Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO and DFT calculations
In recent times, ultra-thin films of hafnium oxide (HfO 2 ) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO 2 with space group Pca 2 1 . This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases...
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Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2023-08, Vol.25 (32), p.21479-21491 |
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creator | Banerjee, D Dey, C. C Kumar, Ravi Modak, Brindaban Hazra, Snehamoyee Datta, Subarna Ghosh, Barnali Thakare, S. V Jha, S. N Bhattacharyya, D |
description | In recent times, ultra-thin films of hafnium oxide (HfO
2
) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO
2
with space group
Pca
2
1
. This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases of HfO
2
could be stabilized in Gd-doped bulk polycrystalline HfO
2
. Rietveld analysis of XRD data shows that the relative population of o-phases in the presence of the monoclinic (m) phase of HfO
2
increases with increasing Gd-content. The local environment around the host atom has been investigated by time differential perturbed angular correlation (TDPAC) spectroscopy, synchrotron based X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) measurements showed a reduction in grain size with increasing Gd-dopant indicating a solute drag effect. It could be established that the segregation of the Gd-dopant in the grain boundary is a thermodynamically favorable process and the solute drag effect plays an important role in nucleation of the o-phase in bulk HfO
2
. Stabilization of Gd in both
Pbca
and
Pca
2
1
phases of HfO
2
was supported by defect formation energy calculations using density functional theory (DFT). The present study has important implications in future applications of HfO
2
in ferroelectric devices and in understanding the role of dopants in stabilizing the o-phase of HfO
2
in the bulk.
The grain size of HfO
2
is reduced from ∼50 nm to ∼25 nm by a Gd-dopant (1-5 at%) with concomitant stabilization of the orthorhombic phase over the monoclinic phase. |
doi_str_mv | 10.1039/d3cp00062a |
format | Article |
fullrecord | <record><control><sourceid>rsc</sourceid><recordid>TN_cdi_rsc_primary_d3cp00062a</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>d3cp00062a</sourcerecordid><originalsourceid>FETCH-rsc_primary_d3cp00062a3</originalsourceid><addsrcrecordid>eNqFz7sKwjAYBeAgCtbL4i78L1BNjFY719vm4i4xSU1K24SkFerTW0V0dDoHzrcchCYEzwim8VxQbjHG0YJ1UECWEQ1jvFl2v30d9dHA-6w1ZEVogLLEFNZJJUuv7xJ8VYsGTAmVkmCcvukSTNq2ShmnTHHVHKxi_iXZVef6wSrd8pYdRCiMlQKO6QlYKWC7PwNnOa_zt_Ej1EtZ7uX4k0M03e_OyTF0nl-s0wVzzeV3gP7bn70LSjU</addsrcrecordid><sourcetype>Publisher</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype></control><display><type>article</type><title>Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO and DFT calculations</title><source>Royal Society Of Chemistry Journals</source><source>Alma/SFX Local Collection</source><creator>Banerjee, D ; Dey, C. C ; Kumar, Ravi ; Modak, Brindaban ; Hazra, Snehamoyee ; Datta, Subarna ; Ghosh, Barnali ; Thakare, S. V ; Jha, S. N ; Bhattacharyya, D</creator><creatorcontrib>Banerjee, D ; Dey, C. C ; Kumar, Ravi ; Modak, Brindaban ; Hazra, Snehamoyee ; Datta, Subarna ; Ghosh, Barnali ; Thakare, S. V ; Jha, S. N ; Bhattacharyya, D</creatorcontrib><description>In recent times, ultra-thin films of hafnium oxide (HfO
2
) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO
2
with space group
Pca
2
1
. This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases of HfO
2
could be stabilized in Gd-doped bulk polycrystalline HfO
2
. Rietveld analysis of XRD data shows that the relative population of o-phases in the presence of the monoclinic (m) phase of HfO
2
increases with increasing Gd-content. The local environment around the host atom has been investigated by time differential perturbed angular correlation (TDPAC) spectroscopy, synchrotron based X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) measurements showed a reduction in grain size with increasing Gd-dopant indicating a solute drag effect. It could be established that the segregation of the Gd-dopant in the grain boundary is a thermodynamically favorable process and the solute drag effect plays an important role in nucleation of the o-phase in bulk HfO
2
. Stabilization of Gd in both
Pbca
and
Pca
2
1
phases of HfO
2
was supported by defect formation energy calculations using density functional theory (DFT). The present study has important implications in future applications of HfO
2
in ferroelectric devices and in understanding the role of dopants in stabilizing the o-phase of HfO
2
in the bulk.
The grain size of HfO
2
is reduced from ∼50 nm to ∼25 nm by a Gd-dopant (1-5 at%) with concomitant stabilization of the orthorhombic phase over the monoclinic phase.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/d3cp00062a</identifier><ispartof>Physical chemistry chemical physics : PCCP, 2023-08, Vol.25 (32), p.21479-21491</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>315,781,785,27929,27930</link.rule.ids></links><search><creatorcontrib>Banerjee, D</creatorcontrib><creatorcontrib>Dey, C. C</creatorcontrib><creatorcontrib>Kumar, Ravi</creatorcontrib><creatorcontrib>Modak, Brindaban</creatorcontrib><creatorcontrib>Hazra, Snehamoyee</creatorcontrib><creatorcontrib>Datta, Subarna</creatorcontrib><creatorcontrib>Ghosh, Barnali</creatorcontrib><creatorcontrib>Thakare, S. V</creatorcontrib><creatorcontrib>Jha, S. N</creatorcontrib><creatorcontrib>Bhattacharyya, D</creatorcontrib><title>Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO and DFT calculations</title><title>Physical chemistry chemical physics : PCCP</title><description>In recent times, ultra-thin films of hafnium oxide (HfO
2
) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO
2
with space group
Pca
2
1
. This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases of HfO
2
could be stabilized in Gd-doped bulk polycrystalline HfO
2
. Rietveld analysis of XRD data shows that the relative population of o-phases in the presence of the monoclinic (m) phase of HfO
2
increases with increasing Gd-content. The local environment around the host atom has been investigated by time differential perturbed angular correlation (TDPAC) spectroscopy, synchrotron based X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) measurements showed a reduction in grain size with increasing Gd-dopant indicating a solute drag effect. It could be established that the segregation of the Gd-dopant in the grain boundary is a thermodynamically favorable process and the solute drag effect plays an important role in nucleation of the o-phase in bulk HfO
2
. Stabilization of Gd in both
Pbca
and
Pca
2
1
phases of HfO
2
was supported by defect formation energy calculations using density functional theory (DFT). The present study has important implications in future applications of HfO
2
in ferroelectric devices and in understanding the role of dopants in stabilizing the o-phase of HfO
2
in the bulk.
The grain size of HfO
2
is reduced from ∼50 nm to ∼25 nm by a Gd-dopant (1-5 at%) with concomitant stabilization of the orthorhombic phase over the monoclinic phase.</description><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2023</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNqFz7sKwjAYBeAgCtbL4i78L1BNjFY719vm4i4xSU1K24SkFerTW0V0dDoHzrcchCYEzwim8VxQbjHG0YJ1UECWEQ1jvFl2v30d9dHA-6w1ZEVogLLEFNZJJUuv7xJ8VYsGTAmVkmCcvukSTNq2ShmnTHHVHKxi_iXZVef6wSrd8pYdRCiMlQKO6QlYKWC7PwNnOa_zt_Ej1EtZ7uX4k0M03e_OyTF0nl-s0wVzzeV3gP7bn70LSjU</recordid><startdate>20230816</startdate><enddate>20230816</enddate><creator>Banerjee, D</creator><creator>Dey, C. C</creator><creator>Kumar, Ravi</creator><creator>Modak, Brindaban</creator><creator>Hazra, Snehamoyee</creator><creator>Datta, Subarna</creator><creator>Ghosh, Barnali</creator><creator>Thakare, S. V</creator><creator>Jha, S. N</creator><creator>Bhattacharyya, D</creator><scope/></search><sort><creationdate>20230816</creationdate><title>Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO and DFT calculations</title><author>Banerjee, D ; Dey, C. C ; Kumar, Ravi ; Modak, Brindaban ; Hazra, Snehamoyee ; Datta, Subarna ; Ghosh, Barnali ; Thakare, S. V ; Jha, S. N ; Bhattacharyya, D</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-rsc_primary_d3cp00062a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><creationdate>2023</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Banerjee, D</creatorcontrib><creatorcontrib>Dey, C. C</creatorcontrib><creatorcontrib>Kumar, Ravi</creatorcontrib><creatorcontrib>Modak, Brindaban</creatorcontrib><creatorcontrib>Hazra, Snehamoyee</creatorcontrib><creatorcontrib>Datta, Subarna</creatorcontrib><creatorcontrib>Ghosh, Barnali</creatorcontrib><creatorcontrib>Thakare, S. V</creatorcontrib><creatorcontrib>Jha, S. N</creatorcontrib><creatorcontrib>Bhattacharyya, D</creatorcontrib><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Banerjee, D</au><au>Dey, C. C</au><au>Kumar, Ravi</au><au>Modak, Brindaban</au><au>Hazra, Snehamoyee</au><au>Datta, Subarna</au><au>Ghosh, Barnali</au><au>Thakare, S. V</au><au>Jha, S. N</au><au>Bhattacharyya, D</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO and DFT calculations</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><date>2023-08-16</date><risdate>2023</risdate><volume>25</volume><issue>32</issue><spage>21479</spage><epage>21491</epage><pages>21479-21491</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>In recent times, ultra-thin films of hafnium oxide (HfO
2
) have shown ferroelectricity (FE) attributed to the orthorhombic (o) phase of HfO
2
with space group
Pca
2
1
. This polar o-phase could be stabilized in the doped thin film of the oxide. In the present work, both polar and non-polar o-phases of HfO
2
could be stabilized in Gd-doped bulk polycrystalline HfO
2
. Rietveld analysis of XRD data shows that the relative population of o-phases in the presence of the monoclinic (m) phase of HfO
2
increases with increasing Gd-content. The local environment around the host atom has been investigated by time differential perturbed angular correlation (TDPAC) spectroscopy, synchrotron based X-ray near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) measurements. Field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) measurements showed a reduction in grain size with increasing Gd-dopant indicating a solute drag effect. It could be established that the segregation of the Gd-dopant in the grain boundary is a thermodynamically favorable process and the solute drag effect plays an important role in nucleation of the o-phase in bulk HfO
2
. Stabilization of Gd in both
Pbca
and
Pca
2
1
phases of HfO
2
was supported by defect formation energy calculations using density functional theory (DFT). The present study has important implications in future applications of HfO
2
in ferroelectric devices and in understanding the role of dopants in stabilizing the o-phase of HfO
2
in the bulk.
The grain size of HfO
2
is reduced from ∼50 nm to ∼25 nm by a Gd-dopant (1-5 at%) with concomitant stabilization of the orthorhombic phase over the monoclinic phase.</abstract><doi>10.1039/d3cp00062a</doi><tpages>13</tpages></addata></record> |
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source | Royal Society Of Chemistry Journals; Alma/SFX Local Collection |
title | Comprehensive study on the origin of orthorhombic phase stabilization in Gd-doped HfO and DFT calculations |
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