CHAPTER-II

LITERATURE SURVEY

2.1 REVIEW OF LITERATURE

Single nonlinear optical crystals of L-Proline Potassium Bromide

(LPPB) were synthesized and grown by dissolving L - proline and potassium
bromide in 1:1 molar ratio using deionized water as the solvent. The crystal
parameters of the grown crystals have been evaluated by single crystal and
powder XRD methods. Optical spectral studies have been carried out to find
the band gap and optical constants of the material. Second Harmonic
Generation (SHG) study reveals the nonlinear optical (NLO) property of
sample. Mechanical strength of the grown samples is tested by hardness
studies. TG/DTA studies were carried out to confirm the thermal stability to
the grown crystals. EDAX test was also carried out to test the presence of
elements in the sample. The details of the method adopted for crystal growth
and the results obtained through various characterizations are analyzed and
interpreted in detail. [16]

Optically cleared single crystal of L-proline dimercury chloride

(LPDMC) has been successfully grown from aqueous solution by slow
evaporation solution growth technique. Single crystal X-ray diffraction
analysis confirms that the crystal is found to be a crystallized complex
crystallizes in triclinic system with space group P1. Optical transmittance
studies on this sample shows the minimum absorption region which is well
suited for optical applications. The mechanical strength of the grown crystal
has been studied using Vicker’s microhardness tester. The melting point is
reported to be 101.8º C using thermal analysis [17]
Crystals of L-Proline Succinate (LPS), an organic nonlinear optical
material, was obtained by slow evaporation solution growth method using
water as a solvent. Purity of the LPS crystals was increased by the method of
recrystallization. The structure, lattice parameters and cell volume of LPS
crystals were obtained by powder X-Ray diffraction studies. The LPS
crystals were found to be monoclinic in structure. The presence of various
functional groups of LPS and their modes of vibration were identified from
Fourier Transform Infrared (FTIR) spectral analysis. The crystals of LPS
were found to have wide range of transparency in the visible region. The
nonlinear optical property of the grown crystals of LPS was measured
through second harmonic generation using Kurtz-Perry powder test. Thermal
stability of the grown crystals was confirmed using TGA and DTA. [18]

The growth and characterization of semi organic L proline potassium

chloride (LPPC) crystal is reported. Single crystals of L- proline potassium
chloride were successfully grown for the first time by solution method with
slow evaporation technique at room temperature. Crystals of size 7 x 6 x 3
mm3 have been obtained in fifteen days. Single crystal X-ray diffractometer
was utilized to measure the unit cell parameters and to confirm the crystal
structure. The powder xray diffraction pattern of the grown LPPC crystal has
been indexed. The modes of vibration of different molecular groups present
in the sample were identified by FTIR spectral analysis and EDAX test was
also carried out for confirmation. The optical transmittance window and the
lower cut off wavelength of LPPC have been identified by UV-Vis-NIR
studies. Thermal stability of the LPPC was determined by TG/DTA studies.
The Vicker’s micro hardness test was also carried out to test the mechanical
stability and the hardness parameters are determined. [19]

Single crystals of metal-organic complex dibromo bis (L-Proline)

Cd(II) (DBPC) were grown by low temperature solution growth method. The
synthesized material was purified by the process of repeated
recrystallization. The grown crystal was confirmed by Fourier Transform
Infrared (FT-IR), Nuclear Magnetic Resonance spectralstudies and single
crystal X-ray diffraction. Single crystal X-ray analysis showsthat DBPC
crystallizes in orthorhombic crystal system with space group P212121. The
coordination geometry around the cadmium (II) center is distorted
tetrahedral. The title compound was characterized by UV-Vis-NIR study
shows that the crystal is transparent in the wavelength range 200-1100 nm
and TG/DTA analysis. The magnetic property of DBPC is investigated at
room temperature. The microhardness test was carried out. The second
harmonic efficiency of powdered DBPC was determined by Kurtz and Perry
method and it is 2.25 times that of KDP [20].

In this work, a systematic study of an organic nonlinear optical (NLO)

material, trans-4-hydroxy-l-proline (THP), C5H9NO3 is reported. An optical
quality single crystals of THP have been successfully grown by using slow
evaporation solution growth technique (SEST). The single crystal x-ray
diffraction (SXRD) analysis reveals that grown crystal belongs to the
orthorhombic system with non-centrosymmetric space group (NCS), P212121.
Powder x-ray diffraction (PXRD) analysis shows relatively a good
crystalline nature. The molecular structure of THP was recognized by NMR
(1H and 13C) studies and its vibrational modes were confirmed by FTIR and
FT-Raman vibrational studies. UV–Vis–NIR spectrum of grown crystal
shows high optical transparency in the visible and near-IR region with low
near-UV cut-off wavelength at 218 nm. Photoluminescence study confirms
ultraviolet wavelength emission of THP crystal. The second harmonic
generation (SHG) efficiency of grown crystal is 1.6 times greater with
respect to standard potassium dihydrogen phosphate (KDP). Nonlinear
refractive index (n 2) and nonlinear absorption coefficient (β) were
determined using the Z-scan technique. The title compound owns high
thermal stability of 294 °C and specific heat capacity (C P) of 1.21 J
g−1 K−1 at 300 K and 11.33 J g−1 K−1 at 539 K (melting point). The laser-
induced damage threshold (LDT) value of grown crystal was measured as
7.25 GW cm−2. The crystal growth mechanism and defects of grown crystal
were studied by chemical etching technique. Mechanical strength was
extensively studied by Vickers microhardness test and crystal void
percentage analysis. Moreover, density functional theory (DFT) studies were
carried out to probe the Mulliken charge distribution, frontier molecular
orbitals (FMOs) and first order hyperpolarizability (β) of the optimized
molecular structure to get a better insight of the molecular properties. These
characterization results endorse that grown THP crystal as a suitable
candidate for NLO applications with large LDT. [21]

Single crystals of a new organic material, 4-hydroxy- L-proline-L-

tartaric acid (HPTA) adduct, were grown by slow evaporation of an aqueous
solution containing equimolar concentrations of 4-hydroxy- L-proline and L-
tartaric acid at room temperature. Formation of new crystal has been
confirmed by single crystal X-ray diffraction and NMR spectroscopic
techniques. The single crystal XRD analysis shows that a molecule of 4-
hydroxy-L-proline and a molecule of free L-tartaric acid both of which are
interlinked to each other by two types of H-bonding interactions, namely
O(6)–H(6)⋯O(2) and N(1)–H(1B)⋯O(10). The title compound (HPTA)
crystallizes in monoclinic crystal system with non-centrosymmetric space
group P21. The suitability of the crystal for optical applications was studied
by UV–Vis–NIR spectroscopy. Fourier transform infrared (FT-IR) spectral
analysis was used to confirm the presence of various functional groups in the
grown crystals. The thermal stability of the compound was investigated by
thermogravimetric and differential thermal analyses. The dielectric constant
and dielectric loss of the crystal were studied as a function of frequency and
temperature. The fluorescence spectral analysis of the title crystal shows an
indigo emission. The second order nonlinear optical (NLO) property of the
crystal was confirmed by the modified Kurtz–Perry powder second harmonic
generation (SHG) test. [22]

L-Proline lithium bromide monohydrate (LPLBM), a promising

semiorganic nonlinear optical material, was synthesized and single crystals
of LPLBM were grown from solution by slow evaporation technique. Single
crystal X-ray structure solution reveals that the grown crystal belongs to
monoclinic system with space group P21. Presence of various functional
groups was identified by FT-IR and FT-Raman spectral analyses. UV–Vis–
NIR spectroscopic study shows that the LPLBM crystal possesses 90% of
transmittance in the range of 250–1100 nm. Vickers microhardness values,
the dielectric constant and dielectric loss of the LPLBM crystal were
reported. Elemental analysis by energy dispersive X-ray analysis shows the
presence of carbon, nitrogen, oxygen and bromine. The surface morphology
of the crystal was investigated using scanning electron microscopic study.
The thermal stability of the LPLBM crystal was studied from TGA and DSC
analysis. Second harmonic generation efficiency of the LPLBM crystal
measured by Kurtz and Perry powder technique using Nd: YAG laser is
about 0.3 times that of urea. [23]

The semi-organic non linear optical single crystal of L-proline cadmium

chloride monohydrate was successfully synthesized and the single crystal was
grown by a slow evaporation solution growth technique, using double distilled
water as the solvent. The lattice dimensions of the grown crystal were examined
by powder X-ray diffraction and it was found to belong to the orthorhombic
crystal system with a noncentrosymmetric space group. Its crystallinity was
assessed by a high resolution X-ray diffraction method and its structural
imperfections were recorded using X-ray topography. The presence of
functional groups was identified from heteronuclear correlation methods. Its
optical behavior was examined by birefringence and photoluminescence and its
optical constants were determined from UV-Vis. analysis. Its thermal and third
order nonlinear optical properties were characterised by photopyroelectric and
Z-scan methods, respectively. The mechanical and ferroelectric behavior was
also assessed on the grown single crystal of L-proline cadmium chloride
monohydrate. [24]

The growth and characterization of semiorganic L-Proline Potassium

Sulphate (LPPS) crystal is reported. Single crystals of L- proline potassium
sulphate were successfully grown for the first time by solution method with
slow evaporation technique at room temperature. Single crystal X-ray
diffractometer was utilized to measure the unit cell parameters and to
confirm the crystal structure. The planes observed in the powder xray
diffraction pattern of the grown LPPS crystal have been indexed. The modes
of vibration of different molecular groups present in the sample were
identified by FTIR spectral analysis and EDAX test was also carried out for
confirmation. The optical transmittance window and the lower cut-off
wavelength of LPPS have been identified by UV-Vis-NIR studies. Thermal
stability of the LPPS was determined by TG/DTA studies. The Vickers
microhardness test was also carried out to test the mechanical stability and
the hardness parameters were determined. The second harmonic efficiency
of the sample was also tested and compared with the standard KDP crystal
[25].
2.2 PRESENT STUDY

Single crystals are essential in the research especially condensed

matter physics,material science etc.,In the present study L-Proline and
Sodium Sulphate were mixed in the stoichiometric ratio of 1:1 in distilled
water and forming L-Proline sodium sulphate crystals.The technique adopted
for the preparation of L-Proline sodium sulphate crystal was slow
evaporation method.

The structural characterization of the grown crystal was done using X-

ray diffraction and presence of various functional groups in L-Proline
Sodium Sulphate protonation of the ions were confirmed by Fourier
Transform Infrared Spectroscopy (FT-IR) analysis.Transmittance of these
grown crystals were analysed using UV-Vis-NIR studies.