Research Article
Growth and Characterization of Potassium succinate crystal
M.Vijayalakshmi
1, B.Ravindran
2*, M.Anitha
1*1 Assistant Professor of Physics, Rabiammal Ahamed Maideen College for Women, Thiruvarur. (Affiliated to Bharathidasan University)
2,*PG and Research Dept of physics, Thiru Vi Ka Govt Arts and College, Thiruvarur (Affiliated to Bharathidasan University)
1 Assistant Professor of Physics, Rabiammal Ahamed Maideen College for Women, Thiruvarur.(Affiliated to Bharathidasan University)
*Corresponding author
Article History:Received:11 november 2020; Accepted: 27 December 2020; Published online: 05 April 2021 ABSTRACT : Potassium succinate single crystals with attractive optical property like non linearity were grown
by proper synthesis. The crystal was grown by utilizing slow evaporation technique from the solution taking water as solvent. At room temperature the growth of crystal arises maintain constant rate of evaporation results in a formation of transparent crystals with high optical quality. Non volatile devices with high memory fabricated with ferroelectric materials observers the concentration of the researchers. Actually the ferroelectric materials have sufficient capability function as an actuator with high permittivity, good piezoelectric behaviour to create new NLO device. The following investigations were carried out to confirm the grown crystals. Single crystal and Powder X-ray diffraction studies were carried out to confirm the crystal structure, Uv-Visible studies for transparency and TGA/DSC for thermal stability. Finally the NLO property was determined by SHG efficiency. .
Keywords:Crystal Growth, Solution method, Powder XRD, FTIR, TG/DSC, UV-VIS, SHG, NLO.
1. INTRODUCTION
Devices with non-volatile memory fabricate using succinic acid crystal because of its special ferroelectric behaviour. [1, 2] The high permittivity of the ferro electric materials took the responsibility for the special optical non –linear behaviour which will satisfy the functional device. Variety capabilities such as piezoelectric actuator ,NLO devices etc., The dicarboxylic acid(succinic acid) in other words named an ber acid (cv) butane dioxic acid may be used as a precursor for a large number of important industrial chemicals like 1,4 butanediol, adipic acid, N-n ethyl pyrrolidinone, gamma – butyrolactone 2- pyrrolidipone[3-8] from the literature it was concluded that characterization and growth studyof the succinic acid various inclusion leads to an invention of a new quality NLO crystal due to the presence of high mobile electrons [9-10]. May suits for fabrication transistors. Because of they attract much attention of our researchers to focus on the growth and characterization of succinic acid with variety of dopants. The sustain were characterized using X-ray diffraction (with powder and single crystal) FTIR, UV-VIS-NIR, NLO properties.
2. Experimental procedure 2.1 Synthesis
Taking deionized water as a solvent the saturated solution was prepared by mixing SA and PB maintained under a ratio 1:1. The prepared solution was mixed by proper stirring using a magnetic stirrer for an about 2 hours. Then the solution was filtered by Whatmann filter paper collected in a clean dry beaker. The beaker with the collected homogenious solution was covered with a perforated paper and allows it to evaporate under a vibration free environment an after 15 days a transparent colourless crystal of size 12x13x4mm was harvested. The photo of the grown crystal was shown in the fig (i)
CH2COOH CH2COOK
+ 2KBr +2HBr
Fig (1) Morphology of Potassium Succinate crystal
3. Characterization
The potassium succinate single crystal were subjected to various studies to characterize X-ray diffraction studies such as single crystal and power were carried out using ENRAF NONIUS Cad4 single crystal diffractometer and BRUKER advanced D8 spectrometer with a wavelength of λ=1.54Aº utilizing a radiation of CuKα as source. The collected data were tabulated as shown in the fig (2). Functional group’s detection was recorded using the Fourier transform infra red spectrum using an instrument named as JASCO 4100. SHIMADZU 2600 instrument is used to predict the UV –Vis – NIR spectrum Q-switched laser emitted out from the Nd:YAG laser source is used to determine in the non linear optical property of the grown crystal under the technique developed by Kurtz and Perry on 1968. Thermal analyzers with a specification of TGA Q-500V20.10, build 36 are used to test the grown sample by heating the sample at a heating rate of 10Kmm-1 surrounded by nitrogen.
RESULT AND DISCUSSION 3.1 Powder X-rd Studies
Verification of reflection planes was done by subjectivity the grown Potassium Succinate crystals to Powder diffraction of X-rays. Fig (2) exposes the exhibiting X-ray diffraction pattern of Potassium Succinate crystals which confirms that the inclusion of Potassium interrupts the structure on comparision with pure Succinic acid reported values (2) Table 2 records the 2θ, spacing and hkl value obtained from the diffraction studies.
Table 2 Powder XRD of Potassium Succinate
3.2 Single crystal X- ray diffraction studies
ENRAF NONIUS Cad4 diffractometer is used to analyse the single crystal X-ray diffraction for the grown Potassium Succinate crystal. The lattice parameters and the crystal system along with the volume of the unit cell were calculated. The grown Potassium Succinate cryatal system was confirmed as monoclinic and the lattice parameter is tabulated below in the table 3. The cell parameters and volume of the unit cell were found to be in very good agreement with the reported data (3).
Table 3 Crystallographic data of Potassium Succinate crystal
2θ hkl 20 011 24 111 27 200 31 200 39 220 43 122 48 322 Crystal system
Unit cell parameters Volume
Axial length Interfacial angles Monoclinic a = 5.09 Aº b = 8.84 Aº c = 5.52 Aº α = 90.00 β = 91.74 γ = 90.00 248 A º 3
Figure 2: PXRD Patterns of Potassium Succinate crystal 4. UV – Visible Spectral Analysis
The optical transmission spectrum of Potassium Succinate crystals was predicted between ranges of 200-1200 nm wavelength and in shown in fig 3. From the transmission UV spectrum, it was found to be noted that there is high transmittance in the entire Infra- red, ultraviolet and visible region. Enhanced transmittance with a lower cut of wavelength at 245 nm concludes it and a material of high potential for optical device fabrication. The Ultra violet –Visible –Near Infra Red spectrum has vital importance in identification of right material for NLO application due to its excellent transparency without any absorption [11]. predict molecular structure details is also possible from UV-VIS –NIR spectrum due to their involvement in the excitation of e- in the π and σ orbital’s from the lower states of energy to higher energy states [12-13]. The wide range of visible transmission confirms the adoptability of grown crystals for NLO application [14].
Fig 3: UV- VIS transmittance spectrum of Potassium succinate crystal
4.1 Determination of optical constants
Refractive index extinction co-efficient of a material is highly essential to analyses the potential materials opto-electronic application which is used to decide the usage of optical behaviour materials [15]. Linear Part Extrapolation determines the band gap Eg [16] occurred in the high region of energy. The occurrence of a direct band gap of the crystal was suggested by the energy dependence of the absorption co-efficient which obeys the following high energy photon equation
(α h ν) 2 = A (Eg - hν)
Where , the term ‘A’ is assumed to be a constant, Eg is taken as optical band gap and the fig 3(a) shows the variation of (α h ν) 2 with E= hν(ev) in the absorption fundamental region. From the tauc’s plot the band gap was found to be recorded as 5.7 eV and extinction co-efficient of the grown Potassium Succinate crystal was found to be 5.3eV as shown from the fig 3(b).The following equation determined the extinction coefficient [16]. ‘T’ is the transmittance obtained from
T=(1−R)2exp(−at) 1−R2exp(−2at)
Come exist.
R=exp(−at)±√exp(−at)T−exp(−3at)T+exp−(2at)T2 exp(−at)T+exp−(2at)T
The following equation decided the refractive index(x) from the reflectance data n = - (R+1)±2 √R
(R−1)
Fig.3 (a) Plot of (αhν) 2 versus E (eV)
Fig. 3(b) Photon energy Vs extinction coefficient of Potassium succinate crystal 5. FTIR spectral studies
Association of various functional groups identification was determined using Fourier Transform –Infra red spectrum analysis. The grown Potassium succinate crystals spectrum of FTIR was recorded under a range of 4000-500 cm-1 wave numbers. Burker spectrometer utilizing the pellet KBr method was adopted for this study. Fig 5 exposes the FTIR spectrum and the take 5 exposes the functional group assignments O-H stretching was assigned to the strong bond formed at 3959.58 cm-1 .Observation of the peak at 2938.42 cm-1 corresponds to C-H stretching vibration. Sharp peak observation at 2649.32 cm-1 is due to O-H stretching. Formation of broad band at 2536.11 cm-1 is because of stretching vibration of C=O forms a peak at 1694.21 cm-1. Bending vibration of C-OH arised at 1418.30 cm-1 .The peak at 1309.64 cm-1 arises due to the symmetric stretching of COO -.Wagging vibration of CH2 takes the responsibility for the peak at 1201.35 cm-1. The peak at 914.69 cm-1 is became the out of plane bending of the bonded OH. The peak occurred at 801.52 cm-1 and 636.60 cm-1 are due to –CH bending and COO- Wagging respectively.
Table: 5 Functional group assignments of Potassium Succinate crystal
S.NO Frequency cm-1 Fuctional group assignments
1 3959.58 O-H Stretching
2 2930.42 C—H stretching vibrations
3 2649.32 O-H Stretching
4 2536.11 Broad Stretching vibration of O-H group
5 1694.21 -C=O group
6 1418.30 C-O-H in plane bending
7 1309.64 Symmetric stretch of COO-
8 1201.35 CH2 Wagging vibration
Wave number cm-1
Fig: 4 FTIR Spectrum of Potassium Succinate 6. TGA/DSC
The thermo gravimetric analysis was carried out for the grown Potassium Succinate sample at a rate of heating 20°C/min under a temperature range 0 to 1000°C in the atmosphere of nitrogen. The material decomposes rapidly above 249 ºC but the intial decomposition states at 192.80°C which was exposed but the accurence of two endothermic peaks. From the studies revealed that the Potassium Succinate crystal’s thermal stability extends up to 192°C. The DTA examination shows that the grown Potassium Succinate crystal undergoes two endothermic transistion around 192°C. No weight loss was occurred up to 190 °C which was Almost 90 % decomposition takes place at 925 °C. A residue of 10.91%was found. Hence the thermal stability with a operating temperatureof 192°C was determined for the grown Potassium succinate crystal using TGA/DSC analysis.
Fig.5 TG\DSC spectrum of Potassium Succinate 7. SHG measurement
The existence of delocalized π- electrons took the sole responsibility for the NLO behaviour by connecting the donors and acceptors. The enhancement of the asymmetrical polarizibility is due to the microscopically interactions. The total contribution for the non-linearity was each and every type of chemical essential bond as one whole crystal part. Presence of valence electrons in the metallic elements distributed to create an import on the linear and non linear behaviour of every constituent chemical bond[17] Testing of second Harmonic concentration is most important to check whether the grown crystal was active NLO material or not and it was done by Kurts Perry Powder process [18].Input pulse supply of 1.1 mj/ pulse was applied and an output of 2 mV is recorded which made us to decide that the grown Potassium succinate crystal will be used in NLO device fabrication application.
8. Conclusion
Optically good in quality single crystals of Potassium Succinate were synthesized and grown transulation by utilizing the seady technique the good crystalline nature of Potassium Succinate crystals was revealed from the Powder X-ray diffraction studies. The transparency profile obtained from the UV-VIS-NIR studies same an
10 801.51 -C-H bending
opinion that the grown crystal has very good optical transparency. On extension the UV-VIS-NIR studies the band gap determination was also done and it was predicted as Eg =5.7 eV from the slop obtained. Appearance of functional groups was identified using FTIR spectrum. TGA/DSC analysis confirms the thermal stability of the grown crystal as 192°C. Which indicates that the device fabrication using this crystal can with stand up to 192°C temperature The second harmonic generation is the Potassium Succinate was found to be recorded as 2 mV and it confirm that the grown crystal has very good NLO efficiency which leads to an idea to fabricate future NLO devices.
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