Molecular sieves assisted chemical vapor deposition preparation of high-<i>κ</i> dielectric m-ZrO<sub>2</sub> nanosheets

Ting Lu; Zhuojun Duan; Ling Zhang; Yuanyuan Jin; Huimin Li; Song Liu

doi:10.1088/1674-4926/24090034

J. Semicond. > 2025, Volume 46 > Issue 4 > 042703

ARTICLES

Molecular sieves assisted chemical vapor deposition preparation of high-κ dielectric m-ZrO₂ nanosheets

Ting Lu¹, Zhuojun Duan^1,, Ling Zhang¹, Yuanyuan Jin², Huimin Li¹ and Song Liu^{1, 3,}

+ Author Affiliations

Corresponding author: Zhuojun Duan, duanzj@hnu.edu.cn; Song Liu, liusong@hnu.edu.cn

DOI: 10.1088/1674-4926/24090034CSTR: 32376.14.1674-4926.24090034

Abstract: In order to address challenges posed by the reduction in transistor size, researchers are concentrating on two-dimensional (2D) materials with high dielectric constants and large band gaps. Monoclinic ZrO₂ (m-ZrO₂) has emerged as a promising gate dielectric material due to its suitable dielectric constant, wide band gap, ideal valence-band offset, and good thermodynamic stability. However, current deposition methods face compatibility issues with 2D semiconductors, highlighting the need for high-quality dielectrics and interfaces. Here, high-quality 2D m-ZrO₂ single crystals are successfully prepared using a one-step chemical vapor deposition (CVD) method, aided by 5A molecular sieves for oxygen supply. The prepared ZrO₂ is utilized as a gate dielectric in the construction of MoS₂ field-effect transistors (FETs) to investigate its electrical property. The FETs exhibit a high carrier mobility of up to 5.50 cm²·V⁻¹·s⁻¹, and a current switching ratio (I_on/off) of approximately 10⁴, which aligns with the current standards of logic circuits, indicating that ZrO₂ has application value as a gate dielectric. The successful one-step preparation of single-crystal ZrO₂ paves the way for the utilization of high-κ gate dielectrics and creates favorable conditions for the development of high-performance semiconductor devices, offering new possibilities for transistor miniaturization.

Key words: ZrO₂, high-κ gate dielectric, chemical vapor deposition, field effect transistors, molecular sieves

References

[1]	Li M Y, Su S K, Wong H P, et al. How 2D semiconductors could extend Moore’s law. Nature, 2019, 567, 169 doi: 10.1038/d41586-019-00793-8
[2]	Arden W. Future semiconductor material requirements and innovations as projected in the ITRS 2005 roadmap. Mater Sci Eng B, 2006, 134, 104 doi: 10.1016/j.mseb.2006.07.004
[3]	Liu Y, Duan X D, Shin H J, et al. Promises and prospects of two-dimensional transistors. Nature, 2021, 591, 43 doi: 10.1038/s41586-021-03339-z
[4]	Buchanan D A. Scaling the gate dielectric: Materials, integration, and reliability. IBM J Res Dev, 1999, 43, 245 doi: 10.1147/rd.433.0245
[5]	Valasa S, Tayal S, Thoutam L R, et al. A critical review on performance, reliability, and fabrication challenges in nanosheet FET for future analog/digital IC applications. Micro Nanostruct, 2022, 170, 207374 doi: 10.1016/j.micrna.2022.207374
[6]	Chen J X, Xu W T. 2D-materials-based optoelectronic synapses for neuromorphic applications. eScience, 2023, 3, 100178 doi: 10.1016/j.esci.2023.100178
[7]	Meng Z Y, Qiu Z M, Shi Y X, et al. Micro/nano metal-organic frameworks meet energy chemistry: A review of materials synthesis and applications. eScience, 2023, 3, 100092 doi: 10.1016/j.esci.2023.100092
[8]	Peimyoo N, Barnes M D, Mehew J D, et al. Laser-writable high-κ dielectric for van der Waals nanoelectronics. Sci Adv, 2019, 5, eaau0906 doi: 10.1126/sciadv.aau0906
[9]	Ribes G, Mitard J, Denais M, et al. Review on high-κ dielectrics reliability issues. IEEE Trans Device Mater Reliab, 2005, 5, 5 doi: 10.1109/TDMR.2005.845236
[10]	Houssa M, Pantisano L, Ragnarsson L Å, et al. Electrical properties of high-κ gate dielectrics: Challenges, current issues, and possible solutions. Mater Sci Eng R Rep, 2006, 51, 37 doi: 10.1016/j.mser.2006.04.001
[11]	Huang T, Ding J F, Liu Z R, et al. Insight into the underlying competitive mechanism for the shift of the charge neutrality point in a trilayer-graphene field-effect transistor. eScience, 2022, 2, 319 doi: 10.1016/j.esci.2022.03.005
[12]	Kim H J, Osada M, Ebina Y, et al. Hunting for monolayer oxide nanosheets and their architectures. Sci Rep, 2016, 6, 19402 doi: 10.1038/srep19402
[13]	Shin G H, Lee G B, An E S, et al. High-performance field-effect transistor and logic gates based on GaS-MoS₂ van der waals heterostructure. ACS Appl Mater Interfaces, 2020, 12, 5106 doi: 10.1021/acsami.9b20077
[14]	Wen C, Lanza M. Calcium fluoride as high-κ dielectric for 2D electronics. Appl Phys Rev, 2021, 8, 021307 doi: 10.1063/5.0036987
[15]	Holler B A, Crowley K, Berger M H, et al. 2D semiconductor transistors with van der waals oxide MoO₃ as integrated high-κ gate dielectric. Adv Elect Materials, 2020, 6, 2000635 doi: 10.1002/aelm.202000635
[16]	Chamlagain B, Cui Q S, Paudel S, et al. Thermally oxidized 2D TaS₂ as a high-κ gate dielectric for MoS₂ field-effect transistors. 2D Mater, 2017, 4, 031002 doi: 10.1088/2053-1583/aa780e
[17]	Tu T, Zhang Y C, Li T R, et al. Uniform high-κ amorphous native oxide synthesized by oxygen plasma for top-gated transistors. Nano Lett, 2020, 20, 7469 doi: 10.1021/acs.nanolett.0c02951
[18]	Mleczko M J, Zhang C F, Lee H R, et al. HfSe₂ and ZrSe₂: Two-dimensional semiconductors with native high-κ oxides. Sci Adv, 2017, 3, e1700481 doi: 10.1126/sciadv.1700481
[19]	Wong Y H, Cheong K Y. ZrO₂ thin films on Si substrate. J Mater Sci Mater Electron, 2010, 21, 980 doi: 10.1007/s10854-010-0144-5
[20]	Jia B B, Zhang B H, Cai Z, et al. Construction of amorphous/crystalline heterointerfaces for enhanced electrochemical processes. eScience, 2023, 3, 100112 doi: 10.1016/j.esci.2023.100112
[21]	McDonnell S, Brennan B, Azcatl A, et al. HfO₂ on MoS₂ by atomic layer deposition: Adsorption mechanisms and thickness scalability. ACS Nano, 2013, 7, 10354 doi: 10.1021/nn404775u
[22]	Zou X M, Wang J L, Chiu C H, et al. Interface engineering for high-performance top-gated MoS₂ field-effect transistors. Adv Mater, 2014, 26, 6255 doi: 10.1002/adma.201402008
[23]	Wang J L, Li S L, Zou X M, et al. Integration of high-κ oxide on MoS₂ by using ozone pretreatment for high-performance MoS₂ top-gated transistor with thickness-dependent carrier scattering investigation. Small, 2015, 11, 5932 doi: 10.1002/smll.201501260
[24]	Qiu H, Yu Z H, Zhao T G, et al. Two-dimensional materials for future information technology: Status and prospects. Sci China Inf Sci, 2024, 67, 160400 doi: 10.1007/s11432-024-4033-8
[25]	Zhao T G, Guo J X, Li T T, et al. Substrate engineering for wafer-scale two-dimensional material growth: Strategies, mechanisms, and perspectives. Chemical Soc Rev, 2023, 52, 1650 doi: 10.1039/D2CS00657J
[26]	Yamada T, Kubota Y, Makinose Y, et al. Single crystal ZrO₂ nanosheets formed by thermal transformation for solid oxide fuel cells and oxygen sensors. ACS Appl Nano Mater, 2019, 2, 6866 doi: 10.1021/acsanm.9b01312
[27]	Jin Y Y, Sun J, Zhang L, et al. Controllable oxidation of ZrS₂ to prepare high-κ, single-crystal m-ZrO₂ for 2D electronics. Adv Mater, 2023, 35, e2212079 doi: 10.1002/adma.202212079
[28]	Li M J, Feng Z C, Xiong G, et al. Phase transformation in the surface region of zirconia detected by UV Raman spectroscopy. J Phys Chem B, 2001, 105, 8107 doi: 10.1021/jp010526l
[29]	Ding S, Zhao J K, Yu Q. Effect of zirconia polymorph on vapor-phase ketonization of propionic acid. Catalysts, 2019, 9, 768 doi: 10.3390/catal9090768
[30]	Mañas-Valero S, García-López V, Cantarero A, et al. Raman spectra of ZrS₂ and ZrSe₂ from bulk to atomically thin layers. Appl Sci, 2016, 6, 264 doi: 10.3390/app6090264

Fig. 1. (Color online) (a) Schematic diagram of two-dimensional ZrO₂ nanosheets prepared by one-step CVD. The lower part shows the formation of m-ZrO₂ at the atomic level. (b) Optical image of ZrO₂ grown on a silicon substrate. Scale bar: 20 μm. (c) Raman spectra of m-ZrO₂ nanosheets. (d) SEM image of ZrO₂ nanosheet at 18 000x magnification. Scale bar: 1 μm. (e) AFM image and corresponding height maps of ZrO₂ nanosheets. Scale bar: 1 μm.

DownLoad: Full-Size Img PowerPoint

Fig. 2. (Color online) (a) XRD spectra of ZrO₂ nanosheets. (b) XPS broad spectra of ZrO₂ nanosheets. (c) XPS narrow spectra of Zr 3d. (d) XPS narrow spectra of O 1s.

DownLoad: Full-Size Img PowerPoint

Fig. 3. (Color online) (a) TEM. Scale bar: 500 nm. (b) HRTEM. Scale bar: 2 nm. (c) SEAD. Scale bar: 2 nm⁻¹. (d) EDS of ZrO₂ nanosheets.

DownLoad: Full-Size Img PowerPoint

Fig. 4. (Color online) (a) Optical image and (b) Raman spectra of ZrS₂ without the introduction of 5A molecular sieves. Scale bar: 10 μm. (c) Optical image and (d) Raman spectra of ZrO₂ with the incorporation of 5A molecular sieves. Scale bar: 30 μm. (e) Optical images of ZrO₂ grown on the SiO₂/Si substrate at different deposition temperatures (780/830/880 °C). Scale bar: 20 μm.

DownLoad: Full-Size Img PowerPoint

Fig. 5. (Color online) (a) The schematic of MoS₂−ZrO₂ heterojunction FET. (b) Optical picture of the prepared FET, with the corresponding AFM image in the upper left corner. Scale bar: 10 μm. (c) Output characteristic curve of FET. (d) Transfer characteristic curve of FET.

DownLoad: Full-Size Img PowerPoint

[1]	Li M Y, Su S K, Wong H P, et al. How 2D semiconductors could extend Moore’s law. Nature, 2019, 567, 169 doi: 10.1038/d41586-019-00793-8
[2]	Arden W. Future semiconductor material requirements and innovations as projected in the ITRS 2005 roadmap. Mater Sci Eng B, 2006, 134, 104 doi: 10.1016/j.mseb.2006.07.004
[3]	Liu Y, Duan X D, Shin H J, et al. Promises and prospects of two-dimensional transistors. Nature, 2021, 591, 43 doi: 10.1038/s41586-021-03339-z
[4]	Buchanan D A. Scaling the gate dielectric: Materials, integration, and reliability. IBM J Res Dev, 1999, 43, 245 doi: 10.1147/rd.433.0245
[5]	Valasa S, Tayal S, Thoutam L R, et al. A critical review on performance, reliability, and fabrication challenges in nanosheet FET for future analog/digital IC applications. Micro Nanostruct, 2022, 170, 207374 doi: 10.1016/j.micrna.2022.207374
[6]	Chen J X, Xu W T. 2D-materials-based optoelectronic synapses for neuromorphic applications. eScience, 2023, 3, 100178 doi: 10.1016/j.esci.2023.100178
[7]	Meng Z Y, Qiu Z M, Shi Y X, et al. Micro/nano metal-organic frameworks meet energy chemistry: A review of materials synthesis and applications. eScience, 2023, 3, 100092 doi: 10.1016/j.esci.2023.100092
[8]	Peimyoo N, Barnes M D, Mehew J D, et al. Laser-writable high-κ dielectric for van der Waals nanoelectronics. Sci Adv, 2019, 5, eaau0906 doi: 10.1126/sciadv.aau0906
[9]	Ribes G, Mitard J, Denais M, et al. Review on high-κ dielectrics reliability issues. IEEE Trans Device Mater Reliab, 2005, 5, 5 doi: 10.1109/TDMR.2005.845236
[10]	Houssa M, Pantisano L, Ragnarsson L Å, et al. Electrical properties of high-κ gate dielectrics: Challenges, current issues, and possible solutions. Mater Sci Eng R Rep, 2006, 51, 37 doi: 10.1016/j.mser.2006.04.001
[11]	Huang T, Ding J F, Liu Z R, et al. Insight into the underlying competitive mechanism for the shift of the charge neutrality point in a trilayer-graphene field-effect transistor. eScience, 2022, 2, 319 doi: 10.1016/j.esci.2022.03.005
[12]	Kim H J, Osada M, Ebina Y, et al. Hunting for monolayer oxide nanosheets and their architectures. Sci Rep, 2016, 6, 19402 doi: 10.1038/srep19402
[13]	Shin G H, Lee G B, An E S, et al. High-performance field-effect transistor and logic gates based on GaS-MoS₂ van der waals heterostructure. ACS Appl Mater Interfaces, 2020, 12, 5106 doi: 10.1021/acsami.9b20077
[14]	Wen C, Lanza M. Calcium fluoride as high-κ dielectric for 2D electronics. Appl Phys Rev, 2021, 8, 021307 doi: 10.1063/5.0036987
[15]	Holler B A, Crowley K, Berger M H, et al. 2D semiconductor transistors with van der waals oxide MoO₃ as integrated high-κ gate dielectric. Adv Elect Materials, 2020, 6, 2000635 doi: 10.1002/aelm.202000635
[16]	Chamlagain B, Cui Q S, Paudel S, et al. Thermally oxidized 2D TaS₂ as a high-κ gate dielectric for MoS₂ field-effect transistors. 2D Mater, 2017, 4, 031002 doi: 10.1088/2053-1583/aa780e
[17]	Tu T, Zhang Y C, Li T R, et al. Uniform high-κ amorphous native oxide synthesized by oxygen plasma for top-gated transistors. Nano Lett, 2020, 20, 7469 doi: 10.1021/acs.nanolett.0c02951
[18]	Mleczko M J, Zhang C F, Lee H R, et al. HfSe₂ and ZrSe₂: Two-dimensional semiconductors with native high-κ oxides. Sci Adv, 2017, 3, e1700481 doi: 10.1126/sciadv.1700481
[19]	Wong Y H, Cheong K Y. ZrO₂ thin films on Si substrate. J Mater Sci Mater Electron, 2010, 21, 980 doi: 10.1007/s10854-010-0144-5
[20]	Jia B B, Zhang B H, Cai Z, et al. Construction of amorphous/crystalline heterointerfaces for enhanced electrochemical processes. eScience, 2023, 3, 100112 doi: 10.1016/j.esci.2023.100112
[21]	McDonnell S, Brennan B, Azcatl A, et al. HfO₂ on MoS₂ by atomic layer deposition: Adsorption mechanisms and thickness scalability. ACS Nano, 2013, 7, 10354 doi: 10.1021/nn404775u
[22]	Zou X M, Wang J L, Chiu C H, et al. Interface engineering for high-performance top-gated MoS₂ field-effect transistors. Adv Mater, 2014, 26, 6255 doi: 10.1002/adma.201402008
[23]	Wang J L, Li S L, Zou X M, et al. Integration of high-κ oxide on MoS₂ by using ozone pretreatment for high-performance MoS₂ top-gated transistor with thickness-dependent carrier scattering investigation. Small, 2015, 11, 5932 doi: 10.1002/smll.201501260
[24]	Qiu H, Yu Z H, Zhao T G, et al. Two-dimensional materials for future information technology: Status and prospects. Sci China Inf Sci, 2024, 67, 160400 doi: 10.1007/s11432-024-4033-8
[25]	Zhao T G, Guo J X, Li T T, et al. Substrate engineering for wafer-scale two-dimensional material growth: Strategies, mechanisms, and perspectives. Chemical Soc Rev, 2023, 52, 1650 doi: 10.1039/D2CS00657J
[26]	Yamada T, Kubota Y, Makinose Y, et al. Single crystal ZrO₂ nanosheets formed by thermal transformation for solid oxide fuel cells and oxygen sensors. ACS Appl Nano Mater, 2019, 2, 6866 doi: 10.1021/acsanm.9b01312
[27]	Jin Y Y, Sun J, Zhang L, et al. Controllable oxidation of ZrS₂ to prepare high-κ, single-crystal m-ZrO₂ for 2D electronics. Adv Mater, 2023, 35, e2212079 doi: 10.1002/adma.202212079
[28]	Li M J, Feng Z C, Xiong G, et al. Phase transformation in the surface region of zirconia detected by UV Raman spectroscopy. J Phys Chem B, 2001, 105, 8107 doi: 10.1021/jp010526l
[29]	Ding S, Zhao J K, Yu Q. Effect of zirconia polymorph on vapor-phase ketonization of propionic acid. Catalysts, 2019, 9, 768 doi: 10.3390/catal9090768
[30]	Mañas-Valero S, García-López V, Cantarero A, et al. Raman spectra of ZrS₂ and ZrSe₂ from bulk to atomically thin layers. Appl Sci, 2016, 6, 264 doi: 10.3390/app6090264

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Received: 18 September 2024 Revised: 19 November 2024 Online: Accepted Manuscript: 03 January 2025Uncorrected proof: 28 February 2025Published: 10 April 2025

Article Navigation > Journal of Semiconductors > 2025 > 46(4): 042703

Ting Lu, Zhuojun Duan, Ling Zhang, Yuanyuan Jin, Huimin Li, Song Liu. Molecular sieves assisted chemical vapor deposition preparation of high-κ dielectric m-ZrO2 nanosheets[J]. Journal of Semiconductors, 2025, 46(4): 042703. doi: 10.1088/1674-4926/24090034 ****T Lu, Z J Duan, L Zhang, Y Y Jin, H M Li, and S Liu, Molecular sieves assisted chemical vapor deposition preparation of high-κ dielectric m-ZrO2 nanosheets[J]. J. Semicond., 2025, 46(4), 042703 doi: 10.1088/1674-4926/24090034

Citation:

Ting Lu, Zhuojun Duan, Ling Zhang, Yuanyuan Jin, Huimin Li, Song Liu. Molecular sieves assisted chemical vapor deposition preparation of high-κ dielectric m-ZrO₂ nanosheets[J]. Journal of Semiconductors, 2025, 46(4): 042703. doi: 10.1088/1674-4926/24090034 ****

T Lu, Z J Duan, L Zhang, Y Y Jin, H M Li, and S Liu, Molecular sieves assisted chemical vapor deposition preparation of high-κ dielectric m-ZrO₂ nanosheets[J]. J. Semicond., 2025, 46(4), 042703 doi: 10.1088/1674-4926/24090034

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Molecular sieves assisted chemical vapor deposition preparation of high-κ dielectric m-ZrO₂ nanosheets

DOI: 10.1088/1674-4926/24090034

CSTR: 32376.14.1674-4926.24090034

1.
College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China
2.
Department of Applied Physics, The Hong Kong Polytechnic University, Hong Kong 999077, China
3.
Shenzhen Research Institute, Hunan University, Shenzhen 518000, China

More Information

Ting Lu received her BS degree from Chongqing Normal University in 2022 and is now a master's candidate at Hunan University under Professor Song Liu. Her research direction is two-dimensional materials and devices
Zhuojun Duan received her M.Sc degree of Physics from Xiangtan University in 2021. She is a Ph.D. student of chemistry in Hunan University supervised by Professor Song Liu. Her research mainly focuses on controllable synthesis of two-dimensional materials by CVD method
Song Liu received his BS degree from Nankai University in 2006 and PhD degree at Peking University in 2011. Then he joined the team of Professor Liming Dai at Case Western Reserve University in the United States as a postdoctoral fellow. He joined the National University of Singapore as a research fellow. He joined Hunan University in 2016 as a full professor. His research interests include controlled synthesis of low-dimensional layered materials, application research of functional devices, and flexible wearable sensors
Corresponding author: duanzj@hnu.edu.cn; liusong@hnu.edu.cn
Received Date: 2024-09-18
Revised Date: 2024-11-19

Available Online: 2025-01-03

Abstract

Abstract

In order to address challenges posed by the reduction in transistor size, researchers are concentrating on two-dimensional (2D) materials with high dielectric constants and large band gaps. Monoclinic ZrO₂ (m-ZrO₂) has emerged as a promising gate dielectric material due to its suitable dielectric constant, wide band gap, ideal valence-band offset, and good thermodynamic stability. However, current deposition methods face compatibility issues with 2D semiconductors, highlighting the need for high-quality dielectrics and interfaces. Here, high-quality 2D m-ZrO₂ single crystals are successfully prepared using a one-step chemical vapor deposition (CVD) method, aided by 5A molecular sieves for oxygen supply. The prepared ZrO₂ is utilized as a gate dielectric in the construction of MoS₂ field-effect transistors (FETs) to investigate its electrical property. The FETs exhibit a high carrier mobility of up to 5.50 cm²·V⁻¹·s⁻¹, and a current switching ratio (I_on/off) of approximately 10⁴, which aligns with the current standards of logic circuits, indicating that ZrO₂ has application value as a gate dielectric. The successful one-step preparation of single-crystal ZrO₂ paves the way for the utilization of high-κ gate dielectrics and creates favorable conditions for the development of high-performance semiconductor devices, offering new possibilities for transistor miniaturization.
- ZrO₂,
- high-κ gate dielectric,
- chemical vapor deposition,
- field effect transistors,
- molecular sieves

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