GROWTH AND CHARACTERIZATION OF NONLINEAR OPTICAL 4 · PDF filev ACKNOWLEDGEMENT First of all,...
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GROWTH AND CHARACTERIZATION OF
NONLINEAR OPTICAL 4-APMP, AMINO ACIDS
DOPED NaAP AND DGBCM SINGLE CRYSTALS
A THESIS
Submitted by
G. MARUDHU
Under the guidance of
Dr. S. KRISHNAN
in partial fulfilment for the award of the degree of
DOCTOR OF PHILOSOPHY in
PHYSICS
B.S.ABDUR RAHMAN UNIVERSITY (B.S. ABDUR RAHMAN INSTITUTE OF SCIENCE & TECHNOLOGY)
(Estd. u/s 3 of the UGC Act. 1956) www.bsauniv.ac.in
MARCH 2015
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B.S.ABDUR RAHMAN UNIVERSITY
(B.S. ABDUR RAHMAN INSTITUTE OF SCIENCE & TECHNOLOGY) (Estd. u/s 3 of the UGC Act. 1956)
www.bsauniv.ac.in
BONAFIDE CERTIFICATE
Certified that this thesis GROWTH AND CHARACTERIZATION OF
NONLINEAR OPTICAL 4-APMP, AMINO ACIDS DOPED NaAP AND
DGBCM SINGLE CRYSTALS is the bonafide work of MARUDHU. G
(RRN: 1090206) who carried out the thesis work under my supervision.
Certified further, that to the best of my knowledge the work reported herein
does not form part of any other thesis report or dissertation on the basis of
which a degree or award was conferred on an earlier occasion on this or any
other candidate.
SIGNATURE SIGNATURE
Dr. S. KRISHNAN Dr. I. RAJA MOHAMED RESEARCH SUPERVISOR PROFESSOR & HEAD Assistant Professor (Sr.Gr) Department of Physics Department of Physics B. S. Abdur Rahman University B. S. Abdur Rahman University Chennai – 600 048 Chennai – 600 048
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ACKNOWLEDGEMENT
First of all, I am truly grateful to my supervisor
Dr. S. Krishnan, Assistant Professor of Physics, B. S. Abdur Rahman
University, Chennai who has been tremendously cooperative throughout my
research.
My sincere thanks to the Doctoral Committee members
Dr. R. Gopalakrishnan, Associate Professor of Physics, Anna University,
Chennai-25 and Dr. S.S.M. Abdul Majeed, Professor and Head, Department
of Polymer Technology, B. S. Abdur Rahman University, Chennai for their
critical comments and suggestions for my research work.
I am thankful to Dr. I. B. Shameem Banu, Dean (School of Physical
and Chemical Sciences) and Professor of Physics, B. S. Abdur Rahman
University, Chennai.
I express my heartfelt thanks to Dr. I. Raja Mohamed, Professor and
Head, Department of Physics, B. S. Abdur Rahman University, Chennai.
I place a record of thanks to The Principal, and the management of
Sri Ramanujar Engineering College, Chennai, for giving an opportunity to
teaching as an Assistant Professor in the Department of Physics, in this
esteemed institution.
It is my great pleasure to thank Dr. G. Vinitha, Assistant Professor of
Physics, School of Basic sciences, VIT University, Chennai.
I sincerely thank to Dr. P. Samuel, Assistant Professor, Department of
Physics, Ramco College of Engineering, Palayamkottai.
I am whole heartedly thank to Mr. G.V. Vijayaraghavan, Assistant
Professor (Sel. Grade), Department of Physics, B. S. Abdur Rahman
University, Chennai, for his constant support and encouragement throughout
my research work.
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I am always thankful to Dr. R. Indirajith, Assistant Professor,
Department of physics, B. S. Abdur Rahman University, Chennai, for his
tireless and moral support throughout my research work.
I am deeply indebted to Dr. M. Basheer Ahamed, Mr. S. Sathik
Basha, Mrs. U. Majitha Parvin, Mr. Md. Sheik Sirajuddeen, Dr. S. Begam
Elavarasi, Dr. J. Thirumalai, Dr. Jahir Abbas Ahmed and all non
teaching staff, Department of Physics, B. S. Abdur Rahman University,
Chennai, for their constant encouragement and support.
I am also thankful to Mr. T. Thilak, Mr. G. Shanmuganadhan,
Mr. R. Krishnan and all research scholars in the department of physics,
B. S. Abdur Rahman University, Chennai, for their help and support rendered
towards my research work.
I am truly grateful to Dr. G. Pasupathi, Assistant Professor of Physics,
Department of Physics, A.V.V.M. Sri Pushpam College, Thanjavur.
I wholeheartedly express my immense gratitude to my beloved
parents Mr. M. Gangatharan, Mrs. G. Kanniammal, my lovable wife
Mrs. Sudha, my cute son Jr. M. S. Thamizh, my uncle Mr. S. Balamurugan
and my Lovable sisters Mrs. Mala and her gifted son
Jr. B. M. Prahatheeshwaran, and Miss. Malar for their unlimited love,
boundless affection and support and blessings.
I thankfully remember to my uncle Mr. G. Vijayamohan, who is like
my father, my aunt Mrs. V. Senthamarai, who is like my mother and his
family for their huge support and encouragement to complete my research.
I must mention the huge encouragement received from my wonderful
B. Tech IT (2010-14) students of Sri Ramanujar Engineering College.
Finally, I thank all those who helped me directly or indirectly to
complete the research work in time.
G. MARUDHU
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ABSTRACT
Nonlinear optical 4-aminopyridinium monophthalate (4-APMP) single
crystals were grown by the slow evaporation technique using methanol as
the solvent. Single crystal X-ray diffraction confirmed that the grown crystal
belonged to the orthorhombic system. The presence of functional groups
was qualitatively determined by FTIR. The optical absorption studies
revealed very low absorption over the entire visible region. The fluorescence
spectrum at 430 nm indicated blue light emission. The thermal stability of the
grown crystal was found to be approximately 197.2˚C. Microhardness
studies revealed that the hardness number was 4.89. The second harmonic
generation (SHG) efficiency of the grown crystal was found to be 1.1 times
that of KDP crystals.
Amino acid-doped sodium acid phthalate (NaAP) crystals were
successfully grown by the slow evaporation technique at room temperature.
The effect of amino acids on the growth and properties of NaAP was
investigated thoroughly. Single crystal X-ray diffraction was carried out on the
grown crystals to identify the structural and lattice parameters. The presence
of dopants in NaAP single crystals was determined qualitatively by FTIR.
The optical transparency for the doped crystals was observed using optical
absorption. The mechanical strength of the grown crystals was determined
by Vickers microhardness measurements. The SHG efficiency for the grown
crystals was determined using the Kurtz powder technique.
Nonlinear optical single crystals of diglycine barium chloride
monohydrate (DGBCM) were grown by the slow evaporation solution growth
technique from a mixture of an aqueous solution of glycine and barium
chloride in the ratio 2:1 at room temperature. The grown crystals were
characterized by various techniques such as single crystal X-ray diffraction,
FTIR, UV-Vis-NIR spectra, Vickers hardness testing, thermogravimetric
analysis, and fluorescence spectra. Their SHG efficiency was measured by
the Kurtz and Perry powder technique using a Nd:YAG laser, and the results
were discussed in detail.
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TABLE OF CONTENTS
CHAPTER NO. TITLE PAGE NO.
ACKNOWLEDGEMENT v
ABSTRACT vii
LIST OF TABLES xii
LIST OF FIGURES xiii
LIST OF SYMBOLS xvii
1. INTRODUCTION 1
1.1 INTRODUCTION TO CRYSTAL GROWTH 1
1.2 IMPORTANCE OF NLO CRYSTALS 2
1.3 INORGANIC CRYSTALS 4
1.4 ORGANIC CRYSTALS 5
1.5 SEMIORGANIC CRYSTALS 6
2. LITERATURE OVERVIEW 8
2.1 INTRODUCTION 8
2.2 4-AMINOPYRIDINIUM MONOPHTHALATE
(4-APMP) SINCLE CRYSTAL 8
2.3 AMINO ACID DOPED SODIUM ACID
PHTHALATE (NaAP) SINGLE CRYSTALS 9
2.4 DIGLYCINE BARIUM CHLORIDE
MONOHYDRATE (DGBCM) SINGLE
CRYSTAL 9
2.5 CONCLUSION 10
3. EXPERIMENTAL 12
3.1 INTRODUCTION 12
3.2 MATERIALS 12
3.3 GLASSWARE AND APPARATUS 13
3.4 MATERIAL SYNTHESIS 13
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CHAPTER NO. TITLE PAGE NO.
3.4.1 SYNTHESIS OF 4-AMINOPYRIDINIUM
MONOPHTHALATE 13
3.4.2 SYNTHESIS OF AMINO ACID DOPED
SODIUM ACID PHTHALATE 14
3.4.3 SYNTHESIS OF DIGLYCINE BARIUM
CHLORIDE MONOHYDRATE 20
3.5 CHARACTERIZATIONS 21
3.6 CONCLUSION 21
4. STRUCTURAL, OPTICAL,
FLUORESCENCE, MECHANICAL AND
THERMAL PROPERTIES OF NONLINEAR
OPTICAL 4-AMINOPYRIDINIUM
MONOPHTHALATE SINGLE CRYSTAL 22
4.1 INTRODUCTION 22
4.2 RESULTS AND DISCUSSION 22
4.2.1 Single crystal X-ray diffraction analysis 22
4.2.2 FTIR Spectral Study 25
4.2.3 Optical Absorption Spectral Studies 25
4.2.4 Fluorescence Studies 27
4.2.5 Thermal analysis 28
4.2.6 Microhardness studies 29
4.2.7 NLO studies 34
4.3 CONCLUSION 35
5. OPTICAL AND MECHANICAL STUDIES
ON AMINO ACID DOPED SODIUM
ACID PHTHALATE (NaAP) SINGLE
CRYSTALS 36
5.1 INTRODUCTION 36
5.2 RESULTS AND DISCUSSION 36
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CHAPTER NO. TITLE PAGE NO.
5.2.1 Single crystal X-ray diffraction analysis 36
5.2.2 FTIR studies 38
5.2.3 UV-vis-NIR spectral analysis 40
5.2.3.1 Determination of Optical Constants 44
5.2.4 Microhardness measurements 51
5.2.5 Nonlinear Optical studies 53
5.3 CONCLUSION 54
6. STRUCTURAL, OPTICAL, MECHANICAL,
THERMAL AND FLUORESCENCE
PROPERTIES OF NONLINEAR OPTICAL
DIGLYCINE BARIUM CHLORIDE
MONOHYDRATE (DGBCM)
SINGLE CRYSTAL 55
6.1 INTRODUCTION 55
6.2 RESULTS AND DISCUSSION 55
6.2.1 Single crystal X-ray diffraction analysis 55
6.2.2 FTIR studies 57
6.2.3 Optical absorption studies 58
6.2.3.1 Determination of Optical Constants 60
6.2.4 Microhardness studies 62
6.2.5 TGA/DTA studies 66
6.2.6 Fluorescence studies 66
6.2.7 Second harmonic generation study 67
6.3 CONCLUSION 68
7. CONCLUSION 69
xi
CHAPTER NO. TITLE PAGE NO.
8. SCOPE FOR FURTHER WORK 71
REFERENCES 72
APPENDIX 1
(BASIC CONCEPTS) 95
APPENDIX 2
(PREPARATION TECHNIQUES) 99
APPENDIX 3
(CHARACTERIZATION TECHNIQUES) 108
TECHNICAL BIOGRAPHY 118
xii
LIST OF TABLES
TABLE
NO. TITLE PAGE NO.
4.1 Crystal data and structure refinement for 4-APMP 24
4.2 FTIR analysis of the grown crystal 26
4.3 Microhardness value obtained on the 4-APMP crystal 34
5.1 Lattice parameters for Pure and doped crystals 37
6.1 Some theoretical parameters on DGBCM crystals 57
6.2 Microhardness value obtained on the DGBCM crystal 65
6.3 Comparative of SHG efficiencies of NLO crystals
relative to KDP 68
A.1.1 Seven Crystal Systems 97
xiii
LIST OF FIGURES
FIGURE NO. TITLE PAGE NO.
3.1 Photograph of as grown 4-APMP crystal 14
3.2 Photograph of Pure NaAP crystal 15
3.3
Photograph of NaAP crystal doped with 1 mol%
L-alanine 15
3.4
Photograph of NaAP crystal doped with 3 mol%
L-alanine 16
3.5
Photograph of NaAP crystal doped with 5 mol%
L-alanine 16
3.6
Photograph of NaAP crystal doped with 1 mol%
L-arginine 17
3.7
Photograph of NaAP crystal doped with 3 mol%
L-arginine 17
3.8
Photograph of NaAP crystal doped with 5 mol%
L-arginine 18
3.9 Photograph of NaAP crystal doped with 1 mol% Glycine 18
3.10 Photograph of NaAP crystal doped with 3 mol% Glycine 19
3.11 Photograph of NaAP crystal doped with 5 mol% Glycine 19
3.12 Photograph of as grown DGBCM crystal 20
4.1 Molecular structure of 4-APMP crystal 23
4.2 FTIR spectrum of the grown crystal 25
4.3 Optical absorption spectrum the grown crystal 27
4.4 Emission Spectrum of 4-APMP crystal 28
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FIGURE NO. TITLE PAGE NO.
4.5 TG-DTA spectrum of the title crystal 29
4.6 Plot of load (P) vs. Hv 30
4.7 Plot of Log d vs. log P 30
4.8 Plot of dn vs. Load P 31
4.9 Plot of d vs. dn/2 32
4.10 P vs. σv
33
4.11 P vs C11
33
5.1 FTIR Spectra of L-alanine doped NaAP crystals 39
5.2 FTIR Spectra of L-arginine doped NaAP crystals 39
5.3 FTIR Spectra of Glycine doped NaAP crystals 40
5.4 Absorption spectra of L-alanine doped NaAP crystals 41
5.5 Absorption spectra of L-arginine doped NaAP crystals 41
5.6 Absorption spectra of Glycine doped NaAP crystals 42
5.7 Plot of (αhν) 2 vs. (hν) for pure and L-alanine doped
NaAP crystals 43
5.8 Plot of (αhν) 2 vs. (hν) for pure and L-arginine doped
NaAP crystals 43
5.9 Plot of (αhν) 2 vs. (hν) for pure and Glycine doped
NaAP crystals 44
5.10 Extinction Coefficient of L-alanine doped NaAP crystals 45
xv
FIGURE NO. TITLE PAGE NO.
5.11 Extinction Coefficient of L-arginine doped NaAP crystals 46
5.12 Extinction Coefficient of Glycine doped NaAP crystals 46
5.13 Reflectance of L-alanine doped NaAP crystals 47
5.14 Reflectance of L-arginine doped NaAP crystals 47
5.15 Reflectance of Glycine doped NaAP crystals 48
5.16 Optical Conductivity of L-alanine doped NaAP crystals 48
5.17 Optical Conductivity of L-arginine doped NaAP crystals 49
5.18 Optical Conductivity of Glycine doped NaAP crystals 49
5.19 Electrical Conductivity of L-alanine doped NaAP
crystals
50
5.20 Electrical Conductivity of L-arginine doped NaAP
crystals
50
5.21 Electrical Conductivity of Glycine doped NaAP crystals 51
5.22 Hardness number of L-alanine doped NaAP crystals 52
5.23 Hardness number of L-arginine doped NaAP crystals 52
5.24 Hardness number of Glycine doped NaAP crystals 53
5.25 SHG efficiency of doped amino acid crystals 54
6.1 FTIR spectrum of the grown crystal 58
6.2 Optical absorption spectrum of the grown crystal 59
6.3 Plot of (hν) vs. (αhν) 2 60
xvi
FIGURE NO. TITLE PAGE NO.
6.4 Plot of extinction coefficient (K) vs. photon energy (hν) 61
6.5 Plot of photon energy (hν) vs. Refractive index (n) 61
6.6 Plot of P vs. Hv 62
6.7 Plot of Log d vs. log P 63
6.8 Plot of dn vs. Load P 64
6.9 Plot of d vs. dn/2 64
6.10 TG/DTA analysis of the title crystal 66
6.11 Fluorescence spectrum of the DGBCM crystal 67
A.2.1 Mason jar crystallizer 106
A.3.1 Powder X-ray Diffractometer 109
A.3.2 Schematic diagram of a FTIR spectrometer 111
A.3.3 Schematic representation of a UV-Vis-NIR
spectrophotometer 112
A.3.4 Second Harmonic Generation (SHG) Instrument 118
xvii
LIST OF SYMBOLS AND ABBREVIATIONS
XRD - X-ray diffraction
FTIR - Fourier Transform Infrared
KBr - Potassium Bromide
UV - Ultraviolet
NIR - Near Infrared
TGA - Thermogravimetric Analysis
DTA - Differential Thermal Analysis
NLO - Nonlinear Optics
SHG - Second Harmonic Generation
Nd : YAG - Neodymium Yttrium Aluminium Garnet
Eg - Energy gap
h - Planck’s constant
σelec - Electrical conductivity
n - Refractive index
K - Extinction coefficient
P - Polarization
HV - Vickers hardness number
nm - Nanometre
Å - Angstrom
KDP - Potassium Dihydrogen Phosphate
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LIST OF INTERNATIONAL PUBLICATIONS
[1] Marudhu G, Krishnan S, Thilak T, Samuel P, Vinitha G, and
Pasupathi G, “Growth, thermal and optical studies on nonlinear
optical material Diglycine Barium Chloride Monohydrate (DGBCM)
single crystal”, Journal of Nonlinear Optical Physics & Materials,
Vol. 22, pp. 1-13, 2013.
[2] Marudhu G, Krishnan S, and Vijayaragavan G. V, “Optical, theoretical
and mechanical studies on sodium acid phthalate crystal”, Optik,
Vol. 125, pp. 2417-2421, 2014.
LIST OF PAPERS COMMUNICATED IN INTERNATIONAL JOURNALS
[1] Marudhu G, Krishnan S, and Vijayaragavan G. V, “Optical and
mechanical studies on Amino acids doped Sodium acid phthalate
(NaAP) single crystals by slow evaporation method” to Journal of
Optoelectronics and Advanced Materials-Rapid Communications.
[2] Marudhu G, Krishnan S, and Palanichamy M, “Growth, structural,
optical, thermal and mechanical studies on 4-Aminopyridinium
monophthalate: A novel nonlinear optical crystal” to Journal of Optics
and Laser Technology.
121
LIST OF PRESENTATIONS IN NATIONAL CONFERENCE/SEMINAR
[1] Marudhu G, Thilak T and Vinitha G, “Growth and Characterization of
KDP crystals in different pH values by Solution Growth method” in the
Padiga Valarchi Ariviyal Karutharangu, conducted by Anna University,
Chennai, held on 18-19 October, 2010.
[2] Marudhu G, Krishnan S, Vinitha G and Vijayaragavan G. V, “Growth,
optical, thermal and mechanical properties of nonlinear optical sodium
acid phthalate single crystal by slow evaporation technique” in the
XVIII NATIONAL SEMINAR ON CRYSTAL GROWTH (XVIII NSCG-
2014), conducted by SSN Engineering College, Chennai-603 110,
held on 24-26 October, 2014.
[3] Marudhu G and Krishnan S, “Growth and Characterizations of
Nonlinear Optical Diglycine Barium Chloride Monohydrate (DGBCM)
single crystal” in the Second National conference on Recent advances
in materials (NCRAM-2014), conducted by B.S.Abdur Rahman
University, Chennai, held on 03-04 September, 2014.
72
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nonlinear optical single crystal”, Mat. Che. and Phys., Vol. 109,
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[154] Marudhu G, Krishnan S, Vijayaragavan G. V, “Optical, theoretical and
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Pasupathi G, “Growth, thermal and optical studies on nonlinear
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1
1. INTRODUCTION
1.1 INTRODUCTION TO CRYSTAL GROWTH
Many modern technological devices would not exist without the use of
synthetic single crystals, obtained by the technique for preparing and
producing bulk single crystals known as crystal growth [1]. Crystal growth
has consistently been a key aspect in some of the most important advances
of the past 80 years. Crystal growth is an applied science that underpins a
number of the world’s major industries because the accomplishments of most
of the extraordinary modern day technologies are very much attributed to the
development of microelectronic, optoelectronic and optical devices made
from artificial crystals [2, 3]. The most in demand research area in the field of
physics is crystal growth; currently, it addresses how to grow crystals and
what their properties are, as well as how they can be suitably fabricated for
device applications. The above questions were answered by developing
novel nonlinear optical (NLO) crystals for a wide range of applications such
as optical switching, frequency conversion and electro-optic modulation [4].
The crystalline quality of NLO crystals must be improved to be able to
fabricate large single crystals for fruitful applications [5]. Here, crystal
engineering involves the development of new crystalline materials with
superior properties, functions and applications, e.g., polarized materials for
NLO applications and materials tailored with magneto-photo properties such
as luminescence for electronic applications and molecular sensors [6]. In
chemistry, the compositions of crystals are based on atomic and molecular
concepts. In particular, X-ray diffraction has been used to reveal the internal
structure of single crystals.
Materials science is primarily concerned with the fundamental
understanding of the internal structure, properties and processing of
materials and is ultimately responsible for many of the recent technological
innovations [7]. Thus, crystals are considered the pillars of modern
technology. In recent years, crystals have been used in the development of
2
photonics technology, which uses both electrons and photons to carry, store
and process information [8-12]. Crystals are also typically used in laser
technology, optoelectronics, photovoltaic devices, infrared detectors and
other technologically important scientific applications [13-15].
A single crystal or monocrystalline solid is a material in which the
crystal lattice of the entire sample is continuous with no grain boundaries.
This allows the material to exhibit unique properties, in particular mechanical,
optical and electrical properties, which can be anisotropic depending on the
crystal structure. Anisotropic crystals can be obtained if the origin of the
crystal growth is along a single direction. The additional free energy for each
crystal growth volume can be determined from the interface types and the
final size of the crystal and is an important factor for the mechanical
properties. Anisotropy is useful in single crystals of silicon, used in
semiconductor industries, especially in semiconductor fabrication and
functioning field effect transistors, for altering local electrical properties. The
importance of single crystals in various applications is evident from the recent
advancements in the fields of semiconductors; polarizers; transducers;
infrared detectors; ultrasonic amplifiers; ferrites; magnetic garnets; solid state
lasers; nonlinear optic, piezoelectric, acousto-optic, and photosensitive
materials; and crystalline thin films used in microelectronics and hardware
industries [16-18]. Hence, to achieve high performance devices, high quality
single crystals are needed. The growth and characterization of single
crystals for device fabrication have created a great stimulus due to their
significance for both academic and applied research.
1.2 IMPORTANCE OF NLO CRYSTALS
The appropriate development of crystal growth is nonlinear optics,
which means the extension of the motion of the linear propagation of an
electromagnetic field. In mathematics, this is based on Maxwell’s equations,
in which the polarization of a medium is expressed in terms of a power series
[19]. In recent years, great efforts have been made in the field of nonlinear
optics through investigating several classes of materials, including organic,
3
inorganic, and semiorganic, which are expected to be important for
optoelectronics, frequency conversion effects, high speed information
processing, optical advantages such as optical data storage technology, etc.
[20, 21] Here, NLO materials are a special criteria class of the materials,
which have a huge impact on laser and information technology and industrial
applications because of their ability to change the frequency of an incoming
laser beam by modifying its amplitude and phase [22]. Therefore, lasers
alone cannot be used widely in modern science and technology without NLO
crystals [23]. Hence, the development of NLO crystals with better linear
optical (LO) and NLO properties, wider spectral transmission and phase-
matching range is obviously essential for further broadening the applications
of lasers such as image applications, frequency multipliers, mixers,
parametric oscillators, and other functions in the deep-UV, far IR, and even
THz spectral regions [24].
Finally, our aim is to develop novel materials with large nonlinearities
that exhibit exceptional properties such as a wide transparency range, fast
response in data processing, and high damage threshold [25-27]. For this,
we grew and fabricated application-oriented crystals by mixing various
materials into grown NLO materials. Some materials could allow the entry of
light depending on the orientation at room temperature, i.e., receiving high
energy of photons in the blue and green range from incident infrared light
through a NLO crystal [28-30]. Some of the familiar crystals that exhibit the
property of frequency conversion over the entire UV and visible regions are
KTP, LBO, BBO, KDP, KNbO3, LiNbO3, AgGaS2, AgGaSe2, etc. These
crystals are selected based on their optical, mechanical, and physical
properties, such as transmission, damage threshold, and efficiency of the
nonlinear effect, phase matching range and laser beam quality [31, 32].
In the current decade, many researchers have focused on the growth
and characterization of aminopyridine groups to establish NLO behaviour
[33]. The slow evaporation technique is used to grow NLO crystals with good
optical transparency, better orientation, defect-free structures, and good
mechanical and thermal stability [34].
4
1.3 INORGANIC CRYSTALS
Inorganic materials are preferred for NLO applications over organic
materials. The single crystals of pure inorganic materials, such as quartz,
lithium niobate (LINbO3), potassium dihydrogen phosphate (KDP), potassium
titanyl phosphate (KTP), and urea, exhibit excellent NLO properties. These
are the pure inorganic materials used in second harmonic generating
devices, parametric oscillators, etc. [35-39]. Some of the familiar properties
of inorganic host materials are large mechanical strength, excellent thermal
stability, good transmittance, and high electro-optic coefficients as well as
high degree of chemical inertness [40-43]. The most familiar single crystals
of KDP exhibit superior NLO properties and have been used as reference
materials for comparison with other crystalline materials. The transmittance,
hardness and dielectric constants are improved by growing KDP crystals
using the Sankaranarayanan-Ramasamy method compared with the normal
slow evaporation method [44, 45]. NLO materials such as lithium sulphate,
potassium lithium niobate and lithium triborate have peculiar advantages
such as a large damage threshold, high phase matching angle, wider
transparency range and chemical stability. Additionally, lithium sulphate
monohydrate has been classified as a promising material for Raman laser
frequency converters [46]. We have been growing several inorganic
materials that exhibit high transparency, good chemical stability and tensile
strength as well as second harmonic generation (SHG), frequency
conversion, optical parametric amplification (OPA), optical parametric
oscillation (OPO), optical emission [47] and electro-optical applications.
However, in these systems, the nonlinear responses are undoubtedly related
to individual bond polarizabilities. Due to a lack of extended π electron
delocalization, the inorganic materials have modest optical nonlinearities.
Due to the difficulty of synthesizing towards particular directions, newer
materials are currently being explored, and this has led to a new class of
NLO materials [48].
5
1.4 ORGANIC CRYSTALS
Organic materials exhibit excellent NLO properties because of their
electronic structure with π conjugated systems between donors and
acceptors [49, 50]. This is due to non-centrosymmetry leading to huge NLO
efficiency, exhibited by organic materials on the order of 10 to 100 times
larger than that of inorganic NLO materials through macroscopic second
order NLO response [51]. These materials exhibit excellent properties such
as optoelectric coefficients, large second-order NLO coefficients, small
dielectric constants, molecular designing, faster optical responses, and ultra-
fast responses to external electric fields. [52]. Hence, organic materials are
superior to their inorganic counterparts in terms of crystal preparation, device
fabrication, and production of better devices with large nonlinearities, i.e.,
they have wide applications in areas such as information storage, optical
communication, optical data storage, optoelectronics, laser technology, and
telecommunications [53]. Moreover, they can be in bulk and single form for
NLO device fabrication. Additionally, they are important for frequency
modulation device applications, such as frequency conversion, integrated
circuitry, optical switching, and terahertz wave generation with detection [54].
The slow evaporation technique is one of the simplest techniques for growing
high quality organic single crystals [55]. Recently, Paul M. Dinakaran had
grown 4-Bromo 4-nitrostilbene (BONS) single crystals that exhibited a peak
NLO efficiency of 67 times greater than the reference KDP crystal [25].
Another organic host crystal L-phenylalanine-4-nitrophenol (LPAPN)
demonstrated a high NLO efficiency of 1.2 times that of KDP [50]. One of the
newest organic NLO materials is thiourea with quinine sulphate dehydrate
(TQS) grown by the gel method by Lekshmi P. Nair. This exhibited 1.4 times
higher NLO behaviour than the KDP reference crystal [54]. Redrothu
Hanumantharao had grown l-threonine formate, which had an SHG efficiency
of 1.21 times that of reference KDP [56]. Even though organic materials
have many advantages, they exhibit some drawbacks, as they have a low
laser damage threshold, low optical transparency, etc. [57].
6
1.5 SEMIORGANIC CRYSTALS
The inability of organic materials to grow to large crystal sizes
impedes device fabrication, which has led to the discovery of a new class of
crystals called semi organics to satisfy technological requirements [58, 59].
The most promising candidates among metal-organic compounds have
attracted researchers in recent years due to their various properties such as
NLO response, magnetism, and luminescence, as well as applications in
photography and drug delivery [6] due to the combination of organic and
inorganic components. Hence, they have shown large NLO behaviour and
also favourable properties such as high optical transparency over the entire
visible region, a large laser damage threshold value, low deliquescence, high
resistance, and low angular sensitivity [4, 21].
In semiorganic materials, the organic ligand is ionically bonded with
the inorganic host, which promotes exceptional mechanical strength and
chemical stability [42]. Because of this, semiorganic materials are promising
for many other applications such as frequency conversion, light amplitude
and phase modulation and phase conjugation [60]. One significant example
of semiorganic hosts is alkali hydrogen phthalate single crystal, which is used
in long-wave X-ray spectrometers. Several semi organics are used as
substrates for depositing thin films of organic NLO samples, and their
centrosymmetric or non-centrosymmetric forms depend on how the cations
are arranged in the chemical bonding during crystal growth [52] and are thus
suitable for the fabrication of optoelectronic devices [61]. Moreover, metal–
organic complexes offer higher environmental stability combined with greater
diversity of tunable electronic properties by virtue of the coordinated metal
centre [6]. Furthermore, organic ligands combined with inorganic hosts
thereby become semiorganic crystals, which lead to more attractive
applications such as SHG, THG, optical bistability, laser remote sensing,
optical disc data storage, laser driven fusion, medical and spectroscopic
image processing, colour displays and optical communication [33].
7
Recently, Soma Adhikari grew L-leucine hydrobromide (LEHBr) single
crystals, which demonstrated a peak NLO efficiency 4 times greater than that
of reference KDP [61]. Another semiorganic host crystal, bis (thiourea) silver
(I) nitrate (TuAgN), exhibited a better NLO efficiency of 0.85 times that of
KDP [58]. Another NLO material, 2-aminopyridine bis thiourea zinc sulphate,
was grown by the slow evaporation method. This exhibited higher NLO
behaviour than KDP [33].
8
2. LITERATURE OVERVIEW
2.1 INTRODUCTION
Currently, most of the published research has focused on semiorganic
crystals to enhance the nonlinear optical properties. Due to familiar
properties of both inorganic and organic hosts, until now, semiorganic
materials have been grown for more familiar broad applications, such as
frequency modulation, data storage technology, fibre optic communication,
optical modelling, and electro-optic modulations, because of their good
mechanical strength, high optical transmittance, large damage threshold,
chemical stability, etc. [62].
2.2 4-AMINOPYRIDINIUM MONOPHTHALATE (4-APMP) SINGLE
CRYSTAL
Pyridine and its derivatives of 4-aminopyridine are used as proton
acceptors. 4-Aminopyridine (4-NH2Py) has an amine group present in the
para-position of the nitrogen of the heterocycle. The phthalic acid is an
aromatic dicarboxylic acid group, which has two carboxylic groups in the
ortho positions so that it can act in bidentate ligand (COO-, COO-)
coordination, thereby acting as a donor in the nucleation process. In donor-
acceptor series, the organic ligands are favourable for growing NLO crystals
by the slow evaporation technique, in which one of the pyridine derivatives of
2-aminopyridine is combined with some of the organic ligands such as
benzoic acid, malic acid, etc. Work has been published on the well-known 2-aminopyridinium benzoate [63] and 2-aminopyridinium malate [64] single
crystals, which provides better information on the structural, functional,
optical, thermal, and mechanical properties, dielectric behaviour and
enhancements to the NLO properties. However, there are currently no
reports on the above properties for 4-aminopyridine combined with phthalic
acid, i.e., 4-aminopyridinium monophthalate single crystals produced by the
slow evaporation method. In the present work, the structural, optical,
thermal, mechanical and fluorescence properties of 4-aminopyridinium
9
monophthalate single crystals grown by slow evaporation are reported for the
first time.
2.3 AMINO ACID DOPED SODIUM ACID PHTHALATE (NaAP) SINGLE
CRYSTALS
The most significant phthalic acid families are potassium acid
phthalate (KAP) and sodium acid phthalate (NaAP) single crystals, which are
used for various scientific applications such as substrates for organic thin film
NLO materials [65], standards in volumetric analysis, etc. [66] Generally,
KAP crystals are discussed much more in the literature, while very limited
information is available on NaAP single crystals. These phthalate family
materials exhibit large optical transmission with low absorption over the entire
UV-visible region, superior thermal stability in the presence of moisture and
good mechanical hardness; moreover, photo-electric devices can be
fabricated to take advantage of their SHG behaviour [154]. One research
group has used zinc, an inorganic metal, as a dopant in NaAP single crystals
for the improvement of optical, thermal and dielectric properties [52].
Rigorous literature surveys reveal that amino acids are not used as dopants
in NaAP crystals. Hence, L-alanine, L-arginine and glycine are added as
dopants to NaAP single crystals. In the present work, we discuss the optical
and mechanical properties of pure and doped NaAP single crystals grown by
the slow evaporation technique.
2.4 DIGLYCINE BARIUM CHLORIDE MONOHYDRATE (DGBCM) SINGLE
CRYSTAL
Glycine is a simple and effective amino acid with a zwitterionic
structure. Its complexes with inorganic materials have attracted the attention
of many researchers [67]. Furthermore, they show high optical nonlinearity
as well as the chemical flexibility of organic materials and physical
ruggedness of inorganic materials [6]. Glycine zinc sulphate, glycine oxalic
acid, glycine nitrate, and glycine lithium sulphate are the stoichiometric ratio-
based NLO crystals. At an appropriate ratio of 2:1, glycine can be combined
10
with familiar inorganic materials, such as zinc chloride, cadmium chloride,
calcium bromide, and magnesium sulphate, and organic materials, such as
picric acid, oxalic acid and hydrochloric acid. These combinations have
enabled developments in bulk growth and have provided new structural,
optical, thermal, mechanical, dielectric and NLO properties. Here, we
mention that some of the diglycine derivatives, such as diglycine zinc chloride
(DGZC) NLO single crystals [68], diglycine cadmium chloride (DGCC) single
crystals [69], calcium dibromide bis (glycine) tetrahydrate single crystals [62],
diglycine hydrobromide NLO crystal [70], bisglycine oxalate single crystals
[71], and diglycine picrate single crystals [72], were grown by the slow
evaporation method. In the series of glycine derivatives we have
investigated, the familiar one is diglycine barium chloride single crystal, which
is a nonlinear optical semiorganic crystal with non-centrosymmetry belonging
to the orthorhombic crystal system. Some of the researchers who have
investigated this material have produced significant studies [73]. Studies
from the current decade are discussed in Chapter 6. The growth of diglycine
barium chloride monohydrate single crystals has been investigated to
improve their optical, mechanical and NLO properties for fabrication tailored
towards device applications.
2.5 CONCLUSION
From the above discussions, it is clear that growth, optical, thermal,
and mechanical studies of 2-aminopyridinium benzoate and 2-aminopyridinium malate single crystals have been conducted that use the
slow evaporation method. A rigorous literature survey reveals that nonlinear
optical 4-aminopyridinium monophthalate single crystals obtained from slow
evaporation were not reported elsewhere. Likewise, the addition of zinc to
NaAP single crystals has been reported elsewhere. However, amino acid-
doped (L-alanine, L-arginine and glycine) NaAP single crystals obtained by
slow evaporation have been reported for the first time by us. Additionally, the
growth and theoretical, optical, and mechanical properties of diglycine barium
chloride monohydrate single crystals obtained by slow evaporation have
been reported and published [155]. All of the above mentioned compounds
11
were subjected to various characterizations, and the results were discussed
in detail.
12
3. EXPERIMENTAL
3.1 INTRODUCTION
This chapter addresses the crystal growth technique, in particular the
slow evaporation solution growth technique. This technique is used to grow
a crystal in a simple manner and provide improvements in purity.
Additionally, this technique can produce organic, inorganic and semiorganic
NLO crystals at ambient temperature in different solvents. Hence, we chose
this technique to grow our crystals, including 4-aminopyridinium
monophthalate, amino acid-doped NaAP and diglycine barium chloride
monohydrate single crystals.
4-Aminopyridinium monophthalate (4-APMP) crystals based on
organic materials were subjected to many characterization studies to
measure their structural, vibrational, optical and mechanical properties.
Other work on semiorganic materials, such as amino acid-doped NaAP, has
demonstrated modifications to the optical and mechanical behaviours. The
final works were on diglycine barium chloride monohydrate (DGBCM) crystal
semiorganic materials; characterizations of these materials were carried out
to improve their physical properties. Hence, the experimental methods used
for the various types of crystals are briefly discussed in this chapter.
3.2 MATERIALS
4-aminopyridine
Phthalic acid
Sodium bicarbonate
L-alanine
L-arginine
Glycine
Barium chloride dihydrate
13
3.3 GLASSWARE AND APPARATUS
Magnetic stirrer
Magnetic pellets
Beakers
Whatmann filter paper
Tissue paper
Petri dish
Digital weight balance
3.4 MATERIAL SYNTHESIS
3.4.1 SYNTHESIS OF 4-AMINOPYRIDINIUM MONOPHTHALATE
The title compound was synthesized by dissolving (AR grade)
4-aminopyridine and phthalic acid in methanol in a 1:1 molar ratio. After
continuous stirring, the supersaturated solution was filtered with Whatmann
filter paper and kept it in a dust free atmosphere. The saturated solution was
allowed to dry at room temperature by the slow evaporation technique. After
a period of 30 days, optically transparent and defect free crystals with
dimensions of 15 × 3 × 2 mm3 were grown, and the photograph of the grown
crystal is shown in Fig. 3.1. The chemical reaction of the synthesized
materials is given as follows:
C5H6N2 + C8H6O4 → C13H12N2O4
14
Figure 3.1: Photograph of as grown 4-APMP crystal
3.4.2 SYNTHESIS OF AMINO ACID-DOPED SODIUM ACID PHTHALATE
The amino acid-doped NaAP single crystals were prepared by doping
1 mol%, 3 mol%, and 5 mol% of each amino acid (AR grade L-alanine,
L-arginine, and glycine) into NaAP in double distilled water at ambient
temperature and stirring thoroughly for five hours. The impurities were
removed by successive recrystallization. The supersaturated solutions were
filtered using Whatmann filter paper and were kept in dust free atmosphere.
15
Figure 3.2: Photograph of pure NaAP crystal
Figure 3.3: Photograph of NaAP crystal doped with 1 mol% L-alanine
16
Figure 3.4: Photograph of NaAP crystal doped with 3 mol% L-alanine
Figure 3.5: Photograph of NaAP crystal doped with 5 mol% L-alanine
17
Figure 3.6: Photograph of NaAP crystal doped with 1 mol% L-arginine
Figure 3.7: Photograph of NaAP crystal doped with 3 mol% L-arginine
18
Figure 3.8: Photograph of NaAP crystal doped with 5 mol% L-arginine
Figure 3.9: Photograph of NaAP crystal doped with 1 mol% Glycine
19
Figure 3.10: Photograph of NaAP crystal doped with 3 mol% Glycine
Figure 3.11: Photograph of NaAP crystal doped with 5 mol% Glycine
20
All 9 mixtures were allowed to undergo slow evaporation. L-alanine,
L-arginine, and glycine-doped NaAP crystals with different concentrations
were obtained within the periods of 22, 20, and 21 days, respectively. The
photographs of the doped NaAP crystals are shown in Figs. 3.2 - 3.11.
3.4.3 SYNTHESIS OF DIGLYCINE BARIUM CHLORIDE MONOHYDRATE
Diglycine barium chloride Monohydrate (DGBCM) salt was
synthesized by dissolving (AR grade) glycine and barium chloride dihydrate
in a 2:1 molar ratio in double distilled water. The supersaturated solution of
DGBCM was prepared and filtered using Whatmann filter paper. The filtered
solution was tightly closed with a thin plastic sheet, so that the rate of
evaporation could be minimized. After a period of 25 days, a colourless,
transparent crystal with dimensions of 10 x 8 x 2 mm3 was obtained and is
shown in Fig. 3.12.
(NH2CH2COOH)2 + BaCl2. 2H2O → Ba (NH2CH2COOH)2 Cl2. H2O
Figure. 3.12: Photograph of as grown DGBCM crystal
21
3.5 CHARACTERIZATIONS
There was various characterization techniques used to analyse the
grown crystals. A single crystal X-ray diffractometer was used to determine
the structure of the grown crystals. Fourier transform interferometry
confirmed the presence of functional groups in the crystalline materials.
Spectroscopic methods are widely used for qualitative and quantitative
analyses of chemical compounds. The UV-Vis-NIR spectrum gave the
optical transmittance and absorption of the grown crystals. The fluorescence
spectrum showed excitation and emission wavelengths for the crystalline
materials. Thermal analysis was used for studying the thermal stability of the
grown crystals. The Vicker’s hardness measurement was used for
investigating the mechanical behaviour of the grown crystals. The Kurtz and
Perry powder technique was used to find the SHG efficiency of the grown
crystals.
3.6 CONCLUSION
The various types of grown crystals were successfully prepared by the
slow evaporation solution growth technique. They exhibited superior
transparency without major imperfections. Hence, they were selected to
undergo further characterization, and the exhibited properties for each crystal
are reported in the upcoming chapters.
22
4. STRUCTURAL, OPTICAL, FLUORESCENCE, MECHANICAL
AND THERMAL PROPERTIES OF NONLINEAR OPTICAL
4-AMINOPYRIDINIUM MONOPHTHALATE SINGLE CRYSTAL
4.1 INTRODUCTION
In recent years, nonlinear optical materials (NLO) have attracted many
researchers due to its wide applications in the field of telecommunication,
optoelectronic and optical information storage devices [74-81]. Organic NLO
materials exhibits much larger NLO efficiencies compared to their inorganic
counterpart, thus promises to meet future requirements for ultrahigh
bandwidth photonic devices [82-84]. Organic materials have been known for
their potential applications in semiconductors, superconductors and nonlinear
optical devices [85]. Hence, Organic NLO crystals with high second
harmonic generation efficiency and transparency in UV-Vis region are
required for numerous device applications. In the present work, single
crystals of 4-Aminopyridinium monophthalate have been grown from
aqueous solution by slow evaporation technique and the grown crystals were
subjected to various characterizations such as single crystal XRD, FTIR, UV,
Fluorescence, thermal and mechanical analysis and the results were
discussed in detail.
4.2 RESULTS AND DISCUSSION
4.2.1 Single crystal X-ray diffraction analysis
The grown crystal having dimensions 0.35 x 0.30 x 0.25 mm3 was
subjected to single crystal XRD analysis using Enraf Nonius CAD 4/MACH 3
single crystal X-ray diffractometer using Mo Kα radiation (λ = 0.71073 Å).
The crystal structure of the title compound was solved by the direct method
using the program SIR-92 (WINGX) [86]. Data were collected in frames
using oscillation method with µ ranging between 2.59 and 25.00 θ. Full
matrix least-squares refinement was done using SHELXL-97 (WINGX)
computer program [87, 88].
23
Figure. 4.1: Molecular structure of 4-APMP crystal
Table 4.1 gives the details of the crystal and experimental data.
Figure. 4.1 represents the ORTEP (Oak Ridge Thermal Ellipsoid Plot)
diagram of the molecule with atom numbering with the unit cell projected
down the b-axis. There are two molecules of the title compound in the
asymmetric unit. The phthalate ion is getting attached to 4-Aminopyridine
molecules. Further, the analysis reveal that the title crystal belongs to
orthorhombic system with non-centrosymmetric space group P212121 and the
lattice parameters are a = 5.340 Å, b = 8.223 Å, c = 27.366 Å,
α = = = 90◦ and V = 1201.66 Å3.
24
Table 4.1: Crystal data and structure refinement for 4-APMP crystal
CRYSTAL DATA
Formula C13 H12 N2 O4
Formula weight [g / mol] 260.25
Crystal color, habit Pale yellow, Rod
Crystal system Orthorhombic
Crystal size [mm] 0.35 x 0.30 x 0.25 mm3
Space group P212121
Z 4, 1.439 Mg / m3
Unit cell parameters
a = 5.340 (10) Å b = 8.223 (2) Å c = 27.366 (8) Å α = 90º, = 90º, = 90º
Volume [Å3] 1201.66(5) A^3
F (000) 544
µ [mm-1] 1.064
DATA COLLECTION
Diffractometer ENRAF NONIUS CAD 4/MACH 3
Radiation MoKα
Wavelength [Å] 0.71073
Temperature [K] 293(2)
θ min ; θ max [º] 2.59 to 25.00 deg.
Total reflections measured 5415 / 2122
R int 0.0187
Range h = -6→6, k = -9→9, l = -32→31
REFINEMENT
Refinement method Full-matrix least squares
No. of reflection 5415
No. of parameters 185
Final R(F) [ I>2σ (I)] reflections 0.0308
w R [F2] 0.0740
Goodness-of-fit on F2 1.064
Absolute structure parameter 0.3 (11)
Δρ (min; max) [eÅ-3] -0.124 ; 0.154
25
4.2.2 FTIR Spectral Study
Fourier transform infrared spectrum (FTIR) of the 4-APMP crystal was
recorded in the range of 400-4000cm-1 using Perkin Paragon-500 through
KBr pellet technique and is shown in Figure. 4.2. A broad band at 3350 cm-1
is due to NH2 symmetric stretching. The peaks at 1928 and 955 cm-1 are
assigned to C-C-C ring breathing. The C – H in plane is found to be at 1157,
1026 and 620 cm-1. The peaks at 833 and 732 cm-1 is due to C – H out of
plane. All these assignments illustrate the presence of 4-Aminopyridinium
monophthalate and the assignments were shown in the Table 4.2.
Figure. 4.2: FTIR spectrum of the grown crystal
4.2.3 Optical Absorption Spectral Studies
An optical absorption spectrum of the grown crystal was carried out
between from 200 to 800 nm using VARIN CARY 5E UV-VIS-NIR
spectrophotometer and is shown in Figure. 4.3. The optical studies reveal
very low absorption in the entire visible region, which is one of the desired
properties for the device fabrication. The UV cut off wavelength of the crystal
26
was found to be around 335 nm. This very low absorption in the entire visible
region suggests its suitability for second harmonic generation.
Table. 4.2: FTIR analysis of the grown crystal
Wavenumbers (cm-1) Band Assignment
3350 NH2 Symmetric stretching
1928 C-C-C ring breathing
1644 C - C stretching
1371 C – NH2 stretching
1157 C – H in plane bending
1026 C – H in plane bending
955 C-C-C ring breathing
833 C – H out of plane
732 C – H out of plane
620 C – H in plane
27
Figure. 4.3: Optical absorption spectrum the grown crystal
4.2.4 Fluorescence Studies
The Fluorescence gives information about excitation of molecule
brought by absorption of photon. It may be expected in molecules that will be
aromatic or contain multiple conjugated double bonds with a high degree of
resonance stability. The emission spectrum of the grown single crystal of
4-Aminopyridinium monophthalate was recorded in the range of 350-600 nm
using Varian Carry Eclipse Fluorescence spectrometer and is shown in
Figure. 4.4. The sample was excited at 335 nm. The broad peak ranges from
400 to 600 nm with a maximum at 430 nm which indicates that 4-APMP
crystal has blue color of fluorescence emission.
28
Figure. 4.4: Emission Spectrum of 4-APMP crystal
4.2.5 Thermal analysis
The thermal stability of the title crystal was carried out by
thermogravimetric (TG) and differential thermal analysis (DTA) studies using
NETZSCH STA 409 C analyzer in the nitrogen atmosphere at the heating
rate of 10 ◦C/min in the temperature range between from 25 to 400 ºC and
the resultant thermogram is shown in the Figure. 4.5. The TGA curve shows
that there is a loss of weight in the range between 96 ◦C and 306 ◦C in
association with a sharp endothermic peak in DTA, which can be ascribed to
the absorption of energy for breaking of bonds at the initial stage of
decomposition. The TGA illustrates that there is no loss below 197.2 ºC,
thus assigned as the melting point of the crystal. From the results of DTA,
this is observed that there is no transformation inside the structure was
observed before melting point of 197.2◦C. Thus from the thermal studies, the
crystal can retain its texture up to 197.2º C, which proves its suitability for the
fabrication of nonlinear optical devices.
29
Figure. 4.5: TG/DTA spectrum of the title crystal
4.2.6 Microhardness studies
The mechanical hardness studies for the grown crystal were carried
out by a Leitz Wetzler Microhardness tester with a diamond pyramidal
indenter. The indentations were made using a Vickers pyramidal indenter for
various loads from 25 to 100g in the steps of 25g with a constant indentation
period of 25 s for all loads. Vicker’s hardness number (Hv) is calculated using
the relation
2
2
1.8544/
v
PH kg mm
d (4.1)
Where P is applied load in kg and d the diagonal length in mm. The variation
of Hv with applied load P is shown in Figure. 4.6. From the graph it becomes
clear that the hardness value increases with increasing load, thus satisfying
the normal indentation effect.
30
Figure. 4.6: Plot of load (P) vs. Hv
A plot of log p versus log d (Figure. 4.7) yields a straight line graph
and its slope gives the work hardening index n, and is found to be 4.89,
according to Meyer’s relation
1
nP K d (4.2)
Figure. 4.7: Plot of Log d vs. log P
31
Where K1 is the standard hardness value, which can be found out from the
plot of P versus dn (Figure. 4.8).
Figure. 4.8: Plot of dn vs. Load P
Since the material takes some time to revert to the elastic mode after
every indentation, a correction χ is applied to the d value and Kick’s law is
related as
2
2( )P K d x (4.3)
From Equations. (2) and (3), we get
1/2
/2 2 2
1 1
n K Kd d x
K K
(4.4)
The slope of dn/2 versus d yields (K2/K1)1/2 and the intercept is a
measure of χ and is shown in Figure. 4.10. The fracture toughness (Kc) is
given by
Kc = P/ c 3/2 (4.5)
32
Figure. 4.9: Plot of d vs. dn/2
Where C is the crack length measured from the centre of the
indentation mark to the crack tip, P is the applied load and geometrical
constant = 7 for Vicker’s indenter. The brittleness index (B) is given by
= Hv / Kc (4.6)
Yield strength σv of the material can be found out using the relation
2
12.5(2 )1 (2 )
2.9 1 (2 )
n
v
v
H nn
n
(4.7)
The stiffness constant gives an idea about the nature of
bonding between successive atoms. This property of the material by virtue of
which it can absorb maximum energy before the fracture occurs. For various
loads the stiffness constant is calculated using Wooster’s empirical relation
[89]
C11 = Hv7/4 (4.8)
33
Figure. 4.10: P vs σv
The variation of stiffness constant plotted with load is shown in Figure.
4.11. All the determined mechanical parameters are shown in the Table. 4.3.
Figure. 4.11: P vs C11
34
4.2.7 NLO studies
The powder SHG efficiency of the grown crystal was studied using
Q-switched Nd: YAG laser by employing the Kurtz and Perry powder
technique. The Nd: YAG laser emits fundamental wavelength of 1064 nm.
The output from Nd: YAG laser was used as source and it was illuminated to
the crystal powder. Pulse energy was 850 mj /second and pulse width was
about 9 ns, also repetition rate was 10 Hz. The SHG radiation at 532 nm
green light was obtained through photomultiplier tube. Hence the output
power of the grown crystal was 9.681 mj for the input power of 0.68 j, and the
powder SHG efficiency obtained is 1.1 times than that of well-known
reference material (KDP crystal).
Table 4.3: Microhardness value obtained on the 4-APMP Crystal
Hardness Parameters Values
n 4.89
K1 in kg/m 121.43
K2 in kg/m 48.86
Hp 64.9
Hv 28.25
Pm 100
Ps 25
Kc (MNm-3/2) 0.0282
(m-1/2) 10.017 x 102
σv (MPa) 929.32 x 102
C11 (Pa) 346.16
35
4.3 CONCLUSION
A novel nonlinear optical 4-Aminopyridinium monophthalate have
been grown by slow evaporation solution growth technique. The grown
crystal belongs to orthorhombic system. The presence of functional groups
was confirmed by FTIR analysis. The optical absorption studies reveal very
low absorption in the entire visible region. The title material has blue color
fluorescence emission at 430 nm. The thermal stability of the title compound
is found to be 197 °C. From Vickers hardness studies, work hardening
coefficient n is 4.89, thus confirms the exceptional hardness of the crystal.
Kurtz Perry powder method, used to confirm the SHG of the crystal, having
SHG efficiency 1.1 times that of KDP. All these studies confirm that the
grown crystal is the potential candidate for the fabrication of nonlinear optical
devices.
36
5. OPTICAL AND MECHANICAL STUDIES ON AMINO ACID DOPED
SODIUM ACID PHTHALATE (NaAP) SINGLE CRYSTALS
5.1 INTRODUCTION
Nonlinear optical materials have attracted many researchers due to its
potential applications in the field of photonics, lasers, electro - optic switches
and frequency conversion etc. [90-100]. During the past decade, number of
organic and inorganic materials with high nonlinear susceptibilities has been
synthesized. However, their device applications have been impeded by the
inadequate optical transmittance, poor optical quality and low laser damage
threshold [101]. The molecules in pure organic crystals are often bonded by
weak Vander Waals forces of hydrogen bonds, which result in poor
mechanical robustness. In the case of inorganic NLO materials, they have
excellent mechanical and thermal properties but relatively modest optical
susceptibilities due to the lack of π – electron delocalization [102-105, 42].
Phthalic acid family crystals are potential nonlinear optical materials and are
widely used in variety of applications [106]. Sodium acid phthalate is an
excellent material for SHG applications [107, 108]. In the present work,
attempts were made to grow amino acids (L-alanine, L-arginine, Glycine)
doped sodium acid phthalate by slow evaporation technique. Effect of
dopants is significant, because of the influence of doping on intrinsic defects
[109-114]. The results and characterization reveal that the presence of
dopants enhances optical, mechanical properties etc.
5.2 RESULTS AND DISCUSSION
5.2.1 Single crystal X-ray diffraction analysis
The amino acid doped sodium acid phthalate crystals were subjected
to single crystal X-ray diffraction analysis using by ENRAF NONIUS CAD4
single crystal X-ray diffractometer. The lattice parameters are measured and
are shown in Table 5.1. All the grown crystals belong to orthorhombic crystal
37
system having space group of B2ab which is in good agreement with that of
the literature [107, 108].
Table 5.1: Lattice parameters for Pure and doped crystals
compound
Name
Crystal
system
Space
group Unit cell parameters Volume
NaAP (pure) Orthorhombic B2ab a = 6.60 Å, b = 9.08 Å,
c = 25.84 Å, α = = = 90° V = 1548 Å3
NaAP + 1mole%
L-alanine Orthorhombic B2ab
a = 6.73 Å, b = 9.24 Å,
c = 26.25 Å, α = = = 90° V = 1631 Å3
NaAP + 3mole%
L-alanine Orthorhombic B2ab
a = 6.74 Å, b = 9.23 Å,
c = 26.28 Å, α = = = 90° V = 1635 Å3
NaAP + 5mole%
L-alanine Orthorhombic B2ab
a = 6.77 Å, b = 9.28 Å,
c = 26.35 Å, α = = = 90° V = 1655 Å3
NaAP + 1mole%
L-arginine Orthorhombic B2ab
a = 6.78 Å, b = 9.29 Å,
c = 26.38 Å, α = = = 90° V = 1661 Å3
NaAP + 3mole%
L-arginine Orthorhombic B2ab
a = 6.77 Å, b = 9.30 Å,
c = 26.39 Å, α = = = 90° V = 1662 Å3
NaAP + 5mole%
L-arginine Orthorhombic B2ab
a = 6.87 Å, b = 9.45 Å,
c = 26.76 Å, α = = = 90° V = 1737 Å3
NaAP + 1mole%
Glycine Orthorhombic B2ab
a = 6.68 Å, b = 9.19 Å,
c = 26.06 Å, α = = = 90° V = 1600 Å3
NaAP + 3mole%
Glycine Orthorhombic B2ab
a = 6.74 Å, b = 9.28 Å,
c = 26.29 Å, α = = = 90° V = 1644 Å3
NaAP + 5mole%
Glycine Orthorhombic B2ab
a = 6.81 Å, b = 9.38 Å,
c = 26.62 Å, α = = = 90° V = 1701 Å3
38
5.2.2 FTIR studies
The presence of functional groups and vibrational frequencies of pure
and doped NaAP single crystals identified by FTIR spectroscopy. The
recorded spectrum of the grown crystals were carried out between the range
400-4000 cm-1 using Perkin - Elmer spectrum one and is shown in Figures.
5.1- 5.3. An absorption band in the range 538-858 cm-1 appears due to C-H
out-of-plane deformations of the aromatic ring. The spectral band attributed
at 1118 cm-1 is due to C-H in-plane deformation of the aromatic ring. The
C-O stretching vibrations obtained as peak at 1354 cm-1. The peak at 1613
cm-1 assigned due to C-C skeletal aromatic ring vibrations. The carboxyl
group C=O vibrations appear near 1696 cm-1. All these assignments are in
very good agreement with NaAP crystals that of the reported values [108].
The L-alanine dopants assigned at 2867 cm-1 due to NH3+ asymmetric
stretching mode and 1468 cm-1 assigned for deprotonated carboxylic group
(COO-) characteristic absorption band. In the L-arginine dopants the peaks
at 3501 cm-1 NH2 asymmetric stretching vibrational mode, C-H stretching of
CH2 vibrations assigned at 2468 cm-1, the minute peak at 1466 cm-1 due to
NH2 symmetric bending mode.
And the Glycine dopants identified at 3161 cm-1 due to NH3+
Asymmetric stretching vibrational mode, C-O symmetric stretching mode
assigned at 1467 cm-1, and the peak at 1125 cm-1 for NH3+ rocking mode for
out plane bending respectively. From the above assignments verified that
amino acids were presence as dopants in NaAP single crystals.
39
Figure. 5.1: FTIR Spectra of L-alanine doped NaAP crystals
Figure. 5.2: FTIR Spectra of L-arginine doped NaAP crystals
40
Figure. 5.3: FTIR Spectra of Glycine doped NaAP crystals
5.2.3 UV-Vis-NIR spectral analysis
The UV-Vis-NIR spectrum of the grown crystals was recorded in the
range 300-800 nm using Perkin Elmer Lambda 35 UV-Vis spectrophotometer
and the resultant spectra is shown in Figures. 5.4, 5.5, and 5.6. The optical
absorption studies reveal that amino acids doped NaAP crystals show good
transparency in entire visible region and the UV cut off wavelength is found to
be around 313 nm, 320 nm and 317 nm for L-alanine, L-arginine and Glycine
doped NaAP crystals respectively. Moreover it is observed that the
absorbance decreases with increase in the doping concentration for all the
three dopants. This proves that the presence of dopants enhance the optical
property of the material. The very low absorbance in the entire visible region
suggests its suitability for the fabrication of optoelectronic devices [115].
41
Figure. 5.4: Absorption spectra of L-alanine doped NaAP crystals
Figure. 5.5: Absorption spectra of L-arginine doped NaAP crystals
42
Figure. 5.6: Absorption spectra of Glycine doped NaAP crystals
The optical absorption coefficient (α) was calculated from the
transmittance using the following relation,
1 1log
t T
(5.1)
Where T is transmittance and t is thickness of the crystal.
Owing to the direct band gap, the crystal under study has an
absorption coefficient (α) obeying the following relation for high photon
energies (hν); 1/2( )
gA h E
h
(5.2)
Where Eg is optical band gap of the crystal and A is a constant.
43
Figure. 5.7: Plot of (αhν) 2 vs. (hν) for pure and L-alanine
doped NaAP crystals
Figure. 5.8: Plot of (αhν) 2 vs. (hν) for pure and L-arginine
doped NaAP crystals
44
Figure. 5.9: Plot of (αhν) 2 vs. (hν) for pure and Glycine
doped NaAP crystals
The plot of variation of (αhν) 2 vs. hν is shown in Figures. 5.7, 5.8, 5.9.
Eg is evaluated by the extrapolation of the linear part and the band gap for
pure NaAP crystal is found to be 4.050 eV. But for L-alanine doped NaAP
the band gap values are 4.070, 4.075 and 4.077 eV respectively for 1mole%,
3mole%, 5mole% concentrations. Similarly, for L-arginine doped NaAP, Eg is
found to be 4.048, 4.051 and 4.052 eV respectively for 1mole%, 3mole%,
5mole% concentrations. Whereas for glycine doped NaAP the values are
4.054, 4.063 and 4.066 eV respectively for 1mole%, 3mole%, 5mole%
concentrations.
5.2.3.1 Determination of optical constants
The optical behaviour of materials is important to determine its usage
in optoelectronic devices. Knowledge of optical constants of a material such
as optical band gap and extinction coefficient is quite essential to examine
the material’s potential opto-electronic applications. Further, the optical
45
properties may also be closely related to the material’s atomic structure,
electronic band structure and electrical properties. The extinction coefficient
(K) for the grown crystals can be determined using formula
4K
(5.3)
The plot of K vs. photon energy (hν) is shown in the Figures. 5.10-
5.12. It is observed that the K decreases with increase in energy.
The reflectance (R) in terms of photon energy (Figures. 5.13-5.15) is
derived from the relation,
R (5.4)
Figure. 5.10: Extinction Coefficient of L-alanine doped NaAP crystals
46
Figure. 5.11: Extinction Coefficient of L-arginine doped NaAP crystals
Figure. 5.12: Extinction Coefficient of Glycine doped NaAP crystals
47
Figure. 5.13: Reflectance of L-alanine doped NaAP crystals
Figure. 5.14: Reflectance of L-arginine doped NaAP crystals
48
Figure. 5.15: Reflectance of Glycine doped NaAP crystals
The optical conductivity (σop) is a measure of the frequency response
of the material when irradiated with light (Figures. 5.16-5.18)
σop = (5.5)
Where c is the velocity of light.
Figure. 5.16: Optical Conductivity of L-alanine doped NaAP crystals
49
Figure. 5.17: Optical Conductivity of L-arginine doped NaAP crystals
Figure. 5.18: Optical Conductivity of Glycine doped NaAP crystals
Also, the electrical conductivity has been determined for the grown crystals
by optical method using the relation
σelec = 2λσop/α (5.6)
and the electrical conductivity is shown in Figures. 5. 19-5.21.
50
Firgure. 5.19: Electrical Conductivity of L-alanine doped NaAP crystals
Firgure. 5.20: Electrical Conductivity of L-arginine doped NaAP crystals
51
Firgure. 5.21: Electrical Conductivity of Glycine doped NaAP crystals
5.2.4 Microhardness measurements
The title crystals were carried out to Vickers microhardness tests using
Leitz Wetzler Microhardness tester with a diamond pyramidal indenter. A
diamond indenter was pressed the plane of pure and doped NaAP crystals
under the known load 25 –100g and the resulting indentation was measured.
The indentation time was 25s for all trials. The Vickers hardness number
was calculated using the relation
Hv = 1.8544 (P/d2) kg/mm2 (5.7)
Where P is the applied load in kg and d is the diagonal length of the
indentation impression mm2. The variation of it Hv when the applied load P is
shown in Figures. 5.22-5.24. The microhardness value is gradually increases
after load 50g which is lightly increased in the range of load from 25 to 100g
for different mole% of L-alanine doped NaAP crystals. The same results
were observed for different mole% of L-arginine and Glycine doped NaAP
52
crystals. Thus we can conclude that the presence of dopants increases the
hardness of the material.
Figure. 5.22: Hardness number of L-alanine doped NaAP crystals
Figure. 5.23: Hardness number of L-arginine doped NaAP crystals
53
Figure. 5.24: Hardness number of Glycine doped NaAP crystals
5.2.5 Nonlinear Optical studies
The second harmonic generation efficiency of pure and amino acid
doped sodium acid phthalate single crystals were studied using Q-switched
Nd: YAG laser by Kurtz powder test. The fundamental radiation of 1064 nm,
with pulse energy was 850 mj per second, pulse width of 9ns, and repetition
rate was 10Hz of infrared light beam focused on the powder samples of
amino acids doped NaAP crystals. The SHG efficiency of the doped crystal
is found to be lesser than that of KDP crystal. The relative SHG efficiency for
different doping concentration is shown in the Figure. 5.25.
54
Figure. 5.25: SHG efficiency of Doped amino acid crystals
5.3 CONCLUSION
Single crystals of amino acid doped sodium acid phthalate single
crystals were grown by slow evaporation solution growth technique at room
temperature. Single crystal X-ray diffraction analysis reveals that the title
crystals belong to orthorhombic system having space group B2ab. The
functional groups of the presence of dopants revealed with parent material.
The optical absorption spectra reveal that the amino acid dopants enhanced
the optical properties of the materials. The mechanical hardness study
reveals that the hardness increases with increase in the doping
concentration. The SHG efficiency is found to be lesser than that of KDP
crystal. All these studies confirm that the amino acid doped NaAP crystal
could be considered as a potential candidate for the fabrication of
optoelectronic devices.
55
6. STRUCTURAL, OPTICAL, MECHANICAL, THERMAL AND
FLUORESCENCE PROPERTIES OF NONLINEAR OPTICAL DIGLYCINE
BARIUM CHLORIDE MONOHYDRATE (DGBCM) SINGLE CRYSTAL
6.1 INTRODUCTION
The Nonlinear optical (NLO) materials have attracted many
researchers due to their wide applications in the area of photonics, lasers,
electro-optic switches and frequency conversion [116, 90-95]. In recent
years, complexes of amino acids with organic and inorganic acids possess
excellent nonlinear optical properties [61, 117-121]. Amino acids are
interesting materials for NLO applications, as this contains an asymmetric
carbon atom which makes them optically active and most of them crystallize
in non-centrosymmetric space groups. Also, amino acids exist as zwitterionic
nature, favours exceptional crystal hardness, making them ideal for the
fabrication of NLO devices [122, 123]. In addition, amino acid mixed
inorganic compounds are widely used in device fabrication because of their
high nonlinear optical coefficient and high degree of chemical inertness [124].
Hence in the present work, our aim is focused towards the growth of
Diglycine barium chloride monohydrate, a semi organic nonlinear optical
crystal, by slow evaporation solution growth technique. The grown crystals
were subjected to various characterisations and were discussed in detail.
6.2 RESULTS AND DISCUSSION
6.2.1 Single crystal X-ray diffraction analysis
The single crystal X – ray diffraction analysis for the grown crystals
was carried out using ENRAF NONIUS CAD-4 X-ray diffractometer to
determine the cell parameters. The results indicate the DGBCM
[Ba (NH2CH2COOH)2 Cl2. H2O] crystal belongs to orthorhombic crystal
system and space group Pbcn. The calculated unit cell parameter values are a = 8.26 Å, b = 9.29 Å, c = 14.82 Å, α = = = 90o and V = 1139 Å3. Which
are in very good agreement with that of the reported values [125-127].
56
The valence electron plasma energy, p is given by
2/1)(8.28 MZp (6.1)
Where Z = ((4 × ZC) + (12 × ZH) + (5 × ZO) + (1 × ZBa) + (2 × ZN) + (2 × ZCl)) =
58 is the total number of valence electrons, ρ is the density and M is the
molecular weight of the grown crystal. Explicitly p dependent Penn gap
and the Fermi energy [128], is given by
2/1)1(
p
pE
(6.2)
And
3/4)(2948.0 pFE (6.3)
Polarizability α obtained using the relation [129]
324
2
0
2
0
2
10396.0]3)(
)([ cm
M
ES
S
pp
p
(6.4)
Where, S0 is a constant for a particular material which is given by
2
0 ]4
[3
1]
4[1
F
p
F
p
E
E
E
ES (6.5)
The value of α so obtained agrees with that obtained using Clausius-
Mossotti equation which is given by,
)2
1(
4
3
aN
M (6.6)
All these calculated data for the grown crystal are shown in the Table 6.1.
57
Table 6.1: Some theoretical parameters on DGBCM crystals
6.2.2 FTIR studies
The FTIR study on the grown crystal was carried out between the
range 400 – 4000 cm-1 using Perkin-Elmer spectrum one and the resultant
spectrum is shown in the Figure. 6.1. The broadband around 3478 cm-1 is
due to NH asymmetric stretching. A peak at 2587 indicates the presence of
NH3+ stretching vibrations. The peaks at 1480 and 1111 cm-1 is due to the
NH3+ group of glycine molecule. The carboxylate group of the glycine
molecule is found to be around 671 and 1582 cm-1. The peaks at 896 and
1326 cm-1 are attributed to CCN and COO- stretching groups respectively.
All these assignments are in very good agreement with that of the reported
values [126, 127].
Parameters Values
Plasma energy (eV) 18.20
Penn gap energy (eV) 2.65
Fermi energy (eV) 14.11
Polarizability (cm3)
By Penn analysis 5.38 X 10-23
By Claussius- Mosotti equation 5.41 X 10-23
58
Figure. 6.1: FTIR spectrum of the grown crystal
6.2.3 Optical absorption studies
The optical absorption spectrum of the DGBCM crystals was recorded
in the range 200-1200 nm using Perkin Elmer Lambda 35 UV-Vis
spectrophotometer and is shown in Figure. 6.2. It is observed that the lower
cut off wavelength is around 240 nm and the crystal is found to be
transparent in the entire visible region, thus suggesting its suitability for the
fabrication of second harmonic generation devices. The optical absorption
coefficient (α) was calculated from the transmittance using the following
relation,
1 1log
t T
(6.7)
Where T is transmittance and t is thickness of the crystal.
59
Figure. 6.2: Optical absorption spectrum of the grown crystal
Owing to the direct band gap, the crystal under study has an
absorption coefficient (α) obeying the following relation for high photon
energies (hν); 1/2( )
gA h E
h
(6.8)
Where Eg is optical band gap of the crystal and A is a constant. The plot of
variation of (αhν) 2 vs. hν is shown in Figure. 6.3. Eg is evaluated by the
extrapolation of the linear part and the band gap is found to be 5.19 eV.
60
Figure. 6.3: Plot of (hν) vs. (αhν) 2
6.2.3.1 Determination of optical constants
The optical behaviour of materials is important to determine its usage
in optoelectronic devices. Knowledge of optical constants of a material such
as optical band gap and extinction coefficient is quite essential to examine
the material’s potential opto-electronic applications. Further, the optical
properties may also be closely related to the material’s atomic structure,
electronic band structure and electrical properties. The extinction coefficient
(K) for the grown crystals can be determined using formula [130, 131]
4K
(6.9)
The plot of K vs. photon energy (hν) is shown in the Figure. 6.4. It is
observed that the K decreases with increase in energy. The refractive index
(n) can be derived from the following relations,
61
2( 1) 3 10 3
2( 1)
R R Rn
R
(6.10)
Figure. 6.4: Plot of extinction coefficient (K) vs. photon energy (hν)
Figure. 6.5: Plot of photon energy (hν) vs. Refractive index (n)
62
The dependence of refractive index (n) as a function of photon energy
is shown in the Figure. 6.5. Initially, it is observed that the refractive index
decreases with increase in the photon energy. Later it becomes constant for
the all values of energy.
6.2.4 Microhardness studies
The microhardness of DGBCM crystal was carried out by a Leitz
Wetzler Microhardness tester with a diamond pyramidal indenter. The
indentations were made using a Vickers pyramidal indenter for various loads
from 25 to 100g in the steps of 25g with a constant indentation period of 25 s
for all loads. Vicker’s hardness number (Hv) were calculated using the
relation
2
2
1.8544/
v
PH kg mm
d (6.11)
Where P is applied load in kg and d is the diagonal length in mm. The
variation of Hv with applied load P is shown in Figure. 6.6. From the graph it
becomes clear that the hardness value increases with increasing load, thus
satisfying the normal indentation effect.
Figure. 6.6: Plot of P vs. Hv
63
A plot of log p versus log d (Figure. 6.7) yields a straight line graph
and its slope gives the work hardening index n, and is found to be 2.89,
according to Meyer’s relation
1
nP K d (6.12)
Where K1 is the standard hardness value, which can be found out from the
plot of P versus dn (Figure. 6.8). Since the material takes some time to revert
to the elastic mode after every indentation, a correction χ is applied to the d
value and Kick’s law is related as
2
2 ( )P K d x (6.13)
From Equations. (12) and (13), we get
1/2
/2 2 2
1 1
n K Kd d x
K K
(6.14)
Figure. 6.7: Plot of Log d vs. log P
64
Figure. 6.8: Plot of dn vs. Load P
The slope of dn/2 versus d yields (K2/K1)1/2 and the intercept is a
measure of χ and is shown in Figure. 6.9. The fracture toughness (Kc) is
given by
Kc = P/ c 3/2 (6.15)
Figure. 6.9: Plot of d vs. dn/2
65
Where C is the crack length measured from the centre of the indentation
mark to the crack tip, P is the applied load and geometrical constant = 7 for
Vicker’s indenter. The brittleness index (B) is given by
= Hv / Kc (6.16)
Yield strength σv of the material can be found out using the relation
2
12.5(2 )1 (2 )
2.9 1 (2 )
n
v
v
H nn
n
(6.17)
All the determined mechanical parameters are shown in the Table 6.2.
Table 6.2: Microhardness value obtained on the DGBCM Crystal
Hardness Parameters Values
n 2.89
K1 in kg/m 0.0319 x 10-2
K2 in kg/m 2.177 x 10-4
Hp 48.45
Hv 31
Pm 100
Ps 25
Kc (MNm-3/2) 0.013239
(m-1/2) 2.341 x 103
σv (MPa) 701.31
66
6.2.5 TGA/DTA studies
The thermal analysis was carried out for the grown crystals using by
NETZSCH STA 409C analyzer in nitrogen atmosphere at heating rate of
20 oC per minute from 25 oC to 400 oC and is shown in Figure. 6.10. From
DTA curve, the first endothermic peak at 171.7oC indicates the starting point
for the decomposition of the material, thus confirms that the materials can
retain its texture till 171.7oC. Another endothermic broad peak obtained at
312.6 oC illustrates the liberation of volatile substances like ammonia and
carbon dioxide in the compound. The TG analysis shows that the 34.9 % of
weight loss takes place during this transition. From the analysis, it is
observed that the material is stable up to 171.7˚C without any intermediate
loss.
Figure.6.10: TG/DTA analysis of the title crystal
6.2.6 Fluorescence studies
The Fluorescence spectrum was recorded to DGBCM crystal sample
using Varian Cary Eclipse Fluorescence spectrometer at room temperature.
The sample was excited at 240 nm and the spectra was recorded in the
67
range from 200 to 700 nm is shown in Figure. 6.11. A high intense peaks at
418 nm and 489 nm are observed and shows that DGBCM exhibits blue and
bluish green fluorescence. Either different low intensity peaks can be
intrinsic defects of crystal.
Figure. 6.11: Fluorescence spectrum of the DGBCM crystal
6.2.7 Second harmonic generation study
The second harmonic generation efficiency (SHG) was determined for
the DGBCM crystal using a Q-switched high energy Nd: YAG laser emitting
1064 nm radiation. The emission of green radiation by the sample was
confirmed and the SHG efficiency of DGBCM is 2.18 times more than that of
the KDP single crystal. The comparative SHG efficiencies of some semi
organic crystals relative to KDP are shown in Table. 6.3. [132].
68
Table. 6.3: Comparative of SHG efficiencies of NLO crystals relative to KDP
Name of the samples SHG efficiency
KDP 1.0
-glycine
L – Tyrosine Hydrochloride
L – Alanine Lithium Chloride
L – Alanine Acetate
L – Alanine Chloride
L – Alanine Bromide
Bis thiourea Lithium chloride
Bis thiourea cadmium zinc chloride
1.5
0.15
0.43
0.30
0.20
0.30
0.90
1.10
Diglycine barium chloride Monohydrate*
(Current Study) 2.18
6.3 CONCLUSION
Single crystal of Diglycine barium chloride monohydrate, a semi
organic NLO material, has been grown by slow evaporation solution growth
technique. The single XRD analysis confirmed that the grown crystals
belong to orthorhombic system having space group Pbcn. FT-IR analysis
confirms the presence of all the functional groups in the crystal lattice. The
optical absorption spectrum reveals that the crystal has good optical
transmittance in the visible IR region, also has high optical band gap energy.
Micro hardness test reveals that the material has good mechanical stability
and good yield strength. The thermogravimetric (TGA) and differential
thermal analysis (DTA) reveals that the material has high thermal stability.
The fluorescence spectrum shows that the grown crystals emit blue
fluorescence. The nonlinear optical study confirms that the SHG efficiency of
DGBCM is 2.18 times higher than KDP crystals. All these studies confirm
that the diglycine barium chloride monohydrate, a semiorganic nonlinear
optical material, is a potential candidate for the fabrication of nonlinear optical
devices.
69
7. CONCLUSION
The summary of the results of the present study and conclusions
drawn are presented below.
A novel NLO 4-aminopyridinium monophthalate crystal was grown by
the slow evaporation solution growth technique. The grown crystal belongs
to the orthorhombic system. The presence of functional groups was
confirmed by FTIR analysis. The optical absorption studies revealed very
low absorption over the entire visible region. The title material had a blue
fluorescence emission at 430 nm. The thermal stability of the title compound
was found to be 197 ◦C. From Vickers hardness studies, the work hardening
coefficient n was found to be 4.89, thus confirming the exceptional hardness
of the crystal. The Kurtz Perry powder method was used to confirm the SHG
behaviour of the crystal, and SHG efficiency was found to be 1.1 times that of
KDP. All of these studies confirmed that the grown crystal is a promising
candidate for the fabrication of NLO devices.
Amino acid-doped NaAP single crystals were grown by slow
evaporation solution growth at room temperature. Single crystal X-ray
diffraction analysis revealed that the title crystals belonged to the
orthorhombic system with space group B2ab. The presence of functional
groups was determined qualitatively using FTIR analysis. The optical
absorption spectra revealed that the amino acid dopants enhanced the
optical properties of the materials. The mechanical hardness study revealed
that the hardness increased with increasing doping concentrations. The
SHG efficiency was compared with that of KDP. All of these studies
confirmed that the amino acid-doped NaAP crystal could be considered a
promising candidate for the fabrication of optoelectronic devices.
Single crystal diglycine barium chloride monohydrate, a semiorganic
NLO material, was grown by the slow evaporation solution growth technique.
The single crystal XRD analysis confirmed that the grown crystals belonged
to the orthorhombic system with space group Pbcn. FTIR analysis confirmed
70
the presence of all of the functional groups in the crystal lattice. The optical
absorption spectrum revealed that the crystal had good optical transmittance
in the visible IR region as well as a high optical band gap energy.
Microhardness tests revealed that the material had good mechanical stability
and good yield strength. The thermogravimetric (TGA) and differential
thermal analyses (DTA) revealed that the material had high thermal stability.
The fluorescence spectrum showed that the grown crystals emitted bluish-
green fluorescence. The NLO study confirmed that the SHG efficiency of
DGBCM was 2.18 times higher than that of KDP. All of these studies
confirmed that diglycine barium chloride monohydrate, a semiorganic NLO
material, is a promising candidate for the fabrication of NLO devices.
71
8. SCOPE OF FURTHER WORK
In the future, attempts will be made to grow bulk single crystals (4-
APMP, SAP and DGBCM) along their growth axes to investigate their
growth rate, transparency and nonlinear optical properties such as
nonlinear coefficients, threshold frequency, phase matching behaviour,
other higher harmonic generations and ferroelectric hysteresis studies,
etc.
A systematic study on solution pH will shed more light on the habit
morphology, growth rate and physical properties.
Additionally, attempts can be made to grow application oriented crystals
using the Sankaranarayanan – Ramasamy (SR) method.
Advanced microscopic techniques, such as AFM and TEM, can be used
to characterize the grown samples.
The etching behaviour on the growth planes can be done using various
organic solvents to estimate the dislocation density and lattice
inhomogeneity and to identify the growth mechanism.
119
TECHNICAL BIOGRAPHY
Mr. G. Marudhu (RRN. 1090206) was born on 6th March 1983, in
Vandavasi, Tamil Nadu. He completed his schooling in Govt. Higher
Secondary School at Vandavasi. He received his B.Sc. degree in Physics
from Govt. Arts College at Cheyyar, University of Madras in 2003. He
completed his M.Sc. in Physics at A.V.V.M. Sri Pushpam College at Poondi,
Thanjavur, Barathidasan University in 2007. He completed his B.Ed. degree
in Physical Science from Paulson’s Teacher Training College at
Pulichapallam, Vanur, Thiruvalluvar University in 2008. He received his
M.Phil. degree in Physics from A.V.V.M. Sri Pushpam College at Poondi,
Thanjavur, Barathidasan University in 2009. He has six years of experience
in the teaching field. Currently, he is working as an assistant professor in Sri
Ramanujar Engineering College at Chennai. He is pursuing his Ph.D. in
Physics in the Department of Physics in B.S. Abdur Rahman University at
Chennai. His research area is “growth and characterization of NLO crystals
for optoelectronic device applications.” He has published two papers in peer-
reviewed international journals and has presented three papers at national
conferences. His e-mail address is [email protected], and his contact
number is 9566751751.