J Mater Sci: Mater Electron (2023) 34:2040

Crystal formation, structural, optical, and dielectric

measurements of l‑histidine hydrochloride hydrate
(LHHCLH) crystals for optoelectronic applications
Helen Merina Albert1,* , Kashmiri Ashish Khamkar2, Archana Asatkar3, Vaishali Bhagwan Adsul4,5,
Vaishnavi Raja6, M. Kalyan Chakravarthi7, Nellore Manoj Kumar8, and C. Alosious Gonsago9

1
Department of Physics, Sathyabama Institute of Science and Technology, Chennai, India
2
MIT WPU School of Polytechnic and Skill Development, Pune-38, MIT WPU, Pune, Maharashtra, India
3
Department of Chemistry, Govt. Nagarjuna P.G. College of Science, Raipur, Chhattisgarh, India
4
Department of Chemistry, Bharati Vidyapeeth (Deemed to Be) University, Pune, India
5
Yashwantrao Mohite College of Arts, Science and Commerce, Pune, Maharashtra, India
6
Department of Physics, Mother Teresa Women’s University, Attuvampatti, Kodaikanal, Tamil Nadu, India
7
School of Electronics Engineering, VIT-AP University, Amaravathi, Andhra Pradesh, India
8
Department of Mathematics, Saveetha School of Engineering, Saveetha Institute of Medical and Technical Sciences (SIMATS),
Chennai, India
9
Department of Electronics Science, Mohamed Sathak College of Arts and Science, Chennai, India

Received: 24 August 2023 ABSTRACT

Accepted: 25 September 2023 The progress in crystal growth and characterization methods allows the possibil-
Published online: ity of engineering novel compounds with enhanced nonlinear optical properties.
27 October 2023 This study used a slow evaporation process at room temperature with water as a
solvent to create a nonlinear optical material of l-histidine hydrochloride hydrate
© The Author(s), under (LHHCLH). Single-crystal and powdered- X-ray crystallography, Nuclear mag-
exclusive licence to Springer netic resonance (NMR) spectroscopy, UV–visible (UV–Vis) spectroscopy, second
Science+Business Media, LLC, harmonic generation (SHG) test, dielectric, and electrical conductivity studies
part of Springer Nature, 2023 were used to characterize the grown crystals. The crystallographic findings show
that the LHHCLH sample crystallized in an orthorhombic form with the ­P212121
space group. NMR spectroscopy was used to find the molecular identity of the
sample. The absorbance and transmittance spectra of the UV–Vis study have
shown substantial transparency and less absorbance of the LHHCLH in both UV
and the entire visible regions. The SHG test shows that the LHHCLH sample gen-
erated a significant quantity of second harmonic generation signal and was found
to be 3 times more than that of the KDP sample. The dielectric experiments have
explored the frequency and temperature dependence of the dielectric constant
and dielectric loss. Both dielectric constant and dielectric loss were observed to be
decreased exponentially with increasing frequency. The temperature-dependent
changes in the dielectric constant and dielectric loss of the LHHCLH have been

Address correspondence to E-mail: [email protected]

https://doi.org/10.1007/s10854-023-11396-5

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2040 Page 2 of 12 J Mater Sci: Mater Electron (2023) 34:2040

investigated. The AC and DC conductivities of the samples were analyzed. The

activation energies of AC and DC conduction processes were calculated using the
Arrhenius equation and found to be 2.03 and 1.91 eV, respectively.

1 Introduction inorganic materials and mediocre performance in gen-

erating device-grade crystals of organic compounds,
Crystal growth has become an essential and basic com- investigators have taken an alternate route. As a result,
ponent of material science and engineering since crys- semi-organic materials have gained popularity due to
tals of suitable dimensions and quality are required their unique mix of both inorganic and organic fea-
for devices such as harmonic generators, electro-optic tures [12–14]. Semi-organic hybrid crystals are being
modulators, and electronic circuits for technological investigated for nonlinear functions to address these
benefits [1–3]. Crystals are ideal for the manufacture issues. In semi-organic substances, the organic com-
of optoelectronic equipments and in the technological ponent is stoichiometrically bound to suitable metal
device industries. Optoelectronic applications require ions or inorganic counterparts, increasing the sample’s
materials with high nonlinearities, a wide transpar- strength and thermal resistance. Amino acid com-
ency range, and stable physical and chemical prop- plexes with inorganic salts have piqued the interest of
erties. As a result, there is an increasing demand for researchers because they share features of both inor-
crystal formation technologies. Nonlinear optics is an ganic and organic substances. Except for glycine, most
exploration of phenomena that occur when the optical amino acids exhibit chiral symmetry and crystallize
characteristics of a substance are altered by an intense in the non-centrosymmetric structure. Furthermore,
light source such as a laser. Electric polarization, or amino acids are dipolar in their solid state, with a unit
the resulting dipole moment per unit volume, is cru- cell containing donor and acceptor electron groups.
cial in nonlinear optical processes. Over the process, This results in significant second-order optical non-
the intrinsic charges of the substance interact with the linearity due to the intramolecular transfer of charges
incident electromagnetic radiation, thereby changing between the two opposing groups. Because of their
its amplitude, frequency, or phase. Nonlinear optical dipolar behavior, amino acids have been regarded
(NLO) compounds have received greater interest in as prospective NLO candidates [15–17]. The exist-
recent times than traditional substances due to their ence of the imidazole ring distinguishes l-histidine
uses in the fields of lasers, optical communications, from other amino acids. Following the finding of the
information storage, optical mixing, optical switching, potential NLO compound l-histidine tetrafluorobo-
and electro-optic systems [4–6]. It has been discov- rate [18], the fundamental amino acid l-histidine has
ered that natural extracts show improved nonlinear been extensively studied. Hydrochloric acid is a potent
responses. One of the earliest organic NLO com- inorganic acid. It can release a single proton since it is
pounds is Coumarin, which was originally synthe- monoprotic. It completely dissociates in water-based
sized from a naturally occurring substance–the Tonka solvents, generating hydrogen and chloride ions. Since
bean. Several natural substances were discovered to hydrochloric acid is a covalent polar molecule, it may
have a substantial NLO response in the visible and form coordination complexes with organic amino
infrared spectral range in addition to coumarin [7–9]. acids.
Organic crystals play a critical role in instantane- Various kinds of semi-organic salts of amino acids
ous data processing, which is essential in numerous and hydrochloric acid coordination complexes such
emerging technologies. Molecules in organic sub- as l-alanine hydrochloride monohydrate, l-arginine
stances are frequently linked by weak Vander Waals hydrochloride, l-cystine hydrochloride, l-glutamic
interactions or hydrogen bonds, resulting in low ther- acid hydrochloride, l-tryptophan hydrochloride,
mal and mechanical resistance [10, 11]. Due to inher- l-tyrosine hydrochloride, l-valine hydrochloride,
ent constraints on maximizing possible nonlinearity in l-lysine hydrochloride dehydrate, and diglycine
J Mater Sci: Mater Electron (2023) 34:2040 Page 3 of 12 2040

hydrochloride [19–27] have been identified with good stirred for about 4 h. It was next passed through What-
nonlinear optical characteristics. The semi-organic man filter paper before being allowed to evaporate at
L-histidine hydrochloride hydrate’s structure was first ambient temperature. After attaining supersatura-
described by Oda and Koyama in 1972 [28]. We used tion, small crystals began to form as a result of spon-
the slow evaporation method in this study to generate taneous nucleation. The growing procedure was then
LHHCLH crystals with the optimum size. We detail employed with the tiny, transparent, self-nucleated
LHHCLH’s dielectric properties, including its dielec- seed crystals. After a 28-day process of gradual solvent
tric constant and loss factor, as well as its electrical evaporation, well-defined, optically transparent sin-
properties, including its conductivities in both the AC gle crystals were created. The chemical that solidified
and DC axes, for the first time. We detail LHHCLH’s into crystals remained stable, non-hygroscopic, and
electrical properties, including its conductivities in did not deteriorate in the presence of air. The hardness
both the AC and DC ranges, as well as its dielectric behavior of the crystal has previously been reported
properties, including its dielectric constant and loss [6]. Figure 1 depicts an image of the as-grown LHH-
factor, for the first time. Precise measurements of these CLH crystal.
attributes can provide researchers with data to effi-
ciently integrate the substance into its desired usage 2.3 Characterization methods
for more dependable designs or to track the process
of production. Much research, including single-crystal Characterization involves evaluating the structure,
and powder-XRD, 1H-NMR, 13C-NMR, UV–Vis trans- composition, linear optical and nonlinear optical
mittance and absorbance, SHG, dielectric, and electric characteristics, and dielectric properties of the grown
tests are covered. compound LHHCLH. The crystal structure and lat-
tice parameters of l-histidine hydrochloride hydrate
were identified using a “BRUKER Kappa Apex II-
CCD diffractometer” and a ­M0Kα radiation source
2 Experimental details
with a wavelength of 0.71073 Å. The produced sam-
ples were smashed into fine powders and analyzed
2.1 Synthesis
using the powder X-ray diffraction method. The PXRD
By adopting a slow evaporation procedure at room analysis was performed using a JEOL JDX apparatus
temperature, l-histidine hydrochloride hydrate was and a ­CuKα source of radiation of wavelength 1.5406 Å
produced in an aqueous solution. The chemicals l-his- in a continuous scan mode with a scan speed of 1°/
tidine and hydrochloric acid (both AR-grades) were min. The 1H-NMR and 13C-NMR spectral investiga-
used to grow the LHHCLH crystals. The starting mate- tions were performed using a “Bruker AVANCE III-
rials l-histidine and hydrochloric acid were mixed in 500 MHz Multi nuclei solution NMR spectrometer”.
deionized water in a 1:1 molar ratio and continuously
stirred for around two hours to produce the desired
chemical. The chemical reaction that took place in the
deionized water is as follows:

C6 H9 N3 O2 + HCl + H2 O → C6 H10 O2 N+
3
Cl− ⋅ H2 O

The resulting products were gradually heated to

dryness at a temperature below 50 °C to prevent any
possible decomposition of the compound. The prod-
ucts were refined using successive recrystallization
processes to ensure their purity.

2.2 Crystal growth

The recrystallized salts were dissolved in deionized

water at 32 °C, and the mixture was continuously Fig. 1  Photograph of the as-grown LHHCLH crystal
2040 Page 4 of 12 J Mater Sci: Mater Electron (2023) 34:2040

A Varian Carry-5E UV–Vis spectrophotometer was

applied to obtain UV–Vis spectra for the LHHCLH
samples in the 200–800 nm spectral regions. The SHG
efficiency of the prepared sample was discovered
using the powder approach of “Kurtz and Perry”
with the Quanta Ray Model Lab-170–10 instrument.
Dielectric and electric measurements were obtained
using the Hioki 3532 LCR meter at various tempera-
tures ranging from 313 to 373 K in the spectral range
between 50 Hz and 5 MHz.

3 Results and discussion

3.1 Single‑crystal XRD study

Single-crystal X-ray diffraction analysis is the most

Fig. 2  Asymmetric unit of LHHCLH with 50% probability ther-
effective structural analysis tool to obtain information
mal ellipsoids
about the structural arrangement of molecules [29, 30].
It can determine the atomic coordinates, bond lengths,
bond angles, and molecule orientations of solid mate- serves as an acceptor. The l-histidine cation binds with
rials. The provided sample was thinly cut into tiny the neighboring chlorine anion via N‒H–-O hydrogen
pieces and then subjected to XRD analysis. The crys- bonds.
tal structure of LHHCLH was determined using the
SHELXL-97 program and direct methods. According 3.2 Powder‑XRD analysis
to the crystallographic findings, the LHHCLH crystal
has an orthorhombic structure with the noncentrosym- Powder X-ray diffraction analysis (PXRD) is a critical
metric ­P212121 space group. LHHCLH has the lattice method for determining the crystal structure of any
parameters a = 15.285 (± 0.03) Å, b = 8.884 (± 0.04) Å, compound. It is a non-destructive approach with great
c = 6.876 (± 0.02) Å and V = 933.71 (± 4) Å3. The meas- potential for characterizing bulk and nanomaterials
ured lattice parameters match the reported values [31, 32]. Diffraction patterns are essential for analyz-
quite well [28]. The asymmetric unit of LHHCLH is ing such substances. Since each substance has its dif-
depicted in Fig. 2. fraction pattern, every material can be identified and
The asymmetric unit is made up of an L-histidine recognized by comparing the diffracted beams to the
cation, chloride anion, and a water molecule inter- reference database JCPDS library. The diffraction pat-
connected by N‒H–O bonds. According to the crys- terns reveal the purity of the ingredients. The PXRD
tal structure, l-histidine cation has a protonated and study was carried out to determine the basic structure
positively charged imidazole ring, a protonated amino and unit cell parameters of the LHHCLH sample. An
NH3+ group, and a deprotonated carboxylate group. X-ray of wavelength 1.5406 Å was used to scan the
( )

Hydrochloric acid, on the other hand, is monoprotic. finely ground LHHCLH samples over 10–70° orienta-
Since hydrochloric acid is a polar covalent molecule, tions, and the diffraction patterns are shown in Fig. 3.
it breaks down into hydrogen and chloride ions when The unit cell dimensions were approximated using
it comes into contact with water. There is only one the PROSZKI software based on the notable peaks.
H-Cl single bond in the HCl chemical structure. The Numerous peaks with 2θ orientations of 11.552°,
synthesis of the LHHCLH is caused by the transfer 15.194°, 19.549°, 23.194°, 25.248°, 26.486°, 29.884°,
of a proton from the hydrogen chloride molecule to 36.346°, 39.745°, 43.654° and 47.47° were found in
the lone pair of electrons on the nitrogen ­(N2) atom of the spectra. The peak at 23.19° has the most intensity
the imidazole ring of l-histidine. The electron is left per second. The peaks were indexed and they corre-
on the chlorine, resulting in the formation of a chlo- spond to (100), (110), (111), (200), (210), (201), (22–1),
ride anion. The oxygen atom ­(O3) of the ­H2O molecule (310), (311), (321) and (400) crystal planes. According
J Mater Sci: Mater Electron (2023) 34:2040 Page 5 of 12 2040

of LHHCLH obtained at 298 K with DMSO as the sol-

vent. The chemical shifts of the molecules by 1H-NMR
and 13C-NMR analyses are represented as δ (ppm).
Figure 4a depicts the 1H-NMR and Fig. 4b depicts the
13
C-NMR spectra of LHHCLH. In the 1H-NMR spec-
tra, the resonance peaks at δ = 7.98 ppm and 7.06 ppm
are attributable to the presence of the CH group of
the imidazole ring of l-histidine. The signal appearing
at δ = 3.81 ppm is caused by CH(NH3) and is divided
into a triplet due to the interaction of side chain pro-
tons ­(CH2). The peaks at δ = 2.95 ppm and 3.09 ppm
are caused by the ­CH2 group on the side chain of
l-histidine, and they are divided into a quartet due
to interactions of adjacent aliphatic CH groups. The
Fig. 3  The PXRD pattern of LHHCLH
presence of multiplet at about δ = 2.51 ppm is caused
by the solvent effect of DMSO.
In the 13C-NMR spectra, the peak at δ = 169.94 ppm
is caused by the C = O group on the side chain of
l-histidine. The presence of the imidazole ring CH
group accounts for the peak resolved at δ = 140.06 ppm
and the presence of the C atom of the imidazole ring
causes the signal at = 134.43 ppm. The resonance
peaks at δ = 51.48 ppm and 26.28 ppm are because
of the existence of CH and ­CH2 groups on the side
chain of l-histidine. The presence of multiplet at about
δ = 40.15 ppm is caused by the solvent DMSO effect.

3.4 UV–Vis spectral study

UV–Vis spectroscopy is a low-cost, adaptable, and

non-invasive analytical method that can detect a wide
range of the transmission or absorption of light related
to the wavelength of organic and inorganic molecules
[34, 35]. The method can be used with a variety of
sample types, including solids, liquids, glasses, and
thin films. The amount of light that a chemical sub-
stance absorbs can be determined quantitatively
Fig. 4  a 1H-NMR, b 13C-NMR spectra of LHHCLH using UV–Visible spectroscopy. This is accomplished
by comparing the amount of light that is transmit-
to PXRD analysis, the LHHCLH crystallized in an ted through a substance to the amount of light that
orthorhombic crystal structure. It has been noted is passed through a reference substance. The wave-
that the PXRD results and the single-crystal XRD test length of light has an inverse relationship with its
results agree quite well. energy. To stimulate the electrons in an element to a
higher energy state, which can be observed as absorp-
tion, a precise amount of light energy is required. In
3.3 Nuclear magnetic spectroscopy an element, electrons in various bonding conditions
require different amounts of light energy to move
Nuclear magnetic spectroscopy provides information them to higher energy states. This explains why vari-
about the chemical structure and molecular identity ous compounds absorb light at different wavelengths.
of substances [33]. Figure 4 shows the NMR spectra The UV–Vis spectral analysis of the LHHCLH crystal
2040 Page 6 of 12 J Mater Sci: Mater Electron (2023) 34:2040

was performed to ascertain its transmittance range method. As an optical source, an Nd: YAG laser with a
and suitability for optical applications. Figure 5 fundamental wavelength of 1064 nm, a pulse width of
shows the optical absorbance and transmittance spec- 8 ns, and a pulse rate of 10 Hz was applied. Typically,
tra of LHHCLH that were obtained in the wavelength a filter was used to guide the laser beam onto the pow-
range of 200–800 nm. The spectra indicate a substan- dery samples. The sample’s emission of green radiation
tial decrease in absorption at 232 nm, which relates to supported the generation of a second harmonic signal.
the crystal’s lower cut-off wavelength or fundamen- The LHHCLH’s SHG efficiency was compared with the
tal absorbance. Additionally, it demonstrates that the potassium dihydrogen phosphate (KDP) samples. The
LHHCLH crystal is highly transparent in both the UV LHHCLH samples generated a 26.5 mJ SHG output;
and visible spectrums, making it suitable for optoelec- whereas the reference KDP samples generated an 8.9 mJ
tronic and second harmonic generating applications. SHG signal with an identical input energy. As a result,
it was found that the SHG efficiency of LHHCLH was
3.5 Kurtz and Perry SHG test around three times greater than that of the KDP sam-
ple. The SHG efficiency of LHHCLH is compared with
The second harmonic generation efficiency of the the reported l-histidine complexes and is presented in
LHHCLH crystal was evaluated using the Kurtz & Table 1.
Perry powder method [36, 37]. The crushed samples
were carefully wedged between two glass plates in this 3.6 Dielectric studies

Dielectric measurements provide essential design ele-

ments for a variety of electrical and electronic applica-
tions. A better understanding of dielectric properties
has enhanced applications in the automobile, aerospace,
food, and healthcare industries [44].

3.6.1 Dielectric constant

The amount of electric potential energy in a material

when an electric field is applied is expressed by the die-
lectric constant. The dielectric constant (εr) is calculated
using the following equation:

Cd
𝜀r = ,
𝜀0 A

Fig. 5  UV–Vis absorbance and transmittance spectra of LHH-

CLH

Table 1  Comparison of SHG

Compound SHG efficiency
efficiencies of l-histidine
complexes KDP (reference sample) 1.0
l-histidine nitrate [38] 0.8
l-histidine bromide [39] 1.0
l-histidine perchlorate [40] 3.19
l-histidinium L-tartrate hemihydrates [41] 0.79
l-histidine trichloroacetate [42] 0.33
l-histidinium maleate 1.5-hydrate [15] 0.65
l-histidinium fumarate fumaric acid monohydrate [43] 1.7
l-histidine tetrafluoroborate [18] 5.0
l-histidine hydrochloride monohydrate (present work) 3.0
J Mater Sci: Mater Electron (2023) 34:2040 Page 7 of 12 2040

where A is the area, d is the thickness, and C is the

capacitance of the test sample. ε0 represents the abso-
lute permittivity. Most suitable samples of LHHCLH
were used for the dielectric tests. The dielectric con-
stant and dielectric loss were calculated by evaluating
the capacitance and dissipation factor as functions of
frequency and temperature. Experiments were car-
ried out for frequencies ranging from 50 Hz to 5 MHz
at different temperatures from 313 to 373 K. Figure 6
depicts the relationship between the dielectric constant
and log frequency over a broad temperature range.
It has been discovered that the dielectric constant is
larger at low frequencies. With rising frequency, it
exponentially falls until it reaches a minimum value
of 20 at 3 MHz.
The polarization process can be used to explain Fig. 7  Temperature dependence of dielectric constant for LHH-
CLH
the changes in the dielectric process. At the micro-
scopic level, several dielectric phenomena can influ-
ence the dielectric behavior of the sample. Interfacial, frequency range, the temperature-sensitive variation
dipolar, ionic, and electronic polarization processes in the dielectric loss is modest and rises only mini-
frequently contribute to a material’s dielectric constant mally with temperature. The diagram shows that the
at low frequencies. As frequency increases, the slower dielectric constant is highest at low frequencies and
processes gradually disappear, leaving the faster ones lowest at higher frequencies.
to contribute to the dielectric constant. As frequency
increases, the tendency of interfacial and dipolar
polarizations to pursue the applied field decreases, 3.6.2 Dielectric loss
resulting in decreasing dielectric constant values. Only
electronic polarization adds to the dielectric constant The dielectric loss is a measurement of the quantity of
at extremely high frequencies [45, 46]. The relationship electrical energy lost as thermal energy due to conduc-
between temperature and the dielectric constant at dif- tion. The following expression can be used to deter-
ferent frequencies is seen in Fig. 7. Over the whole mine the loss factor:
1
D = tan𝛿 = ,
2𝜋fRC

where f denotes the frequency, R and C represent the

corresponding resistance and capacitance. The cor-
relation between log frequency and dielectric loss at
different temperatures is seen in Fig. 8. The graphic
demonstrates that the dielectric loss falls off as fre-
quency increases and reaches nearly zero at higher
frequencies. Following are some possible explanations
for the decrease in dielectric loss with the increase in
frequency. The degree of dielectric loss at low fre-
quencies is triggered by the mobility of ions in the
substance. Dielectric loss is influenced by ion jumps,
ionic conduction losses, and ionic polarization losses
at lower and intermediate frequencies [47]. Since ionic
vibration can be the only factor contributing to dielec-
Fig. 6  Frequency dependence of dielectric constant for LHH- tric loss, dielectric loss is at its lowest point at high fre-
CLH quencies. The correlation between dielectric loss and
2040 Page 8 of 12 J Mater Sci: Mater Electron (2023) 34:2040

3.7 Electrical conductivity

In many electronic applications, the ability of a mate-

rial to conduct electricity is a crucial property. By
measuring a material’s electrical conductivity, one
may determine the ease with which it can transfer an
electrical current over a specific distance. A conductiv-
ity meter is employed to determine the conductance
and measure the electric charges.

3.7.1 AC conductivity

The resultant conductivity of a material is calculated

by the addition of its AC and DC components. The
Fig. 8  Frequency dependency of dielectric loss for LHHCLH study of AC conductivity is an effective method for
evaluating the electrical characteristics of a substance.
The following formula can be applied to determine the
temperatures for various frequencies is seen in Fig. 9. AC conductivity [48].
The temperature-sensitive variation in the dielectric
loss is small and the dielectric loss slightly increases 𝜎ac = 𝜔𝜀o 𝜀r tan 𝛿,
with temperature across the whole frequency range.
where εo and εr represent the absolute permittiv-
The diagram demonstrates that the dielectric loss is
ity and dielectric constant, and tanδ denotes the loss
highest at low frequencies and lowest at higher fre-
component. Figure 10 depicts the relationship between
quencies. In light of this, the dielectric constant and
temperature and the change in AC conductivity. It has
dielectric loss exhibit comparable variations in fre-
been found that the AC conductivity increases non-
quency and temperature. The LHHCLH crystal has an
linearly with an increase in temperature (or decreases
excellent optical level with fewer defects as evidenced
non-linearly with the reciprocal of temperature as
by the minimal loss factor at higher frequencies. This
shown in the graph). The following could be used to
factor is crucial for nonlinear optical compounds in
demonstrate how the conductivity rises with tempera-
their various uses.
ture. In this instance, electrical conductivity rises with
temperature because more electrons from the valence
band can move to the conduction band as the tem-
perature rises. The band gap decreases as temperature

Fig. 9  Temperature dependency of dielectric loss for LHHCLH Fig. 10  Variation of 𝜎ac with 1000/T for LHHCLH
J Mater Sci: Mater Electron (2023) 34:2040 Page 9 of 12 2040

rises, allowing for the “free movement” of electrons conductivity is observed in Fig. 12. The DC conductiv-
between the bands. This causes the conductivity to ity of the LHHCLH increases non-linearly as a func-
increase. The electrical conduction mechanism in tion of temperature (or decreases non-linearly as a
LHHCLH is “thermally activated”. function of temperature reciprocal). This temperature-
The AC activation energy has been determined related increase in conductivity is attributed to the rise
using the Arrhenius equation [49]: in charge density. Due to the temperature rise, the
inter-grain boundary region contracts, and this leads
𝜎ac = 𝜎o e−Eac ∕KT , to the reduction of the electron scattering [50]. The
conductivity is improved as a result of the increase in
where Eac refers to the activation energy, 𝜎o represents
carrier concentration and inter-grain domain mobil-
the pre-exponential factor, and k represents the Boltz-
ity. The activation energy ( Edc ) is evaluated using the
mann constant. The least squares fit method is used
slope of the graph illustrated in Fig. 13. In this case, the
to estimate the AC activation energy by plotting ln 𝜎ac
DC activation energy is found to be 1.91 eV.
vs 1000/T, as seen in Fig. 11. The AC activation energy
for the LHHCLH was found to be 2.03 eV.

3.7.2 DC Conductivity

The DC conductivity of the LHHCLH sample was cal-

culated using the following expression:
L
𝜎dc = ,
RA
where R denotes the equivalent resistance, L and A are
width and area of the test sample. The change in DC
conductivity of the given sample with temperature is
calculated using the Arrhenius relation.

𝜎dc = 𝜎o e−Edc ∕KT

where Edc represents the activation energy, 𝜎o rep-

resents the pre-exponential factor, k represents the
Boltzmann constant, and T represents the tempera-
ture. The impact of temperature on the sample’s DC Fig. 12  Variation of 𝜎dc with 1000/T for LHHCLH

Fig. 11  Plot of ln 𝜎ac Versus 1000/T for LHHCLH Fig. 13  Plot of log 𝜎dc Vs 1000/T for LHHCLH
2040 Page 10 of 12 J Mater Sci: Mater Electron (2023) 34:2040

4 Conclusion preparation, Formal analsis, and Investigation, Writ-

ing- review and Editing. VR: Conception and design,
l-histidine hydrochloride hydrate, a semi-organic non- Writing- original draft preparation, Formal analysis,
linear optical substance was produced at 32 °C using and Investigation, Writing- review and Editing. MKC:
a slow evaporation process using water as a solvent. Conception and design, Figures, Formal Analysis and
The produced LHHCLH crystals were characterized Investigation, Writing- review, and Editing. NMK:
by Single-crystal and powder-XRD, NMR, UV–Vis, Conception and design, Material preparation, Data
SHG, dielectric, and electrical conductivity studies. collection and analysis, Formal analysis and Investi-
The crystallography data indicates that the LHHCLH gation, Software, Writing- review and Editing. CAG:
crystal corresponds to an orthorhombic structure Conception and design, Material preparation, Data
with the ­P212121 space group. The chemical struc- collection and analysis, Figures, Data. Formal analy-
ture and molecular identity of the sample have been sis and Investigation, Software, Writing- review and
established by NMR investigations. The absorbance Editing,
and transmittance spectra of the UV–Vis study have
shown substantial transparency or less absorbance in
both the UV and entire visible regions. The SHG effi- Funding
ciency of the LHHCLH was found to be three times
higher than that of the KDP sample. The frequency No funding was received for conducting this study.
and temperature dependency of the dielectric constant
and dielectric loss have been analyzed using dielec-
tric experiments. With a rise in frequency, both the Data availability
dielectric constant and the dielectric loss fall off expo-
nentially, reaching a low value at higher frequencies. The datasets generated during and/or analyzed during
The temperature-dependent variation in the dielectric the current study are available from the corresponding
constant and dielectric loss is quite marginal at all fre- author on reasonable request.
quency ranges. Both the AC and DC conductivities
have been observed to increase non-linearly with the
temperature. The activation energies of AC and DC Declarations
conduction processes have been calculated using the
Arrhenius formula and found to be 2.03 and 1.91 eV, Conflict of interest The authors declare that no
respectively. The characterized LHHCLH samples funds, grants, or other support were received during
show significant growth, unique structure, molecular the preparation of this manuscript.
identity, dielectric, electrical, and SHG performance.
Ethical approval This article does not contain any
According to the experimental results, LHHCLH crys-
studies with human participants or animals per-
tal is an appropriate semiorganic material for use in
formed by any of the authors.
optoelectronic devices.

Authors contribution References

HMA: Conception and design, Material preparation,
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