Compliance Engineering Journal ISSN NO: 0898-3577

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Compliance Engineering

THE PHYSICAL AND NLO BEHAVIER OF AMMONIUM DIHYDROGEN PHOSPHATE

CRYSTALS (ADP) CRYSTALS IN THE VARIATION OF pH

G. Ramasamy*
Department of Chemistry, Annamalai University, Annamalainagar 608 002, India.

ABSTRACT:

The influence of pH of the growth medium from pH = 2.5 to 12.5 on the physical and non
linear optical properties of ammonium dihydrogen phosphate (ADP) crystals has been described.
Incorporation of ions from growth medium into the crystalline matrix is well confirmed by
energy dispersive X-ray spectroscopy (EDS) technique. The reduction in the intensity observed
in powder X-ray diffraction (XRD) of the specimens and slight shifts in vibrational frequences
(FT-IR) confirms minor structural variations. Surface morphological changes due to the
incorporation of ions are confirmed by scanning electron microscopy (SEM). The
thermogravimetry and differential thermal analysis curves show the purity of the materials and
no composition up to the melting point. Changing the pH of the growth medium of ADP
enhances the second harmonic generation (SHG) effiency to a significant extant.

Keyword: ammonium dihydrogen phosphate, nonlinear optical properties, pH, growing from
solution

*Corresponding author
Mail: [email protected],

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1. INTRODUCTION

Ammonium dihrdogen phosphate crystals are widely used as the second, third and fourth
hormonic generatior for Nd:YAG and Nd:YLF lasers. It belongs to the tetragonal system with
the space group 1-42d [1]. This crystals are widely used for electro-optical applications such as
Q-switches for Ti-Sapphire and Alexandrite lasers, as well as for acousto-optical applications [2-
4]. Single crystals of ADP are used for frequency doubling , frequency tripling of laser systems
[2].

The effect of metal ions Cr3+, Fe3+ and Al3+ on ADP crystals has been studied elaborately in
past few years [5-7]. Recently,we have investigated the effect of KCl doping on ADP specimens
in detail and the studies reveal that the dopant KCl predominantly occupies the interstitial
positions of ADP crystal [8, 9]. The effect of metal doping on the physical and NLO properties
of KHP and ZTS crystals are studied in detail [10–15]. We have also proved the influence of
organic complexing agents and chelating agents on ADP, KHP, and ZTS crystals [16–18]. We
are also reporting the effect of metal ions doping (Cs, Sb, Ce and Pd) on the physical and NLO
properties of ADP crystals in recent past [19]. It was inferred that the cationic substitution on
crystal lattice influences the lattice parameters, XRD intensities, and crystallite size, and
effective particle size, changes in FT-IR spectral peaks, morphology and SHG conversion
efficiency. The partial anionic substitions of AsO43- for PO 4 3- in ADP increases the curie
temperature from 148 to 198K [20]. Hence it is clear that the partial substitution of anion or
cation resulting the formation of crystal defects on the host framework, it causes the changes in
the physical properties of the parent compound. In this present investigation, we are growing the
ADP crystals in six different pH of the growth medium (pH = 2.5 to 12.5) and reporting the
effects on the lattice constants, XRD intensities, crystallite size, FT-IR, EDS, morphology,
thermal and SHG conversion efficiency of ADP crystal.
2. Experimental

Synthesis and crystal growth

ADP (E. Merck) was purified by repeated recrystallization. The crystals were grown by a
slow evaporation solution growth technique (SEST). A saturated aqueous solution of ADP was
prepared using triply distilled water mixed with concentrated hydrochloric acid in various

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proportions for acetic solutions (pH = 2.5 (A), 4.6 (B) and 6.5 (C)) and in basic solutions (pH =
8.7 (D), 10.6 (E) and 12.5 (F)) using the mixture of sodium hydroxide in various proportions
with triply distilled water as a growth medium. The seed crystals are allowed to float on the
surface of the saturated solution and left for slow evaporation at room temperature (30 C). The
prepared solution was filtered with a micro filter. The crystallization took place within 15−20
days and the crystals were harvested when they attained an optimal size and shape. Bulk crystals
are grown using optimized growth parameters. High quality transparent crystals were harvested
from the growth medium. Photographs of the as grown ADP crystals are shown in Fig. 1.

Fig. 1 Photographs of ADP as-grown crystals a − A, b - B

c − C, d - D , e – E and f – F ADP crystals.

Characterization techniques

The FT-IR spectra were recorded using AVATAR 330 FT-IR by KBr pellet technique.
Bruker Axs (Kappa Apex II) X-ray diffractometer was used for single crystal XRD studies.
Morphologies of the samples and energy dispersive X-ray spectrocopy (EDS) were observed

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using a JEOL JSM 5610 LV scanning electron microscope with the resolution of 3.0 nm, an
accelerating voltage 20 kV, and maximum magnification 3,00,000 times..

The second harmonic generation test on the crystals was performed by the Kurtz powder
SHG method [21]. An Nd:YAG laser with modulated radiation of 1064 nm was used as the
optical source with an input radiation of 2.5 mJ/ pulse and the grown crystals were ground to a
uniform particle size of 125 to 150 μm and then packed in a micro-capillary of uniform bore and
exposed to laser radiation. The output from the sample was monochromated to collect the
intensity of the 532 nm component and to eliminate the fundamental. Microcrystalline KDP was
used as a reference material. TG–DTA studies were carried out on a SDT Q600 Thermal
analyzer TA Instrument between 25–500 ˚C in nitrogen atmosphere, at a heating rate of 10 ˚C
min-1. 0.5 g of sample taken in an Al2O3 crucible is placed on top of a thermocouple resting on a
balance, and the system is sealed into a chamber and heated with a constant heating rate.

3. RESULTS AND DISCUSSION

FT-IR analysis

The characteristic vibrational frequencies of the pure ADP and crystals grown in
difference pH A, B, C, D, E and F are similar (Fig-2). Oxygen stretching and bending
frequencies of P-O, υPO and δPO are similar in the pure and the samples A, B, C, D, E and F. The
NH- group hydrogen stretching frequency at 3500-3000cm-1 is slightly broadened in the presence
of hydrogen bonding. (Table-1). O-H stretching frequency in the doped ADP is in the range of
2850-2860cm-1 [22].

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Fig. 2 FT-IR spectra of ADP crystals, a − A, b- B, c− C, d- D, e – E and f -- F .

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Table-1 IR Spectrum of pure and metal doped crystals

System PO4 PO4 bending -NH4 -OH N-H---O
stretching cm-1 stretching cm- strectching strectching
cm-1 1 cm-1 cm-1
Pure ADP 1092 544 1402 2870 3200
932 470
A 1101.94 544.62 1400.98 2854.79 3129.64
924.86 470.26
B 1100.10 545.25 1401.45 2865.75 3135.87
917.83 447.43
C 1104.36 544.65 1401.38 2860.27 3135.59
920.91 460.69
D 1101.35 547.60 1402.06 2854.79 3236.72
910.36 436.35 3123.29
E 1104.24 545.24 1401.25 2843.84 3140.97
921.94 462.45
F 1101.78 544.80 1402.05 2854.79 3129.27
920.72 449.32

XRD analysis
XRD patterns of ADP grown from the solutions with different pH compared with that of
ADP grown from neutral medium (Fig. 3). Reduction and slight deviations are observed in the
intensities of the XRD patterns shows incorporation of ions are occupies only intertisial positions
and not much disturb the lattice structure of ADP and there is no new phases are formed due to
different growth conditions.

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Fig. 3 powder XRD of ADP crystals, p - pure ADP, . a – B, b – D and c - E

The cell parameters have been determined from single crystal X-ray diffration analysis of
ADP crystals. Only slight variations are shown in latttice constants values. This may be due to
incorporation of ions on ADP in different growth medium. The values of the lattice constants of
ADP crystals are given in the Table. 2.
Table 2
Lattice parameter and cell volume values of doped and pure ADP crystals

Crystal a=b c Cell System

volume
Pure ADP 7.5024(±0.0004) 7.566 (±0.0004) 428.6 Tetragonal

A 7.5131(±0.0015) 7.5601(±0.0001) 431.56 Tetragonal

B 7.5158(±0.0003) 7.5674(±0.0006) 433.66 Tetragonal
C 7.5154(±0.0006) 7.5701(±0.0005) 437.04 Tetragonal
D 7.5087(±0.0004) 7.5774(±0.0011) 436.18 Tetragonal
E 7.5117(±0.0008) 7.5674(±0.0006) 431.18 Tetragonal
F 7.5069(±0.0006) 7.5664(±0.0009) 437.18 Tetragonal

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SEM AND EDS:

The investigation of the effect of pH on the surface morphology of ADP crystal faces reveals
the formation of structure deface centers. More scattered canters and voids are shown in surface
of ADP grown in strong acetic (pH = 2.5) and strong basic (pH = 12.5) medium. Evenly placed
blisters like structures in plate morphology of crystals are shown in ADP grown from the
medium with pH 4.5, 6.6 and 8.7. Small scattered centers are appeared in the case ADP grown
from the solution with pH 10.6 (Fig. 4).

Fig. 4 SEM pictures of ADP crystals, p – pure ADP, a – A, b – B, c – C, d – D, e – E and f - F.

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The incorporation of ions due to different growth conditions into the crystalline matrix were
confirmed by EDS performed on ADP (Fig. 5). Presence of sodium in ADP crystalline matrix
grown from basic solution and presence of chloride ion in ADP crystalline matrix grown from
acetic solution are clearly shown from EDS. It shows that the accommodating capability of the
parent ADP is limited and only a small quantity of the ions is incorporated into the ADP caystal
matrix.

Fig. 5 EDS spectra of ADP crystals, a − B, b - E.

Thermal studies

TG/DTA thermogram reveals the purity of the material. The thermogram curve shows a
gradual mass loss and residual mass obtained at 500 ˚C is ~75% in case ADP grown from pH
and 12.5 (Fig. 6(a) & (b)). A sharp endothermic peak is obtained in the DTA analysis at
a

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higher temperature (210 ˚C) than the pure ADP crystals (191 ˚C). Melting point of the material
was confirmed by using Sigma instruments melting point apparatus (210 ˚C). The investigation
shows that there is no physically absorbed water in molecular structure of crystals grown from
the solution. No decomposition up to the melting point ensures the stability of the material for
application in laser, where the crystals are required to withstand high temperatures.

Fig. 6 DSC curves of ADP crystals, a - B, b − E.

SHG:
In order to confirm the influence of doping on the nonlinear optical properties (NLO) of
the as-grown crystals, these were subjected to SHG test. Green color output indicates that the
doped material exhibits second order NLO effect. The depressed SHG efficiency is quite likely
due to the disturbance of charge transfer. The efficient SHG demands specific molecular
alignment of the crystal to be achieved facilitating nonlinearity in the presences of a dopant. It
has been reported that the SHG can be greatly enhanced by attaining the molecular alignment
through inclusion complexation [23]. Recently, we have reported that enhancement in crystalline
perfection could lead to improvement in SHG efficiency [8]. Growing ADP in different pH of
the growth medium enhances the SHG efficiency by influence of sodium (in basic condition) and

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chloride ion (in acetic condition) (Table . 3) as useful dopant. The efficient SHG demands
specific molecular alignment of the crystal facilitating nonlinearity in the presence of dopant or
it may be due to the improvement in the crystalline perfection of ADP crystals by the
incorporation of ions.

Table 3 SHG outputs

Input 2.5 mJ/Pulse, KDP 43(mV); Urea 173(mV)

System I2ω (mV)

Pure ADP 35
A 39
B 42
C 43
D 41
E 45
F 46

4. CONCLUSIONS
We have used XRD, FT-IR, SEM, EDS, TG/DTA and kurtz powder techniques to study the
influence of growth condition on ADP crystals. Intensity variation in some of the powder XRD
lines reveals crystal undergoes considerable lattice stress as a result of pH variation during
crystallization. FT-IR studies also clearly confirmed the above observations. SEM images reveal
that the external morphology of ADP crystal is changed by the difference in growth condition.
EDS confirms the presence of Cl in Na in the speciman. The TG/DTA studies reveal the purity
of the material and no decomposition is observed upto the melting point. The SHG efficiency of
ADP is slightly increased by growing in different pH.
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