Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc0.5Ta0.5O3) films

Gupta, Sanju

doi:10.1111/jace.18874

Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc_0.5Ta_0.5O₃) films

Journal Article · Thu Dec 01 00:00:00 EST 2022 · Journal of the American Ceramic Society

DOI:https://doi.org/10.1111/jace.18874· OSTI ID:1961834

^[1]

Pennsylvania State Univ., University Park, PA (United States); Penn State University

Lead scandium tantalate (PbSc_0.5Ta_0.5O₃, PST), an order/disorder ferroelectric, is a potential candidate for electrocaloric cooling and pyroelectric infrared (IR) detector. In this work, we report the phase transformation kinetics from two series of samples containing pure amorphous and mixture of amorphous and pyrochlore to desired perovskite phase using postdeposition rapid thermal processing (RTP) as well as growth mechanism of RF sputtered PST thin films using excess lead target on platinized silicon (Pt/Ti/SiO₂/Si) substrates. We find that small changes in the temperature ramp have a large effect on the degree of perovskite conversion (ferroelectric phase), orientation (crystallographic texture), and long-range order parameter (< S₁₁₁ >). Through isothermal annealing, we obtained optimal perovskite phase at ≥700°C temperature. The phase transformation is characterized by spontaneous formation of center-type in-plane radial rosette-like structures revealed by scanning electron microscopy. The PST perovskite crystallites were found to coexist with pyrochlore in RTP annealed films. The volume fractions for perovskite and pyrochlore phase were obtained from the analysis of “rosettes” and respective X-ray diffraction intensities which helped to determine various parameters associated with phase kinetics (n, k, and activation energy, Ea) and accompanying growth. The effective activation energies of perovskite transition and growth were found to be 332 ± 11 kJ/mol (345 ± 11 kJ/mol) and 114 ± 10 kJ/mol (122 ± 10 kJ/mol), respectively, for pure amorphous only (and mixed amorphous and pyrochlore) phase following nucleation-growth controlled Avrami's equation. A linear growth rate (n~1) for the perovskite phase indicates predominant interface-controlled process and diffusion-limited phenomena thus inhibiting rosette size owing to reactant depletion and soft impingement at the grain boundary. However, the growth behavior is isotropic in two-dimension parallel to the plane of the substrates for both sample series. Furthermore, lead loss was severe for in-situ growth and RTP combined with conventional furnace annealing than those of RTP only films, which were closer to stoichiometric albeit with excess lead and marginal oxygen vacancies (V_o).

View Accepted Manuscript (DOE)

Research Organization:: Pennsylvania State Univ., University Park, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0021118

OSTI ID:: 1961834

Journal Information:: Journal of the American Ceramic Society, Journal Name: Journal of the American Ceramic Society Journal Issue: 4 Vol. 106; ISSN 0002-7820

Publisher:: American Ceramic SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (50)

Optical Properties of Pyrochlore Lead Scandium Tantalate Crystals Marinova, V.; Petrova, D.; Veleva, M. Crystal Research and Technology, Vol. 33, Issue 1 https://doi.org/10.1002/(SICI)1521-4079(1998)33:1<119::AID-CRAT119>3.0.CO;2-8	journal	January 1998
Scavenging Energy Sources Using Ferroelectric Materials Li, Hongyu; Bowen, Chris R.; Yang, Ya Advanced Functional Materials, Vol. 31, Issue 25 https://doi.org/10.1002/adfm.202100905	journal	April 2021
Scalable Synthesis of Morphotropic Phase Boundary Lead Zirconium Titanate Nanowires for Energy Harvesting Zhou, Zhi; Tang, Haixiong; Sodano, Henry A. Advanced Materials, Vol. 26, Issue 45 https://doi.org/10.1002/adma.201403286	journal	October 2014
Enabling Distributed Intelligence with Ferroelectric Multifunctionalities Yao, Kui; Chen, Shuting; Lai, Szu Cheng Advanced Science, Vol. 9, Issue 1 https://doi.org/10.1002/advs.202103842	journal	October 2021
Unveiling Center‐Type Topological Defects on Rosettes of Lead Zirconate Titanate Associated to Oxygen Vacancies Neckel, Itamar T.; da Silva, Francisco M. C.; Guedes, Eduardo B. Annalen der Physik, Vol. 534, Issue 2 https://doi.org/10.1002/andp.202100219	journal	December 2021
Normal mode determination in crystals Rousseau, D. L.; Bauman, R. P.; Porto, S. P. S. Journal of Raman Spectroscopy, Vol. 10, Issue 1 https://doi.org/10.1002/jrs.1250100152	journal	January 1981
Crystallization kinetics of polyetheretherketone (peek) matrices Velisaris, Chris N.; Seferis, James C. Polymer Engineering and Science, Vol. 26, Issue 22 https://doi.org/10.1002/pen.760262208	journal	December 1986
Order–disorder reactions in the ferroelectric perovskites Pb(Sc1/2Nb1/2)O3 and Pb(Sc1/2Ta1/2)O3. I. Kinetics of the ordering process Stenger, C. G. F.; Burggraaf, A. J. Physica Status Solidi (a), Vol. 61, Issue 1 https://doi.org/10.1002/pssa.2210610132	journal	September 1980
The three activation energies with isothermal transformations: applications to metallic glasses Ranganathan, S.; Von Heimendahl, M. Journal of Materials Science, Vol. 16, Issue 9 https://doi.org/10.1007/BF01113575	journal	September 1981
Effect of excess PbO on microstructure and orientation of PZT(60/40) films Park, Chee-Sung; Lee, Jae-Wung; Lee, Sung-Mi Journal of Electroceramics, Vol. 25, Issue 1 https://doi.org/10.1007/s10832-009-9584-9	journal	July 2009
Effect of excess Pb on fatigue properties of PZT thin films prepared by rf-magnetron sputtering Park, Young; Jeong, Kyu Won; Song, Joon Tae Materials Letters, Vol. 56, Issue 4 https://doi.org/10.1016/S0167-577X(02)00536-0	journal	October 2002
Influence of processing parameters on the growth characteristics and ferroelectric properties of sputtered PZT thin films on stainless steel substrates Bose, Ankita; Sreemany, Monjoy; Bysakh, Sandip Applied Surface Science, Vol. 282 https://doi.org/10.1016/j.apsusc.2013.05.103	journal	October 2013
Electrocaloric refrigeration: Thermodynamics, state of the art and future perspectives Ožbolt, M.; Kitanovski, A.; Tušek, J. International Journal of Refrigeration, Vol. 40 https://doi.org/10.1016/j.ijrefrig.2013.11.007	journal	April 2014
Electrocaloric Cooling Materials and Devices for Zero-Global-Warming-Potential, High-Efficiency Refrigeration Shi, Junye; Han, Donglin; Li, Zichao Joule, Vol. 3, Issue 5 https://doi.org/10.1016/j.joule.2019.03.021	journal	May 2019
Distribution of pyrochlore phase in Pb(Mg1/3Nb2/3)O3-PbTiO3 films and suppression with a Pb(Zr0.52Ti0.48)O3 interfacial layer Yang, Sun A.; Cho, Sam Yeon; Lim, Jong Sun Thin Solid Films, Vol. 520, Issue 24 https://doi.org/10.1016/j.tsf.2012.07.112	journal	October 2012
Effective Strategy to Achieve Excellent Energy Storage Properties in Lead-Free BaTiO₃-Based Bulk Ceramics Dai, Zhonghua; Xie, Jinglong; Liu, Weiguo ACS Applied Materials & Interfaces, Vol. 12, Issue 27 https://doi.org/10.1021/acsami.0c02832	journal	June 2020
Thin Film Piezoelectrics for MEMS Trolier-McKinstry, S.; Muralt, P. Journal of Electroceramics, Vol. 12, Issue 1/2 https://doi.org/10.1023/B:JECR.0000033998.72845.51	journal	January 2004
NIH Image to ImageJ: 25 years of image analysis Schneider, Caroline A.; Rasband, Wayne S.; Eliceiri, Kevin W. Nature Methods, Vol. 9, Issue 7 https://doi.org/10.1038/nmeth.2089	journal	June 2012
Giant electrocaloric materials energy efficiency in highly ordered lead scandium tantalate Nouchokgwe, Youri; Lheritier, Pierre; Hong, Chang-Hyo Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23354-y	journal	June 2021
Large electrocaloric effects in oxide multilayer capacitors over a wide temperature range Nair, B.; Usui, T.; Crossley, S. Nature, Vol. 575, Issue 7783 https://doi.org/10.1038/s41586-019-1634-0	journal	October 2019
Prospects and challenges of the electrocaloric phenomenon in ferroelectric ceramics Kumar, Ajeet; Thakre, Atul; Jeong, Dae-Yong Journal of Materials Chemistry C, Vol. 7, Issue 23 https://doi.org/10.1039/C9TC01525F	journal	January 2019
Pyroelectric PbSc_0.5Ta_0.5O₃/Y₁Ba₂Cu₃O_7−x thin‐film heterostructures Björmander, C.; Sreenivas, K.; Grishin, A. M. Applied Physics Letters, Vol. 67, Issue 1 https://doi.org/10.1063/1.115492	journal	July 1995
Kinetics of Phase Change. I General Theory Avrami, Melvin The Journal of Chemical Physics, Vol. 7, Issue 12, p. 1103-1112 https://doi.org/10.1063/1.1750380	journal	December 1939
Kinetics of Phase Change. II Transformation‐Time Relations for Random Distribution of Nuclei Avrami, Melvin The Journal of Chemical Physics, Vol. 8, Issue 2 https://doi.org/10.1063/1.1750631	journal	February 1940
The Impact of chemical ordering on the dielectric properties of lead scandium tantalate Pb(Sc1∕2Ta1∕2)O3 thin films Brinkman, K.; Wang, Y.; Su, D. Journal of Applied Physics, Vol. 102, Issue 4 https://doi.org/10.1063/1.2770834	journal	August 2007
The role of B‐site cation disorder in diffuse phase transition behavior of perovskite ferroelectrics Setter, N.; Cross, L. E. Journal of Applied Physics, Vol. 51, Issue 8 https://doi.org/10.1063/1.328296	journal	August 1980
Sputtered lead scandium tantalate thin films: Pb4+ in B sites in the perovskite structure Whatmore, R. W.; Huang, Z.; Todd, M. Journal of Applied Physics, Vol. 82, Issue 11 https://doi.org/10.1063/1.366432	journal	December 1997
Understanding ferroelectric Al:HfO ₂ thin films with Si-based electrodes for 3D applications Florent, K.; Lavizzari, S.; Popovici, M. Journal of Applied Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.4984068	journal	May 2017
Relaxing with relaxors: a review of relaxor ferroelectrics Cowley, R. A.; Gvasaliya, S. N.; Lushnikov, S. G. Advances in Physics, Vol. 60, Issue 2 https://doi.org/10.1080/00018732.2011.555385	journal	April 2011
Relaxor ferroelectrics Cross, L. Eric Ferroelectrics, Vol. 76, Issue 1 https://doi.org/10.1080/00150198708016945	journal	December 1987
Switching kinetics of lead zirconate titanate sub-micron thin-film memories Scott, J. F.; McMillan, L. D.; Araujo, C. A. Ferroelectrics, Vol. 93, Issue 1 https://doi.org/10.1080/00150198908017317	journal	May 1989
Pyroelectric ceramics and devices for thermal infra-red detection and imaging Whatmore, R. W. Ferroelectrics, Vol. 118, Issue 1 https://doi.org/10.1080/00150199108014764	journal	June 1991
Isomorphous ion substitutions and order-disorder phenomena in highly electrocaloric lead-scandium tantalate solid solutions Shebanovs, L.; Sternberg, A.; Lawless, W. N. Ferroelectrics, Vol. 184, Issue 1 https://doi.org/10.1080/00150199608230266	journal	August 1996
Temperature dependent Raman scattering study of order-disorder lead zinc niobate Gupta, S.; Katiyar, R. S.; Bhalla, A. S. Integrated Ferroelectrics, Vol. 29, Issue 1-2 https://doi.org/10.1080/10584580008216676	journal	March 2000
Sputtered lead scandium tantalate thin films for dielectric bolometer mode thermal detector arrays Todd, Mike A.; Donohue, Paul P.; Harper, Mark A. C. Integrated Ferroelectrics, Vol. 35, Issue 1-4 https://doi.org/10.1080/10584580108016893	journal	February 2001
Sputtered lead scandium tantalate thin films: crystallization behaviour during post-deposition annealing Huang, Z.; Donohue, P. P.; Todd, M. A. Journal of Physics D: Applied Physics, Vol. 34, Issue 21 https://doi.org/10.1088/0022-3727/34/21/304	journal	October 2001
On the phase transformation kinetics in lead scandium tantalate thin films Huang, Z.; Battat, J.; Donohue, P. P. Journal of Physics D: Applied Physics, Vol. 36, Issue 23 https://doi.org/10.1088/0022-3727/36/23/026	journal	November 2003
PST thin films for electrocaloric coolers Correia, T. M.; Kar-Narayan, S.; Young, J. S. Journal of Physics D: Applied Physics, Vol. 44, Issue 16 https://doi.org/10.1088/0022-3727/44/16/165407	journal	April 2011
Local structure and dynamics in relaxor-ferroelectric PbSc _1/2 Nb _1/2 O ₃ and PbSc _1/2 Ta _1/2 O ₃ single crystals Mihailova, B.; Bismayer, U.; Güttler, B. Journal of Physics: Condensed Matter, Vol. 14, Issue 5 https://doi.org/10.1088/0953-8984/14/5/314	journal	January 2002
Order-Disorder Phenomenon in Lead Scandium Tantalate Wang, Hui-Chieh; Schulze, Walter A. Journal of the American Ceramic Society, Vol. 73, Issue 5 https://doi.org/10.1111/j.1151-2916.1990.tb05184.x	journal	May 1990
Role of Defects in the Ferroelectric Relaxor Lead Scandium Tantalate Chu, Fan; Reaney, Ian M.; Setter, Nava Journal of the American Ceramic Society, Vol. 78, Issue 7 https://doi.org/10.1111/j.1151-2916.1995.tb08915.x	journal	July 1995
The Effect of Excess PbO on Dielectric and Pyroelectric Properties of Lead Scandium Tantalate Ceramics Liu, Wei; Wang, Genshui; Cao, Sheng Journal of the American Ceramic Society, Vol. 93, Issue 9 https://doi.org/10.1111/j.1551-2916.2010.03767.x	journal	April 2010
Structures and Properties of Pb(Zr_0.5 Ti_0.5 )O₃ −Pb(Zn_1/3 Nb_2/3 )O₃ − Pb(Ni_1/3 Nb_2/3 )O₃ Ceramics for Energy Harvesting Devices Yuan, Dewang; Yang, Ying; Hu, Querui Journal of the American Ceramic Society, Vol. 97, Issue 12 https://doi.org/10.1111/jace.13175	journal	August 2014
Giant Electrocaloric Effect in Thin-Film PbZr0.95Ti0.05O3 Mischenko, A. S. Science, Vol. 311, Issue 5765 https://doi.org/10.1126/science.1123811	journal	March 2006
Large Electrocaloric Effect in Ferroelectric Polymers Near Room Temperature Neese, B.; Chu, B.; Lu, S.-G. Science, Vol. 321, Issue 5890, p. 821-823 https://doi.org/10.1126/science.1159655	journal	August 2008
Electrocaloric Materials Scott, J. F. Annual Review of Materials Research, Vol. 41, Issue 1 https://doi.org/10.1146/annurev-matsci-062910-100341	journal	August 2011
Über die Dissociationswärme und den Einfluss der Temperatur auf den Dissociationsgrad der Elektrolyte Arrhenius, Svante Zeitschrift für Physikalische Chemie, Vol. 4, Issue 1 https://doi.org/10.1515/zpch-1889-0108	journal	January 1889
Formation kinetics of PbZr _x Ti _{1− x} O ₃ thin films Kwok, Chi Kong; Desu, Seshu B. Journal of Materials Research, Vol. 9, Issue 7 https://doi.org/10.1557/JMR.1994.1728	journal	July 1994
Phase transformations in rapid thermal processed lead zirconate titanate Griswold, Ellen M.; Weaver, L.; Sayer, M. Journal of Materials Research, Vol. 10, Issue 12 https://doi.org/10.1557/JMR.1995.3149	journal	December 1995
Processing and properties of ferroelectric relaxor lead scandium tantalate Pb(Sc _1/2 Ta _1/2 )O ₃ thin films Brinkman, K.; Wang, Y.; Cantoni, M. Journal of Materials Research, Vol. 22, Issue 1 https://doi.org/10.1557/jmr.2007.0023	journal	January 2007

Similar Records

Enhanced ferroelectric and dielectric properties of (111)-oriented highly cation-ordered PbSc{sub 0.5}Ta{sub 0.5}O{sub 3} thin films

Journal Article · Fri Dec 13 23:00:00 EST 2013 · Journal of Applied Physics · OSTI ID:22266146

Ab initio calculation of the ferroelectric phase transition in disordered and ordered PbSc{sub 0.5}Ta{sub 0.5}O{sub 3} and PbSc{sub 0.5}Nd{sub 0.5}O{sub 3} solid solutions with the use of a model Hamiltonian

Journal Article · Sat Mar 15 00:00:00 EDT 2008 · Journal of Experimental and Theoretical Physics · OSTI ID:21075588

Fabrication and orientation control of highly cation-ordered epitaxial PbSc{sub 0.5}Ta{sub 0.5}O{sub 3} thin films on Si (100)

Journal Article · Tue Jan 27 23:00:00 EST 2015 · Journal of Applied Physics · OSTI ID:22412997

Related Subjects

36 MATERIALS SCIENCE
lead scandium tantalate
phase transformation kinetics
growth mechanism
reactive RF sputtering
relaxor ferroelectrics

Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc0.5Ta0.5O3) films

Citation Formats

References (50)

Similar Records

Related Subjects

Phase transformation and growth mechanism of RF sputtered ferroelectric lead scandium tantalate (PbSc_0.5Ta_0.5O₃) films