2. REVIEW ON ADP, KDP AND ADP-KDP
MIXED CRYSTALS
2.1. Introduction
The Overwhelming success of molecular engineering in controlling NLO
properties in last decade has prompted better initiative in crystal engineering. The search
for new, very efficient nonlinear optical materials, for fast and optimum processing of
optical signals has become very important, because of development of optical fibre
communication, laser based imaging and remote sensing etc. A strong need continues to
exist for lower cost, more efficient, higher average power materials for optical
parametric amplifier operation and second harmonic generation (SHG) throughout the
blue near UV spectral regions. Another area of growing need is materials for
birefringent, phase matched optical parametric oscillators (OPO) for the generation of
broadly tunable mid-wave and long wave infrared radiation. Intense attention has been
paid to inorganic materials showing the second order nonlinear optical effect because of
their higher nonlinearity. Among the nonlinear phenomenon, frequency doubling,
frequency mixing and electro-optic modulations are important in the field of optical
image and optical data storage.
Ferroactive materials (ferro- and antiferroelectrics) are widely used in different
fields of science and engineering (electrooptical devices, calculators, laser equipment,
etc.) [1–7]. Since the demand in development of new ferroactive materials is constantly
growing, the research into ferroelectrics and, in particular, their solid solutions allows
the problems of synthesis of new materials with the predetermined properties to be
solved. In many cases, solid solutions of ferroelectrics exhibit intermediate properties of
their constituents. However, they can undergo more complicated specific changes as
38
compared to the intermediate properties when their concentrations are changed [7–15].
Theoretical studies of solid solutions provide information on the stability of
ferroelectric, antiferroelectric, and paraelectric phases, on special features and character
of the changes in their properties resulting from the phase transitions, which makes it
possible to find the ways of their controlled forming.
Potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate
(ADP) have been extensively studied for many years due to their important applications
such as second harmonic generation, Q-switch, and quantum electronics [16,17]. Since
they are isomorphous, their mixed crystal plays a vital role in the field of optical
communication and in ferroelectrics.
2.2. ADP and KDP Single Crystals
Pottassium dihydrogen ortho phosphate (KDP) and ammonium dihydrogen
phosphate (ADP)
are well known nonlinear optical material having application in
photonics for frequency mixing, parametric amplification and electro optical
modulation. ADP and KDP have also attracted extensive attention in the investigation of
hydrogen bonding behaviors in crystal and the relationship between crystal structure and
their properties [18-21]. ADP was among the first material that were used and exploited
for their non-linear optical (NLO) and electro-optic (EO) properties [22]. It belongs to
scalenohedral class of tetragonal crystal system. Also it has the tetra molecular unit cell
having the dimensions given as a=b=7.510 Å and c = 7.564 Å with Z=4 and has a c/a
ratio =1.0072. The molar volume of ADP is 6.4228 x10-5 m3. ADP is an antiferro
electric material with Tc = 148K [23]. The external structural morphology of ADP
single crystal is shown in Figure 2.1. The tetrahedral groups PO4 3− are slightly flattened
into the (0 0 1) plane as the values of the angles O(u)–X–O(u) and O(u)–X–O(l) are
39
111.17(4)ƕ and 108.63(4)ƕ, respectively. Here O(u) is the upper oxygen of a given
tetrahedral group, and O(l) is the lower one as viewed along the c-axis. This may be
caused by a pull exerted by the hydrogen bonds which are positioned in the (0 0 1) plane
between the different tetrahedra. Every NH4
+
in the structure is coordinated by eight
oxygen atoms forming two interpenetrating tetragonal disphenoids. One of the
disphenoids is flat and the other steep with respect to the c-axis. The N–O(f) lengths are
shorter by about 0.30Å than the N–O(s) lengths where O(f) and O(s) refer to the oxygen
atoms of the flat and steep disphenoids, respectively.
Figure 2.1: External morphology of ADP crystals
KDP is an efficient angle – tuned dielectric medium for optical harmonic
generation in and near the visible region [24]. This material offers high transmission
throughout the visible spectrum and meets the requirements for an optical birefringence
large enough to bracket its refractive index for even the extreme wavelength over which
it is transparent. An additional advantage of KDP is its ability to withstand repeated
exposure to high power density laser radiation without inducing strains and subsequent
in homogeneities in the refractive index [25]. These characteristics make KDP a
40
desirable material for frequency doubling and mixing experiments with many solid state
and dye lasers with fundamental wavelengths between 1060 and 525 nm. KDP is
ferroelectric well below room temperature and the Curie temperature Tc is 122 K [26].
The molecular weight and density at room temperature are respectively 136.09 and
2.33 g/cc [27]. The low temperature ferroelectric phase has an orthorhombic unit cell
(space group is Fdd2) having the dimensions (at 115 K) given as
a = 10.467, b =
10.533 and c = 6.926 Å.
Figure 2.2: Morphology of KDP single crystals
The crystallographic structures of KDP and ADP crystals have well been
examined by X-ray analysis and neutron diffraction experiment [28-32]. There are four
formula units per unit cell, both KDP and ADP isostructurally belong to
noncentrosymmetric compounds at room temperature. The very tiny distinction between
them is their different constituent cations (K+ with the radius 1.33 Å and NH4+ with the
radius 1.42 Å [33] ), which consequently arise the disparate interaction with the same
41
anion H2PO4- and the final discrepancy between KDP and ADP crystallite
morphologies. Unit cell structures are clearly shown in Fig. 2.3.
Figure 2.3: Crystal structure of: a) KDP and b) ADP single crystals
Microscopically, chemical bonds affect and determine physicochemical
properties of materials [34,35], which is also true for KDP and ADP crystals. Cerreta et
al. [36] show that the growth units of KDP and ADP crystals are hydrated K+, NH+4 and
H2PO-4 groups. When investigating the above constituent chemical bonds in KDP and
ADP crystals, one may find that anion– anion interactions are very similar. Two
continuous PO4 groups are interlinked through one hydrogen bond (O–H/O) with a
distance of 2.504 Å for KDP and 2.489 Å for ADP, respectively. In fact, hydrogen atom
in O–H/O bond is not properly on the line determined by these two oxygen atoms, it
bonds to the nearer oxygen atom with a short distance of 1.07 Å for these two crystals,
and the separation to the farther oxygen atom is 1.434 Å for KDP and 1.419 Å for ADP.
However, the bond strength of KDP and ADP crystals is very different, chemical bonds
of KDP are ionic while those of ADP are covalent.
42
All constituent chemical bonds of KDP and ADP crystals may be categorized
into three types by the direction and distribution in the lattice. The first kind of chemical
bonds for KDP is K–O ionic bonds (2.897Å ), and that for ADP is H(N)–O covalent
bonds (2.640 Å), which are practically parallel to c- axis symmetrically. Though H(N)–
O bond length is a little shorter than K–O bond, the binding energy of ionic bonds is
generally larger than that of covalent bonds, the bond strength along c- axis are hence
extraordinarily larger in KDP than ADP. The second kind of chemical bonds also denote
K–O ionic bonds (2.824 Å) in KDP and H(N)–O covalent bonds (2.134 Å) in ADP, its
directions generally run parallel to (001) face, these ionic bond strengths are stronger
than those of covalent bonds as well. The last kind of chemical bonds in KDP and ADP
crystals particularly denote hydrogen bonds occurring between two adjacent PO4 groups
via O–H/O bonds, which are perpendicular to c- axis and represented by red dotted
lines. The contributions of all chemical bonds determine the ideal morphology of
crystals, and the fine distinctions between KDP and ADP structures may be the main
reason for the variance of crystal outlines described below.
Figure 2.4: Bond graph of KDP and ADP single crystals
43
Since from the first reports on ferroelectric properties of KDP by Busch and
Scherrer in 1935 [37] and 1938 [38], numerous studies on its electrical and optical
properties were reported. They were for a large part reviewed in 1987 [39].
ADP has been the subject of a wide variety of investigations over the past
decades. Reasonable studies have been done on the growth and properties of pure ADP
[40-47]. In recent years, efforts have been taken to improve the quality, growth rate and
properties of ADP and KDP , by employing new growth techniques, and also by the
addition of organic, inorganic and semiorganic impurities [48-56].
Temperature dependence of solubility of pure and doped ADP, KDP crystals
were reported by several authors [57,58].Nucleation parameters on pure and doped
ADP, KDP single crystals showed that, values of nucleation parameters increase with
increase in impurity concentration for the impurities having higher density values and
decrease with the increase in impurity concentration for the impurities having lower
density values[ 59-60]
Zaitseva et al[61] grew large-scale (40–55 cm) KDP crystals at a rate of 1020
mm/ day, the rapid growth method is based on the useof ‘‘point seed’’. Nakatsuka et al
[62] used external energy to grow KDP crystals of 60mm in size at high rates of excess
of 50 mm/day. The adjustment effect of additives on the growth process and properties
of crystals has been applied in recent years [63-65]. Generally, anion and cation
impurities in the solution are adsorbed on to (101) and(100) faces of ADP crystal and
KDP crystals ,respectively. This selectivity on impurity adsorption has been attributed
to the orientations of anion (H2PO4 ) and cation(K+ or NH4+) on the respective crystal
44
faces [66,67]. In particular, this impurity adsorption causes step- pinning, which affects
the optical property due to the density of lattice defects [68].
Podder [69] reported that the presence of KCl in the growth medium is also
found to suppress the metal ion impurities to a large extent and increases the growth
rate. The increase in the quality of the KDP crystal in presence of KCl is due to the
complexation of trace metal ion impurities in solution by Cl- ion. The growth rate of
KDP is reported to increase 6–8 times when grown from ethylene diamine tetra acetic
acid EDTA added solution as compared to pure solution [70]. The metastable zone
width was also found to be enhanced in the case of EDTA added solution when
compared to the pure system [71]. Anbukumar et al. [72] had made attempts to study the
microhardness of pure KDP family crystals.
Ogorodnikov et al. [73] excited tunnel recombination luminescence in
nonactivated KDP crystals by an electron beam and identified both a hole component
with a band at Ȝ = 350 nm and an electronic component with a band at Ȝ = 220 nm.
Growth of KDP crystals from aqueous solutions with SiO2 particles whose size ranges
from 10–2 to 400 m in the static and dynamic modes has been studied. It was revealed
that capture of particles by a growing crystal face take place at a growth rate exceeding
a certain critical value dependent on particle size: the smaller the particles, the higher
the growth rate [74].
It is well known that the polar phase of ferroelectric KDP crystals exhibits an
anomalous behavior of dielectric properties [75,76]. Nominally pure KDP crystals have
low dielectric losses at room temperature, while in doped KDP crystals, the value of
tanδ is substantially higher [45]. In this case, the losses due to conductivity are
45
especially high in the high-temperature region of the paraphase [65]. In a rapidly grown
KDP crystal, the pyramidal sector has more defects than the prismatic one. In the
traditional growth method, the background impurities are absorbed mainly by the prism,
thus forming numerous defects and blocking its growth [11]. The use of the starting
material with a micro impurity content not exceeding 1 to 5 wt %, microfiltration of the
solution, and the optimum crystallization conditions results in growth of KDP single
crystals with cross sections up to 300 x 300 mm2 and transmission at the wavelength λ =
200 nm of about 86% [79].
It was observed that amino acid dopants enhances the material properties such
as nonlinear optical (NLO) and ferro electrical properties of KDP [77-80]. Glycine
aminoacid addition increases the SHG effecieny by 1.36 times than pure KDP. Glycine
has one Zwitterions and it may be connected with KDP by short O-H-O hydrogen bonds
Hence in reaction with KDP optically active amino group may replaces some potassium
ion and increases its non centrosymmetry which results in increase of nonlinearity of
grown crystal. A bulk single crystal of KDP with the dimension of 5 mm diameter and
60 mm length have been grown successfully by modified unidirectional solution growth
method. The optical transmittance studies reveal the improved transparency of the SR
grown crystal than that of conventional solution grown crystal [81].
The absorption coefficients of rapidly grown KDP crystals are a little higher than
those grown from traditional method, which is the same as Fujioka et al.’s result
[82,83]. Sun et al.[84] have shown that the main reason for light scatter in KDP crystals
comes from some large-scale impurities,such as organic acids and anions . Lglutamicacid, L-histidine and L-valine) doped KDP crystals have been grown by slow
evaporation technique at room temperature. The doping with L-glutamic acid, L46
histidine and L-valine causes much broadening of the peaks in the FTIR spectra when
compared to the pure KDP crystal[85].
Moreover, even a very low impurity concentration in the solution (less than 1
ppm) shows inhibition effect for crystal growth rate in the case of the trivalent and
divalent metal impurities and the impurities are significantly adsorbed onto the crystal .
Big size KDP crystals with structural perfection, optical homogeneity and bulk laser
damage resistance threshold was grown by the water solutions by the method of the
temperature decrease in the range of 40–60oC [86]. The effect of the addition of
potassium thiocyanate on potassium dihydrogen phosphate (KDP) crystals, grown from
aqueous solution by the temperature lowering method using a microcontroller based
seed rotation technique was reported by Dhanaraj et al [87].The presence of KSCN
increases the induction period may be due to the suppression of chemical activity of the
metal ions present in the KDP solution [88]. Dielectric studies indicate that 5 mol%
addition of KSCN to KDP leads to low εr - value dielectrics, which is gaining more
importance nowadays. It is found that the molar concentration of ADP in the saturated
solution is approximately two times that of KDP, while the solubility of KADP is even
bigger at the same condition [89].
The SR method-grown<100> KDP has 15% higher transmittance as against
conventional method-grown crystals. The dielectric constant was higher and dielectric
loss was less in SR method-grown crystal as against conventional method-grown crystal
[90]. <001> KDP crystals have been already grown by SR method [91,92]. Optimized
growth rate of <001> direction KDP crystals is 5mm/day. <001> growth contains four
growth sector boundaries.
47
Third-order nonlinear susceptibilities and nonlinear refractive indices (n2) of
KDP, crystal was measured at the wavelengths of 1064 nm and 532 nm by Z-scan
technique. It was shown that, with the growth of h in KDP crystals, the Kerr
nonlinearity value becomes larger at the wavelength of 1064 nm with respect to that at k
¼ 532 nm, that was in a good agreement with empirical model [93].
Two different growths of one the crystal diameter was the ampoule’s inner
diameter and in the other the crystal thickness was less than the ampoule diameter was
tried in SR method to grow large KDP crystals, The HRXRD analysis indicates that the
crystalline perfection is excellent without having any very low angle internal structural
grain boundaries. [94].
The Vicker’s microhardness as well as parameters such as fracture
toughness(Kc), brittleness index(B) ,yield strength(Sv) and optical band gap of the KDP
crystal grown by modified SR method was reported by Robert et al [95].
Absorption in the UV range is commonly observed in rapidly grown KDP
materials, sometimes with one or two absorption peaks in the [200–300] nm range [9698]. The laser induced damage in KDP samples has been measured with two set-ups
with respectively a large beam (SOCRATE) and a focused beam in order to better
understand the origin of damage in bulk KDP [99].
The thermal evolution of physical property of KDP single crystal has been
studied by several groups [100-107]. O'Keeffe and Perriono [108] had measured the
electrical conductivity of pure KDP and found that there is a knee point at 180 °C. The
activation energies were 0.72 eV and 0.56 eV for the temperature above and below 180
°C, respectively . Harris and Vella [109] measured the DC conductivity, a knee was
48
found in the thermal evolution of conductivity at 100 °C with the slightly different
activation energies of 0.99 eV and 0.53 eV . Sharon and Kalia [110] measured the DC
conductivity with activation energy of 0.76 eV without any anomaly in the conductivity
plot . The carrier of the electrical conduction in KDP-type crystal has been proved to be
proton by coulometric determination [111,112]. The results of TG/DTA and electrical
conductivity studies made by Sen et al [113] suggested that the potassium defects in
KDP are activated at the temperatures above 179 °C. Besides the proton, heavier
potassium ions in crystal are proposed to have contribution to the electrical conduction
at the temperatures above 179 °C.
Many studies on the growth kinetics of KDP crystals in the presence of
impurities have been reported [114-120]. KDP crystals doped with LAHCl in different
molar ratios were grown from aqueous solutions by slow cooling method. The presence
of LAHCl increases the growth rate and improves the quality of the crystal with highest
transparency[121]. An increase in solubility by the addition of urea and KCl impurities
may lead to decrease in the surface energy, which consequently decreases the rates of
layer displacement that cause an increase in the growth rate of KDP [122].The Raman
spectroscopy results of KDP crystal shows only five peaks at 150, 363, 515, 916, and
1082 cm−1, which are seven less than that predicted by space group theory. This implies
that the action of the long-range molecular force in KDP is weak, which would affect
the piezoelectric properties of KDP [123]. For KDP crystals grown from KH2PO4
solution with 0, 50, and 100 ppm EDTA additive, the thermal conductivity along [1 0 0]
and [0 0 1] directions were calculated based on the presented correlation model and
Raman scattering data. The calculated thermal conductivity enhancement along [1 0 0]
49
direction is 0.3 and 3.8%, corresponding to 50 and 100 ppm EDTA additive,
respectively [124].
Effect of cobalt (II) acetate hexahydrate on KDP single crystal was already
investigated and significant enhancement of the crystal properties was reported [125].
Sharon et al. [126] reported that the presence of cobalt in ADP also creates vacancies in
the crystal lattice and affects the electrical conductivity.
Rajesh et al [127] reported that the 1 mol % of DL-malic acid enhanced the
various properties of the ADP crystal. More than 1 mol % of dopant in several cases
decreased the crystalline perfection. The controlled doping of dopants, as long as the
crystal does not develop grain boundaries, results in increasing the second harmonic
generation efficiency [128].
Naturally in ADP and KDP crystals growth, the metallic cations present in the
crystals especially ones with high valency were considered to strongly affect the growth
habit and optical properties of the crystals. The most dangerous impurities are trivalent
metals Cr3+, Fe3+, Al3+, which make also important habit distortions [129]. An impurity
can suppress, enhance or stop the growth of crystal completely. It usually acts on certain
crystallographic
faces.
The
effects
depend
on
the
impurity
concentration,
in
synthesis
supersaturation, temperature,and pH of the solution [130].
ADP
acts
as
an
inexpensive
catalyst
the
of
dihydropyrimidinones which are important materials due to their biological and
therapeutic activities such as protection of wool from moths, antiviral activity,
antibacterial activity, antitumor, anti-inflammatory, analgesics, blood platelets
aggregation inhibitor, cardiovascular activity, potent calcium channel blockers, etc.
50
[131]. ADP is used as fire-prevention agent for fabric, timber and paper; as well as fireprevention coating, and dry powder for fire extinguisher. For food grade it is mainly
used as a fermentation agent, nourishment, and so on. It is also used as a high effective
non-chloride nitrogen and phosphorous compound fertilizer in agriculture. Moreover
ADP is useful in biological activity of humans [132-135].
Still studies on ADP crystals attract interest because of their unique nonlinear
optical, dielectric and anti ferroelectric properties. KDP crystals have attracted the
interests of many theoretical and experimental researchers, probably because of their
comparatively simple structure and very fascinating properties associated with hydrogen
bond system involving large isotope effect.
2.3. ADP –KDP Mixed Crystals
Potassium dihydrogen phosphate (KDP) and ammonium dihydrogen phosphate
(ADP) are the typical hydrogen bond crystals with excellent piezoelectric and nonlinear
optical properties [136–140], their growth rates and qualities have been improved
rapidly to meet the requirements of practical applications [141–144]. However, the
origin of their outstanding performances is still ambiguous and the corresponding
promotion strategies are explored [145–148]. In recent years, the strong dependences of
the structure distortion and hydrogen bond on the nonlinear optical coefficients are
discussed [149–151]. As an effective method to tune the crystal structure and the
hydrogen bond states, the growth of the mixed crystals of KDP and ADP, and the
determination of the detailed crystal structure with respect to composition are therefore
important for understanding the variation of crystal performances [152–166].
51
Figure 2.5: Crystal structure of ADP-KDP mixed crystal
The growth of the mixed crystals K1-X(NH4)XH2PO4 (KADPX) has been
conducted for a long time, because of their interesting physicochemical properties, such
as the competition of ferroelectric and antiferroelectric phase transition [154,155], the
occurrence of the dipolar glass state and the anomalous protonic conductivity [156–
158]. Askenasy and Nessler [128], and Ono et al [129] were reported the growth of
ADP-KDP mixed crystals at 273K and at 293 K respectively [129]. According to the
results obtained by Askensay and Nessler (at 273 K), the incorporation of ADP is high
when its concentration is above 65% in the solution, whereas Ono et al. reported that the
percentage of ADP present in the crystal and in the solution are almost same at 293 K.
Xu et al [169] reported that the induction period of the mixed solution increases
obviously with the approach of ammonium and potassium concentration. The mixed
crystals obtained in KDP-rich or ADP-rich solutions preserve their ideal morphologies
52
as that of KDP or ADP, respectively, though slight taper appears at the end of each run
due to the competition between different cations and the decrease of the growth driving
force. When the concentration of either of the components increases continuously, twin,
multiple twin and dendritic growth occur. KADPX crystals change from bulk to small
needles (the needles frequently self-assemble into a sphere), and the crystal qualities
degrade rapidly.
The mixing of ADP and KDP leads to significant change in the properties of
the crystals. In the past decades, many efforts have been made to promote the crystal’s
quality and increase the growth rate to meet the requirements of inertial confinement
fusion [171]. Mixing of ADP and KDP is being carried out for many years by several
researchers [170-172].
Figure 2.6: Dependence of growth morphology of ADP-KDP mixed crystals
53
The fundamental growth behaviors of potassium dihydrogen phosphate (KDP),
ammonium dihydrogen phosphate (ADP) and mixed crystals (KADP) were investigated
both experimentally and theoretically by Xue at al [171]. For KADP crystals, the
competitive growth between NH4
+
and K+ ions is an important factor, which leads to
the reduction of the growth rate along the a-axis. At the same time, the difference of
bond strength between K-O and HN-O bonds induces the occurrence of the stress along
the c-axis, and to a certain extent results in the formation of twin, multiple twin, and
dendritic crystals.
Srinivasan et al. [173,174] have investigated the different molar ratio
concentrations of the mixed crystals. However, bulk size crystals have not been grown.
AKDP mixed crystals with the ratio of 90:10 were grown from solution by slow cooling
along with bidirectional seed rotation technique by Rajesh et al [179]. The growth rate
of AKDP crystal along the ‘‘c’’ direction is approximately 3 times higher than the pure
ADP crystal. The growth along the a-axis is mainly controlled by the constituent anions,
and the growth along the c-axis is the synergetic results of deposition of anions and
cations [171,175]. The optical transparency of AKDP crystal is higher than pure ADP
and lower than pure KDP single crystals. It is noted that mixed crystal has higher
hardness than pure ADP and lower than pure KDP. This implies that the vacancies
present in the ADP are occupied by the KDP molecules and the lattices become strong
and leads to the increase of hardness.
Boukhiris et al. [10] have shown through X-ray diffraction studies on K1-x(NH4)
x
H2PO4 (0.0<x<1.0) that the thermal vibration of the phosphate group as well as the cell
parameters vary considerably with composition x. These observations below room
54
temperature may be due to a static disorder because of the large difference between cell
parameters of KDP and ADP, or due to fluctuations of their concentration throughout
the system of mixed crystals. At a higher temperature, it is then expected to show a
higher degree of disorder and other phase transitions related to it.
Shenoy et al [177] observed that it is difficult to grow good quality ADP-KDP
mixed crystals in the intermediate range of concentration, i.e., (0.09 ” x ” 0.85) by
isothermal slow evaporation. They have reported that the crystals of pure ADP and KDP
could be grown relatively easily and growth was dendritic in the intermediate range of
concentration, i.e. 0.25 ” x ” 0.75. Further, it has been confirmed that the induction
period is higher for mixed crystals than for the individual compounds and decreases as
the concentration of KDP increases. TG/DTA results revealed that increase in NH4
concentration decreases the decomposition temperature of the mixed crystals.
Sen gupta et al [172] showed that in KDP, O±H- - -O bonds lie almost in the
X±Y plane whereas in ADP, O±H- - -O bonds are inclined to the X±Y plane. It has been
observed that the angle between P±O and O±H- - -O bonds in ADP is 116.8 and that in
KDP is only 113.8. This difference gives rise to the c-direction packing with a
consequent elongation in ADP-KDP mixed crystals.
The KADP: Tl crystal demonstrates the room-temperature photoluminescence at
280 nm with the excitation spectrum well corresponding to the absorption of thallium
ions. Its photoluminescence intensity increases in comparison with KDP:Tl and ADP:Tl
crystals. The work-hardening index, n, is less than 2 for all the mixed crystals, and it
also decreases with the ADP content in the crystal similar to Vickers hardness number
[129]. The range of the optical window and the percentage of transmission of the mixed
55
crystals are compositional dependent, and they decrease when the ADP content of the
crystal increases. When the ADP concentration exceeds 15% in the crystal, the
transmission window in the shorter wavelength region is reduced significantly. The
diminishing transparency in this region indicates the presence of absorbing inclusions in
these mixed crystals [130].
There already exist some preliminary investigations [176-181] on KDP - ADP
mixed crystals grown by gel method. But none of them are complete in the sense of
studying the concentration dependence of physical properties of K1-x(NH4)xH2PO4. By
keeping this in mind, in our present work, we made an attempt to grow Good quality
ADP-KDP mixed crystals by using gel growth method, and we made an attempt to
investigate the effect of concentration on the various physico-chemical properties of K1x(NH4) x
H2PO4.
56
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