A Study on the Morphology of

Conducting Polymer Blends: P3HT:PCBM

System
A
PROJECT REPORT
Submitted to
Department Of Physics, MCM DAV College, Kangra, Himachal Pradesh
University

For the Award of the Degree of

MASTER OF SCIENCE
IN
PHYSICS

Supervised By: Submitted By:

Dr. Manoj Kumar Mohit Soni
(Assistant Professor) Kartik Supehia
Sachin Choudhary
Rishav

DEPARTMENT OF PHYSICS
MCM DAV COLLEGE KANGRA, HIMACHAL PRADESH-176001
(INDIA)
July, 2025
 CERTIFICATE

This is to certify that the project report titled ’A Study on the Morphology of Conducting
Polymer Blends: P3HT:PCBM System’ has been successfully completed by Mr. Mohit Soni,
Mr. Kartik, Mr. Sachin, Mr. Rishabh, students of M.Sc. Physics (4th Semester) at MCM
DAV College, Kangra, affiliated to Himachal Pradesh University, Shimla.

This work is an original research project conducted under my supervision and guidance, and
is submitted in partial fulfillment of the requirements for the degree of Master of Science in
Physics.

Submitted By: Supervised By:

Dr. Manoj Kumar
(Assistant Professor)
Mohit Soni

Kartik Supehia
External Examiner

Sachin Choudhary

Rishav

Date:

Department of Physics
MCM DAV College, Kangra
Himachal Pradesh – 176001 (India)
 ACKNOWLEDGMENT

We would like to express our heartfelt gratitude to Dr. Manoj Kumar, Assistant Professor,
Department of Physics, MCM DAV College, Kangra, for his valuable guidance, constant sup-
port, and encouragement throughout this project. His insights played a key role in shaping the
direction and outcome of our work.

We are also thankful to the faculty members of the Department of Physics for providing a
learning environment that nurtures curiosity and innovation.

A special thanks to our classmates and friends who offered their help, shared ideas, and moti-
vated us during different stages of the project.

Finally, we are deeply grateful to our families for their unwavering support and encouragement
- their belief in us made this journey possible.

Mohit Soni
Sachin Choudhary
Kartik Supehia
Rishav
 TABLE OF CONTENTS

Contents

1 Introduction 6
1.1 Conducting Polymers and Their Role in Electronics . . . . . . . . . . . . . . . 6
1.2 The P3HT:PCBM Blend System . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.3 Importance of Morphology in Device Performance . . . . . . . . . . . . . . . 9
1.4 Parameters Affecting Morphology . . . . . . . . . . . . . . . . . . . . . . . . 10
1.5 Techniques Used to Study Morphology . . . . . . . . . . . . . . . . . . . . . 11

2 Materials and Methods 13

2.1 Materials Used . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.2 Blend Solution Preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
2.3 Thin Film Fabrication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.4 Post-Treatment Process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
2.5 Characterization Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

Conclusion 16

3 Results and Discussion 17

1 Introduction

1.1 Conducting Polymers and Their Role in Electronics

Conducting polymers are a class of organic materials that exhibit electrical conductivity due
to the presence of a conjugated π-electron backbone. These polymers differ significantly from
traditional insulating plastics as they can conduct electricity when properly doped with oxidiz-
ing or reducing agents. The discovery of conducting polyacetylene by Shirakawa, Heeger, and
MacDiarmid in 1977, which led to the Nobel Prize in Chemistry in 2000, laid the foundation
for the field of organic electronics.
The electrical conductivity of these materials arises from delocalized electrons along the
polymer chain, enabling them to support charge transport similar to that of semiconductors.
When doped, the polymer chains develop charge carriers (polarons, bipolarons, and solitons)
that allow electron movement under an electric field. This makes them suitable for applications
where flexibility, lightweight, solution-processability, and transparency are important.
Over the years, researchers have developed several types of conducting polymers, each
with unique properties applications. Some of the most commonly studied conducting polymers
include:

• Polyacetylene (PA).

• Polypyrrole (PPy).

• Polythiophene (PT) and its derivative poly(3-hexylthiophene) (P3HT).

• Polyaniline (PANI).

• Poly(phenylene vinylene) (PPV).

Figure 1: Chemical structures of commonly studied conducting polymers.[1]

 These polymers exhibit diverse molecular structures (as seen in figure 1), and their physical
and electronic properties can be tuned through chemical modification or processing conditions.
Conducting polymers have found widespread applications in a variety of emerging tech-
nologies such as sensors, flexible displays, supercapacitors, and organic electronics. A visual
summary of these applications is shown in figure 2.

Figure 2: Schematic illustration of applications of conducting polymers and their compos-

ites.[1]

1.2 The P3HT:PCBM Blend System

One of the most studied donor-acceptor systems in organic electronics is the mixture of poly(3-
hexylthiophene) (P3HT) and [6,6]-phenyl-C61 -butyric acid methyl ester (PCBM). This binary
mixture forms the active layer in many organic photovoltaic (OPV) and organic electronic
devices.
In this pair, P3HT acts as the donor. It’s a semicrystalline polymer that absorbs sunlight,
generates excited states (called excitons), and helps move positive charges (holes). On the
other hand, PCBM — a fullerene derivative — serves as the electron acceptor. It has a strong
ability to capture electrons, which allows for fast and efficient separation of charge after light
absorption.
When mixed together, P3HT and PCBM create a special nanoscale structure called a bulk
heterojunction (BHJ). Instead of having neat, separate layers, their molecules are interwoven
like a blend of threads in a fabric — this increases the contact area where excitons can split into
free charges. This design dramatically improves the efficiency of light-to-electricity conversion.

Figure 3: Molecular structures of (a) P3HT and (b) PCBM, and (c) schematic representation of
the bulk heterojunction (BHJ) architecture used in P3HT:PCBM-based organic electronics.[2]

Figure 3 illustrates the chemical structures of the donor polymer P3HT and the acceptor
molecule PCBM, along with a schematic of the bulk heterojunction (BHJ) architecture. This
visual representation helps in understanding how nanoscale intermixing of the donor–acceptor
phases facilitates efficient exciton separation and charge transport.

Why is this blend so popular in research? Here are a few reasons:

• It can be processed from simple, low-cost solutions using techniques like spin coating
and doctor-blading.

• It forms smooth, uniform films with predictable structures.

 • Its energy levels are well-aligned to support efficient charge transfer.

• It has been studied extensively, making it a reliable reference system for scientists.

Even though newer materials are constantly being developed, P3HT:PCBM remains a trusted
model system in the world of organic electronics. Its simplicity, stability, and reproducibility
make it an ideal platform for studying how morphology affects performance — and for devel-
oping future technologies.

1.3 Importance of Morphology in Device Performance

The performance of organic electronic devices such as organic solar cells (OSCs) is highly
dependent on the nanoscale morphology of the active layer. In blends like P3HT:PCBM, mor-
phology refers to the spatial arrangement, size, and distribution of donor and acceptor domains
within the bulk heterojunction (BHJ). Proper phase separation and interpenetrating networks
are essential to ensure effective exciton dissociation, charge transport, and extraction.
If the domains are too small, charge carriers may recombine before reaching the electrodes.
Conversely, overly large domains can limit exciton dissociation due to reduced interfacial area.
Therefore, achieving an optimal nanoscale morphology is crucial for balancing charge genera-
tion and transport.

Figure 4: Schematic evolution of P3HT:PCBM bulk heterojunction morphology during pro-

cessing: (a) as-cast, (b) solvent-treated, (c) dried, and (d) post-annealed.[3]

Figure 4 shows how the structure of the P3HT:PCBM layer evolves through different pro-
cessing steps — from the raw mixture to the final, optimized film. Treatments like solvent
washing and thermal annealing play a major role in tuning the internal structure.
 Several factors influence morphology, including:

• Donor–acceptor ratio — controls how charges can move through the film.

• Solvent and additives — influence drying speed and how molecules arrange themselves.

• Annealing temperature and time — help the polymer chains settle into a more ordered
structure.

• Deposition method — affects film thickness and smoothness.

• Crystallinity — especially of P3HT, which helps holes to move more easily via π-π
stacking.

Researchers use powerful tools like atomic force microscopy (AFM) and transmission elec-
tron microscopy (TEM) to actually see how the internal structure looks. Techniques like
Grazing Incidence X-ray Diffraction (GIXRD) and UV-Vis spectroscopy reveal how well the
molecules are ordered.
Hence, morphology engineering through controlled processing and post-treatment tech-
niques is considered a key strategy to optimize the efficiency of polymer-based optoelectronic
devices.

1.4 Parameters Affecting Morphology

The morphology of P3HT:PCBM bulk heterojunction films is highly sensitive to several pro-
cessing parameters and material choices. These factors control the degree of phase separation,
domain size, crystallinity, and vertical composition gradient — all of which directly impact
charge generation, transport, and extraction. Let’s take a closer look at the key factors that
control morphology.

• Donor–Acceptor Ratio: The weight ratio of P3HT to PCBM determines the conductive
pathways and the interfacial area available for exciton dissociation. Commonly used
ratios include 1:1 and 1:0.8, though optimal values may vary depending on the processing
route. Excess PCBM can lead to aggregation and poor hole transport, while excess P3HT
may limit electron mobility.

• Choice of Solvent and Additives: Solvent selection affects drying kinetics and the sol-
ubility of donor and acceptor components. Common solvents include chlorobenzene,
chloroform, and o-dichlorobenzene. Additives such as 1,8-diiodooctane (DIO) are often
used to slow film drying, enhance domain purity, and promote molecular ordering.

• Annealing Temperature and Duration: Thermal annealing improves crystallinity and

phase segregation. Optimal annealing conditions allow polymer chains to reorganize,
 improving π-π stacking in P3HT and improving domain connectivity. However, over-
annealing can result in large domains and recombination losses.

• Deposition Technique: Techniques such as spin coating, blade coating, slot-die coating,
or spray deposition influence film thickness, drying rate, and final morphology. Each
method may require optimization of parameters like speed, temperature, and ambient
conditions.

• Substrate Surface Treatment: Surface energy and roughness of the substrate can in-
fluence vertical phase separation, interfacial adhesion, and initial film formation. Treat-
ments such as UV-ozone or plasma cleaning are used to tune substrate properties for
better film growth.

• Solution Concentration and Viscosity: These parameters affect the thickness and uni-
formity of the film. Higher concentration may lead to thicker films but can also influence
solvent evaporation dynamics and phase behavior.

By fine-tuning these parameters, it is possible to engineer the morphology of the active

layer to achieve balanced charge transport pathways, reduced recombination, and ultimately,
improved device efficiency.

Table 1: Parameters affecting morphology and their impact on device performance.

Parameter Effect on Morphology Impact on Device Perfor-

mance
Donor–Acceptor Domain size and connec- Balance between charge gen-
Ratio tivity eration and transport
Solvent Drying rate, crystallinity Film uniformity and interfa-
cial area
Solvent Additives Selective swelling Enhanced domain purity and
charge separation
Annealing Crystallite size, phase seg- Improved charge mobility
regation and efficiency
Film Thickness Optical absorption depth Trade-off between absorption
and carrier extraction
Deposition Method Film uniformity Affects microstructure and
defects
Substrate Surface Vertical phase distribution Influences charge transport
Energy pathways vertically

1.5 Techniques Used to Study Morphology

To truly understand the morphology of P3HT:PCBM blends,it requires advanced characteri-
zation techniques that can resolve the micro- and nanoscale structure of the active layer. The
following analytical tools are commonly used:
 • Atomic Force Microscopy (AFM): AFM provides high-resolution topographical im-
ages of the film surface, enabling the visualization of phase-separated domains, surface
roughness, and crystallite orientation at the nanoscale.

• Scanning Electron Microscopy (SEM): SEM is used to analyze surface morphology

and phase distribution with excellent depth of field. It helps reveal domain structures and
potential aggregation of PCBM or P3HT.

• Grazing Incidence X-Ray Diffraction (GIXRD): GIXRD provides information about

the crystalline structure and molecular ordering within the film. It is especially useful for
evaluating the π–π stacking distance and polymer crystallinity.

• UV–Visible (UV–Vis) Spectroscopy: UV–Vis absorption spectra reveal changes in the

conjugation length and aggregation behavior of P3HT. Red shifts or vibronic peaks indi-
cate improved ordering and phase separation.

• Transmission Electron Microscopy (TEM): Although less commonly used due to com-
plex sample preparation, TEM provides internal cross-sectional views of phase-separated
morphologies and domain sizes with nanometer-scale resolution.

Each of these techniques offers complementary insights into how processing parameters
influence the blend morphology, and their combined application is essential for correlating
microstructural features with device performance.

Conclusion
This chapter introduced the fundamental concepts of conducting polymers and the importance
of morphology in organic electronic devices, with a particular focus on P3HT:PCBM blend
systems. It highlighted the key factors affecting morphology and their influence on device
performance. Commonly used characterization techniques such as AFM, SEM, GIXRD, and
UV–Vis spectroscopy were also outlined. In the following chapters, experimental details and
results related to these techniques will be presented to further understand the structure–property
relationships in conducting polymer blends.
2 Materials and Methods

2.1 Materials Used

While this project is based on literature analysis rather than hands-on experiments, it focuses
on systems that have been widely explored in research labs.
The materials listed below are commonly used to fabricate P3HT:PCBM blend films, the
building blocks of many organic electronic devices:

• Poly(3-hexylthiophene) (P3HT) – A widely used π-conjugated polymer acting as the

electron donor due to its semi-crystalline nature, good charge mobility, and favorable
optical absorption.

• [6,6]-Phenyl-C61 -butyric acid methyl ester (PCBM) – A fullerene derivative used as

the electron acceptor. Its high electron affinity and solubility make it suitable for blending
with P3HT.

• Chlorobenzene and o-Dichlorobenzene – Common solvents used to dissolve P3HT and

PCBM for solution processing.

• Indium Tin Oxide (ITO)-Coated Glass – Transparent conducting substrates commonly

used in device fabrication.

• PEDOT:PSS (Optional) – Sometimes employed as a hole-transporting interlayer to im-

prove charge collection efficiency.

• 1,8-Diiodooctane (DIO) – A solvent additive often added in small amounts to improve

domain purity and morphology control.

• Cleaning Solvents (Acetone, Isopropanol, DI Water) – Typically used for substrate

preparation prior to film deposition.

2.2 Blend Solution Preparation

In the majority of studies involving P3HT:PCBM-based organic electronic devices, the active
layer is prepared by blending the donor polymer and the acceptor molecule in a suitable solvent
to form a homogeneous solution.
Typically:

• A 1:1 or 1:0.8 weight ratio of P3HT to PCBM is used, though the exact ratio can vary
depending on the desired structure and performance.

• The blend is dissolved in chlorobenzene or o-dichlorobenzene — solvents known for

their high boiling points and good solubility.
 • The total concentration is usually between 15–25 mg/mL.

• The mixture is stirred at 60–70◦ C for several hours to ensure complete dissolution and
uniform mixing.

In some studies, solvent additives such as 1,8-diiodooctane (DIO) are incorporated in small
quantities (typically 3% v/v) to improve phase separation and domain purity. These additives
selectively affect the crystallization behavior of P3HT and the aggregation of PCBM.
Once the solution is prepared, it is typically filtered through a 0.45 µm PTFE syringe filter
to remove any undissolved particles before film deposition.

2.3 Thin Film Fabrication

In most studies involving P3HT:PCBM systems, thin films are fabricated using solution-processing
methods such as spin coating. This technique is widely adopted due to its simplicity, repro-
ducibility, and compatibility with laboratory-scale fabrication.
After preparation, the blend solution is typically deposited onto pre-cleaned substrates such
as ITO-coated glass using spin coating. The spin speed and duration can vary depending on
the desired film thickness, but commonly used parameters include speeds between 1000–3000
rpm for 30–60 seconds.
To improve the film’s morphology and remove residual solvent, the coated films are gen-
erally subjected to post-deposition drying, either in ambient conditions or in a vacuum oven.
The film thickness, uniformity, and drying rate can be further tuned by adjusting spin speed,
solution concentration, and solvent type.
In certain studies, alternative deposition techniques such as blade coating, doctor blade, or
slot-die coating are used, especially when transitioning to scalable or large-area applications.
However, for fundamental studies and morphology analysis, spin coating remains the most
common and accessible technique.

2.4 Post-Treatment Process

Post-deposition treatments play a crucial role in determining the morphology and optoelec-
tronic properties of P3HT:PCBM blend films. These processes are widely reported in literature
and are essential for optimizing phase separation, crystallinity, and charge transport within the
active layer.

Thermal Annealing
Thermal annealing is the most common method used to enhance the crystallinity of P3HT and
to promote diffusion of PCBM molecules. Films are typically annealed at temperatures ranging
from 100–150◦ C for durations of 5–30 minutes. This process facilitates self-organization of
P3HT chains and improves π–π stacking, resulting in improved charge mobility and reduced
recombination.

Solvent Vapor Annealing (SVA)

In solvent vapor annealing, the spin-coated films are exposed to the vapors of a good solvent
such as chloroform or o-dichlorobenzene. The solvent molecules temporarily plasticize the
polymer matrix, allowing better reorganization of the donor and acceptor domains. SVA helps
achieve more controlled and finely phase-separated morphologies.

Additive-Assisted Self-Assembly
In addition to annealing, the incorporation of solvent additives like 1,8-diiodooctane (DIO) dur-
ing solution preparation also serves as a morphological tuning tool. These additives selectively
affect the solubility and crystallization rate of P3HT, leading to better interpenetrating networks
and enhanced domain purity.
Post-treatment strategies, individually or in combination, significantly affect the microstruc-
ture and thus the overall device efficiency. The choice of treatment depends on the specific
processing conditions and desired morphological features.

2.5 Characterization Techniques

In this literature-based study, a number of advanced characterization techniques were reviewed
and considered for their relevance in analyzing the morphology of P3HT:PCBM blend films.
These techniques are not described in detail here, as their theoretical background has already
been outlined in Section 1.5, and their application in reported studies is discussed in Chapter 3.
The key techniques examined in this work include:

• Atomic Force Microscopy (AFM) – for nanoscale surface morphology and roughness
analysis.

• Scanning Electron Microscopy (SEM) – for visualizing surface structures and phase
distribution.

• Grazing Incidence X-Ray Diffraction (GIXRD) – for determining crystallinity and

molecular ordering.

• UV–Vis Spectroscopy – for monitoring optical absorption and aggregation behavior.

These tools were identified as essential in understanding the structure–property relation-

ships of polymer blend systems, and their role in interpreting morphological behavior is further
discussed in the next chapter.
Conclusion
This chapter presented a detailed literature-based overview of the materials and methods com-
monly used in the fabrication of P3HT:PCBM blend films for organic electronic applications.
The key materials, solution preparation strategies, film deposition techniques, post-treatment
processes, and relevant characterization tools were discussed. These insights provide the foun-
dational understanding necessary to interpret morphology–performance relationships, which
are explored further in the next chapter.
3 Results and Discussion