Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO2 Films

Xu, Bohan; Collins, Liam; Holsgrove, Kristina M.; Mikolajick, Thomas; Schroeder, Uwe; Lomenzo, Patrick D.

doi:10.1021/acsaelm.3c00117

Title: Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO₂ Films

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Abstract

Over a decade ago, ferroelectricity was discovered in doped HfO₂ thin films. The HfO₂-based thin films have attracted much attention due to their remarkable scalability and CMOS compatibility. Other than the HfO₂-based thin films, the undoped ZrO₂ thin films are understudied despite their commonly reported antiferroelectric behavior. However, being of the same fluorite structure as HfO₂-based thin films, the undoped ZrO₂ also displayed considerable ferroelectricity as demonstrated in recent studies. Here, 45 nm-thick polycrystalline undoped ZrO₂ films are synthesized using atomic layer deposition with different ozone dose times. The ZrO₂ films are crystallized after atomic layer deposition at 350 °C without anneals. In general, the longer ozone dose time causes a lower in-plane tensile stress and oxygen vacancy content, which help facilitate an irreversible non-polar tetragonal to polar orthorhombic phase transition with electric-field cycling. However, the lower in-plane tensile stress and oxygen vacancy content also stabilize the monoclinic phase so that a long ozone dose time (>17.5 s) reduces the ferroelectric behavior. After wake-up cycles, the ZrO₂ thin film with an ozone dose time of 17.5 s exhibits a remanent polarization of 6 μC·cm^–2and a pyroelectric coefficient of -35 μC·K^–1·m^–2. Moreover, the wake-up behavior is consistent between the ferroelectricmore »« less

Authors:

^[1];

^[2]; Holsgrove, Kristina M. ^[3];

^[1];

^[1]

NaMLab gGmbH, Dresden (Germany)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)
Queen's University, Belfast, Northern Ireland (United Kingdom)

Publication Date:: Thu Mar 30 00:00:00 EDT 2023

Research Org.:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

OSTI Identifier:: 1973338

Grant/Contract Number:: AC05-00OR22725

Resource Type:: Accepted Manuscript

Journal Name:: ACS Applied Electronic Materials

Additional Journal Information:: Journal Volume: 5; Journal Issue: 4; Journal ID: ISSN 2637-6113

Publisher:: ACS Publications

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; zirconium oxide; ferroelectrics; ozone dose time; stress; wake-up effect; irreversible t- to o-phase transition

Citation Formats


                    Xu, Bohan, Collins, Liam, Holsgrove, Kristina M., Mikolajick, Thomas, Schroeder, Uwe, and Lomenzo, Patrick D. Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO2 Films.  United States: N. p., 2023. 
Web.  doi:10.1021/acsaelm.3c00117.

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                    Xu, Bohan, Collins, Liam, Holsgrove, Kristina M., Mikolajick, Thomas, Schroeder, Uwe, & Lomenzo, Patrick D. Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO2 Films.  United States.  https://doi.org/10.1021/acsaelm.3c00117

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                    Xu, Bohan, Collins, Liam, Holsgrove, Kristina M., Mikolajick, Thomas, Schroeder, Uwe, and Lomenzo, Patrick D. Thu .  
"Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO2 Films".  United States.  https://doi.org/10.1021/acsaelm.3c00117.  https://www.osti.gov/servlets/purl/1973338.

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@article{osti_1973338,

  title        = {Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO2 Films},

  author       = {Xu, Bohan and Collins, Liam and Holsgrove, Kristina M. and Mikolajick, Thomas and Schroeder, Uwe and Lomenzo, Patrick D.},

  abstractNote = {Over a decade ago, ferroelectricity was discovered in doped HfO2 thin films. The HfO2-based thin films have attracted much attention due to their remarkable scalability and CMOS compatibility. Other than the HfO2-based thin films, the undoped ZrO2 thin films are understudied despite their commonly reported antiferroelectric behavior. However, being of the same fluorite structure as HfO2-based thin films, the undoped ZrO2 also displayed considerable ferroelectricity as demonstrated in recent studies. Here, 45 nm-thick polycrystalline undoped ZrO2 films are synthesized using atomic layer deposition with different ozone dose times. The ZrO2 films are crystallized after atomic layer deposition at 350 °C without anneals. In general, the longer ozone dose time causes a lower in-plane tensile stress and oxygen vacancy content, which help facilitate an irreversible non-polar tetragonal to polar orthorhombic phase transition with electric-field cycling. However, the lower in-plane tensile stress and oxygen vacancy content also stabilize the monoclinic phase so that a long ozone dose time (>17.5 s) reduces the ferroelectric behavior. After wake-up cycles, the ZrO2 thin film with an ozone dose time of 17.5 s exhibits a remanent polarization of 6 μC·cm–2 and a pyroelectric coefficient of -35 μC·K–1·m–2. Moreover, the wake-up behavior is consistent between the ferroelectric and pyroelectric response. As essential factors in optimizing the growth of fluorite-structure thin films for ferroelectric applications, the in-plane tensile stress and oxygen vacancy content significantly influence the ferroelectric and pyroelectric properties. Additionally, the low thermal budget for processing ferroelectric ZrO2 thin films is valuable for semiconductor back-end-of-line processes.},

  doi          = {10.1021/acsaelm.3c00117},

  journal      = {ACS Applied Electronic Materials},

  number       = 4,

  volume       = 5,

  place        = {United States},

  year         = {Thu Mar 30 00:00:00 EDT 2023},

  month        = {Thu Mar 30 00:00:00 EDT 2023}

}

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Title: Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO2 Films

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Citation Formats

Title: Influence of the Ozone Dose Time during Atomic Layer Deposition on the Ferroelectric and Pyroelectric Properties of 45 nm-Thick ZrO₂ Films