Photodetectors

Photodetectors
• A photodetector is a transducer that converts photons
to an electric current.

• Photodetectors, also called photosensors, are

sensors of light or other electromagnetic radiation.

• There are numerous types of photodetectors ranging

from bolometers to avalanche photodiodes.

• We focus our attention on only the primary types of

detectors that employ organic electronic active
materials.
Some of the applications of photodetectors
Photodetectors respond in
the spectral region ranging
from the ultraviolet (with
wavelengths λ > 300 nm)
into the near infrared (NIR,
at λ < 1500 nm). The NIR
wavelengths of interest are
also known as the short
wavelength IR, or SWIR
band.

They find numerous

applications (shown in
figure).
 Type of photodetectors
• Within the visible to near-visible spectral regions,
organic electronic devices fall into three classes:
photoconductors, photodiodes, and
phototransistors.

• The principal difference between them is that the

photodiode comprises an internal junction that
actively separates photogenerated excitons, while
the photoconductor and phototransistor lack a
junction.
 Photoconductors
As illustrated, the photoconductor is simply a slab of semiconductor
that is sandwiched between ohmic metal contacts.
Light incident on the semiconductor generates excitons that dissociate
into free electrons and holes. These carriers subsequently drift to
opposite contacts due to a small electric field placed across the
semiconductor by an externally applied voltage
The energetics of exciton dissociation

The energetics of exciton

dissociation is illustrated in Fig. 7.2.

This scenario shows that a

photogenerated exciton current, jX,
is generated by absorption of a
photon of energy hν greater than
the HOMO-LUMO gap of the
semiconductor (Eg).

hν > Eg
The energetics of exciton dissociation

kdiss - rate of dissociation of exciton

into a free electron–hole pair
krec –rate for recombination of free
electrons and holes

kD – rate for the exciton recombination, it also refers rate for the
thermally generated excitons.
Here, N is the exciton density with value N0 at Equilibrium
(in the absence of illumination source)
JD – Refers Dark current, JT, refers total current.

Photocurrent, jph = jT - jD
 Internal Quantum Efficiency
• We can define the internal quantum efficiency
(ηext) as the ratio of the number of electrons
generated per photon absorbed in the device
active region, which differs from external
quantum efficiency (ηext) by ignoring reflections
from the surface of absorption in electronically
inactive areas of the sample. This can be
expressed as the ratio of rates:
 External Quantum Efficiency
For a light with wavelength λ, the external quantum efficiency of
photoconductor can be expressed as follows;

ηext = (1-R)ηint (λ) ηA (λ)

where R is the reflectivity of the incident surface

ηint is internal quantum efficiency
ηA is the light absorbance efficiency of the photoconductor
Note that ηint ignores reflections from the surface or absorption in
electronically inactive areas of the sample..
Where as ηext includes reflections from the surface or absorption in
electronically inactive areas of the sample..
 Antireflection coating (ARC)
• An antireflection coating (ARC) is often deposited on the light
incident surface to reduce or eliminate Fresnel reflections,
increasing the photon intensity arriving at the absorbing
photoconductive layer. Use of ARC improves the ηext of the
device.
 Current-Voltage Characteristics of
Organic Photoconductive (OPC) Device

A photoconductor does not have a junction.

This results in symmetrical, Ohmic
characteristics under an applied voltage of
both polarities.
That is, j ∝ V over the full range of normal
operation.
 Lower efficiencies of photocurrent
generation on photoconductors
• A photoconductor lacks a heterojunction, and hence the
exciton must dissociate directly into free charges, an often
inefficient process that lacks an energetic driving force.

• Of course, excitons may diffuse to a contact that can lead to

efficient charge generation, or it can dissociate at a defect
sites within the semiconductor bulk.

• Notwithstanding these secondary processes with their own

inherent inefficiencies (i.e. the exciton may have to diffuse
long distances before finding a dissociation site), organic
photoconductors consequently have considerably lower
efficiencies than do organic photodiodes and solar cells.
 Terms Related to Performance Characteristics of
Photosensitive Devices
1. Quantum Efficiency : The number of electron–hole pair generated
per incident photon energy.

2. Responsivity: The ratio of average current generated (jph) in the

detector to the average optical power incident (Pinc) on the detector;
(Responsivity = jph/Pinc)

3. Dark Current : Dark current is the small current that flows through
the photosensitive devices, such as photocoductors, photodiodes,
and photomultiplier tubes etc. in the absence of incident light, when
no photon is entering in the device.

4. Noise: Noise is the uncertainty in the random arrival of charge at an

electrode (e.g. shot noise (statistical fluctuation of photocurrent and
dark current) , thermal noise (current fluctuation due to
temperature change).
 Terms Related to Performance Characteristics of
Photosensitive Devices
5. Gain: The gain is equal to the ratio of the carrier lifetime (τD) to its
transit time (ttr).
For greater gain ttr < τD; where n and p refers electron and hole.
The photoconductive gain will be greater than unity if the
lifetime exceeds the transit time.

6. Bandwidth (∆f); For a photoconductor ∆f = 1/2πτD

7. Gain-Bandwidth (g∆f);

Unfortunately, photoconductors generally have a slow recovery time

as well as a long transit time, leading to a small g∆f compared to
photodiodes that operate under reverse bias.
 Photodiodes
• Photodiodes are designed to detect photons
and can be used to sense light.

• The primary difference between a photodiode

and a photoconductor is that the photodiode
has a rectifying junction and is operated away
from equilibrium due to a combination of
internal and applied electric fields.
 Photodiode Light-Detector Circuit
In inorganic photodiodes (IPD), pn junction is used.

If photons excite charge carriers in pn

junction, a small current proportional to the
light intensity flows in the circuit.

The sensitivity of photodiode depends on

the wavelength of the light.

In organic photodiodes (OPD), a donor-acceptor

hetero junction (HJ) is used.
p-n junction: Depletion layer, potential Barrier and Biasing
The diode can be forward biased by connecting the p-side of the diode to the positive voltage
and the n-side to the diode to the negative voltage. This causes an decrease in the thickness of
the depletion layer. The majority charge carriers flow through the junction of the diode during
forward bias. The holes are the majority charge carriers in the p-region of the diode and the
electrons are the majority charge carriers in the n-region.

Forward Bias Diode Working Animation

Reverse bias is when the p-side of the diode is connected to the negative voltage of the battery
and the n-side is connected to the positive voltage of the battery. This causes an increase in the
thickness of the depletion layer. This allows very less current to flow through the PN junction.
As the reverse bias voltage is increased beyond the critical level, breakdown occurs in the
depletion layer and a current starts flowing. The breakdown is usually a Zener breakdown or an
avalanche breakdown.

Reverse Bias Diode Working Animation

Q. Why is a photodiode is used in reverse bias?

When a photo- diode is reverse biased, the width of depletion layer increases as
compared to forward biased and a small reverse current (dark current) flows
through the diode. Now, when the light is incident on the junction, electron-hole
pairs are generated in depletion layer in a big amount (due to broad
depletion layer) and these charge carriers can easily cross the barrier, hence
contribute to current across the diode. We can say that in reverse bias, diode changes
the incident light to current, more significantly due to broad depletion layer i.e.
photocurrent is significant in reverse bias as compared to the forward
bias current.
 Q. Why is a photo-diode invariably reverse biased, when it is used as
a photo-detector?

Whether the photo-diode is reverse biased or forward biased, the number of

electron hole pairs produced by the incident photons is the same. In other words,
the change in the diode current is the same in both cases. But in the reverse
biased condition the current drawn by the diode in the absence of the photons
(dark current) is extremely small, of the order of nanoamperes or
microamperes whereas in the forward biased condition this current is significant,
of the order of tens of milliamperes. The fractional change in the current because
of the incident photons is therefore large and easily measurable if the photo-
diode is reverse biased.
 Organic Photodiode (OPD)
The organic photodiode (OPD) comprises a donor/acceptor (D-
A) type II heterojunction (HJ) that separates a photogenerated
exciton into a polaron pair, which subsequently dissociates
into a free electron and hole.
 Steps Involved in Photocurrent
Generation in OPD
• Photogeneration in OPD is a multistep process illustrated in Fig. 7.6
(see previous slide).
• Step 1. The process is initiated by absorption of a photon in the
donor region.

• Step 2. The photon generates an exciton that diffuses toward the D-

A junction.

• Step 3. At the HJ, the electron transfers from the donor to the
acceptor, and the hole remains in the donor. The new state
originating from exciton dissociation is the polaron pair (PP), or CT
state. Processes that occur in step 1–3 are collectively known as
photoinduced charge transfer.

• Step 4. Finally, the electron and hole are dissociated from the
bound PP state via thermal excitation. The free polarons drift away
from the junction and are collected in the external circuit.
Driving force for the charge transfer
• The driving force for the charge transfer is the offset in
energies between the LUMOs and HOMOs of the two
layers, whose magnitude is determined by the energy gaps
and the HOMO–LUMO energy difference, ∆EHL.
Short Circuit Vs Reverse Bias Condition
in OPD
• The energy level diagram in Fig. 7.6 represents
the equilibrium condition where Va = 0. This is
known as short circuit operation.

• Photodiodes are often reverse-biased to achieve

both high bandwidth and high efficiency. Under
reverse bias, the bands are tilted downward from
left to right, thus resulting in efficient hole
collection at the anode contact, and electron
collection and at the cathode (See Figure 7. 19;
next slide)
Energy level diagram for reverse
biased condition

EF – Refers Fermi Energy

WD – Depletion layer of donor region

WA –Depletion layer of acceptor region
Current-Voltage (JV) Characteristics of
OPD
The slope of the j–V characteristic
at Va = 0 gives the shunt resistance:
Illustrated by the diagonal line in the
inset.

The shunt resistance is a function of

charge leakage around the junction, and
is important in devices that are operated
near 0 V.
 Types of Heterojunctions (HJ) in OPD
(a) Planar bilayer D-A HJ,
(b) Bulk HJ (BHJ)
(c) BHJ with blended D and A
(d) Planar mixed HJ (PM-HJ)
 Advantages of HJ
• It was found that semiconductors with
different band gap energy (or Homo-Lumo
gap energy ) reduce charge recombination.

• It has been reported that the charge

separation efficiency improved remarkably
through the construction of junction within
the semiconductors.

https://www.sciencedirect.com/topics/earth-and-planetary-sciences/heterojunctions
 Advantages of HJ
There is minimal charge recombination within the
depletion region following exciton dissociation since
electrons and holes are rapidly swept to the
contacts by the applied and internal fields (resulting
from Va and the built-in voltage, Vbi, respectively).

Hence, unlike a photoconductor, a photodiode has

a gain, g = 1.
Which is higher than that of a g measured for a
photoconductor.
 Photodiode Architecture
• Photodiode architectures (and also solar cell)
1. ITO-Indium Tin Oxide – It acts as a transparent anode
where the light falls at first.

2. Followed by transparent anode buffer layer that

reduces the barrier to charge injection. Typical
materials used for this purpose are PEDOT:PSS
(poly(3,4-ethylenedioxythiophene) polystyrene
sulfonate) or MoO3.

3. Next is the organic active region. This can be a bilayer

D-A HJ, a bulk HJ, or a homogeneously mixed HJ.

4. The active region is often capped by a transparent

exciton blocking/electron conducting layer (EBL).
Photodiode Architecture
-Energy level Diagram

Importance of anode buffer layer:

Has a deep LUMO

This deep LUMO promotes

the transport of electrons to
the interface of heterojunction
where the polarons are formed.
Photodiode Architecture-Example
• Example of a photodiode architectures

Ag – Silver (Cathode)

ITO – Indium Tin Oxide

(Transparent anode)
 Photodiode Architecture
Purpose of EBL
The wide energy gap EBL has multiple purposes;

1. Energy barriers formed at the LUMO and HOMO edges and

its wide energy gap prevents excitons generated in the active
region from diffusing to, and recombining at the cathode.

2. It is a transparent spacer that ensures that the incident

optical field is maximized within the active region.

3. Finally, the EBL serves as a buffer that prevents damage to

the active region during deposition of the metal cathode.
 Seems to be impossible are simply
engineering problems

• What we usually consider as impossible are

simply engineering problems… there’s no law
of physics preventing them.”
- Michio Kaku
 Comparison of Photoconductors and
photodiodes
• HJ OPD shows an asymmetric, rectifying j–V characteristic. Where as a
photocoductor exhibits a symmetric j-V characteristic.

• The bandwidth and noise performance of reverse-biased photodiodes

far exceeds that of photoconductors.

• For these reasons, photodiodes are preferred for almost all sensitive
detection applications.

• While photoconductors can source photocurrent, they are incapable of

providing power to an external load. In contrast, photodiodes operating
in the fourth quadrant of the j–V characteristics (where V > 0 and j < 0
the so-called photovoltaic mode are useful as a power generating solar
cell.
Phototransistors
Phototransistors are operationally similar to the other photodetectors.

In phototransistors the conductance channel is formed between the

source and drain. The conductance can be controlled by light absorption.

Phototransistors (PT) Photoconductors (PC) Photodiodes-based (PD)

From the perspective of the device structure, the majority of PT show three electrodes
which are gate, source, and drain electrode. PC and PD are based on two electrodes.

For PT, an additional photoconductive gain can be realized by using the three-terminal
structure and applying an additional electrical bias. Further introduced hybrid-layered
structures can facilitate charge separation and transportation, thereby improving the
device performance.
Organic Solar Cells (OSC)
or Photovoltaics (OPV)
 Solar cells Basics
A solar cell converts solar irradiance into electrical energy.

In its simplest terms, a solar cell is a photodiode that is operated

in the fourth quadrant of its j–V characteristics, that is, it is
operated in the photovoltaic mode. It is only in this quadrant that
power can be produced.

A solar cell must be optimized to capture the maximum solar

irradiation with minimum loss, whereas a photodiode is tuned to
have low noise and high sensitivity within a narrow spectral band.

For solar cells, the materials, the details of the active region, and
the contacts must be optimized for power rather than current
generation.
 Device Structure of OSC
The design of an OSC comprises a layer stack of two electrodes with a
sandwiched photoactive layer in between.

At least one of the electrodes must be transparent and is typically made of

indium tin oxide (ITO) sputtered or evaporated on a transparent substrate
such as glass or polyethylene terephthalate (PET).

The history of the active layer design began with single layer, then double
layer (bilayer heterojunction), and today intermixed layers (bulk
heterojunction (BHJ) of donor and acceptor, Fig. 17.1) are widely used.
BHJ largely improves the charge separation and transport by its nanoscale
morphology in the range of the diffusion length of the excitons.
Recombination losses of the charge carriers are successfully decreased in BHJ.

An additional buffer layer between the active layer and the electrodes serve
as charge selective transport layer, either blocking holes or electrons.
Device Structure of OSC
-Typical Planar Bilayer Structure

A bulb is connected
to the photovoltaic diode
 Device Structure of OSC
Common types of heterojunctions used for OSC

BHJ largely improves the charge separation and transport by its nanoscale
morphology in the range of the exciton diffusion length ( typical range 4-20
nm).

Recombination losses of the charge carriers are successfully decreased in BHJ.

What is exciton diffusion length?

Exciton diffusion length (LD) is the average length a charge carrier

moves between generation and recombination. Or in simple terms,
the distance that excitons can travel in their lifetime is called the
exciton diffusion length (L ).
 Planar Bilayer Heterojuction Vs Bulk
Heterojuction
For a planar bilayer heterojuntiion, the exciton diffusion length is considerably
smaller than the optical absorption length, leading to a low external quantum
efficiency ηED.

This efficiency bottleneck was eliminated by the introduction of the BHJ and mixed HJ
architectures, where excitons dissociate throughout the active region volume.

Bulk and mixed HJs are nanostructured aggregates of donor and acceptor molecules
that present a large interface area where excitons can dissociate without having to
diffuse long distances from their origin.

However, the inherent disorganization of random structures in bulk and mixed HJs
can impede charge conduction to the contacts due to the circuitous and often
discontinuous paths between the charge point of origin to its respective contact.

To maximize the probability of exciton dissociation and minimize resistance to

charge transport, the morphology of the mixed regions must be controlled with
nanoscale precision.
Working principle of an organic solar cell (OSC)
The working principle of an organic solar cell (OSC) can be
described in four fundamental steps and is illustrated in Fig. 17.1
for bulk heterojunction devices:

1. Exciton generation
2. Exciton diffusion
3. Exciton dissociation
4. Charge carrier transport

(See next slide for detailed

explanation)
Working principle of an organic solar cell (OSC)
1. Exciton generation: Upon illumination of the active material, a photon is absorbed
and promotes the electron to the lowest unoccupied molecular orbital (LUMO). The
same time, a positive charge carrier, or so called hole, stays in the highest occupied
molecular orbital (HOMO). Both charge carriers are attracted to each other and
bound by Coulomb forces forming an exciton, also referred to as electron–hole pair.

2. Exciton diffusion: The generated exciton diffuses inside the donor phase to the
interface of the donor and acceptor material.

3. Exciton dissociation: The exciton dissociates into a free electron and hole at the
interface of donor and acceptor material.

4. Charge carrier transport: The free charge carriers are separated by an internal
electric field caused by electrodes with different work functions. They are
transported through the donor and acceptor material, where the electrons are
collected at the cathode and the holes at the anode. The photocurrent is generated
by short circuiting or applying a load to an external circuit.

Each steps is equally important for efficient power generation

 Device Geometries
Two reference device geometries, shown for BHJ, namely
normal and inverted geometry, are actually used to build OSCs
in lab-scale size and full solution processing.
 Device Geometries
The normal geometry has been used as the traditional device structure
for a long time and is known for relative efficiencies and its relatively
simple production. One drawback is the use of vacuum steps to
evaporate the cathode electrode on top of the active layer and its limited
operational lifetime. Flipping the layer stack and introducing a charge
transport layer allows full solution processing of the anode. The inverted
structure avoids vacuum steps, except for ITO, and has been proved a
better choice for large-scale processing.
 Device Geometries
Of two device geometries of given solar cells, which one has normal
geometry?

Schematic geometry for (top) a standard bulk heterojunction (BHJ)

device and (bottom) an inverted BHJ device. The main component
layers are sketched. ETL, electron transport layer; HTL, hole transport
layer.
Device Geometries; Materials Used

m n

PEDOT:PSS

P3HT

PCBM
OSC –
Designs/Technologies

Dye sensitized solar cells (DSSC)

is also called Gratzel cell
Gratzel Electrochemical Cell: (Dye-Sensitized solar cell (DSSC))
A dye-sensitized solar cell (DSSC) or better known as the Gratzel cell is a low-cost
solar cell from the thin film solar cell group. It consists of few semiconductor
materials that are formed between a photo-sensitized anode and an electrolyte
thus creating a photoelectrochemical effect. The modern version of a dye solar cell
was originally co-invented by Brian O'Regan and Michael Grätzel at UC Berkeley.

Schematic of the construction of Gratzel cell.

J–V characteristics of organic solar cells
Solar cell, or photovoltaic cell, operation can be understood from its J–V
characteristics in given figure. , It is operated in the fourth quadrant of its J–V
characteristics. V > 0 , J < 0

The open circuit voltage (VOC) is the intercept of the J–V characteristics with the V-
axis. Short circuit current density (JSC) is the intercept of the j–V characteristics
with the j-axis.
(Note: Some figure J is given in small case j, both are referring current density)
 J–V characteristics of organic solar cells
What does the terms Jsc and Voc refers?

The photocurrent density (Jph) is referred

to as the short circuit density Jsc, because
there is a current without any external
applied voltage. It is as if there was a short
circuit in the system. The photocurrent is
actually a reverse bias current because
electrons flow toward the cathode and the
holes flow to the anode.

If you start applying a voltage, a forward bias, it will start compensating for that
reverse photocurrent and eventually, you will reach point where the current goes to
zero. At this point, it is referred to as an open-circuit voltage Voc because even with
applying a voltage, there is no current. It is as if the system or the electric circuit is open.
In the dark, the system works as a normal diode: it has a forward bias after a given
threshold and creates a large current, while a reverse bias gives negligible current.
J–V characteristics of organic solar cells

Here, jSC = jT - jD, where jT is the total current

and jD is the dark current.

Typically, jSC ≫ jD such that it is simply equal to

the photocurrent, jph at Va = 0.

In the fourth quadrant, the power density

generated is P= -jphV < 0.

In the first and third quadrants, P > 0 and

hence power is dissipated.

By convention, in solar cells the power (P) generated is taken as positive

Maximum power point (MPP)

The maximum power generated by the cell

(called the maximum power point, or MPP) is
defined by the largest area rectangle (shaded
area) whose corner opposite the origin
intersects with the j–V curve.

Using our sign convention, the maximum

power density generated is given by

where jM and VM are the corresponding current and voltage at the MPP.
 Fill factor (FF)
It is convenient to define the cell figure of merit, the fill
factor, FF, as the ratio of the areas of the rectangles
defined by jSC and VOC to that at PM,

For an organic HJ solar cells, FF is always less than 1;

FF < 1

You want to have a fill factor as large as possible. But often, the fill
factor will end up being around 40-60%. In the most efficient cases, it
is possible to reach up to 80-85%.
Power conversion efficiency (PCE or ηP)
The power conversion efficiency (PCE or ηP) is the ratio of the
electrical power generated by the cell to the optical power
density incident from the sun, Popt. Thus

Clearly, we seek designs that have the highest fill factor, that is, that
conform most closely to a diode whose ideality factor, n  1

For an ideal diode without recombination, n = 1

The ideality factor of a diode is a measure of how closely the

diode follows the ideal diode equation.
 Ideal diode equation

Io is the saturation current

 Power Curve

Power curve is the plot of P as function of V

 Effect of Rshunt and Rser on PM
In describing solar cell characteristics, the fourth quadrant is often “flipped” into the
first quadrant, plotting both jph and V as positive quantities.
A decreasing Rshunt decreases the curvature at the MPP, which depresses both jM and
VM. Similarly, an increasing series resistance (Rser) decreases the forward-biased slope,
which results in a decreased VM. The fill factor is strongly influenced by both the series
and shunt resistances
Shunt resistance defines the resistance offered by undesired
reverse current paths e.g. along the edges of the cell or through
the inherent cell diode.

Low shunt resistance causes power losses in solar cells by

providing an alternate current path for the light-generated
current.

https://doi.org/10.1016/B978-0-323-99560-3.00004-1
 Fullerene Thin Films as Photovoltaic
Material
• Carbon is a unique element existing in a wide variety
of stable forms ranging from insulator/semiconducting
diamond to metallic graphite.

• Crystals and thin films of pristine fullerene (C60) are

found to exhibit n-type semiconductor-like behavior in
their optical and electronic properties while, at the
same time, retaining their molecular character.
C60 Film and Pentacene or Tetracene Layers
Solids of such small molecules as tetracene and pentacene are known
to be molecular semiconductors of p-type with relatively high exciton
diffusion length and carrier mobility.

Very promising results were obtained in experiments with a simple

device configuration containing a heterojunction between C60 thin
films and donor layers of tetracene or pentacene.
In both cases a BCP film was used as an exciton-blocking layer.

In particular,
an ITO/PEDOT:PSS/tetracene (80 nm)/C60(30 nm)/BCP/Al cell
exhibited
Voc = 0.58 V Jsc = 7mA/cm2, FF= 0.57 and η = 2.3% under a simulated
AM 1.5 sunlight of 100mW/cm2.
https://www.sciencedirect.com/topics/engineering/pentacene
Advantages and disadvantages of OSC
Note: Organic solar cells (OSC) are also called organic photovoltaics (OPV)
• Numerical Problems
Figure shown below illustrates the fourth
quadrant J–V characteristics under 1 sun,
AM1.5G illumination of three subcells used in a
multijunction solar cell.
Make a table that lists the JSC, VOC, FF, JM, VM,
and PM of each cell