Author’s Accepted Manuscript

Study on growth, structural, optical, thermal and

mechanical properties of organic single crystal
Ethyl p-amino benzoate (EPAB) grown using
vertical Bridgman technique

A. Muthuraja, S. Kalainathan
www.elsevier.com/locate/jcrysgro

PII: S0022-0248(16)30758-8
DOI: http://dx.doi.org/10.1016/j.jcrysgro.2016.11.070
Reference: CRYS23798
To appear in: Journal of Crystal Growth
Received date: 21 July 2016
Revised date: 3 November 2016
Accepted date: 15 November 2016
Cite this article as: A. Muthuraja and S. Kalainathan, Study on growth, structural,
optical, thermal and mechanical properties of organic single crystal Ethyl p-
amino benzoate (EPAB) grown using vertical Bridgman technique, Journal of
Crystal Growth, http://dx.doi.org/10.1016/j.jcrysgro.2016.11.070
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 Study on growth, structural, optical, thermal and mechanical
properties of organic single crystal Ethyl p-amino benzoate
(EPAB) grown using vertical Bridgman technique.

A. Muthuraja, S. Kalainathan*
Centre for Crystal Growth, School of Advanced Sciences, VIT University,
Vellore-632 014, Tamilnadu, India
Abstract

Ethyl p-aminobenzoate (EPAB) single crystal was grown using vertical Bridgman

technique (VBT). The crystal system of grown crystal was identified, and lattice parameters

have been measured from the powder X-ray diffraction (PXRD). The optical transparency of

EPAB single crystal was 55%, and the cut-off wavelength was found to be 337 nm. The

thermal stability of EPAB single crystal was analyzed by thermogravimetric analysis. Etching

studie were carried out for the grown crystal using different solvents, and etch pit density

(EPD) was calculated and compared. Vickers microhardness (Hv) measurements revealed

that EPAB belongs to the category of soft material. The dielectric studies reveal that the

dielectric constant and dielectric loss of grown crystal decreases with increasing frequency

for various temperatures. The third-order nonlinear optical property of EPAB was

investigated and compared with other organic crystals. The evaluation of third-order optical

properties such as nonlinear refractive index (n2), nonlinear absorption (β) and third-order

nonlinear susceptibility (χ3) have found to be in the range of 10-11 m2/W, 10-4 m/W and 10-
5
esu respectively. The Laser damage threshold energy of EPAB was measured using Nd:

YAG laser. The blue emission of the grown crystal was identified by photoluminescence (PL)

spectra measurements. The second harmonic generation (SHG) for the grown EPAB crystal

was confirmed by Kurtz powder technique.

Keywords: organic crystal, Photoluminescence, Laser damage threshold, Z-scan.

Corresponding author: Phone: +91-416-2202350 Fax: 0416-2243092

Email Address: kalainathan@yahoo.com
Introduction

In recent technologies, researchers are much interested in paying more attention to the

field of organic materials. Organic materials possess high nonlinearities, ultra-fast response,

and high damage threshold [1, 2]. Due to its hydrogen bonds and weak Vander Waal’s force,

organic materials are optically more non-linear than inorganic materials, and it also possesses

a higher degree of delocalization [3]. The third-order nonlinear optical (NLO) crystals

possess weak nonlinear absorption (NLA), but still it attracts more researchers because of its

strong nonlinear refraction (NLR) which can be used in applications like photonic switching

devices [4]. The search for efficient third-order NLO material has become even more crucial

than second order materials. Research on third order nonlinear optical materials from the

organometallic, organic, inorganic and semi-organic single crystalline compounds has

attracted considerable attention because of their potential application in ultrafast, optical

limiters, optical switching and devices [5]. Organic Pi-conjugated materials possess high

optical nonlinearity, and molecular design can quickly tune it. An organic Pi-conjugated

material shows adequate performance in all optical devices [6]. The NLO crystals possess

superior nonlinear performance in terms of high hyperpolarizability values particularly due to

the formation of a molecule with an electron donating (D) and accepting groups (A)

connected via a π-conjugated system. When compared to inorganic materials, this feature is

enormously observed in organic molecules [7, 8]. Most of the organic materials reported so

far possess D– π–A-type structure. The large molecular hyperpolarizability and the nonlinear

susceptibility in the organic molecule happens due to the strong delocalization of π-electron

which further causes the significant enhancement of the third-order nonlinear optical

properties of the materials. The Z-scan technique is an effective experimental method to

measure the third-order optical nonlinearities of the materials. EPAB (C9H11N2) is a non-

hygroscopic organic crystal which possesses good NLO properties [9]. EPAB possesses a D–
π–A-type structure where charge transfer is from the donor to acceptor group. Sinha and

Pattabhi determined the structure of the EPAB materials [10]. Previously, the EPAB single

crystal was grown from the microtube – Czocharlski method and solution growth method by

Arivanandhan et al. [11]. The self seeding vertical bridgman technique were analyzed by

Anandha babu et al. The self seeding vertical bridgamn technique EPAB crystal posses SHG

efficiency 28 times than that of standard KDP[12]. However, no systematic studies of its

optical, third order non-linear, mechanical, surface analysis and laser damage threshold were

made. In the current investigation, the EPAB single crystal was grown using vertical

Bridgman technique. We have reported the powder XRD, UV–Vis, TG-DTA, Etching,

microhardness, Z-scan, LDT studies for the grown crystal.

2. Experiments

2.1 Furnace and ampoule design

The two-zone vertical Bridgman furnace was used to grow the EPAB single crystal. In the

Bridgman technique, the temperature distribution and magnitude of temperature gradient are

the relevant parameters. Depending on the geometry of the furnace, dimension and nature of

the crucible, these two parameters are highly differed. Hence, it is necessary to concentrate

more on these parameters while using Bridgman technique [13]. The furnace was made of

alumina muffle with wall thickness (2 mm), diameter (60 mm) and length (600 mm). The

alumina muffle was entirely covered with nichrome wire with the thickness of 0.5 mm. The

temperature controller with an accuracy of ±0.01oC was used in the growth run. The

ampoule design is another vital factor in the crystal growth. Researchers developed many

ampoules with different shapes to grow crystal using Bridgman technique [14]. The conical

tip of the ampoule is the point of initiation for solidification hence the conical shaped

ampoule is mostly preferred to grow crystal in the Bridgman technique which also controls
the further growth of the crystal [15]. In the present experiment, conical shaped borosil glass

ampoule (Fig. 1.) was used to grow the single crystal. The height and inner diameter of the

ampoule were 23 cm and 12 mm respectively. The temperature gradient of the furnace is 3o

C/cm. The axial temperature profile of the furnace is determined, and it is shown in Fig.2.

2.2. Crystal growth

The EPAB organic material was purchased from Aldrich [number A88409 and CAS

Number119-52-8]. The material was filled in conical shape borosil glass ampoule which was

evacuated up to 10-6 torr and then sealed. The two-zone furnace temperature was maintained

at 110o C. (approximately 20o C more than the melting point of the material). The sealed

ampoule was hanged inside the furnace at the hot region. The material melts completely, and

it was kept inside the furnace for 4 hrs to attain the thermal equilibrium. Due to the slow

growth rate (0.5 mm/hr) organic single crystals grown using Bridgman technique need very

less translation rate (less than 0.5 - 1 mm/h) [16]. Two different translation rates were

maintained in this experiment. From the hot region to cold region the ampoule was slowly

moved at a translation rate of 1 mm/h to the crystallizing temperature point and after that

translation rate of 0.5 mm/h was employed. After growth, the furnace was cooled slowly and

brought back to room temperature. There are more possibilities for the occurrence of cracks

due to the difference in the thermal expansion coefficient of the glass and the crystal, hence

slow cooling rate was preferred to prevent the grown crystal from cracks. The grown crystal

was safely removed from the ampoule using the standard diamond wheel cutter. The grown

EPAB single crystal is shown in Fig 3.

3. Results and discussions

3.1 Thermal studies

The TG-DTA was used to afford the information about the melting and

decomposition point of the materials. EPAB was subjected to TG–DTA to analyze the

thermal behaviour of the grown crystal. NETZSCH Sta-449F3 analyzer was used to analyse

TG-DTA in the nitrogen atmosphere at a heating rate of 10˚C min-1. The thermal property of

the EPAB grown crystal is shown in Fig. 4. The DTA curve reveals a sharp peak at 91˚C,

which indicates the melting point of the crystal. The material remains stable up to 125 ˚C in

TG curve, and the single sharp weight loss curve occurs. No phase transition or

decomposition is observed before the melting point of EPAB. EPAB starts to decompose

after 125oC. The EPAB material 100 % weight loss occurs between 125o C and

206 oC. The crystalline nature of the sample was revealed from the sharp curve in the

differential thermal analysis. Hence, it is clear that the grown EPAB crystal is thermally

constant up to 125˚C.

3.2 Powder XRD analysis

Powder X-ray diffraction studies have been carried out to calculate the lattice

parameters of the grown EPAB crystal. The X-ray powder data were collected using Bruker

X-ray diffractometer with CuKa radiation (k = 1.5418 Å). The powder X-ray diffraction

pattern of the grown crystal is shown in Fig.5. The observed 2θ values and lattice parameters

are calculated using powder X software [17]. EPAB belongs to the orthorhombic crystal

system with space group P212121, and calculated lattice parameters are a = 8.05 Å, b = 20.69

Å, c = 5.10 Å. These values are in good agreement with standard JCPDS File [94097].
3.3 UV–visible analysis

The Perkin Elmer spectrometer was used to analyze the transmission spectrum of the

EPAB crystal for the wavelength range of 200-1100 nm, and it shown in Fig. 6. The

transparent crystal with 1.5 mm thickness was used for the analysis. The cut-off wavelength

was observed at 337 nm. The EPAB single crystal possesses low cut-off wavelength and

greater transparency properties in the visible region. The grown EPAB crystal reveals 55%

transparency, which enables it to be a good material for optoelectronic applications [18].

According to Tauc’s relation, the absorption coefficient (α) of material is related to optical

band gap (Eg) and photon energy (hυ) as [19]

Hvα = A(hυ - Eg)1/2

Where A is a constant, Eg is the optical band gap, h is the Planck’s constant and v, the

frequency of the incident photons. The optical band gap of the EPAB crystal was found to be

3.5eV as shown in Fig.7.

3.4 Chemical etching

The chemical etching process is a vital criterion to analyze the defects and growth

features of a grown single crystal. The surface features were analyzed and examined under

Carl Zeiss metallurgical microscope was used to view the etched patterns in EPAB crystals in

the reflected mode. In this present analysis, the EPAB single crystal with the smooth surface

without cracks was subjected to etching analysis by using acetone and methanol as an

etchant. Fig. 8 shows the flat and crack-free surface of the grown EPAB crystal. At room

temperature, the etching analysis was carried out at an etching period of 60 s and 90 s. Fig 8

(b-e) shows the rectangular shaped growth pattern observed during the etching process using

both the etchants. The etch pits increases when the etching time increases (90 s), and the
observed etch pits is shown in Fig. 8 (d, e). It has noted that there is no new pits have formed,

and the pits formation occurs at dislocation sites due to an increase in their size. From the

obtained result of an etching process, it was identified that the etch pits formed due to the

dislocations present in the grown EPAB crystal. The EPAB crystals quantitatively determined

from the dislocation density of grown crystal which measured from the etch pit counts per

unit area (cm-2). When a real crystal grows in an uncontrolled system, it will usually have a

dislocation density of the order of 108-10 lines cm-2 [20]. The low value of dislocation

density makes the crystal to be used for device fabrication. The etch pit density (EPD) of

EPAB crystal with acetone and methanol were calculated and tabulated in Table 1. The

acetone etch bit density was less compared to methanol etch bit density, and low etch bit

density value shows the crystal contains less number of dislocations. From this analysis the

grown EPAB single crystal having systematic packing of atoms/molecules and greater

crystalline perfections.

3.5 Vickers microhardness measurement

Single crystals with good mechanical strength are very necessary for the device

fabrication. At room temperature, the Vickers microhardness measurement was carried out

for grown EPAB single crystals using an MH-112 Vicker's hardness tester fitted with a

pyramid indenter. By applying load, the indentation marks were made on the polished crack

free surface of the grown crystal. By keeping the indentation time of 10s, the loads were

applied on the sample crystal ranging from 10, 15, 25 and 100 g. Fig. 9. Shows the plot of

Load P vs. hardness number (Hv) for the EPAB crystal. From that graph, it is noticed that the

hardness number increases when load increases. It is termed as reverse indentation size

effect (RISE). The hardness value was calculated using the formula:

Hv = 1.8544 (P/d2) kg/mm2

Where Hv is the Vickers hardness number, P is the applied load in kg, and d is an average

diagonal length in micrometer. 1.854 is a constant geometrical factor for the diamond

pyramid. The cracks occur on the surface of the crystal generated during indentation and the

hardness value increases above 100g.

The plot of log P vs. log d least square fitting gives straight line which is in good agreement

with Meyer’s law. According to onitsch [21], the work hardening coefficient ‘n’ of the grown

EPAB single crystal was derived from the graph plotted between log P vs. log d which is

shown in Fig. 10. The value of n should lie between 1 and 1.6 for harder materials and above

1.6 for softer materials. The value of n for EPAB is 2.1 and which means it belongs to the

soft material category.

3.5.1 Hays-Kendall’s approach

According to Hays- Kendall’s approach [22] load dependence of hardness is given by

P = W + A1d2

Where W is the minimum load to initiate plastic deformation in grams and A1 is a load-

independent constant. These two values estimated from the plots drawn between P vs. d2 for

entire load range 10 - 100 g which is shown in Fig. 11, where W is the intercept along the

load axis and A1 is the slope. The grown crystals exhibit the reverse ISE behaviour, which

revealed from the estimated negative value of W [23]. The corrected hardness Ho for the

crystals was calculated using the following relation and the values are given in Table 2.

Ho =1854.4 X A1

The value of W and Ho was calculated and is found to be -3.01004 g and 99.1362 kg mm2

respectively.
3.6 Dielectric constant and dielectric loss measurements

The information about structural changes, defect behaviour and transport phenomena

of the material can be revealed by the dielectric studies [24]. The dielectric measurement is

essential for non- linear optical materials to find how the non-linear optical materials are

easily polarized in an electric field [25]. Measurements were carried out at the temperature

range of 50, 55, 60, 65 and 70 K with the frequency range of 50Hz – 5MHz. EPAB crystal

with high transparency and defect-free was used in this measurement. The silver paste

applied on both flat sides of the sample crystal to act as an electrode. The dielectric constant

(εr) was computed using the below relation;

ε'=Cd/εA

Where C is the capacitance, d is the thickness of the crystal, εo is the permittivity of the free

space, and A is the area of the crystal. The dielectric loss was derived using the following

relation,

ε′′ = ε′ x D

Where D is the dissipation factor. The variation of dielectric constant with the frequency

at different temperature range is shown in Fig. 12. From the curve, it was apparently noticed

that the dielectric constant and dielectric loss values were high at low frequencies, and the

values gradually decrease when frequency increases. Due to the space charge polarization,

the dielectric constant and loss were very low at low frequency. The low dielectric constant at

high frequency was observed due to space charge polarization and it is an important criterion

for the construction of photonic and NLO devices [26]. Fig. 13 shows the variation of

dielectric loss for various frequencies at different temperatures. It indicates that the dielectric

loss decreases with the increase of temperature. The low dielectric constant and dielectric loss
values at higher frequencies support the enhanced optical quality of the crystal with less

defects [27].

3.7 Z-scan experiment

The Z-scan technique was used to carry out the third-order NLO measurement for the

grown sample. When compared to other techniques, the Z-scan technique is the perfect

method to determine the non-linear index of refraction (n2), nonlinear susceptibility (χ3) and

nonlinear absorption coefficient (β) of samples. In this present investigation, the third-order

NLO properties of the sample crystal was examined using He-Ne laser as a source (5 mW)

with the wavelength and beam diameter of 632.8 nm and 0.5 mm respectively. The third-

order nonlinear absorption coefficient and nonlinear optical refraction were measured using

the open and closed aperture Z-scan measurements.

The sample was transformed from + Z to - Z axial direction using the stepper motor. The

digital power meter (Field Master GS- Coherent) was used to quantify the transmittance

intensity variations through the closed aperture. The input laser beam was modified into

Gaussian form by using Gaussian filter. The perfect single Gaussian beam was suitably

endorsed to scan the sample along the z-axis. The path length detached into positive Z-axis

and negative Z-axis by using the convex lens with 30 mm focal length.

The input intensity increases with the decrease in the transmission which is clearly well-

known from the open aperture Z-scan curve which is shown in Fig. 14. The present curve

indicates a reverse saturable absorption (RSA) (excited state absorption) with a positive

nonlinear absorption coefficient. The reveres saturation absorption means the molecule

absorption state is higher than the ground state.

 Fig.15. shows the valley followed by peak configuration in closed aperture method. The

title crystal possesses a positive sign of third-order non-linear refractive index which is

clearly evident from the valley and peak configurations and also reveals the self-focusing

effect. The calculated value of the non-linear refractive indexes (n2), non-linear absorption

(β), third-order nonlinear susceptibility (χ3) of EPAB crystal is. The experimental and

measurement details of the Z-scan technique are shown in Table 3.

The third-order nonlinear optical susceptibility value (χ3) of EPAB was compared with

some other well-known organic NLO crystals in Table 4. From that above analysis, it was

concluded that the EPAB crystal reveals high value when compared to the other crystals. It is

due to the movement of π electron cloud from the donor to accept, which may induce the

molecules in the crystal highly polarized.

3.8 Laser damage threshold

The laser damage threshold study was carried out using Q-switched Nd-YAG laser

with the wavelength range of 1064nm and pulse duration of 30ns. The convex lens with the

focal length of 300 mm has used for LDT measurement. The diameter of Nd-YAG laser

beam is 1 mm at the focal length. The energy density of the input laser beam at which the

crystal got damaged was measured using power meter during laser radiation. The laser

damage threshold value of EPAB crystal was measured and recorded as 4.40 GW/cm2. The

laser damage threshold value of organic crystal was comparatively high than other crystals.

The surface damage threshold value of the EPAB crystal was computed using the equation P

= (E/τπr2) Where E is the energy (mJ), t the pulse width (ns) and r the radius of the spot

(mm). The obtained laser damage threshold value of EPAB crystal compared with other

crystal and tabulated in Table 5.

3.9 Photoluminescence spectrum

The PL spectrum was recorded at room temperature by using Jobin Yvon–Spex

spectrofluorometer (Fluorolog Version 3: Model FL3-11) with high-pressure xenon lamp

(450 W) as an excitation source. The photoluminescence spectrum of EPAB crystal was

observed at wavelength range of 455 – 570 nm which is shown in Fig.16. At 467 nm

wavelength, the high intensity of fluorescence spectrum is 136,179 a.u and exhibits blue light

emission at the same wavelength. The excitation wavelength of EPAB grown crystal

occurred at 337 nm which was clearly identified from the UV–Visible studies. The PL

emission of the title material possesses many applications especially based on the blue

organic light emitting diodes [31]. At the highest peak intensity, the band gap energy of the

title material was calculated using the following relation Eg = hc/λe Where h, c, e are

constants and λ is the wavelength of fluorescence. The calculated energy band gap of EPAB

crystal is 2.65 eV.

3.10 SHG Measurement

The non-linear optical susceptibility of grown EPAB crystals were précised through

second harmonic generation by using standard Kurtz and Perry method [32]. The Q -

Switched High Energy Nd:YAG Laser ( QUANTA RAY Model LAB – 170 - 10 ) with the

fundamental wavelength of 1064 nm was used as a light source. The grown crystals were

ground and tightly packed in a capillary tube. In the SHG measurement, the potassium di-

hydrogen orthophosphate (KDP) crystal was powdered and used as reference material. The

input energy of KDP and EPAB were obtained and the value is 0.68 J. The output signal

voltages of KDP and EPAB SHG were obtained and it was found to be 7.80 and 7.96 m/J.

The SHG efficiency of EPAB was found to be 1.02 times greater than the KDP.
4. Conclusions

Single crystals of EPAB were grown using vertical Bridgman technique using single wall

ampoule. The lattice parameters of the grown crystal were identified from powder XRD

technique. EPAB crystal exhibits good transparency in the entire visible region. The cut-off

wavelength and band gap energy were found to be 337 nm and 3.5eV respectively. The TG-

DTA measurement confirmed the thermal stability of the EPAB crystal. The mechanical

stability of the crystal was found for various loads, and it belongs to soft materials category.

The low value of dielectric constant and dielectric loss at higher frequencies indicates the

suitability of the material for NLO applications. The third-order nonlinear refractive index (n2

= 1.91 X 10-11 m2/W), nonlinear absorption coefficient (1.59 X 10-4 m/W) and third order

optical susceptibility (1.3827 X 10-5esu) was estimated using Z-scan technique. The laser

damage threshold of EPAB was found to be (4.4GW/cm2). Blue emission was observed in

the PL spectrum of the EPAB crystal. The EPAB SHG efficiency was found to be 1.02 times

greater than the KDP.

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Fig.1. Schematic diagram of single wall growth ampoule
 Fig. 2. Temperature profile

Fig. 3. As grown crystal. Inset cut and polished EPAB crystal

Fig.4 .TG-DTA Spectrum of EPAB

Fig.5. Powder XRD spectrum of EPAB crystal
Fig.6 .UV-Vis-NIR Spectra of EPAB single crystal
 Fig.7. Plot of hυ vs. ( αhυ)½.

Fig.8. (a) Without Etching (b) 60 s Etching in methanol (c) 60 s Etching in Acetone
(d) 90 s Etching in methnaol (d) 90 s Etcing in Acetone

Fig. 9. Plot of Load vs. Hv

 Fig. 10. Log d vs. Log P

Fig. 11. Resistance pressure plot

Fig.12. Frequency dependent dielectric constant
Fig.13.Frequency dependent dielectric loss

Fig. 14. Open aperture Z-scan of EPAB

 Fig. 15. Closed aperture Z-scan of EPAB

Fig. 16. Photoluminescence spectrum of EPAB

 Table.1 Characteristics of etching of EPAB crystal with acetone, and methanol

S. Etchants Etching time Etching behaviour Figure number Etch pit density
No (EPD)

1 Methanol Elongated square 1 (a) 40.9×102 cm-2

shaped pits
2 Acetone 60 s Elongated square 1 (b) 27.4×102 cm-2
shaped pits
3 Methanol Elongated square 1 (c) 73.9×102 cm-2
shaped pits
Acetone 90 s Elongated square 1(d) 56.1×102 cm-2
shaped pits

Table . 2 EPAB crystal Calculated value of W, A1 and Ho

Hays–Kendall approach VBT EPAB Crystal

Resistance pressure (W) - 3.01 (g)

Load independent constant (A1) 0.0534 (g μm-2)

Corrected hardness (Ho) 99.136(g μm-2)

Table-3 Z-scan experiment measurement details of EPAB crystal

Measurement details of Z-Scan experiment

Laser beam wavelength (λ) 632.8 nm

Focal length of lens 30 mm
Optical path length 75 cm
Beam radius of the aperture (wa) 3.5 mm
Aperture radius (ra) 2 mm
Sample thickness (L) 0.50 mm
Beam radius (Wo) 6.03X 10-6
Effective thickness (Leff) 0.299457782 mm
Linear absorption coefficient (α) 2.261392467
Linear transmittance (S) 0.15
Nonlinear refractive index (n2) 1.91 X 10-11 m2/W
Nonlinear absorption coefficient (β) 1.59 X 10-4 m/W
Real part of third order susceptibility [Re(χ3)] 1.2752 X 105esu
Imaginary part of third order susceptibility [Im(χ3)] 5.34324 X 10-6esu
Third order nonlinear susceptibility (χ3) 1.3827 X 10-5esu

Table 4. Comparison of third-order nonlinear optical susceptibility (χ3) value of EPAB

crystal with well-known NLO crystals.

Sample Third-order nonlinear susceptibility (χ3) Ref.

EPAB 1.382 X 10 -5 esu Present work

BTZA 1.679 X 10-6 esu 28

MMST 2.293 X 10-7esu 29

LACC 0.913 X10 -15esu 28

Table-5 Comparison of Laser damage threshold with well know NLO crystals.

S.No Crystal name LDT value in Ref.,

GW/cm2
1 Urea 1.5 30

2 DAST 2.8 29

3 Benzimidazole 2.9 30

4 MMST 3.98 29

5 EPAB 4.40 Present work

Highlights
 EPAB was grown by vertical Bridgman technique with size of 10 x 50 mm.
 Optical transparency of EPAB single crystal was 55%.
 The third-order optical properties such as n2, β and χ3 were 10-11 m2/W, 10-4 m/W and
10-5esu respectively.