Author's Accepted Manuscript

Crystal growth, structural, optical and di-

electric studies of ammonium p-
toluenesulfonate
G. Peramaiyan, R. Mohan Kumar, G. Bhagavan-
narayana

www.elsevier.com/locate/jcrysgro

PII: S0022-0248(14)00628-9
DOI: http://dx.doi.org/10.1016/j.jcrysgro.2014.09.011
Reference: CRYS22421

To appear in: Journal of Crystal Growth

Received date: 24 May 2014

Revised date: 3 September 2014
Accepted date: 8 September 2014

Cite this article as: G. Peramaiyan, R. Mohan Kumar, G. Bhagavannarayana,

Crystal growth, structural, optical and dielectric studies of ammonium p-
toluenesulfonate, Journal of Crystal Growth, http://dx.doi.org/10.1016/j.jcrys-
gro.2014.09.011

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 Crystal growth, structural, optical and dielectric studies of Ammonium
p-toluenesulfonate

G. Peramaiyan*a, R. Mohan Kumarb, G. Bhagavannarayanac

a
Department of Physics, Vel Tech University, Avadi, Chennai-62, India
b
Department of Physics, Presidency College, Chennai-600 005, India
c
Materials Characterization Division, National Physical Laboratory, New Delhi -110 012,
India
Abstract

Ammonium p-toluenesulfonate single crystals (AMPTS) were grown by a slow

cooling solution growth technique. The unit cell parameters and morphology of AMPTS

crystal were found out by single crystal X-ray diffraction study. High-resolution X-ray

diffraction study revealed the crystalline perfection and the absence of structural grain

boundaries. UV-vis-NIR transmission studies revealed that the AMPTS crystal is transparent

in the entire visible region with a lower optical cut-off wavelength of 278 nm. From the

thermogravimetric and differential thermal analyses, the melting point of AMPTS crystal was

found to be 145°C. The single and multiple shots laser damage threshold of AMPTS crystal

were found to be 4.08 and 3.18 GW/cm2 respectively, for 1064 nm wavelength of Nd:YAG

laser radiation. The relative second harmonic generation efficiency of AMPTS was found to

be 0.7 times that of KDP. The three independent dielectric tensor components ε11 = 86.56-

44.32, ε22 = 83.80-41.44 and ε33 = 82.03-42.67 were calculated from the dielectric

measurement studies.

Keywords: A1.High resolution X-ray diffraction; A2.Growth from solutions; B1. Organic

compounds; B2.Nonlinear optical materials; B3.Nonlinear optical

Corresponding author*
Dr R. Mohan Kumar
Assistant Professor
Department of Physics
Presidency College, Chennai - 600005
INDIA, Phone: 9444600670
Email: mohan66@hotmail.com

1 
 
1. Introduction

In recent years, acentric organic crystals have been paid more attention for technological

applications. Nonlinear optical (NLO) materials play an important role in nonlinear optics,

photonics and in particular they have a great impact on laser science and information

technology [1,2]. The photonic materials possess all the desirable characteristics such as a

fast response and a large value of optical nonlinearity simultaneously, materials are chosen

with regard to the specific need for applications. For instance in cases such as ultrafast optical

switching or limiting, materials with ultrafast response are chosen even though they may not

possess large nonlinear optical coefficient. The new development technique for the

fabrication and single crystal growth of nonlinear optical materials has dramatically

contributed to this evolution. In the event of large flexibility for molecular design and higher

second and third harmonic generation efficiencies, there has been much progress in basic

research on the frameworks of organic and semi-organic NLO materials. Organic nonlinear

optical materials may be far superior to their inorganic counterparts, owing to their relatively

high and faster nonlinearities [3,4]. The structure of ammonium p-toluenesulfonate with

noncentrosymmetric space group Pna21 has been reported recently [5]. The counter anion

plays an important role in the formation of acentric crystal structure in ionic organic crystals.

It has been reported that the large nonlinearity in well known 4-N, N- dimethylamino-4’-N’-

methylstilbazolium tosylate (DAST) crystals was interpreted as resulting from the tetrahedral

sulfonate group of p-toluenesulfonate moiety [6]. In the present investigation, the crystal

growth, structural, thermal, optical, mechanical and dielectric properties of ammonium p-

toluenesulfonate have been reported for the first time.

2 
 
2. Experiment

2.1 Synthesis, solubility study and crystal growth

The title material was synthesized by taking ammonia (Merck, 99 %) and

p-toluenesulfonic acid monohydrate (SRL, 99.5%) in an equimolar ratio. Ammonia was

added gradually in the saturated solution of p-toluenesulfonic acid monohydrate with

continuous stirring for half an hour and white precipitate was obtained. Then, the precipitate

was dissolved using water. The scheme of synthesis of the investigated compound is shown

in Fig.1.

Ammonia is a weak base that gains a proton in acidic solution and forms the salt of

the respective acid. During the proton transfer reaction, a proton is transferred from the

electron donor group of p-toluenesulfonic acid to the electron acceptor group of ammonia.

From the molecular structure of ammonium p-toluenesulfonate, it is inferred that the main

fragment of the crystal to provide enhanced second harmonic generation efficiency may be

due to the relatively delocalized electronic cloud of the sulfonate group of p-toluenesulfonate

moiety.

Selection of suitable solvent and solubility equilibrium are crucial for the growth of

bulk and optically good quality single crystals. The solubility of ammonium

p-toluenesulfonate was assessed using water solvent at different temperatures ranging from

30 to 45°C. The amount of AMPTS required to make the saturated solution at different

temperatures was estimated gravimetrically and the obtained solubility curve of AMPTS is

shown in Fig.2. From the solubility study, it is found that the title compound exhibits positive

solubility gradient in water solvent.

3 
 
 The growth solution of AMPTS was prepared at the temperature of 45°C in

accordance with the solubility data. The pH value of growth solution was measured and

maintained at 3.2. Then, the solution was kept in a constant temperature water bath with the

temperature accuracy of ±0.01°C. The solution was maintained at constant temperature

(45°C) and an excess amount of solvent may be evaporated for three days to get good quality

seed crystal. The seed crystal was carefully introduced into the solution and the temperature

was decreased by 0.1 °C per day as the growth progressed. After a span of 25 days, bulk

crystal of AMPTS with dimension 15 x 14 x 4 mm3 was harvested as shown in Fig.3.

3. Results and discussion

The unit cell parameters and morphology of AMPTS crystal were found from the

single crystal X-ray diffraction analysis using a Bruker kappa APEXII single crystal X-ray

diffractometer with MoKα (λ = 0.71073 Å) radiation. The calculated cell parameters are

a = 20.411 Å, b = 7.066 Å, c = 6.272Å, volume (V) = 904.6 Å3 and Z = 4. The grown crystal

belongs to orthorhombic crystal system with noncentrosymmetric space group Pna21 and

these values are in good agreement with the reported data [5]. The crystallographic planes

(001), (00-1), (011), (0-1-1), (01-1), (0-11), (10-2), (-10-2), (110), (1-10), (-110) and (-1-10)

were clearly identified. The cleavage plane of AMPTS crystal was found along (001) plane as

shown in Fig.4(a)&(b).

The crystalline perfection of the grown single crystals was characterized by HRXRD

by employing a multicrystal X-ray diffractometer. Figure 5 shows the high resolution X-ray

diffraction curve using MoKα1 radiation for a typical AMPTS single crystal specimen.

On close observation, one can realize that the curve is not a single peak. On deconvolution of

the diffraction curve, it is clear that the curve contains an additional peak which is 62 arc s

4 
 
away from the main peak. The additional peak corresponds to an internal structural low angle

boundary. For a better understanding, the schematic of a structural grain boundary is given in

the inset of Fig.5. As seen in the inset two regions of the crystal are misoriented by a finite

angle α also known as tilt angle. Tilt angle may be defined as the misorientation angle

between the two crystalline regions on both sides of the structural grain boundary. The two

regions may be perfect. If the value of α is ≤ 1 arc min, we may call it as very low angle

boundary. If α > 1 arc min but less than a deg, we call it as low angle boundary [7, 8].

The angular separation between the two peaks gives the tilt angle α which is 62 arc sec for

the specimen crystal. The FWHM of the main peak and the low angle boundary are

respectively 9 and 120 arc sec. These low values of FWHM and the low angular spread

(~ 300 arc s) of the DC indicate that the crystalline perfection is reasonably good.

However, the broad (120 arc s FWHM) and very low intensity peak of the low angle

boundary indicate that some region of the crystal is not perfect and contains mosaic blocks

which are misoriented each other by a few arc s. This type of structural defects is probably

generated in the crystals due to mechanical/thermal fluctuations occurred during the growth

process and/or also due to fast growth [9]. It may be mentioned here that such minute defects

could be detected with well resolved peaks in the diffraction curve only because of the high-

resolution of the diffractometer, characterized by very low values of wavelength spread i.e.

Δλ/λ and horizontal divergence for the exploring or incident beam, which are respectively

around 10-5 and much less than 3 arc s of the multicrystal X-ray diffractometer used in the

present studies. These defects may not influence much on the physical properties. However, a

quantitative analysis of such unavoidable defects is of great importance, particularly in case

of phase matching applications of nonlinear optical crystals [10].

The thermal behaviour of AMPTS was studied by thermogravimetric (TG) and

differential thermal analyses (DTA). The AMPTS sample weighing 2.50 mg was analysed

5 
 
and the thermogram is depicted in Fig.6. The DT curve indicates the same changes as shown

in TG curve. From the TG curve, it is evident that the material is stable up to 295 °C and

moisture free. The TG curve shows three stage weight loss pattern when the material was

heated from 29 to 450 °C. The first weight loss was occurred between 300 and 340 °C with

the elimination of 2.5 % of the material into gaseous products as seen in the low temperature

region. The second stage weight loss noticed between 325 and 351°C experiences a weight

loss of about 6.2 %. The third stage decomposition occurred between 353 and 385 °C incurs a

weight loss of about 78 %. An endotherm appeared at 145 °C is assigned to the melting point

of AMPTS crystal. The endotherms appeared at 327, 348 and 365 °C are matched with the

successive weight loss in TG curve. Thus, the AMPTS crystal could be exploited for any

applications below 145 °C.

The UV-vis-NIR spectral study was carried out using T90+ spectrophotometer.

A good quality crystal of AMPTS with 1 mm thickness was used for this study. The AMPTS

crystal has sufficient transmittance in the UV, visible and NIR regions. It has good

transparency about 85% with a lower cut-off wavelength of 278 nm as shown in Fig.7.

The optical absorption is due to the direct transition of an electron from a non-bonding ‘n’

orbital to an anti-bonding ‘π’ orbital designated as π* (n → π*). The absence of absorption in

the region between 300 and 900 nm showed that the AMPTS crystal could be exploited for

nonlinear optical applications. The absorption coefficient (α) was determined from the

transmission (T) spectrum based on the following relation,

2.3026
α= log (1/ T ) …….. (1)
t

where T is the transmittance and ‘t’ is the thickness of the crystal.

The optical band gap was estimated from the following relation [11]:

6 
 
 (αhν)2 = A(E g − hν) …….. (2)

where Eg is the optical band gap of the crystal and A is a constant. The variation of (αhν)2

with hν [12] in the fundamental absorption region was plotted (Fig.8). The band gap of the

crystal estimated by extrapolation of the linear part of the graph is 4.44 eV.

The fundamental wavelength of 1064 nm Gaussian beam with pulse width of 10 ns

and a repetition rate of 10 Hz was used to measure the laser damage threshold of AMPTS

crystal. The laser beam of diameter 4 mm was focused on the crystal sample.

The sample was placed at the focus of a plano-convex lens of focal length 20 cm. The pulse

energy of each shot was measured using the combination of a phototube and an oscilloscope.

The measured single and multiple shot (10 pulses) laser damage threshold values were found

to be 4.08 and 3.18 GW/cm2 respectively, for 1064 nm wavelength of Nd:YAG laser

radiation.

The nonlinear optical property was studied by employing Kurtz and Perry powder

technique [13]. The fundamental beam of 1064 nm from Q-switched Nd:YAG laser was used

to measure the SHG efficiency of AMPTS. The AMPTS crystal was ground and sieved into

different particle size ranges <55, 55-125, 125-250, 250-400 and >400 μm. Sieved KDP

crystal sample with particle size >400 μm was used as reference. The pulse energy

of 5.65 mJ/pulse with pulse width 8 ns and repetition rate 10 Hz was used. The SHG signal

voltage increases almost linearly with increase in particle size up to 125-250 μm. The SHG

output voltage deviates from the linearity above 250 μm, and starts to attain saturation.

The SHG signal voltage for KDP was measured to be 6.4 mV. Figure 9 indicates that the

AMPTS crystal belongs to type-1 phase-matching category [14]. Hence, the relative output

SHG signal voltage of AMPTS was found to be 0.7 times that of KDP.

7 
 
 The dielectric permittivity of AMPTS crystal was measured using a HIOKI 3532–50

LCR HITESTER instrument. The dielectric study was carried out for various frequencies

ranging from 100 kHz - 5 MHz at 40°C. The dielectric permittivity of an anisotropic

crystalline material is a second rank tensor [εij] with a maximum number of six independent

coordinates. For an orthorhombic crystal system, there are three independent components:

ε11, ε22 and ε33 corresponding to a, b and c-directions respectively. The AMPTS crystal was

cut along the <100>, <010> and <001> directions with a thickness of 1.5 mm as shown in

Fig.10 as inset. The prepared crystal samples were coated on either sides by silver paste to

make them act as parallel plate capacitor. The dielectric permittivity of AMPTS single crystal

was determined as a function of frequency at 40°C along a-, b- and c-directions. The

variation of the dielectric permittivity with various frequency is shown in Fig.10. From the

Fig.10, it was observed that dielectric permittivity decreases as the frequency increases and

attain constant values at higher frequencies. The low value of dielectric permittivity at higher

frequencies may be attributed to the four polarizations such as electronic, ionic, dipolar and

space charge polarizations [15]. The estimated ε11, ε22 and ε33 values are in the ranges 44.32-

86.56, 41.44-83.80 and 42.67-82.03 respectively. Anisotropy in the dielectric behavior was

observed in the AMPTS crystal [16]. From the dielectric study, it is concluded that the

AMPTS crystal exhibits normal dielectric behaviour.

4. Conclusion

Good quality crystals of ammonium p-toluenesulfonate were grown by the slow

cooling solution growth technique. The unit cell parameters and crystallographic planes were

found out by single crystal X-ray diffraction studies. High-resolution X-ray diffraction study

revealed the crystalline perfection and absence of structural grain boundaries.

UV-vis-NIR transmission studies revealed that the AMPTS crystal is transparent in the entire

8 
 
visible region. From the TG-DT analyses, the melting point of AMPTS crystal was found to

be 145°C. The single and multiple shots laser damage threshold of AMPTS crystal were

found to be 4.08 and 3.18 GW/cm2 respectively. The relative second harmonic generation

efficiency of AMPTS was found to be 0.7 times that of KDP. The three independent

dielectric tensor components were also estimated.

9 
 
References

1. D. S. Chemla, J. Zyss, In Quantum Electronics Principles and Applications Series,

Eds. Academic Press, Orlando, FL. (1985).

2. J. Zyss, F.Nicoud, Curr. Opin. Solid State Mater. Sci. 1 (1996) 533-546.

3. L. Dalton, Nonlinear optical polymeric materials: from chromophore design to

commercial applications. Adv. Polym. Sci. 158 (2002) 1-86.

4. G.R. Meredith, Nonlinear optical properties of organic and polymeric methods (Ed:
D.J. Williams), ACS Symposium Series 223, American Chemical Society,
Washington, DC 1983, 27-56.

5. R. D. Rogers, A. H. Bond, R. F. Henry, Structure of ammonium p-toluenesulfonate

Acta Cryst. C47 (1991) 168-170.

6. B.J. Coe, J.A. Harris, A.K. Clays, G. Olbrechts, A. Persoons, J.T. Hupp, Quadratic
nonlinear optical properties of N-aryl stilbazolium dyes. Adv. Funct. Mater. 12 (2002)
110-6.

7. G. Bhagavannarayana, R.V. Ananthamurthy, G.C. Budakoti, B. Kumar, K.S. Bartwal,

J. Appl. Cryst. 38 (2005) 768-771.

8. G. Bhagavannarayana, S.K. Kushwaha, J Appl. Cryst. 43 (2010) 154-162.

9. G. Bhagavannarayana, P. Rajesh, P. Ramasamy, J. Appl. Cryst. 43 (2010) 1372–1376.

10. G. Bhagavannarayana, B. Riscob, Mohd. Shakir, Mater. Chem. Phys. 126 (2011) 20–
23.

11. A. Ashour, N. El-Kadry, S.A. Mahmoud, Thin Solid films, 269 (1995) 117-120.

10 
 
 12. J. Tauc, R. Grigorovici, A.Vancu, Phys. Status Solidi B, 15 (1966) 627-637.

13. S.K. Kurtz, T.T. Perry, J. Appl. Phys. 39 (1968) 3798-3813.

14. K. M. Ok, E. O. Chi, P. S. Halasyamani, Chem. Soc. Rev. 35 (2006) 710–717.

15. B. M. Sornamurthy, G. Peramaiyan, P. Pandi, S. Das, G. Bhagavannarayana,

V. Manivannan, R. Mohan Kumar, J. Cryst. Growth 397 (2014) 1–5.

16. M. Dhavamurthy, G. Peramaiyan, R. Mohan, J. Cryst. Growth 399 (2014) 13–18.

Figure captions

Fig.1 Reaction scheme for AMPTS compound

Fig.2 Solubility curve of AMPTS in water solvent

Fig.3 Photograph of as-grown AMPTS crystals

Fig.4(a)Morphology and (b) cleavage plane of AMPTS crystal

Fig.5 HRXRD curve of AMPTS crystal

Fig.6 TG-DT curves of AMPTS

Fig.7 UV-vis-NIR transmission spectrum of AMPTS crystal 

Fig.8 Plot of (αhν)2 vs. photon energy of AMPTS crystal

Fig.9 Second-harmonic intensity for AMPTS powder as a function of particle size indicating
the phase matchability
Fig.10 Dielectric tensor vs. log frequency of AMPTS crystal

11 
 
 O O

NH4+ . O
-
NH3 + H3C S OH S CH3

O O

Fig.1 Reaction scheme for AMPTS compound

12 
 
 40
Concentration (g/100 ml)

35

30

25

20

15

10
30 35 40 45 50

Temperature (°C)

Fig.2 Solubility curve of AMPTS in water solvent

13 
 
 Fig.3 Photograph of as-grown AMPTS crystals

14 
 
 Fig.4 (a) Morphology and (b) cleavage plane of AMPTS crystal

15 
 
 AMPTS 62"
2000
MoKα1
Diffracted X-ray intensity [c/s]

(+,−,−,+)
1500

1000
9"
120"
500

0
-200 -100 0 100 200
Glancing angle [arc s]

Fig.5 HRXRD curve of AMPTS crystal

16 
 
 DT curve
TG curve 100
Microvolts Endo Down (µV)

40

80

% Weight
20 60

40

0
20

0 100 200 300 400 500

Temperature (°C)
 

Fig.6 TG-DT curves of AMPTS

17 
 
 100

90

80

70
% Transmittance

60

50

40

30

20

10

200 300 400 500 600 700 800 900

Wavelength (nm)

Fig.7 UV-vis-NIR transmission spectrum of AMPTS crystal

18 
 
 9
4x10

9
3x10
-1 2
(αhυ) (eV m )

9
2x10
2

9
1x10

1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

Photon energy (eV)

Fig.8 Plot of (αhν)2 vs. photon energy of AMPTS crystal

19 
 
 4.5

4.0
SHG Output (mV)

3.5

3.0

2.5

2.0
<55 55-125 125-250 250-400 >400

Particle size (μm)

 

Fig.9 Second-harmonic intensity for AMPTS powder as a function of particle size

indicating the phase matchability

20 
 
 Fig.10 Dielectric tensor vs. log frequency of AMPTS crystal

21 
 
 Research Highlights

¾ Bulk crystal of AMPTS is grown by slow evaporation technique

¾ Crystalline Perfection of AMPTS is studied

¾ Laser damage threshold is found to be 4.08 GW/cm2

¾ Dielectric tensor coefficients ε11, ε22 and ε33 have been calculated

¾ SHG efficiency of AMPTS is measured

22