi, PhD -4 BR
-6 CF
student, UCA -8 CR ETL
-10 AF
-12
AR
BF
Mesospoous PCS -14
-16
BR
CF
Triple Cations -18
-20
CR
-22
Average Efficiency: -24
Back contact HTL
-26
18,2% -28
-30
-200 0 200 400 600 800 1000 1200

Voltage (mV)
• Inverted p-i-n
35
Monocrystalline silicon
30 Triple cation perovsite
W. Riad, PhD student, UCA

Current density (mA/cm2)

 Triple cation
25

 Inverted PCS 20

 NiO and NiCo2O4 HTL 15

10

Achieved Record Efficiency 5

of 20.3% (August 26, 2024) 0

0,0 0,2 0,4 0,6 0,8 1,0 1,2
Voltage (V)

Green BEE SAP+D UM6P

39
 PCS Solar Cell Fabrication

Deposition technique Cs0.05FA0.79MA0.16Pb(I0.86Br0.14)3

 One-step Spin coating
 Anti-solvent (ex. Chlorbenzene)

ETL
FTO/ Glass Perovskite
FTO /Glass FTO /Glass ETL
FTO/ Glass

Paterning and
Cleaning ETL: c-TiO2+m-TiO2 Perovskite
Cs0.05FA0.79MA0.16Pb(I0.86Br0.14)3 HTL (Spiro-Ometad)

Au HTL
HTL
Au- Perovskite
Perovskite
ETL (compact+meso)
Evaporation ETL

FTO /Glass
contacts FTO /Glass

Green BEE SAP+D UM6P 40

Losses in Single Junction Solar cells and the SQ limit
Energy
Lattice thermalization loss

Junction loss

Contact
loss
Sub-bandgap loss qV

Recombination
loss

• Only photons with energies around the band gap are efficiently absorbed
• Sub-bandgap and lattice thermalization losses account for more than 50% of the total loss in Solar cells
• Optical losses (reflection, losses of light): use ARC
• Resistive losses: series resistances (Rs): losses at the junctions (interfaces).
• Shunt resistances (Rsh) account for the leakage currents and bypass paths (e.g. pinholes, device shorting).

Green BEE SAP+D UM6P 41

 Quantum efficiencies of PV cells
EQE= the ratio of the number of carriers collected by the solar cell to the number of photons of a given energy
incident on the solar cell.
Probes generation/losses across the cell (absorption depth of photons)
Expression?
UCA measurements
100
Monocrystalline silicon
Amorphous silicon

External quantum efficiency (%)

Perovskite
80

60

40

20

0
200 400 600 800 1000 1200
Wavelength (nm)

Green BEE SAP+D UM6P 42

 Tandem/Multi-junction Solar Cells:
• Key to efficiencies beyond the QS Limit of Single Junctions
• Tandem: Special case of multi-junction solar cells, consisting of two stacked cells
having absorbers with considerably different band gaps
• The top cell absorbs high energy photons
• The bottom cell absorbs low energy photons that are not absorbed by the top
cell (sub-band gap photons of the top cell)
Two main types of stacking
Four-Terminal (stacked)
2 Terminal (monolithic)

Glass Transparent Electrode

Transparent Electrode
Top Cell
Top Cell
Transparent Electrode Tunnel Junction/ Recombination Layer

Bottom Cell
Transparent Electrode
Rear Contact
Bottom Cell
Rear Contact
• Fewer layers (no parasitic absorption)
• Easier prototyping • Module fabrication easier
• No tunnel junction or recombination • The cells are in series. The current is limited
layer required by the layers that produces the least current.
43
 Green BEE SAP+D UM6P 44
https://www.nrel.gov/pv/interactive-cell-efficiency.html
Evolution of record efficiency Tandem Perovskite/Silicon Solar Cells:

Green BEE SAP+D UM6P 45

Six-junction III–V solar cells with 47.1% conversion efficiency under 143 Suns concentration

John F. Geisz et al. Nat Energy 5, 326–335 (2020). https://doi.org/10.1038/s41560-020-0598-5 (online)

Green BEE SAP+D UM6P 46

 Other recent developments
• Thermo-photovoltaic: uses radiation from heated
absorber(IR!!)
• Thermo-radiative devices

Can be heated by sunlight via a solar absorber or thermal

storage.
• Thermoradiative-Photovoltaic
• Detailed-balance efficiency limit of 85% under
maximum concentration.
• one-sun: 45%
Cell Reports Physical Science 1, 100258, December 23, 2020
- Thermo-radiative PV devices: can generate electricity
at night!!!
- Thermal radiation from the panels to the sky

• Transparent solar cells : solar-to-electricity conversion

efficiency of 10% (MIT).
• Intermediate band gap technology

• Ambient light harvesting devices

Green BEE SAP+D UM6P 47

 In dark, and (at night) when the cell views the sky
(cold), it radiates in the IR towards the sky ++> THE
CELL GETS COLD
Instead of generating excess charge carriers, as
under solar illumination, the carrier
densities decrease compared with their equilibrium
values.
Why? No thermal energy to repopulate the carriers
lost to recombination in equilibrium.

Carrier densities are different from their equilibrium

values, a quasi-Fermi level splitting again occurs.
Voltage

https://www.optica-
opn.org/home/articles/volume_35/november_2024/features/thermoradiative_photov
oltaics/

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