Applied Physics A (2022) 128:422

https://doi.org/10.1007/s00339-022-05559-0

Growth and studies of ­Ba2+‑doped ADP single crystal for optical

and dielectric applications
V. Manivannan1 · N. Bhadusha1 · T. Gunasekaran1 · R. Rajapriya1 · R. Uthrakumar2 · M. Jeyakanthan3

Received: 30 November 2021 / Accepted: 21 March 2022

© The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature 2022

Abstract
Pure and barium ion ­(Ba2+)-doped ammonium di hydrogen ortho phosphate (ADP) crystals were grown from aqueous solu-
tion using a slow evaporation process. The presence of ­Ba2+ ions in the lattice was confirmed by X-ray diffraction (XRD)
pattern of the grown crystals, which revealed improved transparency for the compound. Green emission was observed in
photoluminescence studies of the grown crystals. The results of Fourier-transform infrared (FTIR) spectroscopy, ultravio-
let–visible (UV–visible) spectrum analysis, energy-dispersive X-ray analysis (EDAX) and dielectric studies on the grown
crystals were reviewed in detail. A regular slow cooling evaporation method was used to grow the crystals of pure and
­Ba2+-doped ADP from aqueous solution.

Keywords  Characterization · Crystal growth · XRD · FTIR analysis · UV–visible analysis · SHG · EDAX · Dielectric
properties

1 Introduction and include be extensively investigated used for decades [9,

Investigated inorganic nonlinear materials pay a vital role
in the growing research field due to their molecular con-
nections, bond force, high molecular polarizability, simple
inclusion of ions within the pattern, etc. [1–4]. Here the
explore designed for more effective nonlinear optics (NLO)
resources, inorganic materials among a conjugated π elec-
tron structure and donor and acceptor substituent were found
toward exist good for second harmonic generation (SHG)
[5, 6]. Because of its high laser smash up, the nitrophenol
family of crystals has piqued the interest of researchers in
the last decade [7, 8]. These molecular inorganic compounds
have NLO materials, which are based going on the relations,
which results in high electron migrate in one or more elec-
tron systems in nearby places in charge transmit systems,
* V. Manivannan
manivannanatr@gmail.com
10]. Compared with KDP crystal, the usage of ADP crys-
tal is relatively rare. But recently received the increasing
interest due to use for the fifth-harmonic generation [11] of
powerful neodymium lasers for hot plasma diagnostics [12].
The ADP crystals was formed by rapid growth method by
Amandosov et al. [13] from a point-like seed. Doping effect
on electric and hardness properties of ADP crystal has been
done by Patle et al. [14].
From the deep literature survey, no reports available
for Ba-doped ADP crystal. In this manuscript, for the first
time, the optical and electrical properties of ­Ba2+-doped
ADP crystal has been reported. ­Ba2+-doped ADP crystals
were grown from aqueous solution by regular slow cooling
evaporation method also subjected to categorization studies
such as powder XRD, EDAX, UV–Visible, FTIR spectral
investigation, and dielectric studies to prove improvement of
ocular material goods and recognize development in expand
property of the doped crystals.

1
Department of Chemistry, Government Arts College (A),
Salem, Tamil Nadu 636007, India 2 Materials and methods
2
Department of Physics, Government Arts College (A),
Salem, Tamil Nadu 636007, India The ­Ba2+-doped ADP crystals are obtained from inclusion
3
Department of Physics, Vinayaka Mission’s Kirupananda of ­Ba2+ (0.01 mol%) to a solution of ADP (0.1 mol%) in
Variyar Arts and Science College, Vinayaka Mission’s water by slow cooling evaporation method. The solution
Research Foundation, Salem, Tamil Nadu, India

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 422   Page 2 of 6 V. Manivannan et al.

­ a2+-doped ADP
Fig. 1  The photograph of pure ADP crystal and B
crystals

was washed repeatedly more times in case of removing the

impurities. Then, the solution is kept without any distur-
bance, seed crystals are formed within a week due to the Fig. 2  XRD pattern of the ­Ba2+-doped ADP crystal
impulsive nucleation. The good-quality seed crystals are
engrossed in the prepared solution, the solution is exposed
to slow evaporation at room temperature, optically cleared ­ a 2+-doped ADP is given in
lattice parameters of the B
bulk crystals are obtained within 3 weeks. The prepared pure Table 1.
ADP and B ­ a2+-doped ADP crystals attribute with dimen-
sions of 1 × 0.5 × 0.5 cm and 1.8 × 0.4 × 0.5 cm is, respec- 3.2 UV–Vis spectral studies
tively, shown in Fig. 1.
Optical absorbance measurements along the wavelength
array of 200–800 nm are performed on prepared crystals
using a Shimadzu model UV-1061 UV–Vis spectrometer.
3 Results and discussion
Figure 3 depicts a UV–Vis spectra of pure ADP crystal and
­Ba2+-doped ADP crystal. The crystal is intended to be par-
3.1 XRD analysis
ticularly visible in the extensive wavelength constituency
for optical fabrications [16]. The UV assimilation edge for
Using a Bruker Kappa APEX-2 diffractometer through
the growing crystal was discovered at 244 nm, which is a
MoKa (λ = 0.71073 Å) radiation, single-crystal X-ray dif-
critical parameter for frequency doubling parameter [17],
fraction is worn to estimate the crystalline nature of the ADP
and the invention's crystalline nature is demonstrated by the
crystals in addition to recognize the lattice parameters. The
low incorporation in the entire visible range.
grown crystal was determined to be a tetragonal system with
the space group I42d based on this investigation. From the
3.3 FTIR spectral analysis
previous report, the lattice parameters of the pure ADP crys-
tal are a = b = 7.501 Å and c = 7.905 Å, α = β = γ = 90°. The
FTIR spectroscopic measurement was carried out in the
XRD results of the grown crystal are in excellent agreement
wave number range of 400–4000 ­cm−1 using a THERMO
with the literature [15]. However, the lattice parameters of
SCIENTIFIC, DXR FTIR spectrometer. Figure 4 shows the
­Ba2+ doped ADP crystal is a = b = 7.440 Å and c = 7.635 Å,
FTIR spectra of pure ADP crystal and B ­ a2+-doped ADP
α = β = γ = 90° are slightly lower than those of pure ADP
crystal. To differentiate the purposeful groups as well as
single crystal. Lattice parameter of the B ­ a2+-doped ADP
modes of vibration of the grown-up crystal, IR spectroscopy
crystal has been calculated using the given formula (tetrago-
analysis was used. The peaks at 3000 and 4000 ­cm−1 cor-
nal structure)
responds to symmetric and asymmetric nonlinear of amine,
2
= h2 + k2 ∕a2 + l2 ∕c2 , (1) phosphate, respectively. The peaks at 1468, 1300, 1095 and
( )
1∕dhkl
910 ­cm−1 were assigned to P=O stretching groups, while the
where d is the interplanar distance, a and c are lattice con- bands in the array of 3321–2349 ­cm−1 were related to O–H
stants, h, k, l are miller indices. The XRD pattern of the stretching vibrations of Chelate compound [18, 19]. The fin-
­Ba2+-doped ADP crystal is shown in Fig. 2. Red line in the gerprint region was located below 1500 ­cm−1 frequency. The
figure represents the Pseudo-Voigt fit for (200), (112), (202) observed FTIR frequencies of pure ADP and B ­ a2+-doped
planes for calculating lattice parameters. The calculated ADP crystals are tabulated in Table 2.

13
Growth and studies of ­Ba2+‑doped ADP single crystal for optical and dielectric applications Page 3 of 6  422

­ a2+-doped ADP) of pure and ­Ba2+-doped ADP single crystal

Table1  Structural parameters (derived from XRD data for B
Type of crystal Cell parameter (Å) Volume (Å) Angle Space group Crystal system

Pure ADP a = b = 7.501, c = 7.905 [11] 444.774 α = β = γ = 90° I42d Tetragonal [11]
Ba2+-doped ADP a = b = 7.440, c = 7.635 422.624 α = β = γ = 90° I42d Tetragonal

Table 2  Observed FTIR frequencies (­cm−1) of pure ADP and

­Ba2+-doped ADP crystals
Frequency in wave num- Assign the functional group
ber ­cm−1
Pure ADP Ba2+-
doped
ADP

3249 3321 OH stretching vibration

2874 2764 Combination band vibration (H—bonding)
1642 1600 Band vibration of water (OH—bending)
1444–1408 1420 NH2 vibration
1100 1095 P–O–H vibration
910 950 P=O vibration
600 580 PO4 vibration
Fig. 3  UV–Vis spectra of pure ADP crystal and ­Ba2+-doped ADP
crystal

the eponymous work of art (Fig. 5). Scanning at numer-

ous places in the doped crystal revealed the existence of
nitrogen, phosphorus, barium, and oxygen. Figure 5 shows
EDAX spectrum of a pure ADP and ­Ba2+ doped ADP sin-
gle crystal with peaks assigned to P, N, Cl, Ba and O at
dissimilar energies. Table 3 [20, 21] shows the atomic and
weight percentage consequences of matching elements
present in the crystal.

3.5 Photoluminescence (PL) spectroscopy

The PL emission spectrum provides information in rela-

­ a2+-doped ADP crys-
Fig. 4  FTIR spectra of pure ADP crystal and B
tal
3.4 Chemical composition analysis
The quantitative investigation of the grown crystals was
studied using a scanning electron microscope (JSM 6360
LA, Japan) up to with an energy-dispersive analytical
X-ray unit (EDXS). Before subjecting to SEM/EDXS
analysis, the grown crystals were sputter coated with
platinum for 10 s to eliminate charge enlarge during the
measurement. Powder dispersive X-ray examination of a
­Ba2+-doped ADP crystal indicates to facilitate the exist-
­ a2+ in ADP which is consistent with
ing attentiveness of B
tion to the crystals that discharge photons. The study of
near-band edge emission yields an expected intention
designed for the band gap energy (Eg) as well as the work.
The PL spectrum was obtained at room temperature using
a JOBIN YVON FLUROLOG-3-11 Spectrum fluorometer.
Photoluminescence in solids occurs when light of a spe-
cific intensity energises electronic states of solids; further-
more, the excitation energy is out as beam. Photons are
emitted from the model plane as a result of varied recom-
bination of electrons and holes, and the ensuing photon
emission spectrum is what is purposeful in PL. The emis-
sion of green band at 490 nm and emission of the near blue
band at 360 and 380 nm emission (Fig. 6) is attributed to
an incredible speed of excited-state intermolecular proton
transfer (ESIPT) with hydrogen bonding [22].

13
 422   Page 4 of 6 V. Manivannan et al.

Fig. 5  EDAX spectrum of pure

­ a2+-doped
ADP crystal and B
ADP crystal

Table 3  The estimated weight % and atomic % of pure ADP and source generates nanosecond pulses (8 ns) of 1064 nm light
­Ba2+-doped ADP crystal with an energy of around 300 mJ with a replication rate of
S. no. Elements Pure ADP Ba2+ doped ADP 10 Hz. A photo multiplier tube (PMT) was used to combine
the 532 nm (green light) SHG radiations, and the optical
Wt.% At.% Wt.% At.%
indicator event going on the PMT was changed interested in
1 N 10.50 13.50 5.20 8.40 the voltage amount produced.
2 O 64.40 72.19 64.40 72.19 The discharge of green emission from the crush sample
3 P 24.10 14.31 24.10 14.31 established the second harmonic generation residential in
4 Ba – – 4.60 3.20 the pure and ­Ba2+-doped ADP crystals generated in this
5 Cl – – 1.20 1.90 endeavor. As a result, the B­ a2+-doped ADP crystals have a
higher NLO than pure ADP crystals. This could be related
to a loss of crystalline perfection. Based on the research,
­Ba2+-doping ADP crystals have a 1.5 times efficiency com-
pared to pure ADP crystals. Barium abnormal performance
is attributed to its unique crystal structure. The ADP with
barium fine particles SHG effectiveness was originate to be
1.46 times than that of the normal ADP crystal.

3.7 Dielectric properties

The dielectric properties of the prepared pure ADP and

­Ba2+-doped ADP crystal was performed utilizing the HIOKI
3532–50 LCR HITESTER. The experiment was carried out
at a constant temperature of 35 ºC for frequencies ranging
from 100 Hz to 5 MHz. The following formula is used to
calculate the dielectric constant (ε):

Fig. 6  PL spectra of pure ADP crystal and ­Ba2+-doped ADP crystal

𝜀 = Cd ∕ A𝜀0 , (2)

3.6 SHG efficiency
Kurtz Perry powder technique was used to determine the
NLO characteristic of ADP crystal. The crystal was view
into a powder and crammed snugly interested in an even-
width micro-capillary tube. The Q switched Nd:YAG laser
𝜀� = 𝜀 tan𝛿, (3)
where 'C' stands for capacitance, ‘d’ for thickness, and ‘A’
for the grown crystals cross-section position. The varia-
tion of dielectric constant (ε) and dielectric loss with fre-
quency (f) at a fixed temperature is shown in Figs. 7 and 8,
respectively.

13
Growth and studies of ­Ba2+‑doped ADP single crystal for optical and dielectric applications Page 5 of 6  422
Fig. 7  Variation of dielectric constant with log frequency (f)
Fig. 8  Variation of dielectric loss with log frequency (f)
The dielectric constant and dielectric loss of pure and
barium metal ion the same as a function of applied meadow
frequency, due to the being there of all types of polariza-
tions, such as electronic, ionic, orientation, and space charge
polarisation, the dielectric constant is high in the low-fre-
quency area for all samples. Because the frequency rises,
the polarisation input decreases one by one. The dielectric
constant drops at high frequencies due to the electric dipole's
inability to detect with a deviation of the applied electric
field. The magnitude of the dielectric constant for barium
metal ion-doped ADP is much lower than for pure ADP;
this discrepancy may be explained using the relationship
between polarisation and atom or molecule dimension.
The polarizability of an atom otherwise molecule is deter-
mined by its dimensions; for a spherical atom or molecule,
the polarizability is relative to the cube of its radius, accord-
ing to a simple estimate. The change in optical indicatrix/
refractive index as a consequence of an externally applied
electric field is referred to as the electro-optic effect. For a
high standing dielectric constant and/or a strong polarization
optic response in the material, the successful electro-optic
reaction is large. During high-speed electro-optic inflection
along with electric field revealing applications, wherever low
driving voltages are required, the low dielectric constant has
significant advantages. Although the doping of barium metal
ion in ADP has little effect on physical parameters like as
structure and thermal stability, as discussed in the preceding
sections, the reduced dielectric constant in the doped crystal
may have uses in electro-optics.
The dielectric loss curves for both samples show greater
values at lower frequencies and steadily decrease as fre-
quency increases. The presence of gap charge polarization
causes the dielectric loss to be larger at lower frequencies.
The decreased dielectric loss of barium metal ion-doped
ADP when compared in the direction of pure ADP is owing
to the existence of barium metal ion at grain locations, which
reduces particle capacity and hence dielectric loss. Accord-
ing to the dielectric loss measurements, the doped sample
has few flaws and good optical quality [23, 24].
4 Conclusion
Using a slow evaporation approach, pure ADP and
­Ba2+-doped ADP crystal was grown from aqueous solu-
tion. The crystal belongs toward the tetragonal system with
space group I42d according to XRD study. The functional
groups of the grown crystals are completed by FTIR analy-
sis. Optical communication studies revealed that B ­ a2+-doped
ADP crystal is optically high quality in the whole UV area
through a lesser cut-off under 300 nm, indicating that the
crystal is validated for good SHG efficiency. Also, hard-
ness of the B ­ a2+-doped ADP may increase compare with
pure ADP crystal due to higher atomic number of Ba.
However, there are some disadvantages for B ­ a2+ doping in
ADP crystal for example higher absorption observed for
­Ba2+-doped ADP crystals in UV region is disadvantage for
fourth (266 nm) and fifth (213 nm) harmonics generation of
neodymium lasers. Photoluminescence and dielectric studies
confirmed the compound's crystalline nature, indicating that
the material is a potential candidate for optical applications.
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