Cryst. Res. Technol. 44, No. 1, 54 60 (2009) / DOI 10.1002/crat.

200811184

Enhancement of stability of growth, structural and NLO properties of KDP crystals due to additive along with seed rotation
P. V. Dhanaraj1, N. P. Rajesh*1, P. Ramasamy1, M. Jeyaprakasan2, C. K. Mahadevan3, G. Bhagavannarayana4
1 2 3 4

Centre for Crystal Growth, SSN College of Engineering, Kalavakkam-603 110, India Advanced Training Institute, Guindy 600 032, India Physics Research Centre, S.T. Hindu College, Nagercoil-629 002, India C.G.C. Section, National Physical Laboratory, New Delhi-110 012, India

Received 12 January 2008, revised 23 July 2008, accepted 13 October 2008 Published online 14 November 2008 Key words solution growth, metastable zone width, dielectric properties, optical properties, XRD. PACS 61.05.cp, 61.72.sd, 81.10.Dn Potassium Acetate (CH3COOK) and Potassium Citrate (K3C6H5O7) as new additives were added into the potassium dihydrogen phosphate (KDP) solutions in different molar ratios. The metastable zone width and induction period with and without these additives were determined and compared. Dielectric measurements on pure and doped KDP crystals at various temperatures ranging from 313 to 423 K were carried out by the conventional parallel plate capacitor method which results low dielectric constant value dielectrics in doped crystals. The high resolution XRD studies show that CH3COOK doped KDP crystal and K3C6H5O7 doped KDP crystal do not contain any internal structural grain boundaries and indicates that the crystalline perfection is very good. Moreover, the addition of these potassium additives improves the quality of the crystal and yields highly transparent crystals with well defined features. The effect of additives on the growth, nucleation kinetics, structural, NLO and optical properties has been investigated.

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Introduction

The crystal growth of potassium dihydrogen phosphate (KDP) has a long history; due to the fact that it has very good piezoelectric and nonlinear optical properties [1], it is often used as a standard to characterize nonlinear optical responses of other crystal samples. It is widely applied as laser radiation converters and Qswitches in laser fusion for its high electro-optic and nonlinear coefficient, wide frequency conversion and high damage threshold against high power laser. Now KDP is the only nonlinear material that meets the requirements of inertial confined fusion [2]. Several researchers have carried out reasonable studies on pure KDP crystals [1,3]. The growth and quality of KDP crystals are affected by many factors such as additives, solution supersaturation and pH value. The key importance in this context is additives, which influence the physical properties of the crystals like growth kinetics [4-7] and surface morphology of crystal faces [8-10]. Strong changes in growth kinetics and crystal morphology may be caused by even very low additive concentrations, 0.11 ppm [11,12]. The growth promoting effect of KDP crystals is observed in the presence of organic additives [13,14] as well as inorganic additives [15,16]. This contribution can be attributed to the adsorption of additives on the surface of the nuclei resulting in change of the nuclei surface free energy and nucleation mechanism. One of the major growth inhibitors in the KDP system is the transition metal ions like Fe and Cr which are inherently present. For the
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* Corresponding author: e-mail: rajeshnp@ssnce.ac.in

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great majority of elements, segregation coefficient k has a tendency to decrease with increasing impurity concentration in the solution. The decrease is particularly strong in the second group of cations: increasing the initial Co2+, Mn2+, and Ni2+ concentrations by one to two orders of magnitude reduces k by one to three orders of magnitude. However, this effect, typical of metal (M2+) cations, is much weaker in the case of trivalent cations, which occupy the same interstitial position in the structure of KDP [17]. Our previous investigations reveal that the optimal addition of trivalent La3+ ions considerably prevents these bivalent ions from entering into the crystal lattice and results in reduced defects and dislocations [7]. The most efficient additives are reagents with those metal ions that have the same properties as the bulk solutions, or the solution auxiliary which can change the properties of solution, such as viscosity, surface tension etc., but they should not sacrifice the optical qualities of crystals. In order to identify other useful additives, which can have similar effects as La3+, we have chosen two potassium compounds as additives in the present investigation. With the aim of improving the quality of KDP crystals with better nonlinear optical properties for both academic and industrial uses, an attempt has been made in the present work to grow the KDP crystals by doping it with the additives potassium acetate (CH3COOK) and tripotassium citrate (K3C6H5O7) in different molar ratios.

Experimental

Solubility studies Potassium dihydrogen phosphate (GR-grade), potassium acetate and tripotassium citrate from Merck and Millipore water of resistivity 18.2 Mcm were used for all studies. No further purification was done. The solubility studies were done for pure KDP and KDP doped with small amount (5 mol%) of CH3COOK and K3C6H5O7 separately as additives. Solubility studies were carried out in a Constant Temperature Water Bath (CTB) with cryostat facility with an accuracy of 0.01 K. Stirring was done using an immersible magnetic stirrer. The solution was stirred continuously for 6 hours to achieve stabilization. Solubility was determined by gravimetric analysis for different temperatures (30 C 50 C). The solubility curve of pure KDP is shown in figure 1. Determination of metastable zone width Metastable zone width is an essential parameter for the growth of large size crystals from solution since it is the direct measure of the stability of the solution in its supersaturated region. Metastable zone width is an experimentally measurable quantity which depends on number of factors, such as stirring rate, cooling rate of the solution and presence of additional impurities [1820].The metastable zone width studies of pure and doped KDP solutions were carried out by adopting the polythermal method [19].The KDP solution (750 ml) saturated at 30 C was prepared according to the solubility diagram with continuous stirring using magnetic stirrer. Then the solution was filtered by the filtration pump and Whatman filter paper of pore size 11 m. Three similar beakers with 250 ml solution each were used, the first beaker contains pure KDP solution whereas the second and third beakers contain 5 mol% CH3COOK and 5 mol% K3C6H5O7doped KDP solutions respectively. Then pure and doped KDP solutions were kept in a CTB with cryostat facility. The solutions were stirred continuously for a period of 6 hours for stabilization using magnetic stirrer. It was slowly cooled at a desired cooling rate of 4 K/h, until the first crystal appeared, the temperature was instantly recorded. The difference between the saturation temperature and nucleation temperature was taken to be the maximum undercooling tmax. This gives the metastable zone width of the system. The experiment is repeated for different saturation temperatures 35 C, 40 C, 45 C, 50 C and the corresponding metastable zone widths are measured. Several nucleation runs (5-7 times) were carried out under controlled conditions. Determination of induction period The induction period, a measure of the nucleation rate is determined experimentally for KDP solutions with and without the presence of additives at different supersaturations by means of isothermal method [21].The direct vision method is used for measuring induction period. Aqueous solutions of various supersaturated concentrations were prepared. Supersaturation was obtained by natural cooling. Supersaturated solutions of equal volume (100 ml) were taken in the cells at a higher temperature. As the temperature of the cell reached the experimental temperature (35 C), the time was noted. Once the nucleation occurred, it grew quickly and a bright sparkling particle was seen. The time of observation of the sparkling particle in the cell from the time at which the solution reaches the experimental temperature gives the induction period of nucleation. Experiments were performed at selected degrees of supersaturation (C/Co), viz., 1.05, 1.075, 1.1, C being the mole fraction of solute in supersaturated solution and Co is the saturated concentration.
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P. V. Dhanaraj et al.: Enhancement of properties of KDP crystals

Crystal growth KDP crystals doped with CH3COOK and K3C6H5O7 separately (in concentrations 1 mol%, 5 mol% and 10 mol%) were grown from aqueous solutions with a simple apparatus that can be applied in certain forced convection configurations to maintain a higher homogeneity of the solution. This apparatus consists of seed rotation controller coupled with a stepper motor which is controlled by using a microcontroller based drive. This controller rotates the seed holder in the crystallizer. The seed crystal is mounted on the centre of the platform made up of acrylic material and is fixed into the crystallizer. The seed mount platform stirs the solution very well and makes the solution more stable, which resulted in better crystal quality. The uniform rotation of the seed is required so as not to produce stagnant regions or re-circulating flows, otherwise inclusions in the crystals will be formed due to inhomogeneous supersaturation in the solution [22]. The crystal growth is carried out in identical standard crystallizers used for conventional crystal growth by the method of temperature reduction. The crystallizer temperature is controlled using an external water bath and the temperature fluctuations are less than 0.01 K. The saturation temperature was 50oC. The solutions were filtered by filtration pump and Whatman filter paper of pore size 11 m under slight over pressure in a closed system. After filtration the solutions were overheated at 70 C for 24 h. Then the temperature of the solution was reduced slightly above the saturation point and seed crystal is mounted on the platform. The rotation rate of the platform with the crystal was about 40 rpm. From the saturation point, the temperature was decreased at 0.1 K per day at the beginning of the growth. As the growth progressed the temperature lowering rate was increased. After getting reasonable size, grown crystals were harvested for characterizations.

Results and discussion

Metastable zone width The metastability limit of CH3COOK added solution and K3C6H5O7 added solution is shown in figure 1 in comparison with the pure system. It is obvious from the figure that the zone widths for all the solutions decrease as the temperature increases. At the same time, the addition of dopants enhances the metastable zone width of KDP solutions for all the temperatures studied in this work, and makes the KDP solution more stable. Among the two additives, the additive K3C6H5O7 enhances the metastable zone width of KDP than the other additive CH3COOK especially at lower temperatures. Also it was observed that during the experiment the number of tiny crystals formed by spontaneous nucleation was appreciably reduced in the case of additive added solution compared with the pure one. The change in pH of the KDP solution by the addition of these dopants has a major role in the suppression of spontaneous nucleation.

Fig. 1 Solubility curve and metastability limit curves of pure, CH3COOK and K3C6H5O7 added KDP solutions.

Fig. 2 Values of induction period against supersaturation.

Induction period The experimental results of induction period () for the pure and additive added KDP solutions are presented. The experimental values of versus C/Co are plotted in figure 2. Considering the principles of homogeneous and heterogeneous nucleation theories, the free energy of formation of a nucleus under heterogeneous nucleation is less than that of a homogeneous condition [23,24]. Considering the additive added system it can be noticed that the induction period of doped KDP is higher than that of pure and it increases with the increase in the additive concentration. Among the additives, K3C6H5O7 has a higher induction period than CH3COOK at every concentration. The presence of additives in the system affects the
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nucleation behavior very considerably. This may be due to the suppression of chemical activity of the metal ions present in the KDP solution. Single crystal X-ray diffractometry Single crystal X-ray diffraction studies were done by using NONIUS CAD-4/MACH 3 diffractometer with MoK radiation in the wavelength 0.71073 . The cell data were obtained from least-squares refinement of the setting angles of 25 reflections. The unit cell parameters of pure and doped KDP samples are listed in table 1. The cell parameters of the doped KDP crystals are slightly differs from those of pure one, which may be attributed to the presence of CH3COOK and K3C6H5O7 in pure crystals. The XRD results confirm that the incorporation of these potassium compounds in the KDP crystal lattice has not changed the basic structure.
Table 1 Unit cell parameters of pure and doped KDP crystals. Samples Pure KDP KDP+CH3COOK KDP+ K3C6H5O7 a=b () 7.434 (3) 7.448 (3) 7.440 (2) c () 6.945 (2) 6.962 (4) 6.967 (5)

Fig. 3 FTIR spectrums of pure KDP, KDP doped with CH3COOK and KDP doped with K3C6H5O7.

Fig. 5 UV-VIS Transmission spectra of pure and doped KDP crystals.

Fig. 4 a) Plot of dielectric constant versus temperature for CH3COOK doped KDP crystals. b) Plot of dielectric constant versus temperature for K3C6H5O7 doped KDP crystals.

FTIR spectroscopy The influence of additives used in this work on the vibration frequencies of functional groups of pure KDP crystal has been identified by FTIR spectroscopy. The FTIR spectra were recorded in the regions 400-4000 cm-1 using a Perkin-Elmer FTIR Spectrum RXI spectrometer by KBr pellet technique. Figure 3 shows the FTIR spectra of the pure KDP, KDP doped with CH3COOK (5 mol%) and KDP doped with K3C6H5O7 (5 mol%). There is a broad envelope between 3700 cm-1 and 2500 cm-1. It includes O-H stretching vibrations of KDP. Hydrogen bonding within the crystal is suggested to be the cause for the broadening of the peak. The C-H vibrations of CH3 group in Potassium acetate are seen to provide its characteristics peaks just below 3000 cm-1. Its absence in the spectrum of pure KDP and its presence in the
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P. V. Dhanaraj et al.: Enhancement of properties of KDP crystals

spectrum of doped KDP clearly indicate the presence of CH3COOK in the lattice of KDP. The presence of water is well supported by its bending vibrations occurring at the band 1630 cm-1 [25]. The changes in the vibrations between 1600 cm-1 and 1200 cm-1 in the spectrum of K3C6H5O7 doped KDP indicates the presence of K3C6H5O7 in the lattice of KDP. The peaks below 1200 cm-1 are due to PO4 vibrations. Thus the presence of additives in the lattice of KDP is established by the FTIR analysis. Dielectric measurements The dielectric constant is one of the basic electrical properties of solids. Dielectric properties are correlated with electro-optic property of the crystals [26] .Practically, the presence of a dielectric between the plates of a condenser enhances the capacitance. Essentially, dielectric constant r is the measure of how easily a material is polarized in an external electric field. Crystals with high transparency and large surface defect-free (i.e. without any pit or crack or scratch on the surface, tested with a traveling microscope) grown by slow cooling method were used for the dielectric measurements. The size of the crystals was 6 mm x 6 mm x 2 mm. Samples were coated with good quality graphite to obtain a good conductive surface layer. The capacitance (Ccrys) were measured using the conventional parallel plate capacitor method with a fixed frequency (f) of 1 kHz using Agilent 4284A LCR meter at various temperatures ranging from 313 to 423 K. The measurements were done on a-b directions of the crystals. The samples were annealed up to 423 K to remove water molecules if present. The observations were made while cooling the sample. Air capacitance (Cair) was also measured. The dielectric constant of the Ccrys . As the crystal area was smaller than the plate area of the crystal was calculated using the relation r = Cair cell, parallel capacitance of the portion of the cell not filled with the crystal was taken into account and, Acrys C Cair 1 A consequently the above equation becomes r = crys Aair air , where Acrys is the area of the Acrys Cair crystals touching the electrode and Aair is the area of the electrode. The experiments were repeated for several times (5-7) under controlled conditions and the standard deviation was determined. Reproducible results with the accuracy of 2 % were obtained. The values of r obtained in the present study as shown in the figures 4 are of the same order with those obtained by the previous authors for the pure and certain other impurity added KDP crystals [27]. It is obvious from the figures that the values of r increase with the increase in temperature for all impurity concentrations considered in the present study. From figure 4, it is observed that the r values do not vary systematically with impurity concentration. However, it can be seen that these values are minimum for the additive added KDP with impurity concentration 5 mol% and increase when the impurity concentration increases further. These changes occurred in the cases of both additives with maximum in the doping of K3C6H5O7. As the samples were annealed before making measurements this may not be due to adsorbed water. Increase in the additive concentration may lead to high density of induced bulk defect states due to competition in getting the interstitial sites for the additive molecules to occupy. Decrease in additive concentration may lead to high density of induced bulk defect states due to availability of unoccupied interstitial sites. 5 mol% may be the proper concentration for the additive molecules to occupy the available interstitial sites in the KDP crystal structure. This may be the reason for the complex situation observed with the above dielectric parameters in the present study. However, it is interesting to note that 5 mol% additions of CH3COOK and K3C6H5O7 to KDP lead to a significant reduction of r value and consequently lead to low r value dielectric which is gaining more importance nowadays. In accordance with Miller rule, the lower value of dielectric constant is a suitable parameter for the enhancement of SHG coefficient [28]. Optical transmission studies Optical transmission spectra were recorded for the samples obtained from pure as well as additive added crystals grown by slow cooling method. The spectra were recorded in the wavelength region from 200 to 1000 nm using Lambda 35 spectrophotometer. C-cut crystal plates with 2 mm thickness were used for the study. The reported value of the optical transparency for KDP is from 190 to 1500 nm [29]. The UV-VIS spectra recorded for pure and doped (5 mol%) KDP crystals are shown in figure 5. It is clear from the figure that the crystal has sufficient transmission in the entire visible and IR region. The optical transparency of the KDP crystal is increased by the addition of CH3COOK and K3C6H5O7. It has also been observed that the cut off wavelength is the same for pure and additive added KDP crystals. The addition of the dopants in the optimum
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conditions to the solution is found to suppress the inclusions and improve the quality of crystal with higher transparency. HRXRD analysis Crystalline perfection has a strong influence on the efficiency of the physical properties of crystals [30]. Recently a lot of works reported that the changes in the crystalline perfection of KDP and ADP crystals by the effect of additives can analyzed by the high resolution XRD characterization technique [7,31,32]. A multicrystal X-ray diffractometer designed and developed at National Physical Laboratory, New Delhi [33] has been used to study the crystalline perfection of the single crystal(s). Before recording the diffraction curve, to remove the non-crystallized solute atoms which remained on the surface of the crystal and also to ensure the surface planarity, the specimen was first lapped and chemically etched in a non preferential etchent of water and acetone mixture in 1:2 volume ratio. Figure 6 (a) shows the high resolution diffraction curve (DC) recorded for K3C6H5O7 doped KDP specimen using (200) diffracting planes in symmetrical Bragg geometry by employing the multicrystal X-ray diffractometer with MoK1 radiation. The curve is reasonably sharp having the Full Width at Half Maximum (FWHM) of 18 arc s as expected for a nearly perfect crystal from the plane wave dynamical theory of X-ray diffraction [34]. Absence of additional peaks shows that the specimen crystal does not contain any internal structural grain boundaries and indicates that the crystalline perfection is very good.

Fig. 6 a) Diffraction curve recorded for a typical K3C6H5O7 doped KDP single crystal recorded for (200) diffracting planes. b) Diffraction curve recorded for a typical CH3COOK doped KDP single crystal recorded for (200) diffracting planes.

Figure 6 (b) shows the DC recorded for a KDP crystal doped with CH3COOK under the identical experimental conditions as that of figure 6 (a). The FWHM and the shape of the DC are almost same as that of KDP crystal doped with K3C6H5O7. The only difference is the reduction of peak intensity of Figure 6 (b) which is mainly due to the fact that the specimen doped with CH3COOK is considerably lesser than that of specimen doped with K3C6H5O7. Our previous work reported that the FWHM of pure KDP crystal is 22 arc s [7]. From the figure 6, one can conclude that the crystalline quality of KDP crystal is improved by the addition of either K3C6H5O7 or CH3COOK. NLO studies For the measurements of SHG efficiency, the output of Nd : YAG laser (Pro Lab 170 Quanta ray) was obtained through the crystalline powder sample by using Kurtz and Perry technique [35]. A laser beam of fundamental wavelength of 1064 nm, pulse energy of 4 mJ / pulse, pulse width of 10 ns and repetition rate of 10 Hz is used. 90 geometry was employed. The fundamental beam was filtered by using IR filter. The Photo multiplier tube (Philips Photonics) was used as detector. It was observed that the measured SHG efficiency of CH3COOK added KDP crystal was 1.21 and K3C6H5O7 added KDP crystal was 1.28 that of pure KDP crystal. The reason for increase in powder SHG efficiency demands detailed study.

Conclusions

The effect of CH3COOK and K3C6H5O7 addition on KDP solution increases the metastable zone width and induction period. This may be due to the suppression of chemical activity of the metal ions present in the KDP solution. Also growth rate of the crystal is found enhanced during crystal growth process. The incorporation of
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P. V. Dhanaraj et al.: Enhancement of properties of KDP crystals

dopants in the lattice of pure KDP is confirmed by the single crystal XRD studies and FTIR analysis. Dielectric studies indicate that 5 mol% addition of CH3COOK and K3C6H5O7 to KDP leads to low r value dielectrics, a knowledge gaining importance of late. The transmission spectrum reveals that the crystals have sufficient transmission in the entire visible and IR region. The grown doped KDP crystals are having very good crystalline perfection as determined by HRXRD analysis. This study will be helpful to grow high quality large size single crystals as well as to achieve faster growth rates of KDP crystals.
Acknowledgements This work, supported by the Department of Science and Technology, New Delhi, India under the grant of project ref-SR/FTP/PS-20/2005, is hereby gratefully acknowledged. One of the authors, P.V. Dhanaraj, is also indebted to SSN Educational and Charitable Trust, Chennai, India for providing him with the Junior Research Fellowship. The authors would like to acknowledge Dr. M. Palanichami, Department of Chemistry, Anna University, Chennai, India, for his valuable suggestions and for analyzing the FTIR spectrum.

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