Organic Electronics

(ELEC324)

Organic Schottky diodes

 Overview
 Organic Schottky diodes
 Metal-Organic semiconductor contacts
 Energy band diagrams prior and after Schottky contact formation
 Energy band diagrams under Forward and Reverse bias
 Typical structures of the organic Schottky diode

 Current-Voltage Characteristics of Schottky diodes

 Forward characteristics and Reverse characteristics

 Capacitance-Voltage Characteristics of Schottky diodes

 Variation of depletion capacitance with frequency

 Transient response of disordered organic Schottky diodes

 Potential applications of the organic rectifiers i.e. RFID tags

 Current issues and possible solutions

ELEC324 - [2018]
 Metal - Semiconductor contacts
 When a metal is in contact with a semiconductor (or even insulator), a
potential barrier (either positive or negative) is formed at the interface

 The barrier controls the charge flow and hence the current and capacitance
between the two materials

 Schottky contact is a contact where the barrier height is positive resulting in

high resistance, which limits the flow of carriers between the two materials

 Ohmic contact is a contact where no barrier or negative barrier is formed at

the interface resulting in free flow of carriers between the two materials

 The formation of either an Ohmic or Schottky contacts depend on the work

function difference between the metal and semiconductor

 Work function (q) is the (average) energy required to extract an electron and
measured from the Fermi level EF to the vacuum level Evac

ELEC324 - [2018]
 Schottky contact
a. Schottky contact is normally used for rectification, particularly in applications
which includes mixed signals i.e. in RFID tags
 Carriers are allowed to flow through the contact in one direction (polarity) and blocked
in the other of the applied voltage (depending on the semiconductor)
 Aluminium or titanium are commonly used as Schottky contacts to most p-type organic
semiconductors since qm < qosc (e.g. Al = 4.3 eV and osc = 4.5 – 5 eV)

E.g. Typical Current-Voltage

Rectification of an AC signal
characteristics of a diode (n-type)

ELEC324 - [2018]
 Ohmic contact
b. Ohmic contact in organic Schottky diodes is normally used as a ‘reference’
contact i.e. to make connection to the organic semiconductor

 Ideal Ohmic contact allows equal carriers to flow in

both direction or polarity of the applied voltage i.e. no
potential barriers to carrier flow, and thus equal current

 Gold, copper and platinum/palladium metals are

commonly used as Ohmic contacts to p-type organic
semiconductors since qm > qosc (i.e. Au = 4.8 - 5 eV)

 Most of these contacts however do not form a perfect

Ohmic contact with the organic semiconductor due to
E.g. Typical Current-Voltage
mismatches in the work functions and subsequently characteristics an Ideal Ohmic contact
resulting in small potential barriers

 Such barriers results in ‘contact resistance’ issues that limits the current flow and thus
affects the performance of the devices particularly at low voltages

 In organic devices, the ohmic behaviour can be improved using chemical treatments
where self-aligned monolayers are introduced, and alter the barriers at the interface

 In the following discussion, we will assume initially perfect ohmic contacts

ELEC324 - [2018]
Energy diagram of metal and n-type before contact
 In order to understand the barrier formation at junction/interface of a metal (Schottky
contact) and n-type semiconductor, consider a simplified energy band diagram of the
two prior contact. Note the focus here is on the Schottky contact only

 In this case we assume, the work function of the metal qm is greater than the work
function of the semiconductor qs (Note to make schottky contact with p-type
semiconductors, m needs to be smaller than s)

Evac Evac edge of conduction band

i.e. states are almost empty
qs q of electrons
qm
EC or (LUMO)
EF
EF Probability of finding states
filled with electron is half (0.5)

EV or (HOMO)
edge of valence band
i.e. states are almost full
of electrons

metal n-type semiconductor

ELEC324 - [2018]
 Energy diagram of metal and n-type after contact
 Upon contact, electrons from semiconductor move into the metal to reach thermal
equilibrium. At equilibrium the Fermi levels in both materials are aligned

 This results in energy band-bending at the interface where an energy barrier of qB
and depletion region of width W is formed on the semiconductor side

electrons
Potential barrier which can be lowered
due to Schottky effect

qm
qs qs
potential barrier due to
qVbi work function difference
qB
i.e. qVbi = q (m - s )
EF

energy barrier at interface

seen by the metal
i.e. B = s -  depletion region of ionised dopant ions
W resulting in a field (max at the interface)

Note: At equilibrium the rate at which electrons from semiconductor cross over the barrier into the
metal is balanced, with those flowing in opposite direction such that no net current is flowing
ELEC324 - [2018]
 Schottky effect
 The potential barrier at the interface can be lowered due to combined effects of
Image force and applied Electric field, or combined known as Schottky effect.
Lets consider these two effects sequentially, so as to determine the amount at
which the barrier is reduced by Schottky effect

a. Image force: The image force barrier lowering occurs when an electron in a metal
results in a hypothetical positive charge in semiconductor, at equidistant from interface
x. The image force Fimage is exerted between the two opposite charges.

Fimage
- +
x x

Metal Semiconductor

 Using Coulomb’s inverse law, which describes the electrostatic interaction between the
two charged particles, the image force Fimage can be given as equation on side

where s is the relative permittivity

of the semiconductor and q is the
electronic charge
ELEC324 - [2018]
 Schottky effect
 Consequently, the potential energy Eimage of the electron at distance x is given as:

q2 dx
  Fimage dx 
16 s  x 2
Eimage

q2
Eimage 
16 s x

 Diagrammaticaly, the variation of energy due to image force with distance can be
represented as below

ELEC324 - [2018]
 Schottky effect
b. Electric Field: In the presence of a field F (don’t confuse with the image force Fimage
discussed previously), the potential energy Eef of the charge is given as:

Eef  q Fx

 And the variation of energy due to applied field is as shown below:

Increasing field

ELEC324 - [2018]
 Schottky effect
 The total energy ET due to image force and applied field is thus given by the equation
(on the side) and described diagrammatical in figure below

q2
ET   qFx
16 s x

 Due to the combined effect the potential

barrier has reduced by  i.e. from initial
value of e to B

 The barrier B is at a maximum at distance

xm from the interface, such that the energy
at this point is at a maximum, or

dET
0
dx
 Or

dET d  q 2 
   qFxm0
dx dx  16 s xm 
ELEC324 - [2018]
 Schottky effect
 Upon solving the previous equation, the expression for xm can be determined, such
that,
dET q2
  qF  0
dx 16 s xm 2

 And thus q
xm 
16 s F

 Subsequently, the expression for which the barrier has reduced i.e. , can be
attained by substituting for the expression of xm in total energy expression, and find
the corresponding energy at this point

q2
ETxm   qFxm
16 s xm

 Then,
q2 16 s F q
ETxm   qF
16 s q 16 s F
ELEC324 - [2018]
 Schottky effect
 Upon simplifying the above equation, the energy at x = xm can thus be given as,

qF
ETxm  q
4 s

 Thus the potential at x = xm as given below,

shows the reduction in the potential barrier

qF
   2 F xm
4 s

 Note the electric field is not constant and

dependent on,
1/ 2
 2 q N D Vapp 
Fmax   
 o s 

Exercise: Derive an expression for the reduction in potential barrier in terms of dopant
concentration ND and applied voltage Vapp
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 Energy diagram under Forward bias
 Assuming a vertical diode, when a positive voltage (i.e.
VF > 0) is applied on the Schottky contact, electrons are
injected from external circuit into semiconductor resulting

Semiconductor
in reduction in depletion region

Schottky

Ohmic
 In disordered organic semiconductors, due to their low
mobility the injection of the carriers is thought to be due
to diffusion mechanism

q (Vbi – VF)
qVbi LUMO
qB LUMO
qB EF
qVF
EF EF

HOMO
HOMO
W

+ VF -
Energy diagram after contact, prior to application
of bias. Note simply focus on the LUMO/HOMO Potential barrier and the depletion region at
levels of the n-type semiconductor the interface reduces
ELEC324 - [2018]
 Energy diagram under Reverse bias
 When a negative voltage (i.e. VR < 0) is applied on the
Schottky contact, electrons flow from metal to the
semiconductor resulting in expansion in the depletion
region of width Wd

Semiconductor
Schottky

Ohmic
 In organics Schottky diode, small bulk leakage current
(i.e. off-currents) flows under reverse

qVbi q (Vbi + VR)

qB LUMO qB
LUMO
EF EF
qVR
EF

HOMO
W HOMO
Wd

Energy diagram after contact, prior to application + VR -

of bias. Note simply focus on the LUMO/HOMO Potential barrier and depletion region at the
levels of the n-type semiconductor interface increases ELEC324 - [2018]
 Organic Schottky diode
 Organic Schottky diode is a simple two-terminal device which utilises both Schottky
and Ohmic contacts, with typical structures include vertical and lateral structures as
shown below:

Schottky
Organic Semiconductor
Ohmic OSC Schottky
Ohmic
Substrate Substrate

Structure of a Vertical Schottky diode Structure of a Lateral Schottky diode

 In vertical structure, the organic semiconductor is sandwiched between the two

contacts whilst in lateral structure, the contacts lie on the substrate and organic
semiconductor is deposited on top

 Typically, gold is used as the ohmic contact and aluminium or titanium as the
Schottky contact in organic diodes

 Vertical structure is preferred over lateral structure due to higher diode performance
however its vice versa in terms of processing since lateral diode has compatible
processes to other lateral devices i.e. organic thin-film transistors (OTFTs)
ELEC324 - [2018]
 Organic Vertical Schottky diode
i. Vertical Schottky Diode Schottky

Vertical Schottky diode can be built on Organic Semiconductor to

either a glass or flexible substrate. An Ohmic

organic semiconductor is sandwiched Substrate

between Schottky and Ohmic contacts E.g. Flexible Schottky
diode made at Liverpool
Structure of a Vertical Schottky diode

 Fabrication processes of the vertical Schottky diode include:

 Ohmic contact (i.e. gold) is deposited using evaporation technique, through a mask (not same
mask as in used in Photolithography) with specific layout and dimensions, on a pre-cleaned
glass or flexible substrate. Typical thickness of the gold is about 50 – 100 nm
 Solution of the organic semiconductor is then deposited, using either spin-coating, drop-cast
or other printing techniques. These methods can result in different morphology and thickness
of the film i.e. from few 100 nm (spin-coated) to 10 µm (drop-cast). For some of these
techniques, controlling the thickness and morphology can be challenging
 Once deposited, the solvent is allowed to dry for sometime (at times through gentle heating)
resulting in a formation of a thin layer of the organic semiconductor of thickness to
 Finally, a Schottky contact (i.e. aluminium), is deposited onto the substrate using evaporation
technique though a mask
ELEC324 - [2018]
 Equivalent Circuit of the Vertical Diode
Vapp Vapp Vapp

Schottky
Cdep Rd
Organic Semiconductor to
Ohmic RS
Substrate

Structure, symbol and DC equivalent circuit of the Vertical Schottky diode

 Voltage (Vapp) is applied on the Schottky diode with respect to Ohmic contact. Depending on
the polarity of Vapp, the diode is either forward or reverse biased

 Equivalent circuit of the diode is as shown above where Cdep and Rd are the depletion
capacitance with parallel resistance, and RS is the series resistance which accounts for
potential contact resistance and resistance of the neutral region of the semiconductor

 For a vertical diode, uniform films of the semiconductor are crucial so as to reduce short-
circuiting effects between the contacts

 The applied voltage and film thickness defines the electric field strength (i.e. F = Vapp/to) and
thus the current density i.e. thinner films results in higher fields and thus higher currents
ELEC324 - [2018]
 Organic Lateral Schottky diode
ii. Lateral structure
Vapp Rd
tg
Vapp RS
Vapp
Ohmic OSC Schottky

Substrate
Cdep

Structure and equivalent circuit of the Lateral Schottky diode

 For a lateral structure, the metal contacts are deposited consecutively on a pre-cleaned
substrate, followed by deposition of the organic semiconductor. This structure eliminates the
issue of short-circuiting observed in the vertical structure

 The gap (tg) between the contacts defines the electric field (i.e. F = Vapp/tg) and thus current.
Note in the vertical structure, the electric field strength depends on thickness of semiconductor,
which can be in range of 100 nm. To achieve this range of gap in lateral structures is difficult
due to low resolution of the equipment. Typical gap sizes are in the range of 10 m

 This lateral structure however is preferred as it has ‘compatible processes’ with other lateral
devices i.e. organic thin-film transistors (OTFTs) thus reducing the overall processing costs
when developing integrated organic circuits
ELEC324 - [2018]
 J-V characteristics of vertical Al/OSC/Au diode
 Below is the Current-Voltage (linear/linear axis) characteristics of three vertical
Schottky diodes with different organic (p-type) semiconductors i.e. pentacene, P3HT
and PTAA, with aluminum as the Schottky and gold as ohmic contact

 When negative voltage is applied on aluminum contact wrt gold, the diode is under
forward bias and the current is high (on current), whilst under positive voltage, the
current is low (off current)
2
2.0x10
Note these semiconductors are
P3HT
p-type, thus the diode is on when
Current Density (Am )
-2
PTAA
negative voltage is applied on 2 Pentacene-derivative
Schottky contact 1.5x10

Derivative of pentacene i.e.

2
small molecule, shows higher 1.0x10
on-currents under forward bias
compared to the disordered
polymers i.e. P3HT and PTAA 1
5.0x10
due to their higher mobility of the
charge carriers
0.0
Useful information can be
attained using logarithmic-linear -10 -5 0 5 10
plots particularly at low currents Voltage applied on Schottky contact (V)
ELEC324 - [2018]
 Log (J) vs. (V) plot of vertical Al/OSC/Au diode
 On-currents vary significantly for different semiconductors, due to difference in potential
barrier formed between the gold and the different semiconductors (i.e. each
semiconductor has a different S for example, P3HT is 4.3 eV, PTAA is 5.1 eV and
pentacene is 5.3 eV. The resistivity of the neutral region is also different for each of the
materials.
forward reverse
 Off-currents are clearly
observed under log-scale. 10
2
P3HT
Reasonably low off-currents

Current Density (Am )

PTAA

-2
are observed for PTAA and Pentacene
pentacene, however higher 10
0

current for P3HT

 Such high off-currents in -2

10
P3HT films are attribute to
the high level of residual
-4
dopant present within the 10
film after synthesis
-6
 Difference film thickness can 10
-10 -5 0 5 10
also contribute to the
Voltage applied on Schottky contact (V)
variation in currents
ELEC324 - [2018]
 Log (J) vs. (V) plot of vertical Al/OSC/Au diode
 In an ideal case, the diode needs to have high on-current and low off-currents. Also
the sub-threshold slope need to be steep i.e. the diode turns on faster under forward
bias. In such organic diodes, there is a some potential drop due to the presence of
potential barrier and for P3HT some kinks are observed

forward reverse On Off On/off

current current ratio
(Am-2) (Am-2)
2
10 P3HT Pentacene 187 1.5  10-5 107
Current Density (Am )

PTAA
-2

Pentacene PTAA 3  10-2 1.5  10-6 104

0
10
P3HT 6.65 5  10-2 102

-2
10
Presence of kinks are associated with
trap states at interface of Al and P3HT
-4
10 Steeper slope is required as it defines
the switching speed of diode. This
exponential region is associated with
-6
10 exponential increase in DOS and
-10 -5 0 5 10 consequently the carrier concentration
Voltage applied on Schottky contact (V)

ELEC324 - [2018]
 PTAA diodes with different ‘Ohmic’ contacts
 Plots below shows changes in on-currents for PTAA diodes only, with different
‘Ohmic’ contacts. Best ohmic contact is obtained with Platinum/palladium alloy (Pt/Pd)
which forms smaller potential barriers with PTAA, due to its larger work function.
However Pt/Pd is expensive and thus gold (Au) is commonly used. The ‘ohmic’ nature
of Au can be improved by chemically treatment prior to deposition of polymer

3 Similar off-currents (approx. 2  10-5 Am-2) in

10
all diodes as it is not directly dependent on
with Pt/Pd
the ohmic but rather Schottky contact and
with treated Au
Current Density, J (Am )

resistivity of the semiconductor bulk

-2

1
10 with untreated Au
Different on-currents are attributed to the
-1 presences of different potential barrier
10
between ohmic contact and semiconductor

Ohmic Work On On/off

-3
10 contact function current ratio
(eV) (Am-2)

-5 Pt/Pd 5.1 - 5.6 3  102 1.5 106

10
Au 4.8 - 5 1 5 104
(treated)
-7
10 Au 2  10-3 102
-15 -10 -5 0 5 10 15
(untreated)
Voltage on Schottky contact (Volts)
NB: Work function of PTAA = 5.1 eV
ELEC324 - [2018]
 PTAA diodes with different gap sizes
 Plots below shows changes in on-currents for PTAA diodes only, with different ‘gap
sizes tg (for a lateral structure). As the gap size reduces, the on-current increases due
to an increase in lateral field. The off-current vary slightly, which results in increase in
the current on-off (rectification) ratios

 Useful information and key parameter can be extracted from the characteristics as
discusses in the next slides

tg (m) Ion/Ioff
3.0 16

2.0 56

1.4 93

0.8 114

0.25 1200

0.05 1500

ELEC324 - [2018]
 Forward Characteristics
 Detailed analysis can be carried out on the forward characteristics and key parameters
can be extracted which provide useful information regarding diode performance. The
two regions in the forward characteristics to be considered are the exponential and
saturation regions (in log scale)
 Upon application of a forward bias, the current initially increases exponentially due to
an exponential increase in DOS and thus exponential increase in carrier concentration.
Once the states within a specific energy are filled with carriers, the current saturates and
thereafter dependent on the bulk resistance of the organic semiconductor

2
In the saturation region, 10 P3HT
the current is dependent
Current Density (Am )

PTAA In the exponential region, the

-2

on voltage as: Pentacene current is given as:

J  VFsat 
0
a 10
 qVFexp 
J  exp  
 kT
a is a constant -2
10  o 
To is a characteristics
-4 temperature describing the
10 distribution of the carriers and k
is Boltzmann’s constant
Current is low until after
certain ‘turn-on’ voltage, -6
required to overcome the 10
-10 -5 0 5 10
potential barrier
ELEC324 - [2018]
Voltage applied on Schottky contact (V)
 Carrier Concentration
 In lecture/tutorial, we determined the expressions for the carrier concentration nf
assuming Maxwell-Boltzmann statistics for the distribution, and either exponential or
Laplace for DOS, which resulted in the two equations below respectively. Note that both
equations show that nf increases exponentially with characteristic temperature of the
states or traps TC

E  E 
n  N ' 0
kTo
n  N ' 0 kTo exp  F  (1) or exp  F  (2)
 kTc  kTc  kTc 

 Assuming the condition leading to Eq. (2), when a

forward bias is applied on the diode, the Fermi
level shifts to higher energy where the DOS
increases exponentially and subsequently the carrier
concentration also increases exponentially with
energy following an expression as given below,

ELEC324 - [2018]
 Carrier Concentration
 Note Tc describes the distribution of the states/traps and is attributed to To which is
the distribution of the carriers as:

1 1 1
 
To T Tc

 Another essential parameter in disordered organic semiconductor is the Meyer-Neldel

Energy (MNE) (discussed in earlier lecture) which is given as:

𝑘𝑇𝑐
𝑀𝑁𝐸 = (𝑢𝑛𝑖𝑡𝑠 𝑖𝑛 𝑒𝑉)
𝑞

 In silicon, the value of the MNE is,

𝑘𝑇 1.38 × 10−23 × 300

×𝑒 = × 𝑒 = 0.026 𝑒𝑉 = 𝟐𝟔 𝒎𝒆𝑽
𝑞 1.6 × 10−19

ELEC324 - [2018]
 Forward Current in Exponential region
VFexp
 In the exponential region (i.e. at low forward bias
VFexp) the current density can be expressed as: 2
10 P3HT

Current Density (Am )

PTAA

-2
 qVFexp  Pentace

J exp  exp   0
10

 kTo 
-2
10

 qVFexp 
Or J exp  J o exp  

(3) -4
10
 kTo 
-6
10
-10 -5 0 5
 Note in Silicon Schottky diodes, the current Voltage applied on Schottky contact (
density is usually expressed as:

  qVFexp    qVFexp 
J  J o exp    1  J o exp   (4)
  kT
      kT 

Where Jo is a constant and  is an ideality factor

ELEC324 - [2018]
 Forward Current in Exponential region
 Ideality factor is an important parameter in diodes as it attributed to the interface
properties between the metal and semiconductor

 For organics, a relationship for the ideality factor can be obtained by equating
equations 3 and 4 in previous slide, such that

 qVFexp   qV 
J o exp    J o exp  Fexp
  kT


 kTo   

 Or the ideality factor is given as,

To

T

 The value of ideality factor can be obtained from the slope in the exponential region.
For ‘ideal’ silicon diodes, the value is typically 1 however for organic diodes, the ideality
factor, in most cases, is greater than 1

ELEC324 - [2018]
 Characteristic Temperature and Ideality factor
 Highest ideality factor is observed on P3HT Schottky diode which may account for the
presence of the kink, probably due to the presence of additional traps at the interface
of the metal and P3HT

 Best ideality factor obtained with pentacene diode which shows a steeper slope in the
exponential region

2 Note kT/q = 0.026eV at T = 300K

10 P3HT qVFexp  or
 J o exp   k/q = 8.66  10-5 eVK-1
Current Density (Am )

J exp PTAA
 kT 
-2


Pentaceneo 
0 To
10 
T
To = 1664 K
-2
10 To 
To = 414 K (K)
-4 Pentacene 414 1.38
10
To = 512 K PTAA 512 1.7

-6 P3HT 1664 5
10
-10 -5 0 5 10
Voltage applied on Schottky contact (V)
ELEC324 - [2018]
 Characteristic Temperature and MNE
 The values for the characteristics 2
temperature of the traps (TC) and 10 P3HT qVFexp 
exp 
J exp  J o PTAA 


Current Density (Am )

-2
also the Meyer-Neldel energy for  kTo
Pentacene 
the diodes with different organic 10
0

semiconductor can be obtained as

summarised in table below
-2
10

 Note: 1 1 1
  -4
To T Tc 10

kTc
MNE  -6
10
q -10 -5 0 5 10
Voltage applied on Schottky contact (V)

Von  To Tc MNE
(V) (K) (K) (meV)

Pentacene - 0.95 1.38 414 1089 94

PTAA - 1.1 1.7 512 725 63

P3HT - 0.6 5 1664 366 32

ELEC324 - [2018]
 Forward Current in Saturation region
 In saturation, the current is limited either by bulk VFsat
conduction or contact resistances (or both). The 2
current depends on the applied voltage to a power 10 P3HT

Current Density (Am )

PTAA

-2
exponent a, Penta

 
0
a 10
J Fsat  VFsat
-2
10

 For perfect Ohmic contacts, a ~ 1 i.e. the current

is controlled by the resistivity of the semiconductor -4
10

 In such case, Ohm’s law can be applied and -6

10
consequently the ‘effective’ bulk mobility b can be -10 -5 0 5
estimated using the equation below, Voltage applied on Schottky contact

J Fsat   F
where F is the field across the
neutral regions and tn is
VF sat thickness of the neutral region
J Fsat  n q b
tn
ELEC324 - [2018]
 Forward Current in Saturation region
 However if a  2, then the current is thought to be controlled by bulk effects following
space-charge limited current (SCLC)

 Space charge occurs when there is excess charge in a system but treated as
continuum of charge distributed over a region of space rather than distinct point-like
charges

 In disordered organic semiconductors, space charge effects are pronounced due

to presence of traps in the bulk of semiconductor and at the interface between the
semiconductor and metal

 In presence of traps, SCLC is consequently expressed given as,

where

and

where s is the relative permittivity of the organic semiconductor, o is the permittivity of free space, tn is the
film thickness, K is the mobility pre-factor (Not Boltzmann’s constant), q is the electronic charge, m is a
constant and  is the carrier concentration dependent factor of trapped nt and free charge nf
ELEC324 - [2018]
 Forward Current in Saturation region
 P3HT diode shows Ohmic conduction since a ~1, possibly due to lower potential barrier
at the interface, which is reduced due to the presence of residual dopants in the film.
This subsequently enhances the transport mechanisms of carriers. PTAA and
pentacene diodes shower higher values of a i.e.  2 suggesting SCLC conduction,
and/or presences of trap within the film

Using the data in exponential region

only (i.e. forward bias voltage
JF saturation region (Am )
-2

100 a~2 between |5 – 10| V), the value of ‘a’

can be determined using equation
below and plotting log (JFsat ) vs. log
P3HT
(VFsat ) plots. The value of ‘a’ is
a~3 estimated from the slope
PTAA
Pentacene

 
10 a
J Fsat  VFsat

a~1
 
loge J Fsat  C  a loge VFsat  
1 C is a constant
5 6 7 8 9 10
| VF | saturation region (Volts)

ELEC324 - [2018]
 Reverse Characteristics
 Upon application of reverse voltage on the
Schottky contact, the potential barrier at
the interface increases i.e. q(VR + Vbi) and
the depletion width Wd expands

 The depletion width continue to expand

with increase in reverse bias, until a
maximum depletion width is reached. This
Wmax corresponds to the concentration of
the dopants present in the semiconductor
Wmax

 Under such condition, the current increases exponentially and is dependent on the
applied field by VR0.5 and on image charge force by VR0.5, which consequently
has a combined effect of VR0.25 as:

J R  exp B  N A VR 
0.25

B is a known constant, NA is the dopant concentration and VR is applied reverse bias

ELEC324 - [2018]
 Reverse Characteristics
2
10 P3HT
J R  exp B  N A VR 
0.25

Current Density (Am )

PTAA
-2
Pentacene
0
10

-2
10

-4
10

-6
10
-10 -5 0 5 10
Voltage applied on Schottky contact (V)

 Doping concentration can be estimated from the slope of log JR against VR0.25 plot. This
however assumes an abrupt depletion region edge i.e. charge density of dopant ions falls
abruptly at the edge of depletion and neutral regions. In real case the depletion region
edge extends into the neutral region by a small distance known as the Debye length Ld,
discussed later in capacitance studies
ELEC324 - [2018]
 Doping Density from Reverse characteristics
 Good linear fit for the log JR against VR0.25 plot is obtained at high voltages and the
doping density estimated from the slope for P3HT is about 4 1016 cm-3 or 4 1022 m-3.
At low voltages deviation is due to built-in potential effects
-1
10
P3HT

-2
(Am )

10
-2

16 -3
NA = 4 x 10 cm
JR

-3
10

-4
10
0.0 0.5 1.0 1.5 2.0
0.25 0.25
| VR | (Volts)

Doping concentration of the semiconductor can also be extracted from Capacitance-Voltage

characteristics as discussed in the next slides
ELEC324 - [2018]
 Charge Density under Depletion
 As mentioned earlier, under reverse bias, depletion
region is formed which consists of ionised dopant ions.
Note for n-type semiconductor, the ions are positively LUMO
charged, and for p-type semiconductor, the ions are
negatively charged

HOMO
 Depletion width extends as the reverse bias increases.
This depletion width Wd reflects concentration of the Wd
dopants ND available in the semiconductor


 Charge density attributed to the dopant within the depletion neutral

depletion region in the semiconductor is given by ND ND
(positive) and on the metal is given by Q (negative)

 The edge between the depletion and neutral region is x

assumed to be abrupt however this extends by the Wd LD
some distance known as the Debye length LD
Q
Metal Semiconductor (n-type)
ELEC324 - [2018]
 Electric Field in Depletion
 The field is at maximum at the interface between
metal and semiconductor, and drops linearly with LUMO
distance. In the neutral region the field is negligible

 The voltage across the junction can be simply HOMO

expressed as the area under the triangle i.e.
Wd

F W
Vbi  max d neutral
2 depletion

ND
 Note d Where d is change in
F  x   potential across the
dx junction with distance dx
x
Wd
 To obtain the expression for the field, we can apply
Q
Gauss law and solve Poisson equation, such that:

dF  x    x  qN D F
 
dx  o s  o s Fmax

Where o is the permittivity of free space and s is the relative

permittivity of the semiconductor F=0
ELEC324 -x[2018]
Wd
 Depletion Width
 Integration both sides, 0 Wd
F
qN D
 dF  x    dx Fmax
Fmax 0 o s

F=0
x
 Such that, qN DWd 0
Fmax  
 o s Wd

 Substituting for field in earlier expression, the voltage can thus be expressed in terms
of the depletion width, dopant density and relative permittivity of semiconductor as:

qN DWd 2
Vbi 
2 o s

2  o s Vbi
 The depletion width (at zero bias) is thus given as , Wd 
qN D

 As the reverse voltage increase,

ELEC324 - [2018]
 Depletion Capacitance of Schottky diode
 The depletion capacitance per unit area, associated with the depletion region is
given as:
 o s
C
Wd
 As the reverse bias increases, depletion region expands to width Wd and the depletion
capacitance C falls i.e. C is inversely proportional to Wd. Note this continues until a
maximum depletion width is reached

 Substituting for Wmax, q  o s N D

C
2 VR  Vbi 

 The dopant concentration can consequently be extracted from the slope of the
capacitance against voltage characteristics using the equation below:

1 2 VR  Vbi 

C2 q o s N D

 The variation of such capacitance with frequency of the applied ac signal is also
important particularly for semiconductors with low charge carrier mobility
ELEC324 - [2018]
 Variation of Depletion Capacitance of P3HT Schottky
diode with frequency
 As the DC bias increases, the depletion width increases resulting in a drop in depletion
capacitance however 1/C2 increases. And under AC measurements, as the frequency
increases, 1/C2 falls which changes the slope and thus the value of NA extracted from the
slope. This change is attributed to the low mobility of the charge carriers of P3HT

8
2.0x10 200 Hz
400 Hz
Increase in frequency
500 Hz
-2 -2

8
1.5x10 1 kHz
(Fm )

2 kHz
3 kHz
8
1.0x10
2
1/C

7
5.0x10

0.0

-4 -2 0 2 4 6

Applied Voltage, Vapp (Volts)

ELEC324 - [2018]
Variation of Dopant Concentration with frequency
 Such variation in slope leads to erroneous values of dopant concentration. The ‘true’
value of NA is obtained at low frequencies (i.e. 100 Hz) where the carriers are able to
follow the AC signal due to their low mobility
 In earlier current density against voltage plot in reverse i.e. JR Vs. VR0.25, the dopant
concentration was found to be approx. 4  1016 cm-3 or 4  1022 m-3, which agrees with
the value measured at low frequency i.e. < 1 kHz. Note this value changes with
semiconductor due to difference in mobility (bulk) of the charge carriers
Calculated doping density, NA (m )

23
-3

10

~21022 m-3

22
10

~ 21021m-3

21
10
100 1k 10k 100k

Frequency, f (Hz) ELEC324 - [2018]

 Bulk mobility
 Assuming Ohmic conduction (only for P3HT Schottky diodes in Figure below since
a =1 ), the ‘bulk’ mobility of the carriers can be obtained assuming that every dopant
concentration results in a free carrier i.e. n ~ ND

 Current density is given as

JF saturation region (Am )

-2
100 a~2
VFsat
J F sat  n q b a~3 P3HT
tn PTAA
Pentacene
10 JFsat = 7
J t
Or b  F sat n VFsat = 10
n qVFsat a~1

1
5 6 7 8 9 10
 Substituting appropriate values: | VF | saturation region (Volts)

b 

7  10 106
 1109 m 2V 1s 1

   19
4 10  1.6 10 10
22

 Crystalline silicon has mobility of 1 m2V-1s-1 whilst amorphous silicon 10-4 m2V-1s-1.
Mobilities of organic polycrystalline semiconductor matches and in some cases, even
higher than those of amorphous silicon
ELEC324 - [2018]
 Effect of Doping of Organic semiconductor
 Organic semiconductors, particularly disordered i.e. P3HT can be doped, by
introducing dopant atoms i.e. DDQ, in solution by percentage in weight

 For doped diodes, the on-currents (and mobility) increases by many orders of
magnitude due to increase in carrier concentration. However doping also increases
off-currents due to enhanced bulk conduction, making the diode non-operational

-3
undoped P3HT film
10 doped P3HT film

-5
10
(A)
Current

-7
10

-9
10

-11
10
-10 0 10
Voltage on Schottky contact (V)
ELEC324 - [2018]
 Doping Concentration of Doped films
 For doped P3HT diode, two doping concentration are obtained which indicates that
the dopants are not uniformly distributed across the film
 Furthermore, the value of the dopant concentration extracted from the plots does not
correspond to the amount of the added which suggests that not all added dopants are
ionised. Doping in organics semiconductors is different to conventional silicon

2 undoped P3HT film

10
doped P3HT film

1.24  1024 m-3

(Am )
-2

18 -3
16 -3
NA2 ~ 3.2 x 10 22cm -3 NA3 ~ 1.24 x 10 cm
3  10 m
0
10
JR

-2
10
4  1022 m-3
16 -3
NA1 ~ 4.75 x 10 cm

-4
10
0.0 0.5 1.0 1.5 2.0
0.25 0.25
VR (Volts)
ELEC324 - [2018]
 Doping of Organic Semiconductors
 Electrical conductivity and consequently mobility of organic semiconductor PolyDOT3
was first varied by introducing ‘dopant’ PEDOT, and measured using thin-film
transistors. Similar results were also obtained on organic semiconductor P3HT using
DDQ as dopant measured using Schottky diodes at Liverpool

 Similar trends were obtained however the ‘bulk’ mobility measured using Schottky
measurements are lower than those of field-effect mobility using transistors. Bulk
mobility values µb tend to be generally about two orders of magnitude lower than field-
effect mobility µfe due to lower carrier concentrations in the bulk

 fe  102 b

 In order to understand the effect of dopant on mobility, lets consider the bulk
measurements carried out on Schottky diodes using P3HT, doped with controlled
amounts of DDQ in solution, as in the next slides

 Note when a material is doped with dopant concentration ND, the bulk conductivity
increases  which subsequently results in increase in bulk mobility µ

ELEC324 - [2018]
 Conductivity vs. Doping Concentration
 Conductivity of disordered organic semiconductor increases with dopant concentration
following expression below:

  N D or   K1 N D  Where K1 and  are constants

Experimental data of P3HT doped with DDQ

-2
doped P3HT Plot of Conductivity of P3HT
10 linear fit (log-scale) against Dopant
Conductivity,  [sm ]
-1

concentration (log-scale)

-4
10 For this polymer, an increase in
dopant concentration enhanced
in conductivity by about x1.7 i.e.
10
-6 2 orders increase in density of
DDQ results in 5 orders increase
slope,  ~ 1.7 in conductivity of P3HT
-8
10 21 22 23 24 25
10 10 10 10 10
-3
Doping density, NA [m ]

 Taking log of above equation, we have: log e    log e K1    logELEC324

e N D- [2018]

 Mobility Vs. Conductivity
 The mobility of organic semiconductors increases with conductivity following the
expression below:
  K2   Where K2 and  are constants

Experimental data of P3HT doped with DDQ

doped P3HT
Bulk mobility,  [m V s ]
-1 -1

-7 linear fit Plot of bulk mobility of P3HT (log)

10 against conductivity (log)
2

An increase in bulk conductivity

enhances in bulk mobility by about
10
-9 0.7 i.e. 2 orders increase in
conductivity results in approximately
an order increase in bulk mobility
slope,  ~ 0.7
-11
10 -8 -7 -6 -5 -4 -3 -2 -1
10 10 10 10 10 10 10 10
-1
Conductivity,  [sm ]

 Taking log of above equation, we have: log e    log e K 2    log e  

ELEC324 - [2018]
 Universal Mobility Law (UML)
 Using the previous equations, a direct relationship between mobility and doping
concentration can be obtained:

  K1 N D  and   K2  

 Such that:

  K 2 K1 N D  
K K 2

1 ND


 Or   K ND   where K = K2K1 is a constant

 The power dependency has also been found to follow:

 1
 

 Substitute this in the above mobility equation, we find

 K N D  1
ELEC324 - [2018]
 Universal Mobility Law (UML)
 Assuming that every dopant added constitutes to a free carrier i.e. ND ~ n (assuming
n-type semiconductor) then ,

  K n  1

or   K nm where m   1

 This empirical relationship between carrier mobility with concentration is known as the
Universal Mobility Law

 The constant m has also been related to the Meyer-Neldel energy as,

Tc
m 1
T

 Values of m changes depending on the type of semiconductor used and also depends
on the region of operation i.e. the value of m measured in diodes is much greater than
that in OTFT. This will be described further later.

ELEC324 - [2018]
 Significance of VRH on UML assuming Laplace DOS

Increase in carrier
concentration results in
increase in mobility due
enhance hopping of
At much high energy, even carriers
though there are more states,
the density of carriers is low as
the EF is much lower, and thus
no conduction occurs LUMO (assuming n-type)

ET Transport energy ET is assumed to be

close to EF i.e. in inorganic
semiconductor, this would be at the
edge of conduction band
Electron energy

 Initial carriers introduced by doping occupy the lower states where the hopping
distances rij are larger thus the carriers are trapped and immobile – low mobility
 Further increase in concentration results in higher level states being occupied where
the hopping distance are smaller hence increase in mobility
ELEC324 - [2018]
 Organic Schottky diode as Rectifiers
 Schottky diodes are important for use as rectifiers in various mixed signal applications
such as in Radio Frequency Identification (RFID)

 RFID uses electromagnetic fields to automatically identify and track tags attached to
object. It is commonly exploited in areas of Automatic identification, transport and
logistics, and improved data handling process

 Organic Schottky diodes are widely being researched for integration as key functional
blocks for use in various mixed signal application particularly in RFID tags, which
needs to operate at a base carrier frequency of 13.56 MHz

 Single diodes may be used for the half-wave rectification of an incoming signal or a
bridge of diodes, for full-wave rectifications

Half wave Rectification of an AC signal ELEC324 - [2018]

 Bridge Rectifiers
 For a sinusoidal input signal, when input is positive,
current flows through the diodes highlighted on the
left and when negative through diodes on the right,
which results in two half rectifications and when
combined the diode bridge achieve a full rectification.
All the diodes must have same operating conditions.

Half rectifications

Full rectification without capacitor Full rectification with capacitor to smoothen the
signal for DC ELEC324 - [2018]
 Basic operation of RFID

Transmitting Sensor

antenna Tag antenna

(13.56MHz) (40.68MHz)

(transmit) (receiver)

Tag Tag Sensor

Transmitting Ctune coil
coil antenna
antenna (rx) (tx) (rx)
(tx)

(13.56MHz) (40.68MHz)

Example of a simplest RFID tag design. In most complex design, an integrated

circuit and memory device are also included
ELEC324 - [2018]
 Basic operation of RFID
 For RFID application, a mixed incoming signal is transmitted via an antenna or coil,
which is picked by tag antenna using inductive approach, tuned at 13.56 MHz

 The tuning capacitor amplifies the signal received by the tag, and subsequently the
signal is rectified by the diode or diode bridge (half wave or full wave) resulting in a
DC signal

 For a simplest design, this signal may then be transmitted to the 2nd antenna on the
tag, and subsequently transmitted to the reader antennae tuned at a different
frequency i.e. 40.68 MHz

 The tag can be ’killed’ if the power of the received signal by the tag is greater than
normal. This may be achieved by placing the tag next to the antenna so that the
induced signal power is at a maximum i.e. the voltage is greater than the breakdown
voltage of the dielectric used in the tuning capacitor resulting in a short circuit

ELEC324 - [2018]
 AC response of Organic Schottky diode
 Schottky diode forms a key part of the tag in RFID applications, and in order for the
diode to be used effectively, it needs to be able to operate at high frequencies
i.e.13.56 MHz

 Simple measurement as indicated in the set-up below can be used to characterise the
AC response of the Organic Schottky diode (labelled DUT)
 An ac signal is input into the Schottky diode. The signal is rectified and the current from the
diode flows through the load resistor, resulting in a voltage measured across such high
resistor (in this case1 M) using an oscilloscope
 The frequency of the AC signal is altered and the output voltage is re-measured
 For use in RFID, the diode needs to be able to rectify the signal at frequency of 13.56MHz

DUT 1MΩ Resistor

Input signal

Agilent Signal
Generator Oscilloscope

Measurement set-up for AC response of the Organic Schottky diode

ELEC324 - [2018]
 AC response of Organic Schottky diode
 Below shows rectification properties of a disordered vertical organic Schottky diode
measured at 50 Hz, 100 Hz and 1 KHz. The responses are poor particularly with
increase in frequency, as the diode was unable to rectify the signal. At such high
frequencies, the carriers are unable to follow the fast AC signal due to the low mobility
of the charge carriers. This is more problematic for disordered diode due to their lower
mobilities of about µ = 10-2 – 10-4 cm2V-1s-1 compared to polycrystalline diodes

 Furthermore, the rectified voltage is lower compared to amplitude (peak-to-peak) of the

input ac signal. This is may be caused by the low on-currents, due to the contact
resistance effect. The current may be enhanced by increasing diode area

3.0µ 3.0µ 3.0µA

50 Hz Vacuum 100 Hz Vacuum Vacuum
1 KHz
Air Air Air
2.0µ 2.0µ 2.0µA
Current (A)

Current (A)
Current (A)

1.0µ 1.0µA
1.0µ

0.0A
0.0 0.0

-1.0µA
-1.0µ -1.0µ
0s 10ms 20ms 30ms 40ms 0s 5ms 10ms 15ms 20ms 0.0 500.0µ 1.0m 1.5m 2.0m
Time (s) Time (s) Time (s)

 Also the performance drops when the diode is exposed to ambient conditions, due
to photo-oxidation effect. Encapsulation of the diodes is vital ELEC324 - [2018]
 Issues of Organic rectifiers
 The low mobility of the charge carriers (i.e. holes) particularly for disordered
semiconductors limits their use in several high frequency applications e.g. RFID, where
the diodes need to operate at 13.56 MHz
 Novel higher mobility semiconductors are needed
 Best diode performance observed are with polycrystalline (i.e. pentacene) semiconductors

 Degradation or photo-oxidation issues can result of formation traps within the

semiconductor thereby limiting the performance i.e. reduce the switching speed (poor
ideality factor)
 Encapsulate the device from exposure to air and light

 Use appropriate metal contacts for the Schottky but more importantly for the Ohmic
contact since the turn-on voltages and on-current may be compromised due to presence
of contact resistance
 Better surface treatments or modifications if using gold contacts
 Better alternative metals could be explored for used in conjugation with different organic
semiconductors layers

ELEC324 - [2018]
 Other issues of Organic rectifiers
 Parameter spreads i.e. turn-on voltages, ideality factors, and on-current between the
various diodes built on the same substrate need to be controlled. For example if a
diode bridge is used, then its crucial that all the diodes on the bridge have identical
operating conditions
 Optimising processing condition i.e. control over film morphology and uniformity
 Encapsulation and isolation process (i.e. leakage paths) developed to reduce cross talk
between integrated devices/components

 For integration of the diode with other devices, it is essential to have compatible
processes with small number of steps so as to reduce costs
 Vertical Schottky diode is tricky to integrate with lateral devices i.e. OTFTs
 Alternative structures for the rectifiers have been explored e.g. Lateral Schottky
diodes and gated-OTFT where the drain and gate of are shortened

ELEC324 - [2018]
 Revision Questions
1. Describe Schottky effect in barrier lowering

2. Describe the operation of an organic Schottky diodes under forward and reverse bias

3. Describe ideality factor and how this compares to inorganic semiconductors i.e.
silicon

4. Describe the current issues of organic Schottky diode hindering its use applications
such as in RFID

Next lecture
Metal-Oxide-Organic Semiconductor (MOS) capacitors

ELEC324 - [2018]