CZTS paper review

Mitzi 1: Loss mechanisms in Hydrazine processed

Cu2Zn(Se,S)4 solar cells - Mitzi
APL 97, 233506 (2010)
4 Characterization techniques to identify main loss
mechanisms limiting device efficiency
1. Light-dark J-V (and pseudo J-V)

Magnitude of FF gives series resistance

Pseudo J-V is what J-V would be without any Rs

2. EQE, EQE(V)

Which wavelengths have low response

3. Voc vs. T

Identify main recomb as interface or bulk

4. Time resolved PL

lifetime

Main observations
Voc is low wrt to Eg
Voc is usually (Eg/q 0.5) for CIGS. CZTS > 0.6
Low FF -> high Rs
CZTSSeA

CZTSSeB

CIGS-A

Efficienc
y

8.73

9.50

13.8

FF

57.8

64.3

72.4

Voc
(mV)

395

499.3

578.4

Jsc
(mA/cm
2)

38.24

29.55

33.06

EG (eV)

1.05

1.21

1.14

EQE
EQE response is low in long lambda (ZB
900nm)

EQE(V)
EQE carrier collection efficiency
EQE(V) ratio: EQE(-1)/EQE(0)
CZTS increases at long wavelengths poor min
carrier collection deep in the abs and a V dep
current collection

Temp dependent Voc

J oo
EA AkT
Voc

ln

q
q
JL

Voc vs. T
A, J_oo and J_L are assumed to be temp
independent
q

J
exp
V

R
J
o
s J L
AkT
Really

there is T dep
E
J o J oo exp A
AkT

Mitzi says rearranging 1st eqn

EA
A ln J o
A ln J oo
kT

Temp dependent Voc

J oo
EA AkT
Voc

ln

q
q
JL

Voc vs. T
Plot should be straight line and T = 0K should
yield activation energy
If intercept yields band gap
Bulk recombination (limited)

If intercept < Egap

Interface recombination

Temp dependent Voc

So, CZTS is interface limited. Why?
Buffer-absorber layer has electrical defects
Cliff-type band alignment -> absorber has
smaller EA than buffer
CIGS shows bulk recombination due to grain
boundaries of poly xtal
Can this work for amorph materials?

TR-PL
Solution for n(t)
n0 excess carrier density; C1/C2 constants

Intially fast rise due to radiative recomb and HLI

that redistributes excess carriers. long tail is LLI
and time constant -> minority carrier lifetime
CZTS 1.2 ns << CIGS 6ns!
With mu = 10,
diffusion length = 180nm! With
Cell thickness ~ 2um!
E-field!
Low lifetime limits Voc and
long wavelength response low Jsc

Series resistance
Low FF due to high Rs (sheet series resistance)
T dep of the efficiency and dark series R
dV
AkT
Rs ,d
J Gs ,dV

dJ
q

So, plot of dV/dJ vs 1/(J-GsdV) gives yintercept as Rsd

Series resistance
Efficiency increases with
lower T and plateaus for CIGS
CZTS efficiency drops at low T
This is due to Rs inc at low T
Why does this happen?
Presence of blocking contact
at abs/Mo interface

Model back contact as Sch diode

Series resistance
When solar cell is fwd biased; back contact
diode is in rev bias and conduction is limited
by the rev. sat. J which diminishes at low T,
increasing Rs
Can now estimate barrier height of this
contact Rs R0 k* exp b
qA T
kT
Ro is contact grid resistance and resistance
from TCO can be ignored at low T

Equivalent cct
When solar cell is fwd biased; back contact
diode is in rev bias and conduction is limited
by the rev. sat. J which diminishes at low T,
increasing Rs

Series resistance
By plotting ln(Rs*T) vs 1/T get barrier heights
as 5.9 for CIGS and 99 ,115 for CZTS
Large barrier leads to large Rs

Also, cross-over of J-V curves indicates

Schottky contact

Summary
Key loss mechanisms
Low Voc limited by buffer/abs interface recomb
Voc vs T indicates this; low min. carrier lifetime
limits Voc, leads to limited long lambda EQE which
limits Jsc
Large series resistance could be because of
Schottky contact at the CZTSSe/Mo interface limits
FF