POTENTIAL APPLICATION OF BIS-CHALCONE IN PLASTIC SUBSTRATE SOLAR

CELL DEVICE

Wee Hung Yee (39316)

Bachelor of Science with Honours

(Resource Chemistry)

2015

Faculty of Resource Science and Technology

Potential Application of Bis-chalcone in Plastic Substrate Solar Cell Device

Wee Hung Yee (39316)

A dissertation submitted in partial fulfilment of the requirement for

the degree of Bachelor of Science (Hons.)

Supervisor: Dr. Tay Meng Guan

RESOURCE CHEMISTRY PROGRAM (WS48)

DEPARTMENT OF CHEMISTRY

FACULTY OF RESOURCE SCIENCE AND TECHNOLOGY

UNIVERSITY MALAYSIA SARAWAK

20th

April 2015

I

Acknowledgements

I would like to thank to my supervisor, Dr Tay Meng Guan for his guidance and support so that I

can complete my research project. Furthermore, I would like to thank to the postgraduate

students, which are Ms. Chia Ying Ying, Ms. Suzie Kuan, Mr. Ong Kok Tong and Mr. Teo Kien

Yung for their willingness to share their knowledge, techniques and give comments and

suggestions to me. Besides, I would like to thank to all my friends who contributed a lot upon

completion of this project.

II

Declaration

I declare that the work in this thesis was carried out in accordance with the regulations of

Universiti Malaysia Sarawak. It is original and is the result of my work, unless otherwise

indicated or acknowledged as referenced work. This thesis has not been submitted at this or any

other university or academic institution for any other degree or qualification.

____________________________

Wee Hung Yee

Program of Resource Chemistry

Faculty of Resource Science and Technology

Universiti Malaysia Sarawak

III

Table of Contents

Acknowledgement…………………………………………………………....…………... I

Declaration………………………………………………………....…………................... II

Table of Contents………………………………………………………………....………. III

List of Abbreviation………………………………………………………….…...………. VII

List of Figures…………………………………………………………...……..…………. X

List of Scheme……………………………………………………….…….………........... XII

List of Table………………………………………………………………………………. XIII

Abstract…………….………………………………………...……………………............ XIV

1.0 Introduction…………………………………………………...……..….………......... 1

1.1 Harvesting energy from light...…………………………………………...…... 2

1.2 Chalcone compounds……………………………………………….....……… 4

1.3 Photovoltaic solar cells…………………………………………………….…. 7

1.3.1 Development history of photovoltaic cells………………………….. 10

1.3.1.1 First generation solar cells……………………………….….. 10

1.3.1.2 Second generation solar cells………………………………... 10

1.3.1.3 Third generation solar cells……………………………….…. 11

1.3.1.3.1 Plastic solar cells……………………….…..… 12

1.3.1.3.2 Dye-sensitized solar cells………….……..…… 12

1.3.1.4 Fourth generation solar cells……………….……………....... 13

1.3.2 Thin-film photovoltaic solar cell……………………….……………. 13

1.4 Problem statement……………………………………………………...……... 14

1.5 Objectives……………………………………….…………...………………... 15

IV

2.0 Literature Review…………………………………………………………..….…..... 16

2.1 Synthesis of chalcone…………………………………………………………. 16

2.1.1 Claisen-Schmidt condensation ………………………………………... 17

2.1.1.1 Base catalytic………………………………………................. 17

2.1.1.2 Acid catalytic…………………………………………………... 18

2.1.2 Suzuki method………………………………………………………. 20

2.1.3 Solvent-free grinding technique…………………………………….. 21

2.2 Bis-chalcone synthesis…………………………………………..................... 23

2.3 Photoinduced electron transfer in chalcone…………………………………... 26

2.4 Uses of chalcone compounds in solar cells…………………………………... 26

2.5 Efficiency enhancement of Dye-Sensitized Solar Cell (DSSC)…..………….. 27

2.5.1 Kinetic dynamic of DSSC………………………………………………. 28

2.5.2 Enhancement through metal oxides…………………………………….. 30

2.5.3 Selection of dyes………………………………………………………... 33

2.5.4 Mediator additive……………………………………………………….. 34

3.0 Methodology……………………………………………………..…………...…........ 36

3.1 Chemicals and reagents…………...…………………………………………... 36

3.1.1 Purification of ethanol.…………………………………………............ 36

3.2 Characterization…………………………………….………………………… 37

3.3 Synthesis of 1,4-bis[2-(2-hydroxybenzoyl)vinyl]benzene (1)….……..…..…. 37

3.4 Preparation of conductive plastic substrate……………………………….….. 38

3.5 Titanium (IV) oxide (TiO2) coating techniques………………………………. 38

3.5.1 Rolling TiO2 paste………………………………………………………. 38

3.5.2 Spin coating technique for conductive glass and aluminium foil…...….. 39

V

3.6 Preparation of KI3…………………………………………………………….. 39

3.7 Photovoltaic cell fabrication…………………………………….……………. 39

3.7.1 Fabrication of Dye-Sensitized Solar Cell……………………………….. 39

3.7.2 Fabrication of plastic solar cell…………………………………………. 40

3.8 Efficiency measurement and calculation……………………………………... 40

4.0 Results and Discussion………………………………………..…………………....... 41

4.1 Synthesis and characterization of 1,4-bis[2-(2-hydroxybenzoyl)vinyl]

benzene (1)……………………………………………………………..……..

41

4.1.1 Spectroscopy analysis……………………………………………...…… 42

4.1.1.1 IR analysis………………………………….…………………... 42

4.1.1.2 NMR analysis………………………………………….……….. 45

4.2 Characterization and testing of glass substrate solar cell (DSSC)…………… 48

4.2.1 SEM analysis…………..………………………………………………. 48

4.2.2 Conversion efficiency of solar cell……………………..……………… 49

4.3 Chemical deposition, characterization and testing of plastic substrate solar

cell…………………………………………………….……………………...

52

4.3.1 Chemical deposition on plastic (PET) substrate.................................... 52

4.3.2 Concentration effect of coating material towards the properties of PET

substrate……………….……………………………….……………...

54

4.3.3 Efficiency of plastic substrate solar cell……………………….…….. 56

5.0 Conclusion…………………………………………………………………………..... 59

6.0 Suggestion for future work………………………………………………………….. 60

VI

7.0 References………………………………...….………………………………………. 61

VII

List of Abbreviation

AlCl3 Aluminium chloride

Ba(OH)2 Barium hydroxide

CdS Cadmium sulfide

CdTe Cadmium telluride

CH3OH Methanol

CHCl3 Trichloromethane

CIGS Copper indium gallium diselenide

CIS Copper indium selenide

Cl-

Chloride ion

Cs2CO3 Cesium carbonate

DCM Dichloromethane

DMF Dimethylformamide

DMSO Dimethylsufoxide

DSSC Dye-sensitized solar cell

Eg Energy band gap

VIII

FTIR Fourier transform infrared

H2O Water molecule

HCl Hydrochloric acid

I-

Iodide ion

I3 Triiodide ion

KBr Potassium bromide

KI3 Potassium triiodide

KOH Potassium hydroxide

MeCN Acetonitrile

Na2S2O3 Sodium thiosulfate

NaOH Sodium hydroxide

Ni Nickel

Ni(II)Cl2·6H2O Hexaaquanickel(II) chloride

NLO non-linear optics

NMR Nuclear magnetic resonance

OH-

Hydroxide ion

Pd(PPh3)4 Tetrakis(triphenylphosphine)palladium(0)

IX

PET Photoinduced electron transfer

Pt Platinum

Ru Ruthenium

SHG second harmonic generation

SOCl2 Thionyl chloride

STC Standard test condition

TCO Transparent conducting oxide

THF Tetrahydrofuran

TiCl4 Titanium chloride

TiO2 Titanium dioxide

TLC Thin layer chromatography

UV-Vis Ultraviolet-visible

X

List of Figures

Figure Title Page

1.1 Wavelength of light 2

1.2 Structure of chalcone 4

1.3 (a) cis-chalcone; (b) trans-chalcone 5

1.4 Second harmonic generation principle 6

1.5 3-(4-methoxyphenyl)-1-(4-pyrrol-1-yl-phenyl) prop-2-en-1-one 7

1.6 p-n junction 8

1.7 (a) Energy level of conduction band and valence band and (b) Formation of positive-

charged hole

9

1.8 Electrons and holes movement drifted by the action of electric field 9

1.9 Structure of second generation solar cells 11

1.10 Basic components in third generation solar cells 11

1.11 Plastic solar cells 12

1.12 Structure of dye-sensitized solar cells (DSSC) 13

2.1 Borondifluoride complexes of 2‟-hydroxychalcones 27

XI

2.2 Electron transfer between components in DSSC 28

2.3 Energy level of TiO2, LUMO and HOMO 29

2.4 Conduction band and valence band of TiO2 and coated metal oxide 31

2.5 Conduction band and valence band of TiO2 and coated metal oxide 32

2.6 Organic dye 33

4.1 Structure of synthesized bis-chalcone 41

4.2 IR spectrum of compound 1 44

4.3 Intramolecular hydrogen bonding 43

4.4 NMR spectrum of compound 1 47

4.5 Hydrogen in bis-chalcone 45

4.6 (a) Hand-coated conductive glass under SEM (200 magnification); (b) Hand-coated

conductive glass under SEM (20000 magnification)

49

4.7 (a) Spin coated conductive glass under SEM (200 magnification); (b) Spin coated

conductive glass under SEM (20000 magnification)

49

4.8 Surface of CuS coated PET under SEM 53

4.9 PET substrate coated with (a) 0.10 M, (b) 0.05 M and (c) 0.01 M concentration

solution; (d) comparison between 0.01 and 0.05 M (0.01 M at left and 0.05 M at right)

55

XII

List of Scheme

Scheme Title Page

2.1 Synthesis pathway of chalcone through base catalytic reaction 18

2.2 Synthesis pathway of chalcone through acid catalytic reaction 20

2.3 Coupling between phenylboronic acids and cinnamoyl chlorides 21

2.4 Coupling between phenylvinylboronic acids and benzoyl chlorides 21

2.5 Reaction between acetophenones and benzaldehydes 22

2.6 Synthesis of bis-chalcones 24

2.7 (a) Conventional and (b) Microwave-assisted synthesis of bis-chalcone 25

XIII

List of table

Table Title Page

4.1 Efficiency of glass substrate solar cells with two different coating methods 50

4.2 Surface resistance of PET in different concentration solution 54

4.3 Efficiency of plastics substrate solar cells with three different concentration 56

XIV

Potential Application of Bis-chalcone in Plastic Substrate Solar Cell Device

Wee Hung Yee

Resource Chemistry

Faculty of Resource Science and Technology

Universiti Malaysia Sarawak

Abstract

Due to depletion of petroleum, global is seeking for renewable energy to replace the conventional energy. In this

study, plastic solar cell was developed by using bis-chalcone (1,4-bis[2-(2-hydroxybenzoyl)vinyl]benzene) as a dye.

Bis-chalcone was successfully synthesized by base-catalytic Claisen-Schmidt condensation between 2-

hydroxyacetophenone and terephthalaldehyde. The synthesized bis-chalcone was characterized using FTIR and

NMR spectroscopy. After that, bis-chalcones were coated on spin coated and hand coated TiO2 which show 3.601 x

10-3

% and 2.439 x 10-3

% of efficiency respectively. Besides, CuS was successfully coated on plastic substrate by

using chemical bath deposition and the resistance per cm square of plastics substrate showed 74.6, 31.1 and 12.5 Ω

cm-2

when 0.01, 0.05 and 0.10 M of precursors were used respectively. Apart from that, plastics substrate solar cells

were fabricated based on 0.01, 0.05 and 0.10 M of concentration which showed 1.503 x 10-3

, 6.269 x 10-4

and 1.575

x 10-3

% of efficiency respectively. It is found that the 0.10 M against the theoretical hypothesis, which caused by a

few factors included the improvement of plastics substrate conductivity, the properties of CuS and thermal barrier of

bis-chalcone compound.

Keyword: Claisen-Schmidt condensation, bis-chalcone, plastic solar cell

Abstrak

Disebabkan petroluem yang semakin berkurangan, seluruh dunia sedang mengkaji tenaga yang dapat diperbaharui

untuk mengganti tenaga asli. Dalam kajian ini, sel suria plastik telah diperkembangkan dengan menggunakan bis-

chalcone (1,4-bis[2-(2-hydroxybenzoyl)vinyl]benzene) sebagai pencelup. Bis-chalcone telah berjaya dihasilkan

secara sintesis dengan menggunakan dasar pemangkin Claisen-Schmidt pemeluwapan antara 2-

hydroxyacetophenone dan terephthalaldehyde. Bis-chalcone yang disintesis mengambarkan sifatnya dengan

menggunakan FTIR dan NMR spektroskopi. Selepas itu, bis-chalcones telah diselaputi atas penyelaput pusing dan

penyelaput secara tangan TiO2, ia menunjukkan efisien 3.601 x 10-3

% dan 2.439 x 10-3

% masing-masing. Selain itu,

CuS telah berjaya diselaputi atas plastik substrat dengan menggunakan mandian pemendapan kimia dan rintangan

untuk plastik substrat bagi setiap empat persegi sentimeter adalah 74.6, 31.1 and 12.5 Ω cm-2

apabila 0.01, 0.05

dan 0.10 M perintis telah digunakan masing-masing. Di samping itu, sel-sel suria yang berplastik substrat telah

difabrik dengan perintis yang berpekatan 0.01, 0.05 dan 0.10 M dan menunjukkan 1.503 x 10-3

, 6.269 x 10-4

and

1.575 x 10-3

% effisiensi masing-masing. Kajian ini mendapati bahawa 0.10 M bertentangan dengan hipotesis dari

segi teori, ini boleh disebabkan oleh beberapa faktor, contohnya, pembaikan perihal pengaliran elektrik tentang

plastik substrat, sifat CuS dan terma penyekat tentang bis-chalcone campuran.

Kata Kunci: Claisen-Schmidt pemeluwapan, bis-chalcone, sel solar plastik

1

1.0 Introduction

Human are depending on energy to sustain their life. Fuel from fossil fuels was used in

transportation and generates electricity for our daily uses. However, fossil fuel is not a renewable

energy and might be used up in future. According to Muda and Tey (2012), Klass model

forecasted that all the fossil fuels will be used up in 2077. Due to the depletion of petroleum,

rising of fuels price and concerns with global warming when keep using fossil fuels as the

primary energy source, many countries are looking for other renewable energy such as solar

energy and hydro energy to replace fossil fuels. Renewable energy is generally defined as energy

from non-depletable resources or resources that can be naturally replenish. Solar energy is one of

the renewable energy that derived from sunlight. According to Smalley (2009), there is 3x1024

J

per year of energy supplied from the sun to the earth, which is 10000 times more than what

human uses. Therefore, it has the resource potential to become global energy demand as it is

widely distributed on Earth‟s surface and causes no pollution to environment. Thus, development

of solar cell that used to harvest solar energy has attracted a great attention in recent year.

The history of solar cell started in 1839 year when Becquerel observed that silver chloride coated

platinum electrode in an aqueous nitric acid electrolyte generated direct current when the

electrode is exposure under sunlight. Few decades later, Adams and Day (1876) observed that

the solid state of selenium is able to generate electric current when exposure by light. However,

due to the very low efficiency of conversion from solar energy to electrical energy, the electricity

generated is not enough to operate electrical equipment. After the law of photovoltaic effect was

discovered in 1905 by Einstein, Chapin and his coworkers developed the first silicon

photovoltaic cell at the Bell Telephone Laboratory, USA. The efficiency of energy conversion

2

for this photovoltaic cell achieved 6% (Bubenzer & Luther, 2003; Chapin et al., 1954;

Fahrenbruch & Bube, 1983). Due to this high percentage of efficiency in energy conversion, the

solar cells are able to generate enough electricity to operate electrical equipment. Besides, this

new invention also acts as power sources in the field of astronautics, especially for satellites.

However, these solar cells are only limited for the space applications, due to its high production

costs. The commercial solar age is officially begun in 1954. Today, solar cells that widely used

in the market, especially in microelectronic market are dominated by silicon type solar cell

(Goetzberger et al., 2002).

1.1 Harvesting energy from light

Light is a form of energy which travels in the form of wavelength (Figure 1.1). Different

wavelengths have different energy contents. The shorter the wavelength of light, the higher the

energy content is. When light travels, the energy (light energy) is carried by elementary particles

called photons. After the law of photovoltaic effect was discovery, scientists develop devices that

can harvest the energy from light, which is commonly known as solar cell.

Figure 1.1: Wavelength of light

The efficiency of energy conversion is defined as the ability to convert solar energy into usable

electricity. It is usually measured under standard test condition (STC). The STC refers to 1000

Wm-2

of sunlight irradiation and cell temperature of 25°C under air mass 1.5 (Arndt & Puto,

3

2011). It can be expressed in term of percentage as described by Equation 1.1 (Emery &

Osterwald, 1986):

η = Pmax x 100 % …………...………..Equation 1.1

A x ESTND

Where, η = conversion efficiency of solar cells under standard test condition

Pmax = maximum power produced by solar cell in unit of watt, W

A = total surface area of solar cells (including frame and borders) in the

unit of square meter, m2

ESTND = standard spectral irradiance, 1000 Wm-2

The maximum power cannot determine directly from the solar sell. It is determined by the

product of fill factor (FF), short circuit current (Isc) and open circuit voltage (Voc) of solar cell

(Equation 1.2).

Pmax = FF x Isc x Voc ……………………....Equation 1.2

The power of solar cell is obtained when the value for both of the short circuit current and open

circuit voltage is zero. Therefore, a term called “fill factor” is used as the parameter in

conjunction with short circuit current and open circuit voltage in order to determine the

maximum power of solar cell. Fill factor is defined as the ratio of maximum power from the sun

to the product of short circuit current and open circuit voltage (Castellano, 2010).

4

According to Green (1981), fill factor can be calculated by using Equation 1.3.

FF = Voc – In(Voc + 0.72)

………………….……...…..Equation 1.3 Voc + 1

By combining the Equation 1.1, Equation 1.2 and Equation 1.3, Equation 1.4 is formed. In

this study, Equation 1.4 is used to calculate the conversion efficiency.

Η = [Voc – In(Voc + 0.72)] x Isc x Voc

x 100 % ………..Equation 1.4 A x ESTND x [Voc + 1]

1.2 Chalcone compounds

Chalcone is a natural compound which can be found in apple seeds (Marcus et al., 2001). It is

also known as benzalacetophenone or benzylideneacetophenone with the IUPAC name of 1,3-

diphenyl-2-propen-1-one. The structure of chalcone (Figure 1.2) consists of two aromatic rings

that linked by ,-keto-enol containing group.

Figure 1.2: Structure of chalcone

Chalcone can exist either in cis- or trans- conformation (Figure 1.3) as the conjugated C-C

double bond is present in the structure. Trans-conformation of chalcone is more

5

thermodynamically favoured in normal condition due to the conjugated -electron-system that

leads to a stable and planar structure (Muller, 2012).

(a) (b)

Figure 1.3: (a) cis-chalcone; (b) trans-chalcone

Chalcone and its derivatives are widely used in materials science fields such as non-linear optics

(NLO), optical computing, optical communication, optical limiting, photoinitiated

polymerization, electrochemical sensing and Langmuir films (Asiri & Khan, 2011; Asiri et al.

2013). Chalcones are used as NLO due to its good optical power limiting properties and third-

order nonlinearity (Kamath et al., 2014). They offer large nonlinear coefficients due to the fact

that they consist of a conjugated double bond in between two planar benzene rings. The

delocalization of -electrons within these double bond and benzene rings are the one that

responsible for the third order nonlinear optical responses (Poornesh et al., 2009). Furthermore,

the responses can be increased by enhancing the ability of electron donating groups.

Besides that, some of the chalcone compounds have second harmonic generation (SHG)

properties (Patil et al., 2007). SHG is a nonlinear optical process which a photon is produced

from two photons with same frequency and energy in a nonlinear material. The produced photon

6

has twice the frequency and amount of energy compared to the initial photons. Moreover, the

wavelengths of the produced photons are only half of their initial photons (Figure 1.4). This

nonlinear optical process allows the laser industry to make a stronger laser light. The incident

laser with lower energy, less intensity and longer wavelength is able to convert into a stronger

laser ray with higher energy, more intensity and shorter wavelength.

Energy level

Figure 1.4: Second harmonic generation principle

Chalcone and its derivatives also play an important role in biological field especially for

pharmalogical activities such as anti-bacterial, anti-malarial, anti-cancer, anti-microbial, anti-

oxidant and anti-inflammatory (Prasad et al., 2008; Rahman, 2011). According to Syam et al.

(2012), some chalcone derivative compounds such as 3-(4-Methoxyphenyl)-1-phenylpropenone

having anti-cancer activity due to their capacity to elicit apoptosis. 3-(4-methoxyphenyl)-1-(4-

pyrrol-1-yl-phenyl) prop-2-en-1-one (Figure 1.5), one of the chalcone derivative compound was

used in anti-malarial which shows about 50% of inhibition concentration of the parasites stain

(Awasthi et al., 2009). Besides, bis-pyrazoline that derived from bis-chalcone is used in anti-

Initial photon

Photon produced with

twice the energy Initial photon

7

bacterial activities. This compound is able to inhibit both Gram-positive and Gram-negative

bacteria (Asiri & Khan, 2011).

Figure 1.5: 3-(4-methoxyphenyl)-1-(4-pyrrol-1-yl-phenyl) prop-2-en-1-one

Due to the widely used of chalcone and its derivative compound, it is commonly synthesized

artificially rather than extract from plants. Claisen-Schmidt condensation reaction is one of the

common methods used in the synthesis of chalcone. Besides, microwave irradiation, ultrasound

irradiation, Suzuki reaction and solvent-free grinding technique are also used in the synthesis of

chalcone (Zangade et al., 2011).

1.3 Photovoltaic solar cells

Photovoltaic solar cell is part of solar power system that converts sunlight into electricity.

According to Saga (2010), there is about 90% of solar cells used in the market are made from

silicon, it is known as conventional solar cell and built up by two layers of semiconductor, which

are positive semiconductor (p-type) and negative semiconductor (n-type). Both p-type and n-type

semiconductor are produced by the doping of silicon and joining together to form a p-n junction

(Figure 1.6). When there is no current flow, a depletion layer is form in between the p-n junction.

When the equilibrium has been achieved, there are negative ions (free electrons) in the p-type

material and positive ions (empty holes) in the n-type material.

8

Figure 1.6: p-n junction

When the semiconductor is exposed under light, the valence electrons that weakly bonded to the

nucleus absorbed sufficient energy and moved away from their particular position toward a

conduction band. This results in the formation of positive holes (Figure 1.7).

a)