Skip to main content
SpringerLink
Log in

Os(VIII) doping effects on the properties and crystalline perfection of potassium hydrogen phthalate (KHP) crystals

  • Published:
Journal of Thermal Analysis and Calorimetry Aims and scope Submit manuscript

Abstract

The effect of dopant, Os(VIII) on the growth process, crystalline perfection and properties of potassium hydrogen phthalate (KHP) single crystals grown by a slow evaporation solution growth technique has been investigated. The XRD analysis of black-colored doped specimen reveals slight structural changes as a result of doping. The SEM images exhibit defect centers and crystal voids. The complex formation of KHP with Os(VIII) is evidenced by the considerable shift in λmax of the doped specimen and enhanced fluorescence intensity is observed by doping. Differential scanning calorimetry (DSC) and TG-DTA studies reveal the purity of the sample and no decomposition is observed up to the melting point. The high resolution X-ray diffraction (HRXRD) studies used to evaluate the crystalline perfection reveal some features on the capability of accommodating the dopant in the crystalline matrix. The diffraction curve (DC) patterns indicate that the high valence transition metal predominantly occupies the interstitial positions and the doping depresses the second harmonic generation (SHG) efficiency owing to the deterioration of crystalline perfection disturbing the charge transfer and nonlinearity.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. Jones JL, Paschen KW, Nicholson JB. Performance of curved crystals in the range 3 to 12 A. J Appl Opt. 1963;2:955–61.

    CAS  Google Scholar 

  2. Yoda O, Miyashita A, Murakami K, Aoki S, Yamaguchi N. Time-resolved X-ray absorption spectroscopy apparatus using laser plasma as an X-ray source. Proc SPIE Int Soc Opt Eng. 1991;1503:463–6.

    CAS  Google Scholar 

  3. Miniewicz A, Bartkiewicz S. On the electro-optic properties of single crystals of sodium, potassium and rubidium acid phthalates. Adv Mater Opt Electron. 1993;2:157–63.

    Article  CAS  Google Scholar 

  4. Kejalakshmy N, Srinivasan K. Growth, optical and electro-optical characterisations of potassium hydrogen phthalate crystals doped with Fe3+ and Cr3+ ions. Opt Mater. 2004;27:389–94.

    Article  CAS  Google Scholar 

  5. Shankar MV, Varma KBR. Piezoelectric resonance in KAP single crystals. Ferroelectr Lett Sect. 1996;21:55–9.

    Article  CAS  Google Scholar 

  6. Okaya Y. The crystal structure of potassium acid phthalate, KC6H4COOH·COO. Acta Crytallogr. 1965;19:879–82.

    Article  CAS  Google Scholar 

  7. Nisoli M, Pruneri V, Magni V, De Silvestri S, Dellepiane G, Cuniberti DC, et al. Ultrafast exciton dynamics in highly oriented polydiacetylene films. Appl Phys Lett. 1994;65:590–3.

    Article  CAS  Google Scholar 

  8. Timpanaro S, Sassella A, Borghesi A, Porzio W, Fountaine P, Goldmann M. Crystal structure of epitaxial quaterthiophene thin films grown on potassium acid phthalate. Adv Mater. 2001;13:127–30.

    Article  CAS  Google Scholar 

  9. Van Enckevort WJP, Jetten LAMJ. Surface morphology of the 010 faces of potassium hydrogen phthalate crystals. J Cryst Growth. 1982;60:275–85.

    Article  Google Scholar 

  10. Ester GR, Price R, Halfpenny PJ. An atomic force microscopic investigation of surface degradation of potassium hydrogen phthalate (KAP) crystals caused by removal from solution. J Cryst Growth. 1997;182:95–102.

    Article  CAS  Google Scholar 

  11. Murugakoothan P, Mohankumar R, Ushashree PM, Jayavel R, Dhansekaran R, Ramasamy P. Habit modification of potassium acid phthalate (KAP) single crystals by impurities. J Cryst Growth. 1999;207:325–9.

    Article  CAS  Google Scholar 

  12. Santos VP, Tremiliosi-Filho G. Effect of osmium coverage on platinum single crystals in the ethanol electrooxidation. J Electroanal Chem. 2003;554:395–405.

    Article  Google Scholar 

  13. Bhagavannarayana G, Parthiban S, Chandrasekaran C, Meenakshisundaram S. Effect of alkaline earth and transition metals doping on the properties and crystalline perfection of potassium hydrogen phthalate (KHP) crystals. CrystEngComm. 2009;11:1635–41.

    Article  CAS  Google Scholar 

  14. Bhagavannarayana G, Parthiban S, Meenakshisundaram S. An interesting correlation between crystalline perfection and second harmonic generation efficiency on KCl- and oxalic acid-doped ADP crystals. Cryst Growth Des. 2008;8:446–51.

    Article  CAS  Google Scholar 

  15. Bhagavannarayana G, Kushwaha SK, Parthiban S, Meenakshisundaram S. The influence of Mn-doping on the nonlinear optical properties and crystalline perfection of tris(thiourea)zinc(II) sulphate crystals: concentration effects. J Cryst Growth. 2009;311:960–5.

    Article  CAS  Google Scholar 

  16. Meenakshisundram S, Parthiban S, Bhagavannarayana G, Madhurambal G, Mojumdar SC. Influence of organic solvent on tristhioureazinc(II)sulphate crystals. J Therm Anal Calorim. 2009;96:125–9.

    Article  Google Scholar 

  17. Swiderski G, Kalinowska M, Wojtulewski S, Lewandowski W. Experimental (FT-IR, FT-Raman, 1H NMR) and theoretical study of magnesium, calcium, strontium, and barium picolinates. Spectrochim Acta A. 2006;64:24–33.

    Article  CAS  Google Scholar 

  18. Flakus HT, Jablonska M. Study of hydrogen bond polarized IR spectra of cinnamic acid crystals. J Mol Struct. 2004;707:97–108.

    Article  CAS  Google Scholar 

  19. Hanai K, Kuwae A, Takai T, Senda H, Kunimoto K. A comparative vibrational and NMR study of cis-cinnamic acid polymorphs and trans-cinnamic acid. Spectrochim Acta A. 2001;57:513–9.

    Article  CAS  Google Scholar 

  20. Hsich T, Su C, Su C, Chen C, Liou CH, Li-Hwa L. Using experimental studies and theoretical calculations to analyze the molecular mechanism of coumarin, p-hydroxybenzoic acid, and cinnamic acid. J Mol Struct. 2005;741:193–9.

    Article  Google Scholar 

  21. Vasudevan G, Anbusrinivasan P, Madhurambal G, Mojumdar SC. Thermal analysis, effect of dopants, spectral characterisation and growth aspects of KAP crystals. J Therm Anal Calorim. 2009;96:99–102.

    Article  CAS  Google Scholar 

  22. Julg A, Francois P. Recherches sur la géométrie de quelques hydrocarbures non-alternants: son influence sur les énergies de transition, une nouvelle définition de l’aromaticité. Theor Chim Acta. 1967;8:249–59.

    Article  CAS  Google Scholar 

  23. Kalinowska M, Siemieniuk E, Kostro A, Lewandowski W. The application of Aj, BAC, I6, HOMA indexes for quantitative determination of aromaticity of metal complexes with benzoic, salicylic, nicotinic acids and benzene derivatives. J Mol Struct. 2006;761:129–41.

    CAS  Google Scholar 

  24. Anbusrinivasan P, Madhurambal G, Mojumdar SC. p-N, N-dimethylaminobenzaldehyde (DAB) grown by solution technique using CCl4 as growth medium. J Therm Anal Calorim. 2009;96:111–5.

    Article  CAS  Google Scholar 

  25. Varsanyi G. Assignments for vibrational spectra of 700 benzene derivatives. Budapest: Academiai Kiado; 1973.

    Google Scholar 

  26. Reva ID, Stepanian SG. An infrared study on matrix-isolated benzoic acid. J Mol Struct. 1995;349:337–40.

    Article  CAS  Google Scholar 

  27. Spanian SG, Reva ID, Radchenko ED, Sheina GG. Infrared spectra of benzoic acid monomers and dimers in argon matrix. Vib Spectrosc. 1996;11:123–33.

    Article  Google Scholar 

  28. Wienda DA, Feng TL, Barron AR. Structure of α-trans-cinnamic acid. Acta Crystallogr C. 1989;45:338–9.

    Article  Google Scholar 

  29. Bryan RF, Fryeberg DP. Crystal structures of α-trans- and p-methoxy-cinnamic acids and their relation to thermal mesomorphism. J Chem Soc Perkin Trans. 1975;2:1835–40.

    Google Scholar 

  30. Madhurambal G, Mojumdar SC, Hariharan S, Ramasamy P. TG, DTC, FT-IR and Raman spectral analysis of Zna/Mgb ammonium sulfate mixed crystals. J Therm Anal Calorim. 2004;78:125–33.

    Article  CAS  Google Scholar 

  31. Lewandowski W, Dasiewicz B, Koczon P, Skierski J, Dobrosz-Teperek K, Swislocka R, et al. Vibrational study of alkaline metal nicotinates, benzoates and salicylates. J Mol Struct. 2002;604:189–93.

    Article  CAS  Google Scholar 

  32. Varshney G, Agrawal A, Mojumdar SC. Pyridine based cerium(IV) phosphate hybrid fibrous ion exchanger: Synthesis, characterization and thermal behaviour. J Therm Anal Calorim. 2007;90:731–4.

    Article  CAS  Google Scholar 

  33. Dichi P, Kellerhals M, Lounila J, Wasser R, Hiltunen Y, Jokisari J, et al. NMR structure of partially oriented tellurophene: correction of molecular deformations and determination of bond interaction parameters. Magn Res Chem. 2005;25:244–7.

    Google Scholar 

  34. Mojumdar SC. Thermoanalytical and IR-spectral investigation of Mg(II) complexes with heterocyclic ligands. J Therm Anal Calorim. 2001;64:629–36.

    Article  CAS  Google Scholar 

  35. Chenthamarai S, Jayaraman D, Meera K, Santhanaraghavan P, Subramanian C, Bocelli G, Ramasamy P. Growth and single crystal XRD characterization of undoped and doped 4-hydroxyacetophenone. Cryst Eng. 2001;4:37–48.

    Article  CAS  Google Scholar 

  36. Hameed SH, Ravi G, Dhanasekaran R, Ramasamy P. Studies on organic indole-3-aldehyde single crystals. J Cryst Growth. 2000;212:227–32.

    Article  Google Scholar 

  37. Patel RN, Pandeya KB. Specific displacement of glutathione from the Pt(II)–glutathione adduct by Cu(II) in neutral phosphate buffer. J Inorg Biochem. 1998;71:109–13.

    Article  Google Scholar 

  38. Mojumdar SC, Madhurambal G, Saleh MT. A study on synthesis and thermal, spectral and biological properties of carboxylato-Mg(II) and carboxylate-Cu(II) complexes with bioactive ligands. J Therm Anal Calorim. 2005;81:205–10.

    Article  CAS  Google Scholar 

  39. Rathore HS, Varshney G, Mojumdar SC, Saleh MT. Synthesis, characterization and fungicidal activity of zinc diethyldithiocarbamate and phosphate. J Therm Anal Calorim. 2007;90:681–6.

    Article  CAS  Google Scholar 

  40. Mojumdar SC, Sain M, Prasad RC, Sun L, Venart JES. Selected thermoanalytical methods and their applications from medicine to construction. J Therm Anal Calorim. 2007;90:653–62.

    Article  CAS  Google Scholar 

  41. Mojumdar SC, Lebruskova K, Valigura D. Thermal stability and spectral properties of pyrazine-2,3-dicarboxylatocopper(II) complexes with ronicol. Chem Pap. 2003;57:245–9.

    CAS  Google Scholar 

  42. Mojumdar SC, Capek I, Capek P, Fialova L, Berek D. Preparation of composite nanoparticles on the base of starch. Res J Chem Environ. 2007;11:5–12.

    CAS  Google Scholar 

  43. Meenakshisundaram S, Parthiban S, Sarathi N, Kalavathy R, Bhagavannarayana G. Effect of organic dopants on ZTS single crystals. J Cryst Growth. 2006;293:376–81.

    Article  CAS  Google Scholar 

  44. Kuznetsov VA, Okhrimenko TM, Rak M. Growth promoting effect of organic impurities on growth kinetics of KAP and KDP crystals. J Cryst Growth. 1998;193:164–73.

    Article  CAS  Google Scholar 

  45. Kurtz SK, Perry TT. A powder technique for the evaluation of nonlinear optical materials. J Appl Phys. 1968;39:3798–813.

    Article  CAS  Google Scholar 

  46. Lal K, Bhagavannarayan G. A high-resolution diffuse X-ray scattering study of defects in dislocation-free silicon crystals growth by the float-zone method and comparison with Czochralski-grown crystals. J Appl Cryst. 1989;22:209–15.

    Article  CAS  Google Scholar 

  47. Bhagavannarayana G, Parthiban S, Meenakshisundarm SP. Enhancement of crystalline perfection by organic dopants in ZTS, ADP and KHP crystals as investigated by high-resolution XRD and SEM. J Appl Crystallogr. 2006;39:784–90.

    Article  CAS  Google Scholar 

  48. Batterman BW, Cole H. Dynamical diffraction of X rays by perfect crystals. Rev Mod Phys. 1964;36:681–717.

    Article  CAS  Google Scholar 

Download references

Acknowledgements

One of the authors GB acknowledges Dr. Vikram Kumar, Director, NPL and Dr. B. R. Chakraborthi for their constant encouragement to carry out the present investigations. The authors are grateful to the authorities of Annamalai University for providing the experimental facilities used in the present investigation.

Author information

Authors and Affiliations

  1. Department of Chemistry, Annamalai University, Annamalainagar, 608 002, India

    K. Muthu, C. Chandrasekaran, S. Parthiban & S. P. Meenakshisundaram

  2. Materials Characterization Division, National Physical Laboratory, New Delhi, 110 012, India

    G. Bhagavannarayana

  3. Department of Engineering, University of New Brunswick, Saint John, NB, E2L 4L5, Canada

    S. C. Mojumdar

Authors
  1. K. Muthu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. G. Bhagavannarayana
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. C. Chandrasekaran
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. S. Parthiban
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. S. P. Meenakshisundaram
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. S. C. Mojumdar
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to S. C. Mojumdar.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Muthu, K., Bhagavannarayana, G., Chandrasekaran, C. et al. Os(VIII) doping effects on the properties and crystalline perfection of potassium hydrogen phthalate (KHP) crystals. J Therm Anal Calorim 100, 793–799 (2010). https://doi.org/10.1007/s10973-010-0759-z

Download citation

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10973-010-0759-z

Keywords

Search

Navigation