Enhancement in pyroelectric detection sensitivity for flexible LiNbO3/PVDF nanocomposite films by inclusion content control

Original Paper


The pyroelectric properties of polymer-ceramic nanocomposites of Lithium niobate/Poly (vinylidene fluoride) or LiNbO3/PVDF (abbreviated LN/PVDF) for thermal/infrared sensing applications are reported in this work. The composites are prepared by dispersing nanoparticles of LiNbO3, with particle size in the range 45–65 nm, in β-PVDF matrix at varying volume fractions, and cast in the form of flexible films by solvent-cast technique. The electro-active β-phase of PVDF is confirmed by powder X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and Differential Scanning Calorimetry (DSC) analyses. The thermal properties, thermal conductivity and specific heat capacity, of the composites are determined by a photothermal technique. The prepared films have been poled in a high dc electric field, and their pyroelectric and dielectric properties measured by direct methods. From these data the pyroelectric figures of merit of the composite films have been determined and their values compared with corresponding values for pure PVDF film. The Shore hardness of the films has been measured to estimate the extent to which the flexibility of the films is affected by the addition of ceramic. Significant enhancement in pyroelectric sensitivity has been obtained with increase in volume fraction of LiNbO3 nanoparticles. However, this enhancement is at the expense of the flexibility of the composite; so one has to strike a balance between the two while selecting a suitable composition for the development of pyroelectric sensors with these materials. The results of this work provide guidelines for this selection.


Lithium niobate Poly (vinylidene difluoride) Nanocomposites Pyroelectricity Pyroelectric figure of merit Photothermal technique 



Work supported by DST, Government of India under Nanomission scheme (SR/NM/NS-30/2010). One of the authors (MSJ) thanks DST, New Delhi for a fellowship under PURSE scheme. Sophisticated Analytical Instrument Facility (SAIF), STIC, Cochin is gratefully acknowledged for sample characterization and technical support.


  1. 1.
    Lee J, Mahendra S, Alvarez PJJ (2010) Nanomaterials in the construction industry: a review of their applications and environmental health and safety considerations. ACS Nano 4:3580–3590CrossRefGoogle Scholar
  2. 2.
    Saji VS, Choe HC, Yeung KWK (2010) Nanotechnology in biomedical applications: a review. Int J Nano Biomater 3:119–139CrossRefGoogle Scholar
  3. 3.
    Chen X, Xu S, Yao N, Shi Y (2010) 1.6 V nanogenerator for mechanical energy harvesting using PZT nanofibers. Nano Lett 10:2133–2137CrossRefGoogle Scholar
  4. 4.
    Iavicoli I, Fontana L, Leso V, Bergamaschi A (2013) The effects of nanomaterials as endocrine disruptors. Int J Mol Sci 14:16732–16801CrossRefGoogle Scholar
  5. 5.
    Huang X, Li L, Liu T, Hao N, Liu H, Chen D, Tang F (2011) The shape effect of mesoporous silica nanoparticles on biodistribution, clearance, and biocompatibility in Vivo. ACS Nano 5:5390–5399CrossRefGoogle Scholar
  6. 6.
    Sethi M, Pacardo DB, Knecht MR (2010) Biological surface effects of metallic nanomaterials for applications in assembly and catalysis. Langmuir 26:15121–15134CrossRefGoogle Scholar
  7. 7.
    Orvatinia M, Heydarianasl M (2012) A new method for detection of continuous infrared radiation by pyroelectric detectors. Sensors Actuators A Phys 174:52–57CrossRefGoogle Scholar
  8. 8.
    Batra AK, Aggarwal MD (2013) Pyroelectric materials: Infrared detectors, particle accelerators, and energy harvesters. SPIE Press Book, ISBN: 9780819493316Google Scholar
  9. 9.
    Rogalski A (2011) Infrared detectors, 2nd edn. CRC Press, Taylor & Francis Group, USAGoogle Scholar
  10. 10.
    Goniakowski J, Finocchi F, Noguera C (2008) Polarity of oxide surfaces and nanostructures. Rep Prog Phys 71:016501/1-55CrossRefGoogle Scholar
  11. 11.
    Rosenman G, Shur D, Krasik YE, Dunaevsky A (2000) Electron emission from ferroelectrics. J Appl Phys 88:6109–6161CrossRefGoogle Scholar
  12. 12.
    Lang SB (2005) Pyroelectricity: from ancient curiosity to modern imaging tool. Phys Today 58:31–36CrossRefGoogle Scholar
  13. 13.
    Whatmore RW (1986) Pyroelectric devices and materials. Rep Prog Phys 49:1335–1386CrossRefGoogle Scholar
  14. 14.
    Muralt P (2001) Micromachined infrared detectors based on pyroelectric thin films. Rep Prog Phys 64:1339–1388CrossRefGoogle Scholar
  15. 15.
    Corsi C (2012) Infrared: a key technology for security systems. Adv Opt Technol 2012:838752/1-15Google Scholar
  16. 16.
    Cilulko J, Janiszewski P, Bogdaszewski M, Szczygielska E (2013) Infrared thermal imaging in studies of wild animals. Eur J Wildl Res 59:17–23CrossRefGoogle Scholar
  17. 17.
    Kad RS (2013) IR thermography is a condition monitor technique in industry. IJAREEIE 2:988–993Google Scholar
  18. 18.
    Suriani MJ, Ali A, Khalina A, Sapuan SM, Haftirman AS (2012) Detection of defects in natural composite materials using thermal imaging technique. Mater Test 54:340–346CrossRefGoogle Scholar
  19. 19.
    Hanemann T, Szabo DV (2010) Polymer-nanoparticle composites: from synthesis to modern applications. Materials 3:3468–3517CrossRefGoogle Scholar
  20. 20.
    Graca MPF, Prezas PR, Costa MM, Valente MA (2012) Structural and dielectric characterization of LiNbO3 nano-size powders obtained by Pechini method. J Sol-Gel Sci Technol 64:78–85CrossRefGoogle Scholar
  21. 21.
    Rabiei P, Gunter P (2004) Optical and electro-optical properties of submicrometer lithium niobate slab waveguides prepared by crystal ion slicing and wafer bonding. Appl Phys Lett 85:4603–4605CrossRefGoogle Scholar
  22. 22.
    Peng Q, Cohen RE (2011) Origin of pyroelectricity in LiNbO3. Phys Rev B 83:220103/1-4CrossRefGoogle Scholar
  23. 23.
    Jaffe B, Cook WR Jr, Jaffe H (2012) Piezoelectric ceramics. Academic, LondonGoogle Scholar
  24. 24.
    Mohimi A, Richardson P, Catton P, Gan TH, Balachandran W, Selcuk C (2013) High temperature dielectric, elastic and piezoelectric coefficients of shear type lithium niobate crystals. Key Eng Mater 543:117–120CrossRefGoogle Scholar
  25. 25.
    Bhatti IN, Banerjee M, Bhatti IN (2013) Effect of annealing and time of crystallization on structural and optical properties of PVDF thin film using acetone as solvent. IOSR-JAP 4:42–47CrossRefGoogle Scholar
  26. 26.
    Satapathy S, Pawar S, Gupta PK, Varma KBR (2011) Effect of annealing on phase transition in poly(vinylidene fluoride) films prepared using polar solvent. Bull Mater Sci 34:727–733CrossRefGoogle Scholar
  27. 27.
    Seminara L, Capurro M, Cirillo P, Cannata G, Valle M (2011) Electro-mechanical characterization of piezoelectric PVDF polymer films for tactile sensors in robotics applications. Sensors Actuators A Phys 169:49–58CrossRefGoogle Scholar
  28. 28.
    Graz I, Krause M, Gogonea SB, Bauer S, Lacour SP, Ploss B, Zirkl M, Stadlober B, Wagner S (2009) Flexible active-matrix cells with selectively poled bifunctional polymer-ceramic nanocomposite for pressure and temperature sensing skin. J Appl Phys 106:034503/1-5CrossRefGoogle Scholar
  29. 29.
    Jeon J, Lee HBR, Bao Z (2013) Flexible wireless temperature sensors based on Ni microparticle filled binary polymer composites. Adv Mater 25:850–855CrossRefGoogle Scholar
  30. 30.
    Sanchez-Garcia MD, Gimenez E, Lagaron JM (2008) Morphology and barrier properties of solvent cast composites of thermoplastic biopolymers and purified cellulose fibers. Carbohydr Polym 71:235–244CrossRefGoogle Scholar
  31. 31.
    Byer RL, Roundy CB (1972) Pyroelectric coefficient direct measurement technique and application to a nanosecond-response-time detector. Ferroelectrics 3:333–338CrossRefGoogle Scholar
  32. 32.
    Marshall JM, Zhang Q, Whatmore RW (2008) Corona poling of highly (001)/(100)-oriented lead zirconate titanate thin films. Thin Solid Films 516:4679–4684CrossRefGoogle Scholar
  33. 33.
    Yun S, Kim JH, Li Y, Kim J (2008) Alignment of cellulose chains of regenerated cellulose by corona poling and its piezoelectricity. J Appl Phys 103:083301/1-4Google Scholar
  34. 34.
    Menon CP, Philip J (2000) Simultaneous determination of thermal conductivity and heat capacity near solid state phase transitions by a photopyroelectric technique. Meas Sci Technol 11:1744–1749CrossRefGoogle Scholar
  35. 35.
    Lee SH, Cho HH (2010) Crystal structure and thermal properties of poly(vinylidene fluoride)-carbon fiber composite films with various drawing temperatures and speeds. Fibers Polym 11:1146–1151CrossRefGoogle Scholar
  36. 36.
    Yu L, Cebe P (2009) Crystal polymorphism in electrospun composite nanofibers of poly (vinylidene fluoride) with nanoclay. Polymer 50:2133–2141CrossRefGoogle Scholar
  37. 37.
    Murugaraj P, Mainwaring D, Mora-Huertas N (2005) Dielectric enhancement in polymer-nanoparticle composites through interphase polarizability. J Appl Phys 98:054304/1-6CrossRefGoogle Scholar
  38. 38.
    Sakai H, Konno K, Murata H (2009) Tuning of threshold voltage of organic field-effect transistors by space charge polarization. Appl Phys Lett 94:073304/1-3CrossRefGoogle Scholar
  39. 39.
    Sidney BL, Das-Gupta DK (2000) Pyroelectricity: fundamentals and applications. Ferroelectr Rev 2:217–223Google Scholar
  40. 40.
    Whatmore RW, Watton R (2001) Pyroelectric materials and devices’ in ‘infrared detectors and emitters: materials and devices’. Kluwer Academic Publishers, The NetherlandsGoogle Scholar
  41. 41.
    Guggilla P, Batra AK, Currie JR, Aggarwal MD, Alim MA, Lal RB (2006) Pyroelectric ceramics for infrared detection applications. Mater Lett 60:1937–1942CrossRefGoogle Scholar
  42. 42.
    Rogalski A (2003) Review- infrared detectors: status and trends. Prog Quantum Electron 27:59–210CrossRefGoogle Scholar
  43. 43.
    Aggarwal M, Currie JR Jr, Penn BG, Batra AK, Lal RB (2007) Polymer-ceramic composite materials for pyroelectric infrared detectors: an overview. http://ntrs.nasa.gov/archive/nasa/casi.ntrs.nasa.gov/20080013166.pdf
  44. 44.
    Chan HLW, Chan WK, Zhang Y, Choy CL (1998) Pyroelectric and piezoelectric properties of lead titanate/polyvinylidene fluoride-trifluoroethelene 0–3 composites. IEEE Trans Dielectr Electr Insul 5:505–512CrossRefGoogle Scholar
  45. 45.
    Zhang QQ, Bernd Ploss HL, Chan W, Choi CL (2000) Integrated pyroelectric arrays based on PCLT/P(VDF-TrFE) composite. Sensors Actuators A Phys 86:216–219CrossRefGoogle Scholar
  46. 46.
    Hilczer B, Kulek J, Markiewicz E, Kosec M (2003) Dielectric and pyroelectric response of PLZT-P(VDF/TrFE) nano-composites. Ferroelectrics 293:253–265Google Scholar
  47. 47.
    Guggilla P, Batra AK, Edwards ME (2009) Electrical characterization of LiTaO3:P(VDF–TrFE) composites. J Mater Sci 44:5469–5474CrossRefGoogle Scholar
  48. 48.
    Navid A, Lynch CS, Pilon L (2010) Purified and porous poly(vinylidene fluoride-trifluoroethylene) thin films for pyroelectric infrared sensing and energy harvesting. Smart Mater Struct 19:055006/1-13CrossRefGoogle Scholar
  49. 49.
    Dietze M, Krause J, Solterbeck CH, Es SM (2007) Thick film polymer-ceramic composites for pyroelectric applications. J Appl Phys 101:054113/1-7CrossRefGoogle Scholar
  50. 50.
    Jayalakshmy MS, Philip J (2014) Pyroelectric figures of merit and associated properties of LiTaO3/polyvinylidene difluoride nanocomposites for thermal/infrared sensing. Sensors Actuators A Phys 206:121–126CrossRefGoogle Scholar
  51. 51.
    Barber P, Balasubramanian S, Anguchami Y, Gong S, Wibowo A, Gao H, Ploehn HJ, Loye HCZ (2009) Polymer composite and nanocomposite dielectric materials for pulse power energy storage. Materials 2:1697–1733CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  1. 1.Department of InstrumentationCochin University of Science and TechnologyCochinIndia
  2. 2.Amal Jyothi College of EngineeringKottayamIndia

Personalised recommendations