Structural and Optical Characterization of

Zinc Sulphide (ZnS) thin films prepared

by automated set-up for Successive Ionic
Layer Adsorption and Reaction (SILAR)
Abstract
Zinc sulphide is an important II-VI wide band gap semiconductor (3.7 eV) close to ZnO
band gap (3.37 eV) with high refractive index (2.35) and dielectric constant. In recent years,
ZnS is considered as the window/buffer layer in the heterojunction solar cells by its appealing
wide band gap which marginally limits the window absorption loses and improves the short
circuit current of the cell. In several metal sulphide nanocrystal thin films such as CuS, Cu2S,
ZnS, CdS, SnS, FeS2, Sb2S3, PbS, MoS2, CuAlS2, Cu(In,Ga)S2 (CIGS), Cu(In,Ga)Se2 (CIGSe),
CuInS2, Cu2ZnSnS4, Cu2ZnSnSe etc., ZnS is used as a buffer layer as an alternative to the toxic
hazards of CdS in photovoltaic cells. Its high refractive index and high transmittance in the
visible wavelength range along with the wide band gap finds a prominent place in wide range
of applications such as photonic crystal sensors, heterojunction diodes, thin film photovoltaic
cells, optical filters, light emitting diodes and anti-reflection coatings.
ZnS being the widely investigated material, several studies have been made on ZnS thin
films prepared by chemical bath deposition (CBD), sputtering, spray pyrolysis, successive
ionic layer adsorption and reaction (SILAR), thermal evaporation, electrodeposition, film
casting method, pulse laser deposition, metal organic chemical vapour deposition, solvo-
thermal synthesis and sol gel. Among them CBD was the most widely reported as well as
conventional way to deposit ZnS films. In some investigations, unavoidable bulk precipitation
problem has been reported in CBD as both anionic and cationic solutions were mixed together
during the process. It is believed that this particular problem can be avoided by the alternative
layer by layer chemical deposition method called SILAR. In addition to this, the limited
literatures in group II-VI metal sulphides by SILAR method fascinated us to experiment with
this particular technique.

Objectives
✓ To prepare ZnS thin films by SILAR.
✓ To create an automated SILAR set up for thin film deposition.
✓ Optimizing the molar concentration and SILAR cycles.
✓ To analyse the structural and optical properties of the prepared ZnS thin films.
 Growth and characterization of Novel high efficiency organic N-
benzyl-2-methyl-4-nitroaniline(BNA) nonlinear optical crystal
suitable for THz generation
Aim of the Project:
• To grow large size single crystals of organic N-benzyl-2-methyl-4-nitroaniline (BNA)
(reported 1.2x8x6 mm) by slow cooling and slow evaporation technique
• To study solubility in different solvents.
• To find the metastable Zone width and to find the growth parameters
• To grow the BNA crystal using different solvents such as ethanol and methanol
• To grow doped and substituted BNA crystal in Pure and mixture solvents.
• To characterize the crystals samples by powder XRD, HRXRD, UV, FTIR, Dielectric
studies etc
• To study NLO efficiency of pure and doped BNA crystals for its photonic applications

Significance of the Project:

Organic nonlinear optical (NLO) crystals have been extensively studied over several
decades due to their large optical nonlinearities. Some organic NLO crystals have been
demonstrated to be effective in terahertz (THz) wave generation and so have been receiving
lots of attention in the areas of telecommunications, imaging and spectroscopy. Their large
optical nonlinearities are potentially very attractive for various device applications; however
there are often many problems that have so far limited their usefulness. These include
difficulties in growing large single crystals, their hygroscopic character and fragility. Organic
NLO crystals that overcome these problems would be very useful.

In general, organic nonlinear optical (NLO) crystals have a better NLO capacity, with
lower dielectric constants, than their inorganic counterparts. Thus, organic NLO crystals have
attracted significant attention in terahertz (THz)-generation. The basic properties required for
the applied use of NLO crystals are that they have enough optical nonlinearity and are of
sufficient size to be able to be subjected to mechanical processes such as crystal cutting and
polishing at any angle.
These organic NLO crystals have also been studied to obtain a better understanding of
‘‘material designing’’. There are two reasons for this: (i) molecular structures of organic
materials can readily be modified, owing to advanced techniques of organic chemistry
(molecular designing); (ii) optical properties of organic crystals can mainly be attributed to
their molecular properties as van der Waals forces cause intermolecular interactions (crystal
designing). N-Benzyl 2-methyl-4-nitroaniline (BNA) is an N-derivative of MNA and has been
developed to overcome the difficulties discussed above. It easily crystallizes and affords a
larger quadratic optical nonlinearity than MNA. It also easily crystallizes and has a larger
quadratic optical nonlinearity than that of MNA. BNA crystal belongs to the point group of
mm2 and its crystal structure is orthorhombic. The combination of low dielectric constant and
high nonlinearity makes BNA crystal one of the promising candidates for high-speed
modulation and frequency-mixing applications. Knowledge of the linear optical properties of
BNA crystal is essential for phase matching and efficiency considerations. Through the optical
rectification process, a strong THz electromagnetic wave can be generated. Its intensity is
comparable to the leading organic THz emitter 4-dimethylamino-Nmethyl- 4-stilbazolium
Tosylate (DAST). Recently, the intensity of the THz radiation from the BNA crystal, in the
frequency region until 5 THz, has been improved such that it is two to three folds greater than
that observed in ZnTe and GaP crystals. Furthermore, the non-hygroscopic property of BNA
crystals makes it feasible to manipulate them with water.
Growth of novel high NLO efficient Bismuth Borate (BIBO) crystals
and their optical characterization

The aim of the project proposal

• To grow large size single crystals of BIBO
• To characterize the grown crystals by XRD, UV-Vis-NIR spectroscopy,
FTIR, SEM etc.
• To study its SHG efficiency and THG efficiency
• To study Laser damage threshold.

Abstract
A relatively new monoclinic nonlinear crystal BiB3O6 (BIBO), which belongs to the
same family as a BBO and LBO, is a good candidate for the frequency conversion of
continuous-wave (CW) or low-power pulsed lasers.

The BiBO possesses a high second-order nonlinear coefficient which exceeds that of
BBO and LBO by about 1.7 and 4 times, respectively. Furthermore, BiBO shows the
high optical damage threshold as well as BBO and LBO, versatile phase-matching
properties, and large angular and spectral acceptance bandwidth.

These outstanding features make BIBO very attractive as a nonlinear medium for high-
efficiency frequency conversions of not only high-power pulsed lasers but also low-
power fundamental sources.

Besides, BIBO has a high transmittance, and a wide transparency range covering visible and
near-infrared lights. Such outstanding properties show that BIBO has good application
prospects.

Though Becker et al (1999) were the first to report the growth of bigger size crystals by
flux technique and thereafter some have reported the growth of BIBO and their
applications, growth studies are still in early stages and to the best of our knowledge
there is no much report on the growth of BIBO crystals by Indian researchers.

The objective of the proposal is to grow BIBO crystals form near stoichiometric compositions
and to characterize them for its SHG & THG efficiency, laser damage threshold and dielectric
properties.