Properties of Organic Materials

used as Dielectric in Thin Film

devices

By
Shreyans Toshniwal
Course- Impedance and Dielectric Spectroscopy, MSE 7140
Term- Fall 2023

Department- Materials Science and Engineering

Georgia Institute of Technology
Atlanta, GA

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Abstract
This presentation provides an overview into the properties of Thin Films fabricated using Organic
Dielectrics. We understand the dielectric response of organic dielectrics based Thin Film components
used in Memory Storage Applications, Photovoltaics and Multilayer devices. The characterisation
data for Aloe vera (organic dielectric) is analysed from the perspective of J-V characteristics including
the details for Resistance Switching Cycle and the effect of temperature on the Aloe vera Thin Films.
The dielectric properties of Organic Photovoltaic Materials and Organic dielectrics using Light
Emitting/Electroluminiscent devices have been analysed with varying bias Voltage, V and
determining relation of Capacitance and Dielectric constant of OPV material.

Introduction

 Description of Organic dielectrics

Organic dielectrics are electrically stable polymers that can have enhanced dielectric and energy
storage properties. In simple terms, Organic dielectrics refer to materials with organic (carbon-
containing) compounds that exhibit insulating properties.

The motivation behind using organic materials-

• Simple and low-cost processing/fabrication and

• Lightweight and mechanical flexibility

• compatibility with flexible substrates used for wearable electronics that acquire the major
market share in consumer electronics.

• Low temperature processing condition

With these advantages, organic materials have demonstrated their capability to be used in organic
thin film transistor (OFET), organic light-emitting device, organic solar cell, photovoltaic cell, sensor,
and memory device.

Fig. 1. Pentacene dielectric based PES substrate thin film

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  Thin Film Transistor (TFT) Model description

Fig. 2. Structure of a Thin Film Transistor

The layers of a TFT include:

 Metallic gate electrode

 Gate dielectric film
 Semiconductor channel
 Source/drain electrodes

In TFT, there is a thin film layer between source and drain that could produce carrier to create
conducting channel according to the control voltage from the gate. TFT is a type of metal-oxide-
semiconductor field-effect transistor (MOSFET). However, TFTs are essentially improved versions of
MOSFETs.[13]

The primary difference between TFTs and conventional MOSFETs is their semiconductors. TFTs utilise
distinct substrates and semiconductors — commonly glass and metal oxides, respectively. However,
conventional MOSFETs utilise a semiconductor material that doubles as the substrate.

The performance of TFTs is significantly affected by channel semiconducting materials. Not only
semiconductor layer, as an active region, can be replaced by organic material but organic dielectric,
as a passive region, have been demonstrated as a good insulating layer in organic device, such as
OTFTs, OFETs, etc. The drift motion of carriers in OTFT is achieved though the π-bonding orbitals in
conjugated molecular organic materials. Unlike other TFTs mentioned before, OTFT manufacturing
process usually does not contain doping technology. Compared with TFTs made of inorganic
materials, one key characteristic that OTFT possesses is its amazing compatibility with flexible
substrate. This unique feature has inspired researchers to develop OTFT containing cheap substrates
to realize both portable and foldable display devices.[13]

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Dielectric response of organic dielectrics used in various applications

a. Memory Storage Devices

Fig.3. Organic Field Effect Transistor

Memory is a basic electronic device for many computer systems to store digital information
before or after being processed by the central processing units (CPUs. As the industry players
draw economic sense by continuously downscaling the memory devices, RAMs and flash
memories are approaching their physical miniaturization limits in near future).

Of these emerging memories, RRAM appears to be a promising candidate due to their excellent
down-scalability, fast switching speed, and 3-dimensional (3D) stacking capability. Resistive
Random Access Memories (RRAMs) are being proposed as the next-generation memories for
low-cost, high-density, and low-power information storage.

An RRAM cell is a two-terminal device composes of a resistance switching material interposing in

between two electrodes. Resistance switching phenomena have been demonstrated in several
bioorganic materials such as tobacco mosaic virus, silk proteins, Aloe vera, gelatine, etc.

Aloe vera thin films demonstrate exceptional dielectric properties that can be used in passive
regions of Organic field-effect transistors (OFETs) and Resistance switching phenomena in thin
films based on Aloe vera gel can be employed in active regions of memory devices. Resistance
switching occurs due to charge trapping and filamentary conduction in thin films.

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 Fabrication Process: Drop Casting

1. Synthesis of Aloe vera Solution

Natural Aloe vera gel was extracted from freshly harvested Aloe vera leaves. 50 mg Aloe
powder was dissolved in 10 mL DI water.

2. Drop Casting-
A drop casting method has been used to deposit the Aloe vera solution onto the glass
substrate see fig. 2. This method is best applied to form a variety of thin films and allows high
throughput from a simple device and no material is lost.

Fig. 4. Drop Casting process [1]

3. Drying and Pyrolysis-

The deposited film is dried on hot plate at 100 Celsius and then pyrolyzed in a tube furnace
to let the aloe vera film bind well to the substrate.

4. Ag Electrode Thermal Deposition-

The device was completed after an array of 100-nm thick Ag was thermally evaporated at a
base pressure of ~2.25 × 10–3 Torr through a metal mask.

Fig. 5. Aloe vera RRAM Thin Film structure [10]

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 Measurement / Characterization

 J-V Characteristics of Aloe vera thin films using Probe Station

1. Resistance Switching Cycle

Fig. 6. Electrical characteristics of the device with the Aloe vera layer dried at 50°C:
resistance switching cycle. [10]

Grey solid lines represent the experimental data and red solid lines represent the statistical
mean of the experimental data.

Cycle: 0 -> -1.5 -> 0 -> 1.5 -> 0 volts

• Reset Voltage= -0.75 V. It is accounted for the reverse bias voltage attributed to the
localized Joule heating in the layer that leads to oxidation of Ag. leading to its dissolution
(Ag → Ag+ + e–) and hence the device undergoes resistance state transition from LRS to
HRS.

• Set Voltage= 0.87 V. The residual ions (Ag+) within the Aloe vera layer contribute toward
the reformation of filament at a smaller set voltage when a positive voltage bias is being
applied.

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 2. What happens on varying the Drying temperature?

Fig 4. Electrical characteristics during resistance switching cycle with the Aloe vera layer dried
at 50°C, 80°C, 120°C and 150°C [9]

The drying temperature of the Aloe vera layer is critical in determining the J–V characteristics.

Points to note-

1. The set voltage reduces considerably from 0.85 V to 0.42 V when the drying temperature is
increased from 50°C to 150°C.

2. Meanwhile, variations of the reset voltage in the range of –1.12 V to –0.85 V is less significant
when compared to the set voltages.

3. The large variation of set voltage can be due to -

a. electron transfer rates at the interfaces

b. ionic transport in the bulk
c. nucleation at a foreign substrate

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 3. What happens on varying the Pyrolysis temperature?

Fig 5. Current density–voltage characteristics of structure heated at different temperatures

for 30 min [6]
Key Takeaways-

• Aloe vera gel contained polysaccharide, alike synthetic polymer usually being used as
dielectric layer.

• The leakage current density could be affected by the drying temperature, duration, and
thickness of Aloe vera layer.

4. Dependence on Film Thickness

Fig 5. Current density–voltage characteristics with difference in the number of layers of

Aloe vera been screen printed [6]

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 Key takeaways-

• sample with only one layer of dried Aloe vera has demonstrated the lowest leakage current
density if compared with those test structures with 2, 3 and 5 layers.

• The polysaccharides in between Aloe vera layers have not been fully cross-linked; leading to
porosity appearing inside the layer. Porosity is the major factor affecting the leakage current
density.

b. Photovoltaics

Fig 7. Structure of PC60BM semiconductor [11]

A photovoltaic (PV) cell, commonly called a solar cell, is a nonmechanical device that converts
sunlight directly into electricity. The photovoltaic and electrical properties of organic
semiconductors are characterized by their low dielectric constant which is considered to be
significantly influential in geminate and bimolecular recombination losses in organic
photovoltaics (OPVs).

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We will analyse the dielectric properties of Organic photovoltaic material- PCBM is a soluble
version of the buckminsterfullerene, C60. It is one of the most commonly used electrons
accepting materials in organic photovoltaic devices.

Impedance Analysis of the OPV material, PC60BM was performed on these devices (Solartron SI
1260) and analysed with Zplot measurement software. These measurements were taken from zero
to increasing negative bias across several orders of magnitude of frequencies (101–106 Hz),
additional details are thoroughly discussed in this work. Thickness and device area
measurements were determined using a profilometer (Ambios XP-100).

• Dielectric response analysis with varying bias V

Fig 8. Example Bode plots of impedance data: A) real impedance, B) imaginary impedance [11]

The series resistance affects the real impedance and can be extracted from the Bode plot where
the real impedance saturates in the high frequency (Figure 1A). This saturation resistance
originates from the total resistance of the system minus the resistance of the main polarization
process.

In the OPV devices, this polarization process is attributed to the response of charge carriers in
the device either photogenerated, thermogenerated, or defused from the contacts. Evidence for

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this is seen in the bias dependence of the low frequency where R total = R + Rs, as further
decreasing bias sweeps more charge carriers out of the device.

Figure 8A) shows the reduction of the real impedance in the low-frequency region, because of
charge depletion from the active layer. Charge carriers do not respond in the high frequency
region and the bias-independent low impedance saturation results from the AC contact
resistance.

Figure 8B) shows the effect of bias on the imaginary impedance both reducing the magnitude
and pushing the characteristic frequency higher as the system loses more low-frequency
contribution to the overall impedance.

• Relation of Capacitance and Dielectric constant of OPV material with Frequency

Fig. 9. Plot of Dielectric constant vs Frequency for higher and lower leakage current
cases [11]

Key points-

• The capacitance is expected to have an inverse relationship with thickness when all other
variables are unchanged. This is the observed behaviour in the low-frequency regime, but
devices with higher leakage (dotted lines) show deviation from this trend in the high-
frequency region (>10 kHz) (Figure 3D).

• When the capacitance is corrected by thickness and area to describe a dielectric constant
spectrum (Figure S4, Supporting Information), the thicker, low-leakage devices show good
agreement on the dielectric constant at 1 MHz

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 • The thinner, high-leakage devices, however, differ on the dielectric constant, giving lower
than expected values. For this reason, it is critical that low-leakage devices which show a
frequency-independent geometric capacitance, are used for the determination of the
dielectric constant.

c. Electroluminescent devices

Fig. 10. Image of an Organic Multilayer panel and Illustration of a Multilayer Device structure [12]

• Organic multilayer devices are electronic devices that require complex and finely tuned multi-
layer structures. E.g.- Organic Light Emitting Devices

• Multilayer Organic (MLO) is a technology that integrates extreme low loss organic materials and
has key benefits that include High stability and High Q(Quality factor) over frequency and in
interconnect devices.

• The application of electrical impedance spectroscopy to Light Emitting Devices (LEDs) based on
Langmuir–Blodgett (LB) films is reviewed.

Impedance measurements on organic light emitting devices (LEDs) can be used to gain an
understanding of the equivalent circuit and consequently an insight into the electrical conduction
processes. These measurements have been undertaken on LB film structures incorporating a
conductive polymer (electroluminescent device). The Impedance spectra for the LED structures were
found to depend on the history of the dc bias applied to the samples.

 Circuit model of Multilayered LB Film structure

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 Fig. 11. Equivalent Circuit of metal/Organic dielectric film/metal structure [12]

Equivalent circuit impedance equation -> ZTot = jwLs+ Rs +(RLB-1 + jwCLB)-1

RS, LS represents the series resistance and inductance due to contacts; and RLB, CLB are the resistance
and capacitance of the LB film.

At low frequencies, when w<<(RLBCLB)-1 and jwLs is negligible, Ztot->(RS+RLB)=RT. The total resistance RT
is therefore related to the dc resistance measured from the I–V characteristic. When w>>(RLBCLB)-1 the
admittance of the capacitor dominates the parallel (RLB II CLB) network, and Ztot->Rs+ 1/( jwCLB)+jwLs.

Assuming that jwLS can be neglected, the real part Z’=RS and the imaginary part Z’’ varies as w-1. As
the frequency is increased, Z’’ changes sign when the inductive element dominates.

 Dielectric Response of Multilayer structure

Fig. 12. Nyquist plots for varying DC bias from 0 volts to 4.2 volts [12]

An alternative (but equivalent) representation of the electrical response can be obtained by showing
the data in the form of a Nyquist plot, i.e. plotting the imaginary part against the real part of the
measured impedance, Fig. 12.

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Key points-

1. All the spectra exhibit a single semicircle or arc of circle, which decreased in size with
increasing applied dc bias.

2. A single semicircle in a Nyquist plot suggests a single relaxation time and the data could be
fitted using a parallel combination of a frequency independent resistor RLB and capacitor CLB.

3. This represents the dominant mechanisms of charge transport (RLB) and polarisation (CLB) in
the organic layer. The full lines in Fig. 9 were obtained using Eq. (1) (i.e. with a resistance RS
and inductance LS in series with the parallel RLB/CLB combination).

Conclusion
So, from the data analysed in the previous slides, we can infer that the dielectric or
impedance analysis helps us in-
• Impedance measurements on organic light emitting devices (LEDs) can be used to gain
an understanding of the equivalent circuit and consequently an insight into the electrical
conduction processes.
• Determining the applicability in a very broad frequency range (1 uHz – 100 GHz), which is
one of the needs for the telecommunication sector especially for RF/HF electronics.
• Ability to follow relaxation processes over an extremely wide range of characteristic
times.
• The relationship between the dielectric constant and surface morphology is studied and
determined.
• provide information about a range of processes or reactions occurring inside the
fabricated device system.
• The usefulness of Impedance Spectroscopy (IS) lies in the ability to distinguish the
dielectric and electric properties of individual contributions of components under
investigation.
• Impedance spectroscopy is a non-destructive technique and so can provide time
dependent quantitative and time-dependant information about the electrode processes
and complex interfaces, extract some characteristics of materials including high
resistance materials.

References

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