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Optik 126 (2015) 95–100

Contents lists available at ScienceDirect

Optik

jo ur nal homepage: www.elsev ier .de / i j leo

ynthesis, growth and characterization of nitramino sulphonic acidNASA) NLO single crystals

amson Yesuvadiana,b, Anbarasu Selvarajb, Martina Mejeba Xavier Methodiusb,hagavannarayana Godavarti c, Vijayan Narayanasamyc, Prem Anand Devarajanb,∗

Department of Physics, Annai Velankanni College, Tholayavattam 629157, Tamilnadu, IndiaPhysics Research Centre, Department of Physics, St. Xavier’s College (Autonomous), Palayamkottai 627002, Tamilnadu, IndiaCrystal Growth & X-ray Analysis Activity, CSIR-National Physical Laboratory, New Delhi 110012, India

r t i c l e i n f o

rticle history:eceived 18 December 2013ccepted 2 August 2014

eywords:rystal

a b s t r a c t

New laser NLO (nonlinear optical) inorganic material nitramino sulphonic acid (NASA) [H2N2SO5] wassynthesized and confirmed by NMR and XRD spectral analysis. NASA crystal was grown from aqueoussolution by slow solvent evaporation technique at room temperature. Single crystal XRD revealed thatNASA crystallizes in noncentrosymmetric space group Pba2. The structural purity was confirmed by pow-der XRD. The crystalline perfection of the grown crystal was analyzed by High resolution XRD. The optical

ASATIRigh resolution XRDielectric

transmittance and band gap energies of the crystal were studied by UV–vis–NIR spectral analysis. Polar-izability factors attributing to dielectric properties were analyzed by dielectric studies. Second harmonicgeneration efficiency was also studied by Kurtz–Perry powder technique. Explosive sensitive destablenitramino bond was converted to optically energetic by stabilizing N NO2 bond within sulphonic acidhost molecules.

© 2014 Elsevier GmbH. All rights reserved.

. Introduction

Nonlinear optical crystals play an important role in variousdvanced scientific and technical areas [1] such as resonance ion-zation spectroscopy [2], plasma production [3], photoacousticpectroscopy [4], launching artificial earth satellite [5], remoteensing [6], biology [7], industries [8], high density optical diskystem [9] etc., due to their higher NLO coefficient. Harmonicallyenerated laser’s characteristic properties like directionality, inten-ity, monochromacity and coherence are specified by the opticalature of NLO medium (crystals). The NLO medium is created byood optical active crystalline materials of organic, inorganic andemiorganic molecules. These crystalline materials are designedy growing them by various growth techniques. Optical transpar-nt organic [10], inorganic [11–12] and semiorganic [13] crystalsere reported as good NLO materials. Inorganic NLO crystals are

xplored better than organic crystals for good thermal and mechan-

cal stability and desirable growth nature [14]. They can producearger SHG coefficient, wide transparent region and moderate bire-ringence and they are incorporated into various laser systems for

∗ Corresponding author. Tel.: +91 9994292586.E-mail address: devarajanpremanand@gmail.com (P.A. Devarajan).

ttp://dx.doi.org/10.1016/j.ijleo.2014.08.138030-4026/© 2014 Elsevier GmbH. All rights reserved.

harmonic generation and optoelectrical switching [15,16]. Besidephosphate and borate classes, amino based inorganic crystals hav-ing good SHG efficiency also were grown [17–19]. Amino acidcombined with nitro functionality crystallizes in noncentrosym-metric space group and can produce piezoelectric effect and SHG[20,21], such that these two molecular moieties are interesting forNLO applications. Energetically active nitramino substituted com-pounds are intense fascination of scientists and technologists dueto their potential importance to prepare sensitive/insensitive mate-rials in Defense laboratories [22,23]. The energetic performance ismore in nitramino compounds in regard to intermolecular forceinteractions, oxygen balance, density and other thermodynamicproperties. Such nitramino derivatives of aromatic compounds[22,24] were synthesized and characterized. Recently the dissoci-ation energy of N NO2 bond of 49.4 kcal mol−1, functioning theenergetic behaviors in nitramino substituted compound was cal-culated by Politzen et al. [25] through B3/PW91 DFT calculations.Protonation of amino compounds with concentrated HNO3 yieldsnitramino molecules [24]. Sulphonic acid substituted materials arehighly sensitive in metal ion detecting [26]. The kinetics in reac-

tion of sulphamic acid with nitrous acid [27] and nitric acid [28]was studied. With this reference we aim to make nitramino asexplosively insensitive as well as optically energetic by stabilizingit within sulphonic acid host molecules.

96 S. Yesuvadian et al. / Optik 126 (2015) 95–100

NH2

SO O

OH

Amino su lpho nic ac id

N+

OH

O

-O

Nitric acid

NH

N+

O

-OS

O

O

OH

Nitramino sulph onic ac id

-H2O

2

2

af

2

awwttws

2

cwstoatwttwtwswsNepF

2

pditocdt

504540353020

30

40

50

60

70

Sol

ubili

ty (g

/10m

L)

Temperature (oC)

Fig. 2. Solubility curve of NASA.

DC is asymmetric with respect to the Bragg peak position. For a par-

Fig. 1. Reaction scheme of NASA.

. Experimental techniques

.1. Chemicals

Sulphamic acid (Amino sulphonic acid) (99% pure AR grade)nd concentrated nitric acid (99.5% pure AR grade) were purchasedrom E-merck Co. Ltd.

.2. Synthesis of NASA

NASA was synthesized using the typical synthetic methodpproached by Martin et al. [29]. Sulphamic acid and nitric acidas taken in equimolar ratio. Nitric acid was added drop by dropith sulphamic acid. The resultant mixture was heated up to 79 ◦C

emperature and agitated using a magnetic stirrer for an hour andhen cooled to ambient temperature. White colored precipitatesere obtained at the bottom of the beaker. Fig. 1 shows the reaction

cheme for preparing NASA crystalline salt.

.3. Solubility study

The synthesized salt was used to measure the solubility of NASArystal in water. A 250 ml borosil glass beaker filled with 100 mlater was placed inside a constant temperature bath. An acrylic

heet with a circular hole at the middle was placed over the beakerhrough which a spindle from an electric motor, placed on the topf the sheet was introduced into the solution. A Teflon paddle wasttached at the end of the rod for stirring the solution. The syn-hesized salt was added in small amounts with water and stirringas continued till the formation of precipitate, which confirmed

he supersaturation of the solution. A 20 ml of the saturated solu-ion was withdrawn by means of a warmed pipette and the sameas poured into a clean, dry and weighed Petri dish. The solu-

ion was kept in a heating mantle for slow evaporation till thehole of the solution got evaporated and the mass of the NASA

alt in 20 ml of solution was determined by weighing the Petri dishith salt and hence the solubility, i.e. quantity of salt in grams dis-

olved in 100 ml of the solvent was determined. The solubility ofASA in doubly deionized water was determined for five differ-nt temperatures (30, 35, 40, 45 and 50 ◦C) by adopting the samerocedure. The resulting solubility curve of pure NASA is shown inig. 2.

.4. Crystal growth technique

The saturated solution of NASA in aqueous medium was pre-ared by dissolving the purified crystalline salt of NASA in doublyeionized water at 30 ◦C. The saturated solution of 200 ml was taken

n a 250 ml borosil beaker and properly sealed and then placed inhe constant temperature water bath. The solvent was slowly evap-rated. Nucleation was started after a week. Good quality single

rystals were harvested in a period of 30 days. The NASA crystal ofimension (26 × 20 × 10 mm3) grown by slow solvent evaporationechnique is shown in Fig. 3.

Fig. 3. Photograph of As grown NASA Crystal.

3. Result and discussion

3.1. Single crystal X-ray diffraction

In order to determine the cell parameters and space group,the single crystals of NASA were subjected to single crystal X-raydiffractometer (Model: Brucker-Nonius K appa Apex II CCD) with

Mo radiation of wavelength � = 0.71073 ´A. Lattice parameters ofNASA was found that a = 8.0617 A, b = 8.1116 A, c = 9.2310 A, = 90◦,

= 90◦, � = 90◦ and V = 603.6454 A3. From the X-ray diffraction data,it is observed that NASA belongs to orthorhombic crystal systemwith space group Pba2 which is noncentro-symmetric, thus satis-fying one of the basic and essential material requirements for SHGactivity of the crystal.

3.2. HRXRD

Fig. 4 shows the high-resolution diffraction curve (DC) recordedfor a typical NASA single crystal specimen using (0 1 2) diffrac-ting planes in symmetrical Bragg geometry with Mo K�1 radiation.As seen in the figure, the DC contains a single peak and indicatesthat the specimen is free from structural grain boundaries. The fullwidth at half maximum (FWHM) of this curve is 10 arc s which isquite close to that expected from the plane wave theory of dynam-ical X-ray diffraction [30] and reveals the presence of point defectsand their aggregates. It is interesting to see the shape of the DC. The

ticular angular deviation (��) of glancing angle (�) with respect tothe Bragg peak position (taken as zero for the sake of convenience),the scattered intensity is much more in the positive direction in

S. Yesuvadian et al. / Optik 126 (2015) 95–100 97

Fig. 4. DC recorded for NASA single crystal using (0 1 2) diffracting planes. Inserts

ciobdd(BooiaeslttwLltitggwdiadsg

3

Xtrptt(s[

8070605040302010

0

200

400

600

800

1000

1200

1400

Inte

nsity

(cps

)

Angle 2θ (de gree )

tion.

5001000150020002500300035004000

0

20

40

60

80

100

Tran

smitt

ance

(%)

hows the schematic of an interstitial defect.

omparison to that of the negative direction. This feature clearlyndicates that the crystal contains predominantly interstitial typef defects than that of vacancy defects. This can be well understoody the fact that due to interstitial defects, the lattice around theseefects undergo compressive stress [31] and the lattice parameter

(interplanar spacing) decreases and leads to give more scatteredalso known as diffuse X-ray scattering) intensity at slightly higherragg angles (�B) as d and sin �B are inversely proportional to eachther in the Bragg equation (2 d sin �B = n�; n and � being the orderf reflection and wavelength, respectively, which are fixed). Thenset in the curve shows the schematic to illustrate how the latticeround the defect core undergoes compressive stress. The conversexplanation is true in case of vacancy defects which cause tensiletress in the lattice around the defect core leading to increase ofattice spacing and in turn results in more scattered intensity athe lower Bragg angles. It may be mentioned here that the varia-ion in lattice parameter is confined very close to the defect corehich gives only the scattered intensity close to the Bragg peak.

ong range order could not be expected and hence change in theattice parameter is also not expected [32]. It may be worth to men-ion here that the defects are more or less statistically distributedn the crystal. If the defects are not statistically distributed but dis-ributed here and there as macroscopic clusters, then the strainenerated by such clusters is larger leading to cracks and structuralrain boundaries which can be seen very clearly in HRXRD curvesith additional peak(s) as observed in our recent study on urea-oped crystals in ZTS at various levels of doping [33]. However,

n the present experiments the diffraction curve does not containny additional peak and indicates the absence of clustering of pointefects at macroscopic level. The single diffraction peak with rea-onably low FWHM indicates that the crystalline perfection is quiteood.

.3. PXRPD

The powder sample of NASA crystal was subjected to powder-ray diffraction studies with Riech Single X-ray diffractome-

er using Cu K� radiation of wavelength � = 1.5418 A over theange of 10–80◦ with a scan speed of 0.2◦/s. The powder XRDattern is shown in Fig. 5 and it assures the structural perfec-ion and purity of as grown NASA single crystal. By applyinghe lattice parameter values obtained from single crystal XRD,hkl) values were simulated and the (hkl) index of the corre-

ponding reflecting planes were enumerated by manual indexing34].

Fig. 5. Powder XRD pattern of NASA single crystal.

3.4. FTIR analysis

The FTIR spectrum was recorded in the range 400–4000 cm−1

employing Brukker model IFS 66 V FTIR spectrometer by KBrpellet technique. The recorded FTIR spectrum of NASA singlecrystal is shown in Fig. 6. The stretching vibrations of hydro-gen bonds present in sulfonic host molecules are observed in theregions centered 3400 cm−1 for SO2 N H stretching and cen-tered 900 for SO2 O H stretching vibrations [35]. The strongpeaks at 3142 cm−1 and 1002 cm−1 are due to the stretchingvibrations due to N H and O H hydrogen bonds. The observedpeak at 2873 cm−1 is attributed to N H. . .O vibration. The broadenvelop of peaks belonging to the range 1350–1250 cm−1 cor-responds to the degeneracy of SO3

− stretching [19]. The peakpositioned at 1265 cm−1 proved degeneracy of SO3

− stretching.Symmetric stretching mode of SO3 is observed at 1068 cm−1. TheN S stretching coupled with SO3 rocking is found at the peak at689 cm−1. The peaks at 1450 cm−1 and 530 cm−1 are attributed tothe deformation of NH3

+ and SO3−, respectively. The NH3

+ rockingmode vibration is observed at 1068 cm−1. Aliphatic nitro com-pounds transmit the energy in the region 1600 to 1530 cm−1 byasymmetric stretching and in 1390 to 1300 by symmetric stretch-ing. The peaks at 1572, 1541 and 1315 cm−1 confirm the nitrostretching. In general, symmetric and asymmetric stretching modevibrations of S O in sulfonamide and sulfonic acid (anhydrous)compounds are observed in the regions 1350-1325 cm−1 and1150–1140 cm−1, respectively [36]. The peaks observed at 1315and 1265 cm−1 assure the S O stretching. The peaks at 1572 cm−1

and 1541 cm−1 are corresponding to N H bending mode vibra-

wavenumber (cm )

Fig. 6. FTIR spectrum of NASA single crystal.

98 S. Yesuvadian et al. / Optik 126 (2015) 95–100

3

c4sgrdTNihii

3

cmi2

Ftf

23

45

6

0

2

4

6

8

10

70oC 60oC 50oC

o

Die

lect

ricC

onst

ant (ε r)

log f

Fig. 7. Proton NMR spectrum of NASA single crystal.

.5. Proton NMR

Proton NMR spectral analysis of NASA crystalline molecule wasarried out in the deutrated chloroforms (CDCl3) solvent using00 MHz Brucker AC 200-NMR spectrometer. The proton NMRpectrum is shown in Fig. 7. The proton attached to amide nitro-en in aliphatic compounds normally resonates the signals in theange between ı 3.0 and 0.5 ppm [37]. The proton shift values areepend upon the solvent, concentration and temperature factors.he resonance at 0.1 ppm is corresponding to the aliphatic amine

H proton. The absorption range for aliphatic sulfhydryl protons ı 1.6 to ı 1.2 ppm. The signal at 1.559 is due to the proton in theydroxyl attached with the suphonic molecule. The peak at 7.262

s attributed to the solvent CDCl3. Thus the positions of hydrogen’sn NASA were identified.

.6. UV–vis–NIR analysis

UV–vis–NIR spectral study is an useful tool to measure the opti-al transparency which is a most importantfor laser generative

aterial. Optical transmittance spectrum was recorded using Var-

an Cary 5E-UV–vis–NIR spectrometer in the wavelength region of00–800 nm. Fig. 8(b) shows the plot of transmittance against the

ig. 8. (A) UV–vis–NIR absrption spectrum of NASA single crystal (B) UV–vis–NIRransmittance spectrum of NASA (C) Tauc’s plot for direct band gap (D) Tauc’s plotor indirect band gap.

40 C

Fig. 9. Dielectric constant of NASA single crystal.

wavelength. The transmittance in the entire visible region is about90%. The lower cut-off wavelength of NASA crystal is at 290 nm. Theoptical absorption coefficient (˛) was calculated from the transmit-tance using the relation

=(

2.3036d

)log

(1T

)(1)

where d is the thickness of the crystal and T is the transmittance.The optical band gap Eg is calculated from the Tauc’s expression,

(˛h�)n = A(

h� − Eg

)(2)

where is the absorption coefficient, A is disorder parameter. Eg iscalculated from the plot (˛h�)n versus h�. For the direct band gapenergy n = 2 and for the indirect bandgap energy n = (1/2). Fig. 8(Cand D) shows the plot for direct transition and indirect transi-tion, respectively. From the graph it was observed that the directband gap energy Eg(direct) = 6.10 eV and indirect band gap energyEg(indirect) = 5.87 eV. This enhances the NASA crystal for laser gen-eartion and other NLO applications. As can be seen from the bandgap energy values, direct band gap energy is higher than indirect.

3.7. Dielectric measurement

The dielectric behaviors correlated with electro-optic propertiesin the crystal reveals the information about the electric field distri-bution and charge transport mechanism [38]. The dielctric studiesof the NASA crystal was carried out using HIOKI 3532 LCR HITESTERinstrument in the frequency region of 50 Hz to 5 MHz at varioustemperatures of 40,50, 60 and 70 ◦C. The cut and smoothly pol-ished crystal piece of thickness 1 mm was covered by silver pasteand then mounted between two electrodes. The capacittance of theparallel plate capaccitor with the sample as the dielectric mediumwas measured at the temperature region varrying from 40 to 70 ◦Cin steps of 10 ◦C. The dielectric constant (εr) was calculated usingthe relation

εr = Cd

εoA(3)

where C is the capacittance, d is the thickness of the crystal, εo isthe permitivity of the free space and A is the area of the crystal

surface. The dielectric loss was also calculated. Figs. 9 and 10 showthe variation of the dielectric constant and dielectric loss, respec-tively, with respect to the frequency at various temperaatures.From the graph it is found that dielectric constant and dielectric

S. Yesuvadian et al. / Optik

23

45

6

0

2

4

6

8

10

70oC 60oC 50oC 40oC

Die

lect

riclo

ss(D

)

log f

leptoadttm‘a

3

hms0wTKl

4

sgpaiNtgdam

[

[

[

[

[

[

[

[

[

[

[

[

[

[23] R.P. Singh, H. Gao, T.D. Meshri, J.M. Shreeve, in: D.M.P. Mingos (Ed.), High EnergyDensity Materials, Springer, Heidelberg, 2007.

Fig. 10. Dielectric loss of NASA single crystal.

oss decrease with increasing frequency. The four important ionic,lectronic, dipolar and space charge polarizations contributes theeculiar dielectric behaviors to the crystal. Due to the charged lat-ice defects, space charge polarization attributes the larger valuesf dielectric conastant at lower frequency. The dielectric constantttaines saturation at higher frequencies. At 40 ◦C temperature, theielectric constant is high at low frequency. Te value of dielec-ric constant decreases when temperature increases. This is dueo the temperature dependent dipolar polarization which change

olecule’s orientation in crystal lattice since the dipoles may befrozen in’ at low temperatures [39]. This behavior enhances NASAs the potential candidate for photonic, laser and other NLO devices.

.8. SHG measurement

The primary widely used technique for confirming the secondarmonic generation (SHG) from prospective second order NLOaterial is the Kurtz–Perry powder technique High intensity Q-

witched Nd:YAG laser (� = 1064 nm) with input laser energy of.68 J was used to illuminate the NASA crystalline powder. The SHGas confirmed by the NASA emitting the green radiation (532 nm).

he output SHG efficiency of NASA is nerely 1.6 times of standarddDP crystal. Thus NASA is confirmed as a suitable NLO medium for

aser generation.

. Conclusion

Single crystal of NASA was purely synthesized and grown bylow solvent evaporation method. The lattice parameter and spaceroup of NASA was identified by single crystal XRD analysis. Crystalurity was studied by Powder XRD. The crystalline perfection wasnalysed by HRXRD. Molecular functional groups in NASA weredentified by FTIR spectral analysis. The position of hydrogen inASA was confirmed by proton NMR technique. UV–vis–NIR spec-

ral study revealed the NASA has good value 6.10 eV of direct bandap energy. Dielectric measurement elucidates NASA has lessereffects. Owing to its higher SHG efficiency, NASA is considered

s a promising material for Laser geneartion. Nitramino molecularoiety is optically energetic for laser generation.

[

126 (2015) 95–100 99

Acknowledgements

A thankful acknowledgment is made of the help extended by Dr.M. Basheer Ahmed, The Head, Department of Physics, B.S. AbdurRahman University, Chennai – 600 048, India for testing SHG usingQ-switched Nd: YAG laser. GB and NV wish to extend thanks toDirector, CSIR-NPL for his constant encouragement to establish var-ious characterization facilities and carryout the frontier research.

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