Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255

Contents lists available at ScienceDirect

Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Growth and characterization of pure and doped KHP NLO single crystals
S.R. Thilagavathy a,, P. Rajesh b, P. Ramasamy b, K. Ambujam c
a

R&D Department, Bharathiar University, Coimbatore, India

Centre for Crystal Growth, SSN College of Engineering, Kalavakkam, India
c
Vel Tech Ranga Sanku Arts College, Chennai 600 062, India
b

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 0.5% Doped L-lysine KHP crystals have

high transparency.
 Similarly low dopant of KHP has high

SHG efciency.
 Functional groups from FTIR reveals

the dopand in the crystal.

 Only lower dopant are superior when

compared to pure and high dopants of

L-lysine.
 This proves dopants of KHP crystals
can be widely used for optical
applications.

a r t i c l e

i n f o

Article history:
Received 26 September 2013
Received in revised form 23 January 2014
Accepted 27 January 2014
Available online 12 February 2014
Keywords:
X-ray diffraction
FTIR
TG/DTA
SHG efciency

a b s t r a c t
Single crystals of Potassium Hydrogen Phthalate doped with amino acid L-lysine were grown successfully
by slow evaporation method. The concentration of dopant in the mother solution was 0.5 mol%, 1 mol%
and 2 mol%. There is a drastic change in the morphology due to variation in doping rates which is also
reected in the X-ray diffraction data. The Fourier Transform infrared spectroscopy study conrms the
incorporation of L-lysine into Potassium Hydrogen Phthalate crystal. The thermal study indicates the dissociating nature of the crystal. The nonlinear optical property of the grown crystal has been conrmed by
Kurtz-powder second harmonic generation test. The dopant of 0.5 mol% and 1 mol% shows higher second
harmonic generation result than pure Potassium Hydrogen Phthalate. Results are discussed.
2014 Elsevier B.V. All rights reserved.

Introduction
The search for new materials with nonlinear optical (NLO) properties has been the subject of intense research due to their application in a wide range of technologies such as optical computing and
optical communication [13]. Potassium Hydrogen Phthalate, often called simply KHP (also known as potassium acid phthalate)
is an interesting material as an analyzer material in X-ray spectroscopy [4,5]. KHP, a semi-organic compound crystallizes from its
Corresponding author. Tel.: +91 9444801934.
E-mail address: srthilagavathy@yahoo.com (S.R. Thilagavathy).
http://dx.doi.org/10.1016/j.saa.2014.01.137
1386-1425/ 2014 Elsevier B.V. All rights reserved.

aqueous solution in the orthorhombhic system with space group

Pca21. Its electro optic and nonlinear optical properties have been
studied [6]. Its cleavage faces nd applications as substrates in epitaxial techniques and KHP crystals are used as substrates for the
growth of highly oriented lm of conjugated polymers with high
non-linear optical susceptibility [7].
In this paper we are presenting a preliminary report on the
growth and characterization of pure KHP and L-lysine doped crystals. The KHP saturated solution was made from Merck (GR-grade)
chemical reagents dissolved in Millipore water of resistivity
18.2 MX/cm 1. L-Lysine (pure), an amino acid from HiMedia Laboratories was used as the dopant.

S.R. Thilagavathy et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255

249

Experimental
Crystal growth
Take a clean beaker of 500 ml with double distilled water and
add Potassium Hydrogen Phthalate. Stir evenly with the help of
magnetic stirrer at room temperature. Add KHP salt continuously
till the liquid gets saturated. Now lter the solution evenly in four
different beakers. Leave one beaker for slow evaporation, which is
mentioned here as pure KHP solution. Now add 0.5, 1 and 0.2 mol%
of L-lysine in each beakers. Stir these solutions continuously. As the
salt dissolves lter the solution and leave it for slow evaporation
process. After a period of time single crystals of pure and L-lysine
doped KHP crystals were grown. Transparent colorless KHP of size
16 mm  13 mm  2 mm were harvested in 20 days. For the
growth of L-lysine doped KHP crystals, 0.5 mol percent, 1 mol percent, 2 mol percent of L-lysine as the case may be, was added to the
solution of KHP. Single crystals with good transparency were harvested in 25 days, the size being 17 mm  14 mm  3 mm in the
case of 0.5 mol percent, 9 mm  6 mm  3 mm in the case of
1 mol percent and 9 mm  7 mm  2 mm when doping was
2 mol percent. For the experimental work de-ionized water was
got from Millipore water pre-ltration unit. The resistivity of the
used de-ionized water is 18.2 MX cm. The harvested crystals are
shown in Figs. 1ad.

Fig. 1b. 0.5 mol% lysine doped KHP crystal.

Characterization
The grown crystals have been analyzed by different characterization techniques. The crystal phases of the grown single crystals
of pure and L-lysine doped KHP were conrmed by single crystal
X-ray diffraction using ENRAF NONIUS CAD 4 single crystal Xray diffractometer with Mo Ka radiation. The functional groups
were identied using Perkin Elmer Spectrum 1 in the range of
4504000 cm 1 by KBR pellet technique. The optical properties
of the crystals were examined between 200 and 800 nm using
LAMBDA 35 UVVis Spectrophotometer. The TG/DTA thermogram of pure and L-lysine doped KHP crystals was obtained using
SDT Q600 thermal analyser. The NLO efciency of the grown sample was conrmed using Nd:YAG Laser as the source.

Fig. 1c. 1 mol% lysine doped KHP crystal.

X-Ray diffraction analysis

Single crystal diffractometers are most often used to determine
the molecular structure of new materials. The grown crystals were
subjected to single crystal X-ray diffraction to determine the unit
cell dimensions. A good quality crystal was selected for the X-ray

Fig. 1d. 2 mol% lysine doped KHP crystal.

diffraction studies. The unit cell parameters of pure and doped

KHP crystals are presented in Table 1. It is observed from the table
that the cell parameters of doped KHP slightly differ from those of
pure KHP, which may be attributed to the presence of different
mol% of dopants in KHP crystals. Both pure and doped crystals
are found to be orthorhombic. The results of the present work
are in good agreement with the reported value [8].
UVVis spectroscopy

Fig. 1a. Pure KHP crystal.

UVVis spectroscopy might be dened as the measurement of

the absorption or emission of radiation associated with changes

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Table 1
Cell parameters of pure and L-lysine doped KHP.
Lattice parameters

Pure KHP crystal ()

KHP+ 0.5 mol% L-lysine ()

KHP+ 1 mol% L-lysine ()

KHP+ 2 mol% L-lysine ()

a
b
C

6.46
9.57
13.28

6.46
9.59
13.26

6.53
9.71
13.40

6.45
9.59
13.28

in the spatial distribution of electron in atoms and molecules. In

practice, the electrons involved are usually the outer valence or
bonding electrons, which can be excited by absorption of UV or visible or near IR radiation. Excitation of a bound electron from the
Highest Occupied Molecular Orbital increases the spatial extent
of the electron distribution, making the total electron density larger and more diffuse and often more polarizable.
Grown crystals of pure and L-lysine doped KHP crystals of size
9 mm  6 mm  3 mm were polished and taken for UVVis spectroscopy observation. Optical transmission spectra were recorded
for the crystals in the wavelength region from 200 to 800 nm.
The UVVis transmittance spectra of pure and L-lysine doped
KHP single crystals are shown in Fig. 2. In the gure A represents
pure KHP, B represents 0.5 mol% L-lysine doped, C represents
1 mol% lysine doped and D represents 2 mol% L-lysine doped KHP.
It is observed from the gure that the 0.5 mol% of L-lysine doped
KHP shows more than 70% of transmittance. In order to conrm the
reproducibility, several times the beam was passed through the
various regions of the crystals and the same results were observed.
The pure KHP has 40% transmittance. It is also observed from the
gure that the 1 mol% of L-lysine doped KHP shows about 50% of
transmittance, which is quite higher than pure KHP crystal. But
2 mol% L-lysine doped KHP has only 10% of transmittance. Similar
results have been found in the case of Sn2+ and amino acid-doped
KDP crystals [9,10]. From Fig. 2, it is evident that 0.5 mol% of
L-lysine doping in the crystal leads to improvement in the crystalline perfection. It seems that the vacancies found in the undoped

crystal are now lled with the dopants and hence the crystal is
now free from the tensile stress and lead to improvement in the
transmittance. But as the doping level is increased the transmittance curve decreases because the interstitially occupied dopants
produce dislocations in the crystal, developing more grain boundaries. Thus the gure clearly shows that large amounts of L-lysine
doping in KHP does not have good electro-optic and NLO properties. The large transmission in the entire visible region enables it
to be a good candidate for electro-optic and NLO applications
[11,12]. L-lysine doped KHP of 0.5 and 1 mol% show more transparency than pure KHP. The above results indicate that the addition of
L-lysine of 0.5 and 1 mol% increases the transmittance.
Fourier Transform Infrared (FTIR) analysis
FTIR spectrum of pure and L-lysine doped KHP crystals were recorded using Perkin Elmer Spectrum 1 in the range 4504000 cm 1
by KBR Pellet technique. The FTIR spectra of the grown crystals are
given in Figs. 3.13.4. The broad band lying in the range 3600
4000 corresponds to NH symmetric stretching. The broad band
lying in the range 18001950 corresponds to C@C stretching. The
FTIR spectra of 1 mol% and 2 mol% L-lysine doped crystals show
strong NH symmetric stretching at about 24002650 cm 1. When
KHP is doped with L-lysine more NH stretch vibrations are introduced due to doping and as a result the NH absorption peak
becomes stronger. So, FTIR spectra also establishes the presence
of L-lysine in the lattice of KHP crystals [13]. Table 2 shows the
vibrational band assignments for pure and doped KHP crystals.
Thermal analysis

A - Pure KHP crystal

B - 0.5 mol% l-lysine doped KHP crystal
C - 1 mol% l-lysine doped KHP crystal
D - 2 mol% l-lysine doped KHP crystal
Fig. 2. UVVis spectra of pure and doped KHP crystal.

The TG/DTA thermogram of pure and L-lysine doped KHP crystals was obtained using SDT Q600 thermal analyser and the resultant thermogram is shown in gures. The TG thermogram reveals
that decomposition starts for pure KHP at 222.9 C and steps at
224.6 C as shown in Fig. 4.1. During this decomposition mass of
the sample reduces by 8.5%. The decomposition is also accompanied by the melting of the sample at 314.1 C as shown by DSC.
The second stage of decomposition is from 298.1 C to 324.4 C
resulting in a mass reduction of 44.2%. The third stage of decomposition is from 505.6 C to 549.5 C resulting in the mass reduction
of 16.7%. The residue at the end at 904.3 C is just 0.5%. This shows
that the sample is undergoing complete decomposition in this
study.
The TG thermogram reveals that decomposition starts for 0.5%
L-lysine doped KHP at 288.9 C and steps at 305.7 C as shown in
Fig. 4.2. During this decomposition mass of the sample reduces
by 46.1%. The decomposition is also accompanied by the melting
of the sample at 299 C as shown by DSC. The second stage of
decomposition is from 356.5 C to 381.8 C resulting in a mass
reduction of 5.1%. The third stage of decomposition is from
496.7 C to 538.3 C resulting in the mass reduction of 13.6%. The
residue at the end at 904.3 C is just 13.4%. This shows that the
sample is undergoing complete decomposition in this study.
The TG thermogram reveals that decomposition starts for 1%
L-lysine doped KHP at 289.7 C and steps at 300.4 C as shown in
Fig. 4.3. During this decomposition mass of the sample reduces

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S.R. Thilagavathy et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255
100.0
95
90
85
80
75
70
65
60
55

%T 50
45
40
35
30
25
20
15
10
5
0.0
4000.0

3600

3200

2800

2400

2000

1800

1600

1400

1000

1200

800

600

450.0

cm-1
Fig. 3.1. FTIR of pure KHP crystal.

100.0
95
90
85
80
75
70

3752
469
490
478

65
60
55

%T 50
45
40
35
30
25
20
15
10

1079

851

5
0.0
4000.0

789 719 650

769 693

888

3600

3200

2800

2400

2000

1800

1600

1400

1200

1000

552

582

800

600

450.0

cm-1
Fig. 3.2. FTIR of 0.5 mol% L-lysine doped KHP crystal.

by 43.4%. The decomposition is also accompanied by the melting of

the sample at 371.3 C as shown by DSC. The second stage of
decomposition is from 350.3 C to 373.6 C resulting in a mass
reduction of 3.8%. The third stage of decomposition is from
495.2 C to 541.7 C resulting in the mass reduction of 19.6%. The

residue at the end at 978.3 C is just 12.8%. This shows that the
sample is undergoing complete decomposition in this study.
The TG thermogram reveals that decomposition starts for 2%
L-lysine doped KHP at 296.8 C and steps at 326.1 C as shown
in Fig. 4.4. During this decomposition mass of the sample

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S.R. Thilagavathy et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255
100.0
95
90
481

85
80
75
70
65
60
55

%T

50
45
40

887

35

582

30
650

25

550

20
678

15

850
1948
1586

10

693

1441
1381

789 720

2483

810
764

5
0.0
4000.0

3600

3200

2800

2400

2000

1800

1600

1400

1200

1000

800

600

450.0

cm-1
Fig. 3.3. FTIR of 1 mol% L-lysine doped KHP crystal.

100.0
95
90
85
465
479

80
75

3865

70

3748

65
60
55

%T

50
45
40
35
568

30
25

546
584
555

20
15

779
2627

10

1838

1334

890
847
818

5
0.0
4000.0

3600

3200

2800

2400

2000

1800

1600

1400

1200

1000

800

650
712
694

600

450.0

cm-1
Fig. 3.4. FTIR of 2 mol% L-lysine doped KHP crystal.

reduces by 43.1%. The decomposition is also accompanied by the

melting of the sample at 312.6 C as shown by DSC. The second
stage of decomposition is from 505.9 C to 547.5 C resulting in
a mass reduction of 15.9%. The third stage of decomposition is

from 878.6 C to 892.5 C resulting in the mass reduction of

8%. The residue at the end at 978.4 C is just 12.7%. This shows
that the sample is undergoing complete decomposition in this
study.

S.R. Thilagavathy et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255

253

Table 2
Vibrational band assignments for pure and doped KHP crystals.
Pure KHP crystal

0.5 mol% L-lysine

1 mol% L-lysine

2 mol% L-lysine

Vibrational band assignment

469
494
581
692
770
887

469
490
582
693
789
888

3752

481
582
693
789
887
1948
2483

466
479
584
694
779
890
1838
2627
3748
3865

NH bending
NH3 torsional oscillations
COO wagging
Out of plane deformation of CH
NO2 wagging
OH out of plane bending
C@C Stretching
NH symmetric stretch
OH asymmetric stretch
OH asymmetric stretch

DSC-TGA

Fig. 4.1. TGA of pure KHP crystal.

DSC-TGA

\
-

120

2.5

110

299.00C

100
288.90C

2.0

46.11%
(0.4638mg)

1.5

Weight (%)

80
70
60
356.525.084
(0.05114m
%
C
496.73C
g)
305.56C
381.82 13.59%
(0.1367mg)
C
617.10C

50
40
30

538.32C

20
10
363.74
C

100

200

300

400

521.83
C

500

1.0

Residue:
13.42%
(0.1350mg)

17.09%
(0.1720mg)

Deriv. Weight (%/C)

90

0.5

673.90C
742.42C

600

700

800

Temperature (C)
Fig. 4.2. GA of 0.5 mol% L-lysine doped KHP crystal.

900

0.0
1000

Universal V4.1D TA Instruments

254

S.R. Thilagavathy et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255

Sample: Thilagavathy C Aug.5 2013

Size: 1.0380 mg

File: C:...\2013\Thilagavathy C Aug.5 2013

Operator: TA
Run Date: 2013-08-05 10:59
Instrument: SDT Q600 V8.0 Build 95

DSC-TGA

120
110
289.68C

100

43.39%
(0.4504mg)

Weight (%)

80
70
60

300.36C

350.28C 3.824%
(0.03970mg)

495.19C

50
373.61C

19.63%
(0.2037mg)

40

Deriv. Weight (%/C)

90

30
20

Residue:
829.84C 2.408%
(0.02499mg) 12.83%

541.72C

(0.1332mg)
529.36C

10

829.04C
824.46C

371.27C

100

200

300

400

500

600

700

800

900

0
1000

Universal V4.1D TA Instruments

Temperature (C)
Fig. 4.3. TGA of 1 mol% L-lysine doped KHP crystal.

Sample: Thilagavathy D July 30 13

Size: 3.8750 mg

File: C:...\Thilagavathy D July 30 13.001

Operator: TA
Run Date: 2013-07-30 11:07
Instrument: SDT Q600 V8.0 Build 95

DSC-TGA

2.0

120
110
296.77C

312.55C

90

1.5

Weight (%)

80
44.08%
(1.708mg)

70
60

1.0

505.90C

50

326.13C
15.91%
(0.6166mg)

40

547.45C

30

878.64C 8.031%
(0.3112mg)

532.37C

20

883.18C

0.5
Residue:
12.74%
(0.4936mg)

892.53C

10
0

Deriv. Weight (%/C)

100

100

200

300

400

500

600

700

800

Temperature (C)

900

0.0
1000

Universal V4.1D TA Instruments

Fig. 4.4. TGA of 2 mol% L-lysine doped KHP crystal.

Table 3
SHG efciency.
Input beam energy

3.9 mJ/pulse

Sample
Sample
Sample
Sample

4.4 mV
5.6 mV
5.6 mV
5.1 mV

A: Pure KHP
B: L-Lysine 0.5 mol%
C: L-Lysine 1 mol%
D: L-Lysine 2 mol%

SHG efciency
It is highly desirable to have some technique of screening crystal structures to determine whether they are non-centrosymmetric
and it is also equally important to know whether they are better

than those currently known. Kurtz and Perry [14] proposed a powder SHG method for comprehensive analysis of the second order
nonlinearity. The powder sample was packed in a triangular cell
and was kept in cell holder. The sample was irradiated with
1064 nm laser from Nd:YAG. The monochromator was set at
532 nm. NLO signal was captured by the oscilloscope through the
photomultiplier tube. The powdered material of Potassium Hydrogen Phthalate (KHP) was used in the same experiment as a reference material. Second harmonic generation efciency of 0.5, 1
and 2 mol% L-lysine doped crystals was found and tabulated.
Table 3 shows the SHG efciency of pure and doped KHP crystals.
From the table, it is clear that the doped crystals have different
SHG than pure KHP. And it is also found 0.5 and 1 mol% of L-lysine
doped crystals have higher SHG efciency than pure KHP. This
conrms 0.5 and 1 mol% of doping L-lysine gives good NLO effects.

S.R. Thilagavathy et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 127 (2014) 248255

Conclusion
Optically good quality crystals of L-lysine doped KHP have been
grown by slow evaporation method at room temperature. The lattice parameters have been found by single crystal X-ray diffraction
techniques. The FTIR spectrum reveals the various functional
groups present in the grown crystal. The optical transmittance
spectrum reveals that the transmittance of 0.5 mol% L-lysine doped
crystal is highly transparent. The decomposition behavior of the
crystal for pure and L-lysine doped KHP is conrmed by thermal
analysis study. The studies on the NLO property conrmed that
the SHG efciency of 0.5 mol% L-lysine doped crystal is better than
that of pure KHP crystal.
Acknowledgment
The authors are thankful to Mr. M. Vijayakumar, SRF Physics,
Centre for Soft Matter Research, Jalahalli, Bangalore for NLO studies. The authors are thankful to Dr. R. Ezhilvizhi, VIT University,

255

Vellore for the UV and FTIR studies. The authors are also thankful
to Dr. Jagan, IIT Chennai for XRD and molecular structure studies.
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