Physica B 449 (2014) 61–66

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Physica B
journal homepage: www.elsevier.com/locate/physb

Influence of formic acid on electrical, linear and nonlinear optical

properties of potassium dihydrogen phosphate (KDP) crystals
Mohd Anis a, M.D. Shirsat b, Gajanan Muley c, S.S. Hussaini a,n
a
Crystal Growth Laboratory, Department of Physics, Milliya Arts, Science & Management Science College, Beed 431122, Maharashtra, India
b
Intelligent Material Research Laboratory, Department of Physics, Dr. Babasaheb Ambedkar Marathwada University, Aurangabad 431005,
Maharashtra, India
c
Department of Physics, Sant Gadge Baba Amravati University, Amravati 444602, Maharashtra, India

art ic l e i nf o a b s t r a c t

Article history: In present investigation 0.5 and 1 mol% formic acid (FA) added potassium dihydrogen phosphate (KDP)
Received 12 March 2014 crystals have been grown by a slow evaporation technique. The cell parameters of the grown crystals
Received in revised form were determined using single crystal X-ray diffraction analysis. The presence of different functional
29 April 2014
groups has been qualitatively analyzed by the FT-IR spectral analysis. The optical transparency and
Accepted 1 May 2014
Available online 20 May 2014
optical constants were assessed employing UV–visible studies in the range of 200–900 nm. The wide
optical band gap of 1 mol% FA added KDP has been found to be 5 eV. The frequency dependent dielectric
Keywords: measurements were studied for pure and KDP added FA crystals. The enhanced second harmonic
Crystal growth generation (SHG) efficiency of grown crystals was determined by a classical Kurtz–Perry powder
Growth from solution
technique. The encouraging third order nonlinear properties were examined employing a Z-scan
Nonlinear optical materials
technique using He–Ne laser, at 632.8 nm. The effective negative index of refraction and high figure of
Optical studies
Electrical studies merit (FOM) essential for laser stabilization were determined for grown crystals.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction communication reports the effect of FA on electrical, linear and

nonlinear optical properties of KDP crystals for its effective NLO
Nonlinear optical materials capable of efficient laser frequency applications.
conversion have been actively sought over the last three decades due
to enlarged commercial significance and scope of these materials in
the field of optical communication, signal processing, optical switching 2. Synthesis and growth
and optical data storage. Potassium dihydrogen phosphate (KDP) is a
model system for potential nonlinear optical device applications with The AR grade KDP (KH2PO4) salt was dissolved in deionized
high range of thermal stability [1–4]. The improvement in the optical water and supersaturation is achieved. The doping was achieved
quality, nonlinearity and different properties of KDP crystals can be by adding 0.5 and 1 mol% FA to supersaturated solution of KDP in
realized with suitable noncentrosymmetric and polar dopant. The separate beakers. The solutions were allowed to stir well at a
influence of thiourea, glycine, L-arginine and histidine on the growth, constant speed for six hours to achieve the homogeneity through-
structural, thermal, optical properties and SHG efficiency of KDP out the aqueous volume. The purity of the synthesized salts was
crystal has been reported in the literature [3–5]. Formic acid belongs achieved by successive recrystallization process. The filtered solu-
to the family of carboxylic acid, restrains its research impact with tions were kept for evaporation in a constant temperature bath of
distinct amino acids viz. L-arginine, glycine, L-alanine, L-threonine accuracy 70.01 at 36 1C. Highly transparent and well phased
exhibiting better nonlinearity and physico-chemical properties [6–9]. crystals of FA added KDP were harvested in 20 days. 0.5 and 1 mol%
Rajesh et al. recently reported effect of DL-malic acid and oxalic acid FA added KDP crystals are shown in Figs. 1 and 2.
on structural, optical, thermal, mechanical and dielectric properties of
ADP crystal [10–11]. The effect of different amino acids, metal ions on
KDP has been reported by many researchers, however studies on 3. Results and discussion
FA added KDP crystal are yet to be explored. Therefore, present
3.1. Single crystal X-ray diffraction

n
Corresponding author. Tel.: þ 91 9325710500. The cell parameters of the grown crystals were determined
E-mail address: Shuakionline@yahoo.co.in (S.S. Hussaini). using the single crystal NONIUS CAD4 X-ray diffractrometer.

http://dx.doi.org/10.1016/j.physb.2014.05.007
0921-4526/& 2014 Elsevier B.V. All rights reserved.
62 M. Anis et al. / Physica B 449 (2014) 61–66

Fig. 1. Crystal of KDPþ FA 0.5 mol. Fig. 3. FT-IR spectrum.

The highest enhancement in SHG efficiency is procured by 1 mol%

FA added KDP crystal. It is found to be 1.13 times that of standard
KDP material. Thus FA added KDP crystal can be subjected to
effective laser frequency conversion and NLO applications such as
optical modulation [13]. The enhancement in SHG efficiency of
KDP is notable with increasing FA mole%.

3.3. FT-IR spectral analysis

The influence of formic acid in KDP has been analyzed by

recording the vibration spectrum of grown crystals using a Bruker
α-ATR instrument in the range of 600–4000 cm  1. The absorption
FT-IR spectral vibrations for different characteristic bonds are
depicted in Fig. 3.The absorption peak observed at 624 cm  1 is
due to O–H bending vibrations. The C–H bond deformation peak of
formic acid is assigned at 1392 cm  1. The prominent peak at
1520 cm  1 is evident of C–H bond bending while the peculiar
OQPQOH symmetric stretching mode of KDP is assigned at
Fig. 2. Crystal of KDPþ FA 1 mol.
wavenumber 1697 cm  1. The occurrence of C–H stretching vibra-
tion is evident at 2177 cm  1. The sharp absorption peak cited at
2357 cm  1 is assigned to P–O–H bending vibrations. The mild
Table 1
peak observed at 3617 cm  1 corresponds to O–H bond stretching.
Cell parameters.
The peaks at 3743 cm  1 and 3846 cm  1 are attributed to CH2
Samples a¼ b, c (Å) V (Å)3 stretching vibrations. The incorporation and presence of FA in KDP
has been confirmed from vibrational spectrum.
KDP 7.44, 6.94 384
KDP þFA 0.5 mol 7.46, 6.97 388
KDP þFA 1.0 mol 7.49, 6.99 392
3.4. UV–visible studies

The UV–visible transmission spectra of FA added KDP crystals

The grown FA added KDP crystals were revealed to be crystallized were recorded using a Shimadzu UV-2450 spectrophotometer in
with tetragonal symmetry. The cell volume of the FA added KDP the range 200–900 nm. The materials suitability for optoelectro-
crystals was observed to have slight increase with increase in nics applications can be well understood exploring the transmit-
concentration of FA. The volumetric parameters of grown crystals tance in visible region, shown in Fig. 4. 1 mol% FA added KDP
are discussed in Table 1. crystal exhibited highest transparency in entire visible region and
lowest cut off wavelength (291 nm) substantive for effective laser
3.2. SHG efficiency test frequency conversion [14]. The optical band gap of the material is
of vital importance to illustrate the electron transitions in different
Kurtz's powder technique was employed to investigate the electronic band structures. The absorption coefficient was also
enhancement in SHG efficiency of KDP crystal due to addition of calculated by using the transmittance spectrum, α ¼2.303[log
different mole% of FA [12]. The studies were carried using Nd–YAG (1/T)]/d, were T is the transmittance, α is the absorption coeffi-
laser operating at 1064 nm with repetition rate of 10 Hz and pulse cient, and d is the thickness of the crystal. The optical band gap
width of 8 ns. The error bar in measurement with the current (Eg) can be calculated using relation, (αhν)2 ¼A (hν Eg). The
setup was determined to be 71 mV. The second harmonic signals values of band gap of the grown crystals were determined from
generated by the crystalline sample were confirmed from emission Tauc's extrapolation plot depicted in Fig. 5. The band gap of 1 mol%
of green radiations. The relative SHG signals generated for pure FA added KDP crystal is found to be 5 eV indicating its suitability
KDP, 0.5 and 1 mol% FA added KDP were 75 mV, 82 mV and 85 mV. for fabrication of optoelectronic devices [15]. The change in
 M. Anis et al. / Physica B 449 (2014) 61–66 63

Fig. 4. Transmittance spectrum. Fig. 6. Refractive index vs. wavelength.

Fig. 7. Reflectance vs. wavelength.

Fig. 5. Tauc's plot.

velocity of electromagnetic wave in the material medium can be

assessed with the innate behavior of refractive index in UV–visible
region. The variation of refractive index and reflectance with wave-
length is shown in Figs. 6 and 7. The high transmittance with lower
refractive index and reflectance of 1 mol% FA added KDP crystal in
the entire visible region realizes its prominence for antireflection
coating in solar thermal devices [14]. The optical conductivity,
electrical conductivity and susceptibility are shown in Figs. 8, 9 and
10. The high magnitude of optical conductivity indicates the potential
candidature of the grown crystals for information processing and
computing [14]. The lower electrical conductivity and susceptibility
of FA added crystals are promising properties for semi-conducting
devices [14]. The lower values of extinction coefficient and optical
dielectric constant exhibited by FA added crystals are prerequisite
properties for high conversion efficiency shown in Figs. 11 and 12
respectively. The systematic analysis of data shown in Table 2
revealed that the rising FA concentration triggers improved optical
properties to KDP crystals vital for NLO applications. Fig. 8. Optical conductivity vs. photon energy.
The measure of loss of electromagnetic energy in visible region
due to scattering and absorption phenomenon can be realised
with lower extinction coefficient of material [16]. The extinction 3.5. Dielectric studies
coefficient indicates the propagation of electromagnetic wave
through material evaluated using the relation k ¼ αλ/4π. The The dielectric responses of the grown crystals were studied
electrical susceptibility can be examined in visible region with using the Gwinstek-819 LCR meter at room temperature. The
χ ¼n2  1, were n is the refractive index of the material. variation of dielectric constant for pure and FA added KDP crystals
64 M. Anis et al. / Physica B 449 (2014) 61–66

Fig. 9. Electrical conductivity vs. wavelength.

Fig. 12. Real and imaginary parts of dielectric vs. hν (eV).

Table 2
Optical parameters.

Parameters KDP KDPþ FA 0.5 mol KDP þFA 1 mol

Cutoff wavelength 337 nm 295 nm 291 nm

Band gap 4.7 eV 4.9 eV 5 eV
Reflectance 36.6 29.9 28.8
Extinction coefficient 1  10  4 7  10  5 6.5  10  5

Fig. 10. Electrical susceptibility vs. wavelength.

Fig. 13. Dielectric constant vs. Log F.

traces decreasing dielectric constant with increasing frequency indi-

cating crystal lattice perfection and suppressed space charge polariza-
tions, which benefits material for increasing SHG coefficient [18]. The
decreasing dielectric loss with increasing frequency is depicted in
Fig. 14. Thus FA added KDP crystals possess enhanced optical quality
and low level defects making it potential candidate for nonlinear
Fig. 11. Extinction coefficient vs. wavelength. optical device fabrication [17–18].

3.6. Z-scan measurements

is shown in Fig. 13. The dielectric constant is higher at lower
frequencies ascribed to electronic, ionic, dipolar and space charge The optically transparent FA added KDP crystals were
polarization mechanism of molecular dipoles and saturates with employed to collect the prefocal and post-focal open and closed
further increasing frequency [17]. The 1 mol% FA added KDP crystal aperture Z-scan data using Q-switched He–Ne laser operating at
 M. Anis et al. / Physica B 449 (2014) 61–66 65

Fig. 14. Dielectric loss vs. Log F. Fig. 15. Closed aperture curve.

Table 3
Spectral resolution of Z-scan setup.

Laser beam wavelength (λ) 632.8 nm

Lens focal length (f) 12 cm
Optical path distance (Z) 115 cm
Spot-size diameter in front of the aperture (ωa) 1 cm
Aperture radius (ra) 4 mm
Incident intensity at the focus (Z¼0) 3.13 MW/cm2

632.8 nm. The spectral resolution of the Z-scan setup used in

present study is discussed in Table 3. The studied crystals were
translated with the laser beam intended to focus on a crystal
through a convex lens which causes the spatial distribution of
temperature at the crystal surface due to localized absorption of
incident energy. As the sample is translated along the Z direction
the alternation in intensity evidences the change in refractive
index pre and post the focal point (Z ¼0). The difference between
the maximum value of peak and valley transmission (ΔTp  v) is
evaluated as follows: Fig. 16. Open aperture curve.



ΔT p  v ¼ 0:406ð1 SÞ0:25
Δϕ
ð1Þ
where ε0 is the vacuum permittivity, n0 is the linear refractive
where S ¼[1  exp (  2r2a /ω2a )] is the aperture linear transmittance, index of the sample and c is the velocity of light in vacuum. The
ra is the aperture radius and ωa is the beam radius at the aperture. variation in index of refraction can be evaluated from the closed
The nonlinear refractive index was calculated as follows: aperture transmittance curve. The peak-to-valley transmission
configuration cited in Fig. 15 interprets the self-defocusing nature
Δϕ
n2 ¼ ð2Þ of 0.5 and 1 mol% FA added KDP crystals. The negative index of
KI 0 Leff
refraction is ascertained with addition of FA indicating the promi-
where K ¼2π/λ (λ is the laser wavelength), I0 is the intensity of the nence for optical limiting devices and laser stabilization [19].
laser beam at the focus, Leff ¼ [1  exp (  αL)]/α, is the effective The saturation absorption (SA) or the reverse saturation absorp-
thickness of the sample depending on linear absorption coefficient tion (RSA) phenomenon identifies the potential absorptive non-
(α) and L is thickness of the sample. The nonlinear absorption linearity of the material subjected to open aperture transmission
coefficient (β) of FA added KDP crystals is evaluated as shown data. The open aperture transmission data shown in Fig. 16 assists
below the FA added crystals with effective nonlinear absorption coeffi-
pffiffiffi cient (β). The β values of 0.5 and 1 mol% FA added KDP crystals are
2 2 ΔT
β¼ ð3Þ found to be 1.15  10  7 cm/W and 1.16  10  7 cm/W. Thus non-
I 0 Leff
linear absorption coefficient marginally decreases with increasing
where ΔT is the one valley value at the open aperture Z-scan concentration of FA. The large quantitative nonlinear susceptibility
curve. The real and imaginary parts of nonlinear susceptibility are is of vital importance as it induces higher polarizing innate
calculated using the relations depicted as follows: characteristic to material [20]. The third order nonlinear suscept-
ibility (χ3) of FA added crystals was found to be of the order
Reχ ð3Þ ðesuÞ ¼ 10  4 ðε0 C 2 n0 2 n2 Þ=π ðcm2 =WÞ ð4Þ
10  7 esu which is appreciably larger than pure KDP and KBBF
Imχ ð3Þ ðesuÞ ¼ 10  2 ðε0 C 2 n0 2 λβÞ=4π 2 ðcm=WÞ ð5Þ crystal [20–21]. The nonlinear optical properties are influenced by
intrinsic defects i.e. oxide of phosphorous and π-electron cloud of
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi FA leading to enhanced values of third order nonlinear suscept-
χ 3 ¼ ðReχ 3 Þ2 þ ðImχ 3 Þ2 ð6Þ ibility [22–23]. The high nonlinearity and diverse optical device
66 M. Anis et al. / Physica B 449 (2014) 61–66

Table 4 Acknowledgments
Nonlinear optical parameters.

FA concentration n2  10  18 cm2/W β  10  7 cm/W χ3  10  7 esu FOM

The authors are thankful to the Department of Science and
in KDP Technology (DST/SR/S2/LOP-22/2010), and University Grants Com-
mission (UGC/41–591/2012/SR), New Delhi, for financial assis-
KDP þFA 0.5 mol%  2.23 1.15 3.96 327 tance. One of the authors (Mohd Anis) is thankful to Prof.
KDP þFA 1 mol%  1.41 1.16 3.81 522
Sastikumar, Department of Physics, NIT, Tirucherapalli for extend-
ing the Z-scan measurement facility.

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