The Journal of
the Korean Journal of Metals and Materials

The Journal of
the Korean Journal of Metals and Materials

Monthly
  • pISSN : 1738-8228
  • eISSN : 2288-8241

Editorial Office


  1. ๋ถ€์‚ฐ๋Œ€ํ•™๊ต์žฌ๋ฃŒ๊ณตํ•™๋ถ€ (School of Materials Science and Engineering, Pusan National University, Busan 46241, Republic of Korea)
  2. ์„œ์šธ๋Œ€ํ•™๊ต์žฌ๋ฃŒ๊ณตํ•™๋ถ€ (Department of Materials Science and Engineering & Inter-University Semiconductor Research Center, College of Engineering, Seoul National University, Seoul 08826, Republic of Korea)



ferroelectric, hafnia, zirconia, nanolaminate, superlattice

1. ์„œ ๋ก 

ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ตฌ์กฐ ์‚ฐํ™”๋ฌผ์ธ ์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์—์„œ ๋ฐœํ˜„๋˜๋Š” ๊ฐ•์œ ์ „์„ฑ์€ 2006๋…„ ๋…์ผ์˜ ๋ฐ˜๋„์ฒด ์ œ์กฐ์‚ฌ์ธ Qimonda์—์„œ ์ฒ˜์Œ ๋ฐœ๊ฒฌ๋˜์—ˆ๊ณ , 2011๋…„ Si ๋„ํ•‘๋œ ์‚ฐํ™”ํ•˜ํ”„๋Š„์˜ ๊ฐ•์œ ์ „์„ฑ์ด ์ตœ์ดˆ ๋…ผ๋ฌธ์œผ๋กœ ๋ณด๊ณ ๋˜์—ˆ๋‹ค [1]. Ferroelectric random-access-memory (FeRAM)์ด ์ „์ž ์†Œ์ž์— ์ด์ƒ์ ์ธ ๊ฐ•์œ ์ „์„ฑ์„ ๋ฐ”ํƒ•์œผ๋กœ ์ œ์•ˆ๋œ ์ง€ 50์—ฌ๋…„์ด ์ง€๋‚  ๋•Œ๊นŒ์ง€ ๋ฌผ๋ฆฌ์ ์ธ scaling-down ์‹œ์— ๋‚˜ํƒ€๋‚˜๋Š” ๋‹ค์–‘ํ•œ ์›์ธ์˜ ํŠน์„ฑ ์—ดํ™”๋กœ ์ƒ์šฉํ™”๋œ ์†Œ์ž์— ์ ์šฉ๋˜์ง€ ๋ชปํ•˜๊ณ  ํƒ€ emerging memory์™€์˜ ๊ฒฝ์Ÿ์—์„œ๋„ ๋’ค์ณ์ง€๊ณ  ์žˆ๋˜ ์ƒํ™ฉ์—์„œ ๋„ํ•‘๋œ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ํ˜น์€ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์—์„œ ๋ฐœํ˜„๋˜๋Š” ๋ฉ”์ปค๋‹ˆ์ฆ˜์€ ํ•™๊ณ„์™€ ์‚ฐ์—…๊ณ„์˜ ํฐ ๊ด€์‹ฌ์„ ๋Œ์–ด ์™”๋‹ค [2,3,4,5,6]. ๊ธฐ์กด ๊ฐ•์œ ์ „์ฒด๊ฐ€ ๋ฒŒํฌ๋‚˜ ๋น„๊ต์  ๋‘๊บผ์šด ๋‘๊ป˜์˜ ๋ฐ•๋ง‰์—์„œ ์šฐ์ˆ˜ํ•œ ๊ฐ•์œ ์ „์„ฑ์„ ๋ฐœํ˜„ํ•  ์ˆ˜ ์žˆ์—ˆ์œผ๋‚˜, ์‹ค์ œ ๋ฐ˜๋„์ฒด ์†Œ์ž์— ํ•„์š”ํ•œ 10 nm ์ดํ•˜ ๋‘๊ป˜์˜ ๋ฐ•๋ง‰ ํ˜•ํƒœ์—์„œ๋Š” ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ์†Œ, ๋ˆ„์„ค์ „๋ฅ˜ ์ฆ๊ฐ€, ๋ฉ”๋ชจ๋ฆฌ ์œˆ๋„์šฐ ๊ฐ์†Œ, depolarization field ์ฆ๊ฐ€ ๋“ฑ์˜ ๋‹ค์–‘ํ•œ ์ด์Šˆ๋กœ ์šฐ์ˆ˜ํ•œ ํŠน์„ฑ์„ ๋ณด์ด๊ธฐ ๋งค์šฐ ์–ด๋ ค์› ๋‹ค [2,3,4,5,6]. ํ•˜์ง€๋งŒ, ๋„ํ•‘๋œ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ๊ธฐ๋ฐ˜ ๊ฐ•์œ  ์ „์ฒด์˜ ๊ฒฝ์šฐ์—๋Š” ์ดˆ๊ธฐ ๋ณด๊ณ  ๋…ผ๋ฌธ๋ถ€ํ„ฐ 10 nm ์ •๋„์˜ ๋‘๊ป˜์—์„œ 15 ยตC/cm2 ์ด์ƒ์˜ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์„ ๋ณด์˜€์œผ๋ฉฐ, ์งง์€ ์—ญ์‚ฌ์—๋„ ์ด๋ฏธ ์•ฝ 28 nm ์„ ํญ์„ ๊ฐ€์ง€๋Š” ferroelectric fiel-deffect-transistor (FeFET) ์†Œ์ž์˜ ํŠน์„ฑ์ด ์ฆ๋ช…๋˜์—ˆ๋‹ค [7,8]. 2017๋…„์—๋Š” 22 nm ์„ ํญ์„ ๊ฐ€์ง€๋Š” fully depleted silicon-oninsulator (FDSOI) ์†Œ์ž๊ฐ€ ์‹คํ—˜์ ์œผ๋กœ ๊ฒ€์ฆ๋˜๊ธฐ๋„ ํ•˜์˜€๋‹ค [9].

์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์—์„œ ๊ฐ•์œ ์ „์„ฑ์ด ๋‚˜ํƒ€๋‚˜๋Š” ์›์ธ์€ Pca21์˜ ๊ณต๊ฐ„๊ตฐ์„ ๊ฐ€์ง€๋Š” orthorhombic phase๊ฐ€ ํ˜•์„ฑ๋˜๊ธฐ ๋•Œ๋ฌธ์ธ ๊ฒƒ์œผ๋กœ ์ œ์•ˆ๋˜์—ˆ๊ณ , 2015๋…„ Sang ๋“ฑ์ด ํˆฌ๊ณผ์ „์žํ˜„๋ฏธ๊ฒฝ ๊ธฐ๋ฐ˜์˜ convergent beam electron diffraction ๋ฐฉ๋ฒ•์„ ํ†ตํ•˜์—ฌ ์‹คํ—˜์ ์œผ๋กœ ์ฆ๋ช…ํ•˜์˜€๋‹ค [10]. ํ•˜์ง€๋งŒ, ๋ฒŒํฌ ์ƒํƒœ์˜ ์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ ์ƒํ‰ํ˜•๋„์—์„œ๋Š” ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์ด ์•ˆ์ •์ƒ์ธ ์˜จ๋„๋‚˜ ์••๋ ฅ ์˜์—ญ์ด ์กด์žฌํ•˜์ง€ ์•Š๋Š”๋‹ค [11]. ๊ทธ๋Ÿผ์—๋„ ๋ถˆ๊ตฌํ•˜๊ณ  ์‹คํ—˜์ ์œผ๋กœ๋Š” ๋ฐ•๋ง‰ ํ˜•ํƒœ์—์„œ ์žฌํ˜„์„ฑ ์žˆ๊ฒŒ ๋‹ค์–‘ํ•œ ๊ณต์ •์„ ํ†ตํ•˜์—ฌ ์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๊ธฐ๋ฐ˜ ๋ฐ•๋ง‰์—์„œ ๊ฐ•์œ ์ „์„ฑ์ด ๋ฐœํ˜„๋˜๋Š” ๊ฒƒ์ด ๋‹ค์ˆ˜์˜ ์—ฐ๊ตฌ๊ทธ๋ฃน์— ์˜ํ•ด์„œ ๋ณด๊ณ ๋˜์—ˆ๋‹ค. ํ˜„์žฌ, ์ด๋Ÿฌํ•œ ๊ฐ•์œ ์ „์„ฑ ์ค€์•ˆ์ „์ƒ์˜ ํ˜•์„ฑ์„ ์ดํ•ดํ•˜๊ธฐ ์œ„ํ•œ ๋‹ค์–‘ํ•œ ์—ด์—ญํ•™์  ํ˜น์€ ๋™์—ญํ•™์  ๊ด€์ ์ด ์—ฐ๊ตฌ๊ฐ€ ์ง„ํ–‰๋˜์—ˆ์œผ๋‚˜, ์•„์ง๊นŒ์ง€ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์˜ ํ˜•์„ฑ ๋ฉ”์ปค๋‹ˆ์ฆ˜์— ๋Œ€ํ•œ ํ™œ๋ฐœํ•œ ์—ฐ๊ตฌ๊ฐ€ ์ง„ํ–‰๋˜๊ณ  ์žˆ๋‹ค.

์ดˆ๊ธฐ ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ตฌ์กฐ ๊ฐ•์œ ์ „์ฒด์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋Š” ๋„ํ•‘๋œ ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์— ๋Œ€ํ•œ ์—ฐ๊ตฌ์— ์ง‘์ค‘๋˜์–ด ์™”๋‹ค. ํ•˜์ง€๋งŒ, ๋„ํ•‘๋œ ๋ฐ•๋ง‰์˜ ๊ฒฝ์šฐ์— ๋ฏธ๋Ÿ‰์˜ ๋„ํŽ€ํŠธ๋“ค์ด strain์ด๋‚˜ ๋ถˆ์ˆœ๋ฌผ ๋“ฑ์˜ ๊ฒฐํ•จ์˜ ๊ณต๊ฐ„์ƒ ๋ถ„ํฌ์˜ ๋ถˆ๊ท ์ผ์„ฑ์„ ์•ผ๊ธฐํ•  ๊ฐ€๋Šฅ์„ฑ์ด ์žˆ์œผ๋ฉฐ, ์ด๋Š” ๋ฌผ๋ฆฌ์ , ์ „๊ธฐ์  ํŠน์„ฑ์˜ ๋‘๊ป˜์— ๋ถˆ๊ท ์ผ์„ฑ์„ ์•ผ๊ธฐํ•  ๊ฐ€๋Šฅ์„ฑ์ด ์žˆ๋‹ค. ๋„ํ•‘์ด ๋˜์ง€ ์•Š์€ ์ˆœ์ˆ˜ํ•œ ์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์—์„œ์˜ ๊ฐ•์œ ์ „์„ฑ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋„ ๋ช‡๋ช‡ ์—ฐ๊ตฌ ๊ทธ๋ฃน์—์„œ ๋ณด๊ณ ํ•˜์˜€์œผ๋‚˜, ์‚ฐํ™”ํ•˜ํ”„๋Š„์˜ ๊ฒฝ์šฐ์—๋Š” ์—ด์—ญํ•™์  ์•ˆ์ •์ƒ์ธ monoclinic phase์˜ ์ƒ์„ฑ์„ ์–ต์ œํ•˜๋Š” ๊ฒƒ์ด ๋งค์šฐ ์–ด๋ ต๊ณ , ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ ๊ฒฝ์šฐ์—๋Š” Pt ๋“ฑ ํŠน์ˆ˜ํ•œ ์ „๊ทน ๋ฌผ์งˆ ์œ„์—์„œ๋งŒ ์œ ๋„๋œ ๊ฒฐ๊ณผ๋“ค์ด ๋ณด๊ณ ๋˜๊ณ  ์žˆ๋‹ค. ํ•œํŽธ, ํŽ˜๋กœ๋ธŒ์Šค์นด์ดํŠธ ๊ตฌ์กฐ์˜ ๊ฐ•์œ ์ „์ฒด์—์„œ๋Š” ์ด์ข… ๋ฌผ์งˆ์ด ๋ถ„๋ฆฌ๋œ ์ธต์ƒ์œผ๋กœ ์กด์žฌํ•˜๊ณ  ์žˆ๋Š” nanolaminate๋‚˜ superlattice ๊ตฌ์กฐ์—์„œ ์šฐ์ˆ˜ํ•œ ํŠน์„ฑ์„ ๋ฐœํ˜„ํ•  ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒฐ๊ณผ๋“ค์ด ๋‹ค์ˆ˜ ๋ณด๊ณ ๋˜์—ˆ๋‹ค [12,13,14,15,16,17,18,19]. ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ด ๋ถ„๋ฆฌ๋œ ์ธต์ƒ์˜ ํ˜•ํƒœ๋กœ ์กด์žฌํ•˜๋Š” nanolaminate์—์„œ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฐ•์œ ์ „์„ฑ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋„ 2015๋…„ Park ๋“ฑ์— ์˜ํ•ด์„œ ์ฒ˜์Œ ๋ณด๊ณ ๋œ ์ดํ›„, ๋ช‡๋ช‡ ์—ฐ๊ตฌ ๊ทธ๋ฃน์— ์˜ํ•ด์„œ ์žฌํ˜„์„ฑ์ด ํ™•์ธ๋˜๊ณ  ๊ธฐ์กด ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์— ๋น„ํ•ด์„œ ์šฐ์ˆ˜ํ•œ ํŠน์„ฑ์ด ๋ฐœํ˜„๋  ์ˆ˜ ์žˆ์Œ์ด ๋ณด๊ณ ๋˜์—ˆ๋‹ค. ๋ฌธํ—Œ์—์„œ๋Š” nanolaminate์™€ superlattice๋ผ๋Š” ์šฉ์–ด๊ฐ€ ํ˜ผ์šฉ๋˜๋‚˜ ๋ณธ ๋ฆฌ๋ทฐ์—์„œ๋Š” nanolaminate๋กœ ํ†ต์ผํ•˜์—ฌ ์‚ฌ์šฉํ•˜๊ณ ์ž ํ•œ๋‹ค. ๊ธฐ์กด ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์— ๋น„ํ•ด์„œ ์ˆ˜ํ‰๋ฐฉํ–ฅ์˜ ๊ณต๊ฐ„์ƒ ๋ถˆ๊ท ์ผ์„ฑ์„ ๋‚ฎ์ถœ ์ˆ˜ ์žˆ๋‹ค๋Š” ์žฅ์ ์ด ์žˆ์œผ๋ฉฐ ํ–ฅ์ƒ๋œ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด๋‚˜ ๋” ๋„“์€ ๊ฐ•์œ ์ „์„ฑ ๋ฐœํ˜„์„ ์œ„ํ•œ ์กฐ์„ฑ ์œˆ๋„์šฐ ๋“ฑ์ด nanolaminate ์ƒ˜ํ”Œ์˜ ์žฅ์ ์œผ๋กœ ๋ณด๊ณ ๋˜์—ˆ๋‹ค. ๋ณธ ๋ฆฌ๋ทฐ์—์„œ๋Š” ์„ ํ–‰์—ฐ๊ตฌ์—์„œ ๋ณด๊ณ ๋œ ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๊ธฐ๋ฐ˜์˜ nanolaminate์—์„œ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฐ•์œ ์ „์„ฑ์— ๋Œ€ํ•ด์„œ ์ข…ํ•ฉ์ ์œผ๋กœ ๋ฆฌ๋ทฐํ•˜๊ณ ์ž ํ•œ๋‹ค.

2. ๋ณธ ๋ก 

์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๊ธฐ๋ฐ˜ nanolaminate ์˜ ๊ฐ•์œ ์ „์„ฑ ๋ฐ ๋ฐ˜๊ฐ•์œ ์ „์„ฑ์€ 2015๋…„ Park ๋“ฑ์— ์˜ํ•˜์—ฌ ์ตœ์ดˆ ๋ณด๊ณ ๋˜์—ˆ๋‹ค [20]. ํ•ด๋‹น ์—ฐ๊ตฌ์—์„œ ์ด ๋‘๊ป˜๋ฅผ 8.8 nm๋กœ ๊ณ ์ •ํ•œ ์ƒํƒœ์—์„œ ๋‘ ๋ฌผ์งˆ์˜ ์ƒ๋Œ€์ ์ธ ๋‘๊ป˜์˜ ๋น„์œจ ๋ฐ ํ•œ ์ธต์˜ ๋‘๊ป˜๋ฅผ ์ œ์–ดํ•จ์œผ๋กœ์จ ๋‹ค์–‘ํ•œ ํŠน์„ฑ์„ ๊ฐ€์ง€๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๊ธฐ๋ฐ˜ nanolaminate๊ฐ€ ํ˜•์„ฑ ๊ฐ€๋Šฅํ•จ์ด ๋ณด๊ณ ๋˜์—ˆ๋‹ค [20]. ํ•ด๋‹น ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋Š” 2019๋…„์— ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์ด ํ˜•์„ฑ๋˜๋Š” ๋ฉ”์ปค๋‹ˆ์ฆ˜์— ๋Œ€ํ•œ ํ›„์† ์—ฐ๊ตฌ์™€ ๋”๋ถˆ์–ด ๋ฐœํ‘œ๋˜์—ˆ์œผ๋ฉฐ, ํ•ด๋‹น ๋…ผ๋ฌธ์˜ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๊ฐ€ ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๊ธฐ๋ฐ˜ nanolaminate์— ๋Œ€ํ•œ ๊ฐ€์žฅ ์ข…ํ•ฉ์ ์ธ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋กœ ๋ณธ ๋ฆฌ๋ทฐ์—์„œ ์ž์„ธํžˆ ๋…ผ์˜๋  ๊ฒƒ์ด๋‹ค [21].

์ดํ›„, 2016๋…„์— Lu ๋“ฑ์ด ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ bilayer์—์„œ ๋ฐœํ˜„๋˜๋Š” ๊ฐ•์œ ์ „์„ฑ์„ ๋ณด๊ณ ํ•˜์˜€๋‹ค [22]. ํ•ด๋‹น ์—ฐ๊ตฌ์—์„œ ์›์ž์ธต์ฆ์ฐฉ๋ฒ•(Atomic Layer Deposition, ALD)์œผ๋กœ ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋ฐ•๋ง‰์ด Pt ์ „๊ทน ์œ„์— ์ฆ์ฐฉ๋˜์—ˆ์„ ๋•Œ์—๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„์€ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ๊ณก์„ ์—์„œ ์„ ํ˜•์ ์ธ ์ƒ์œ ์ „ ๊ฑฐ๋™์„, ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์€ ๋ฐ˜๊ฐ•์œ ์ „์„ฑ์— ๊ฐ€๊นŒ์šด pinched hysteresis๋ฅผ ๋ณด์˜€์œผ๋‚˜ ์ด์ค‘์ธต ๊ตฌ์กฐ์—์„œ๋Š” ๊ฐ•์œ ์ „์„ฑ์ด ์œ ๋„๋  ์ˆ˜ ์žˆ์Œ์ด ๋ฐํ˜€์กŒ๋‹ค. Lu ๋“ฑ์€ ํ•˜๋ถ€์— ์‚ฐํ™”ํ•˜ํ”„๋Š„ ์ƒ๋ถ€์— ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์„ ์ฆ์ฐฉํ•œ ์ด์ค‘์ธต ๊ตฌ์กฐ๋ฅผ ๊ฐ€์ง€๋Š” ์บํŒจ์‹œํ„ฐ ์ƒ˜ํ”Œ์„ ์ฃผ๋กœ ์‹œํ—˜ํ•˜์˜€์œผ๋ฉฐ, ํŠนํžˆ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ ๋‘๊ป˜๋ฅผ 1.5, 3, 6 nm๋กœ ๋ณ€ํ™”์‹œํ‚ค๋ฉด์„œ ๊ฐ•์œ ์ „์„ฑ์˜ ๋ณ€ํ™”๋ฅผ ๊ด€์ฐฐํ•˜์˜€๋‹ค. ๊ทธ๋ฆผ 1(a)๋Š” Lu ๋“ฑ์˜ ๋…ผ๋ฌธ์—์„œ ๋ณด๊ณ ๋œ bilayer sample๋“ค์˜ grazing incidence X-ray diffraction pattern (GIXRD)์„ ๋ณด์—ฌ์ค€๋‹ค. ๊ทธ๋ฆผ 1(a)์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด ์ด์ค‘์ธต ๊ตฌ์กฐ์—์„œ ์ƒ๋ถ€ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ธต์˜ ๋‘๊ป˜๊ฐ€ 1.5 nm์—์„œ 6 nm๋กœ ์ฆ๊ฐ€ํ•˜๋ฉด์„œ monoclinic phase์—์„œ ๊ธฐ์ธํ•˜๋Š” 28.5๋„๋‚˜ 31.5๋„ ๋ถ€๊ทผ์˜ diffraction peak์— ๋น„ํ•ด์„œ 30.5๋„ ๋ถ€๊ทผ์˜ orthorhombic 111 diffraction peak์˜ intensity์˜ ์ƒ๋Œ€์ ์ธ ๊ฐ•๋„๊ฐ€ ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ์ด๋Š” ์ƒ๋ถ€ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ธต์˜ ๋‘๊ป˜์˜ ์ฆ๊ฐ€๊ฐ€ ์ด์ค‘์ธต ๊ตฌ์กฐ์˜ ์—ด์—ญํ•™์  ์•ˆ์ •์ƒ์ธ monoclinic phase์˜ ์ƒ๋Œ€์ ์ธ ๋น„์œจ์„ ์ค„์ผ ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒƒ์„ ๋ณด์—ฌ์ฃผ๋ฉฐ, ์ด๋Š” ์ด์ค‘์ธต ๊ตฌ์กฐ์˜ ๊ฐ•์œ ์ „์„ฑ์„ ํ–ฅ์ƒ์‹œํ‚ฌ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋˜๋Š” ๊ฒฐ์ •ํ•™์  ๋ณ€ํ™”์ด๋‹ค. ์‚ฐํ™”ํ•˜ํ”„๋Š„์„ ์ƒ๋ถ€์— ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์„ ํ•˜๋ถ€์— ์ฆ์ฐฉํ•œ ๊ตฌ์กฐ์˜ ์ด์ค‘์ธต ๊ตฌ์กฐ ์—ญ์‹œ ์ œ์ž‘๋˜์—ˆ์œผ๋‚˜ GIXRD ํŒจํ„ด์„ ๋ณด๋ฉด ๊ฐ•์œ ์ „์„ฑ orthorhombic phase์˜ 111 diffraction peak์˜ ์ƒ๋Œ€์ ์ธ intensity๊ฐ€ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ด ์ƒ๋ถ€์— ์ฆ์ฐฉ๋œ ๊ฒฝ์šฐ์— ๋น„ํ•ด์„œ ๋‚ฎ์€ ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ์ด์™€ ๊ฐ™์€ ๊ฒฐ๊ณผ๋ฅผ ํ†ตํ•ด ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ด ์ƒ๋ถ€์— ์ฆ์ฐฉ๋˜๋Š” ๊ตฌ์กฐ๊ฐ€ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ ์ƒ์„ฑ์— ๋” ์œ ๋ฆฌํ•œ ๊ฒƒ์„ ๋ณผ ์ˆ˜ ์žˆ์—ˆ๋‹ค. ์ด๋Š” ์ดํ›„์˜ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋“ค์—์„œ๋„ ๋น„์Šทํ•˜๊ฒŒ ๋ณด๊ณ ๋˜์—ˆ๋Š”๋ฐ, ์ž์„ธํ•œ ๋ฉ”์ปค๋‹ˆ์ฆ˜์— ๋Œ€ํ•ด์„œ๋Š” ๋ณธ ๋ฆฌ๋ทฐ์˜ ํ›„๋ฐ˜๋ถ€์—์„œ ๋” ์ž์„ธํžˆ ๋‹ค๋ฃจ๋„๋ก ํ•œ๋‹ค.

๊ทธ๋ฆผ 1(b)์™€ ๊ทธ๋ฆผ 1(c)๋Š” Lu ๋“ฑ์˜ ๋…ผ๋ฌธ์—์„œ ์ด์ค‘์ธต ๊ตฌ์กฐ์˜ ์บํŒจ์‹œํ„ฐ์—์„œ ๊ด€์ฐฐ๋˜๋Š” ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ๊ณก์„ ๊ณผ ์Šค์œ„์นญ ์ „๋ฅ˜-์ „๊ณ„ ์ด๋ ฅ๊ณก์„ ์„ ๊ฐ๊ฐ ๋ณด์—ฌ์ค€๋‹ค. ๊ทธ๋ฆผ 1(b)์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด 6 nm์˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ƒ๋ถ€์ธต, 6 nm์˜ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ํ•˜๋ถ€์ธต์œผ๋กœ ์ด๋ฃจ์–ด์ง„ ์ด์ค‘์ธต ๊ตฌ์กฐ์—์„œ ๊ฐ€์žฅ ๋†’์€ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด ๊ด€์ฐฐ๋˜์—ˆ๋‹ค(2Pr~30 ยตC/cm2). ์ด๋Š” ๊ทธ๋ฆผ 1(a)์˜ GIXRD ํŒจํ„ด์—์„œ ๊ฐ€์žฅ ๋†’์€ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์˜ ๋น„์œจ์ด ๊ธฐ๋Œ€๋˜๋Š” ๊ฒƒ๊ณผ๋„ ์ผ์น˜ํ•˜๋Š” ๊ฒฐ๊ณผ์ด๋‹ค. ์ƒ๋ถ€์˜ ์‚ฐํ•˜์ง€๋ฅด์ฝ”๋Š„ ์ธต์˜ ๋‘๊ป˜๊ฐ€ ๊ฐ์†Œํ• ์ˆ˜๋ก ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด ๊ฐ์†Œํ•˜๋Š” ๊ฒƒ์ด ๊ด€์ฐฐ๋˜์—ˆ์œผ๋ฉฐ, ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ ์ฆ์ฐฉ ์ˆœ์„œ๋ฅผ ๋ฐ”๊พผ ์ƒ๋ถ€ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ์ƒ˜ํ”Œ์—์„œ๋„ ๊ฐ•์œ ์ „์„ฑ์˜ ์ƒ๋‹นํ•œ ๊ฐ์†Œ๊ฐ€ ๊ด€์ฐฐ๋˜์—ˆ๋‹ค. ๊ทธ๋ฆผ 1(c)๋ฅผ ๋ณด๋ฉด, ์ƒ๋ถ€ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ์— ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ธต์˜ ๋‘๊ป˜๊ฐ€ ๊ฐ์†Œํ• ์ˆ˜๋ก coercive field (Ec) ๊ฐ’์ด ์ฆ๊ฐ€ํ•˜๋Š” ์–‘์ƒ์ด ๊ด€์ฐฐ๋˜๊ธฐ๋„ ํ•˜์˜€๋‹ค. ํ•ด๋‹น ์—ฐ๊ตฌ์—์„œ๋Š” ์ด์ค‘์ธต ๊ตฌ์กฐ์—์„œ ๊ฐ•์œ ์ „์„ฑ์ด ์œ ๋„๋˜๋Š” ์›์ธ์œผ๋กœ ์ถฉ๋ถ„ํ•œ ๋‘๊ป˜์˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ƒ๋ถ€์ธต์ด ์ฆ์ฐฉ๋˜์—ˆ์„ ๋•Œ์— ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์— ์˜ํ•œ mechanical confinement ํšจ๊ณผ์— ์˜ํ•ด์„œ ํ•˜๋ถ€ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ์ธต ๋‚ด์˜ ์—ด์—ญํ•™์  ์•ˆ์ •์ƒ์ธ monoclinic phase์˜ ์ƒ์„ฑ์ด ์–ต์ œ๋˜๋Š” ๊ฒƒ์œผ๋กœ ์„ค๋ช…๋˜์—ˆ๋‹ค. ๋ณธ ์—ฐ๊ตฌ๊ฐ€ ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ด์ค‘์ธต ๊ตฌ์กฐ์—์„œ์˜ ๊ฐ•์œ ์ „์„ฑ์„ ๋ณด๊ณ ํ•œ ์ตœ์ดˆ์˜ ๋…ผ๋ฌธ์œผ๋กœ ํฐ ์˜๋ฏธ๋ฅผ ๊ฐ€์ง€๋‚˜ ๊ทธ๋ฆผ 1(b)์˜ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ ๊ณก์„ ์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด ์ƒ๋Œ€์ ์œผ๋กœ ๋†’์€ ๋ˆ„์„ค ์ „๋ฅ˜ ๊ฐ’์„ ๋ณด์—ฌ ์ด๋กœ ์ธํ•œ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ ๊ณก์„ ์˜ ์™œ๊ณก์ด ๊ด€์ฐฐ๋˜์—ˆ์œผ๋ฉฐ, ๋ณด๊ณ ๋œ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด ๋ˆ„์„ค์ „๋ฅ˜๋กœ ์ธํ•œ ์™œ๊ณก์—๋„ ๋ถˆ๊ตฌํ•˜๊ณ  ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์—์„œ ๊ด€์ฐฐ๋˜๋Š” ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์— ๋น„ํ•ด์„œ ํ–ฅ์ƒ๋œ ๊ฐ’์ด ์•„๋‹ˆ์—ˆ๋‹ค๋Š” ํ•œ๊ณ„๊ฐ€ ์žˆ์—ˆ๋‹ค.

2017๋…„์—๋Š” Weeks ๋“ฑ์ด ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๊ธฐ๋ฐ˜์˜ ๋‹ค์–‘ํ•œ nanolaminate ๊ตฌ์กฐ๋ฅผ ๊ธฐ๋ฐ˜์œผ๋กœ ํ•œ ์บํŒจ์‹œํ„ฐ๋ฅผ ๋งŒ๋“ค๊ณ  ์ „๊ธฐ์ ์ธ ํŠน์„ฑ์„ ์ข…ํ•ฉ์ ์œผ๋กœ ๋ถ„์„ํ•œ ๊ฒฐ๊ณผ๋ฅผ ๋ณด๊ณ ํ•˜์˜€๋‹ค [23]. ๋ณธ ์—ฐ๊ตฌ์—์„œ๋„ ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ธต์€ ์›์ž์ธต์ฆ์ฐฉ๋ฒ•์œผ๋กœ ํ˜•์„ฑ๋˜์—ˆ์œผ๋ฉฐ, ์ด nanolaminate ๊ตฌ์กฐ์˜ ๋‘๊ป˜๋ฅผ 8 nm๋กœ ๊ณ ์ •ํ•œ ์ฑ„๋กœ ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ธต์˜ ๋‘๊ป˜๋ฅผ ๋™์ผํ•˜๊ฒŒ 1, 2, 4 nm๋“ฑ์œผ๋กœ ๋‹ค์–‘ํ•˜๊ฒŒ ๋ณ€ํ™”์‹œ์ผœ ๊ตฌ์„ฑํ•œ nanolaminate ๊ตฌ์กฐ์˜ ๋ฌผ๋ฆฌ์ /์ „๊ธฐ์  ํŠน์„ฑ์„ ๋ถ„์„ํ•˜์˜€๋‹ค. ํˆฌ๊ณผ์ „์žํ˜„๋ฏธ๊ฒฝ์œผ๋กœ nanolaminate ์ƒ˜ํ”Œ์˜ ๋‹จ๋ฉด์„ ๋ถ„์„ํ•˜์—ฌ ๋‘ ์ธต์ด intermixing์ด ๊ฑฐ์˜ ์—†์ด ๋ถ„๋ฆฌ๋˜์–ด ์กด์žฌํ•˜๊ณ  ์žˆ์Œ์„ ํ™•์ธํ•˜์˜€์œผ๋ฉฐ, GIXRD ํŒจํ„ด์œผ๋กœ๋ถ€ํ„ฐ monoclinic phase์˜ ์ƒ์„ฑ์„ ๋งค์šฐ ๋ฏธ๋ฏธํ•จ์„ ํ™•์ธํ•˜์˜€๋‹ค. ์›์ž์ธต์ฆ์ฐฉ๋ฒ•์˜ ์ฆ์ฐฉ์˜จ๋„๋ฅผ 260 ยฐC๊ณผ 285 ยฐC์˜ ๋‘ ์กฐ๊ฑด์—์„œ ์‹คํ—˜ํ•˜์˜€์œผ๋ฉฐ, 285 ยฐC์˜ ์ฆ์ฐฉ์˜จ๋„์—์„œ ๋” ๋†’์€ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์„ ์–ป์„ ์ˆ˜ ์žˆ์Œ์„ ๋ณด๊ณ ํ•˜์˜€๋‹ค. ๊ทธ๋ฆผ 2๋Š” Weeks ๋“ฑ์˜ ๋…ผ๋ฌธ์— ๋ณด๊ณ ๋œ ์ฆ์ฐฉ์˜จ๋„ 285 ยฐC (์ขŒ์ธก ํŒจ๋„๋“ค) ๋ฐ 260 ยฐC (์šฐ์ธก ํŒจ๋„๋“ค)์—์„œ ์ฆ์ฐฉ๋œ nanolaminate ์ƒ˜ํ”Œ (์ƒ๋ถ€๋ถ€ํ„ฐ ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ 4, 2, 1 nm์ธ nanolaminate) ๋ฐ ๊ณ ์šฉ์ฒด (์ตœํ•˜๋‹จ ํŒจ๋„๋“ค) ์ƒ˜ํ”Œ๋“ค์˜ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ ๊ณก์„ ์„ ๋ณด์—ฌ์ค€๋‹ค. ์ฆ์ฐฉ์˜จ๋„ 285 ยฐC ์ƒ˜ํ”Œ๋“ค์˜ ๊ฒฝ์šฐ์— ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ 1, 2, 4 nm์ผ ๋•Œ์˜ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด ๊ฐ๊ฐ 25, 18, 16 ยตC/cm2์˜ ๊ฐ’์„ ๋ณด์—ฌ, ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ ๊ฐ์†Œํ• ์ˆ˜๋ก ๋” ํฐ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด ๋‹ฌ์„ฑ ๊ฐ€๋Šฅํ•จ์„ ํ™•์ธํ•˜์˜€๋‹ค. ํŠนํžˆ, ๊ฐ™์€ ์กฐ๊ฑด์—์„œ ํ˜•์„ฑ๋œ 19 ยตC/cm2์˜ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์„ ๊ฐ€์ง€๋Š” ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์— ๋น„ํ•ด์„œ 285 ยฐC ์ฆ์ฐฉ ์กฐ๊ฑด์—์„œ๋Š” 1 nm์˜ ๋‘๊ป˜๋ฅผ ๊ฐ€์ง€๋Š” nanolaminate๊ฐ€ ๋” ํ–ฅ์ƒ๋œ ํŠน์„ฑ์„ ๋ณด์ด๋Š” ๊ฒƒ์„ ๋ณด๊ณ ํ•˜์˜€๋‹ค. ๋ณธ ์—ฐ๊ตฌ์—์„œ๋Š” nanolaminate์˜ ์ƒ์„ฑ ์กฐ๊ฑด์„ ์ตœ์ ํ™”ํ•  ๊ฒฝ์šฐ ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์— ๋น„ํ•ด์„œ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์„ ์ตœ๋Œ€ 28% ํ–ฅ์ƒ์‹œํ‚ฌ ์ˆ˜ ์žˆ์Œ์„ ๋ณด๊ณ ํ•˜์˜€์œผ๋ฉฐ, ํ•œ ์ธต์˜ ๋‘๊ป˜๋ฅผ 1 nm๋กœ ์ตœ์ ํ™”ํ–ˆ์„ ๋•Œ์— ๊ฐ€์žฅ ์šฐ์ˆ˜ํ•œ ๊ฐ•์œ ์ „์„ฑ์„ ์œ ๋„ํ•  ์ˆ˜ ์žˆ์Œ์„ ํ™•์ธํ•œ ๊ฒƒ์— ํฐ ์˜์˜๊ฐ€ ์žˆ๋‹ค.

์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ nanolaminate ์˜ ๊ฐ•์œ ์ „์„ฑ ๋ฐ ๋ฐ˜๊ฐ•์œ ์ „์„ฑ์„ ์ตœ์ดˆ๋กœ ๋ณด๊ณ ํ•˜์˜€๋˜ Park ๋“ฑ์€ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์˜ ํ˜•์„ฑ ๋ฉ”์ปค๋‹ˆ์ฆ˜์˜ ์ดํ•ด๋ฅผ ํฌํ•จํ•œ ๊ฐ€์žฅ ์ข…ํ•ฉ์ ์ธ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋ฅผ 2019๋…„์— ๋ฐœํ‘œํ•˜์˜€๋‹ค [21]. Park ๋“ฑ์€ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์˜ ์ƒ์„ฑ ๋ฉ”์ปค๋‹ˆ์ฆ˜์„ ์ดํ•ดํ•˜๊ธฐ ์œ„ํ•˜์—ฌ ์ด์ค‘์ธต ๋ฐ ์‚ผ์ค‘์ธต ๊ตฌ์กฐ์˜ nanolaminate์— ๋Œ€ํ•œ ์‹คํ—˜์„ ์šฐ์„  ์ง„ํ–‰ํ•˜์˜€๋‹ค. ์›์ž์ธต์ฆ์ฐฉ๋ฒ•์„ ํ†ตํ•ด ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ธต์„ ์ฆ์ฐฉํ•˜์˜€์œผ๋ฉฐ, ์ „์ฒด nanolaminate ์ƒ˜ํ”Œ์˜ ์›์ž์ธต์ฆ์ฐฉ๋ฒ• cycle ์ˆ˜๋ฅผ 80 cycle๋กœ ๊ณ ์ •ํ•˜์—ฌ ์ƒ˜ํ”Œ์˜ ์ด ๋‘๊ป˜๋Š” 8.8 nm๋กœ ๊ณ ์ •ํ•˜์˜€๋‹ค. ๋˜ํ•œ, ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ ์ด ๋‘๊ป˜์˜ ๋น„์œจ์„ 4.4 nm: 4.4 nm, 2.2 nm: 6.6 nm ๋กœ ๋ณ€ํ™”์‹œํ‚ค๋ฉด์„œ ํŠน์„ฑ์„ ํ‰๊ฐ€ํ•˜์˜€๋‹ค. ๊ทธ๋ฆผ 3(a)์™€ (b)๋Š” ๊ฐ๊ฐ ์ด ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ธต์˜ ๋‘๊ป˜์˜ ๋น„์œจ์ด 4.4 nm: 4.4 nm, 2.2 nm: 6.6 nm์ธ ์ƒ˜ํ”Œ๋“ค์˜ wake-up ์ดํ›„์˜ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ ๊ณก์„ ์„ ๋ณด์—ฌ์ค€๋‹ค. ํŠน์ง•์ ์ธ ์ ์€ ๋‘ ๊ฒฝ์šฐ ๋ชจ๋‘ ์‚ฐํ™”ํ•˜ํ”„๋Š„์„ ํ•˜๋ถ€์— ์ฆ์ฐฉํ•œ nanolaminate ์ƒ˜ํ”Œ๋“ค์ด ๋” ๋†’์€ ์ž”๋ฅ˜๋ถ„๊ทน ํ˜น์€ ํฌํ™”๋ถ„๊ทน ๊ฐ’์„ ๋ณด์—ฌ์ค€๋‹ค๋Š” ์ ์ด๋‹ค. ์ด๋Š” ๋ณธ ๋ฆฌ๋ทฐ์—๋Š” ํฌํ•จ๋˜์ง€ ์•Š์•˜์œผ๋‚˜ GIXRD ๋ถ„์„์„ ํ†ตํ•ด์„œ๋„ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ํ•˜๋ถ€์ธต์„ ๊ฐ€์ง€๋Š” ์ƒ˜ํ”Œ์—์„œ monoclinic phase์—์„œ ๊ธฐ์ธํ•˜๋Š” diffraction peak์˜ ์ƒ๋Œ€์ ์ธ intensity๊ฐ€ ๋” ๋†’๊ฒŒ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์„ ํ†ตํ•ด ์ดํ•ด๋  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ์ด ์—ฐ๊ตฌ์—์„œ๋Š” ์ด๋Ÿฌํ•œ ์›์ธ์„ ์ƒ๋ถ€ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ์ธต์— ํ•˜๋ถ€์˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์— ์˜ํ•ด ์œ ๋„๋˜๋Š” tensile strain์— ์˜ํ•ด์„œ tetragonal phase์—์„œ์˜ monoclinic phase๋กœ์˜ ์ƒ์ „์ด๊ฐ€ ๋‚˜ํƒ€๋‚˜๊ธฐ ์œ„ํ•œ nucleation energy barrier๊ฐ€ ๋‚ฎ์•„์ง€๋Š” ํ˜„์ƒ ๋ฐ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ด ํ•˜๋ถ€์— ์ฆ์ฐฉ๋˜์—ˆ์„ ๋•Œ์— ์ƒ๋Œ€์ ์œผ๋กœ ์ €์˜จ์ธ ์›์ž์ธต์ฆ์ฐฉ๋ฒ• ๊ณต์ • ์ค‘์— ๋†’์€ ๊ฒฐ์ •ํ™”๊ฐ€ ์ด๋ฃจ์–ด์ง€๋Š” ํ˜„์ƒ์œผ๋กœ ์„ค๋ช…ํ•˜์˜€๋‹ค. ์ฆ‰, ์ด๋ฏธ ๊ฒฐ์ •ํ™”๊ฐ€ ์›์ž์ธต์ฆ์ฐฉ๋ฒ• ๊ณต์ • ๋„์ค‘ ํ˜•์„ฑ๋˜๋Š” ๊ฒฝ์šฐ์— ์ƒ๋Œ€์ ์œผ๋กœ ์—ด์—ญํ•™์  ์•ˆ์ •์ƒ์œผ๋กœ์˜ ์ „์ด๊ฐ€ ์‰ฌ์›Œ์ง€๋ฉฐ, ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ ํฐ ๊ฒฉ์ž์ƒ์ˆ˜๊ฐ€ ์‚ฐํ™”ํ•˜ํ”„๋Š„์— tensile strain์„ ์œ ๋„ํ•˜์—ฌ ๋ถ€ํ”ผ ์ฆ๊ฐ€ ๊ณผ์ •์ด ์ˆ˜๋ฐ˜๋˜๋Š” monoclinic phase์˜ ํ˜•์„ฑ์ด ์‰ฌ์›Œ์ง„๋‹ค๋Š” ๊ฒƒ์ด๋‹ค. ์ด๋Š” Park ๋“ฑ์ด ๋‹ค์ˆ˜์˜ ๋…ผ๋ฌธ์—์„œ ์ข…ํ•ฉ์ ์œผ๋กœ ์ˆ˜ํ–‰ํ•œ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ ํ˜•์„ฑ์˜ ๋™์—ญํ•™์  ๋ฉ”์ปค๋‹ˆ์ฆ˜์— ๋Œ€ํ•œ ์—ฐ๊ตฌ์™€๋„ ์ผ์น˜ํ•˜๋Š” ๊ด€์ฐฐ ๊ฒฐ๊ณผ์ด๋‹ค [24,25,26,27,28,29].

์‚ฐํ™”ํ•˜ํ”„๋Š„:์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋‘๊ป˜์˜ ๋น„์œจ์ด 4.4 nm: 4.4 nm, 2.2 nm: 6.6 nm์ธ ์ƒ˜ํ”Œ์˜ ํŠน์„ฑ์„ ๋น„๊ตํ•˜๋ฉด, ์ „์ž๋Š” ๋šœ๋ ทํ•œ ๊ฐ•์œ ์ „์„ฑ์ด ๋‚˜ํƒ€๋‚˜๋Š” ๋ฐ˜๋ฉด์— ํ›„์ž์˜ ๊ฒฝ์šฐ์—๋Š” ์ „๊ณ„ ์œ ๋„ ๊ฐ•์œ ์ „์„ฑ์— ์˜ํ•œ double hysteresis๊ฐ€ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ์ด๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„:์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋‘๊ป˜์˜ ๋น„์œจ์ด 4.4 nm: 4.4 nm์ธ ๊ฒฝ์šฐ์—๋Š” ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์ธ orthorhombic phase๊ฐ€ ํ˜•์„ฑ๋˜๋Š” ๋ฐ˜๋ฉด์— ๋‘๊ป˜์˜ ๋น„์œจ์ด 2.2 nm: 6.6 nm์ธ ์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ์—๋Š” tetragonal phase๊ฐ€ ํ˜•์„ฑ๋˜๊ณ  ๋†’์€ ์ „๊ณ„ ํ•˜์—์„œ๋Š” ์•ˆ์ •์ƒ์ด orthorhombic phase๋กœ ๋ณ€ํ•ด ์ „๊ณ„ ์œ ๋„ ์ƒ์ „์ด๊ฐ€ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์œผ๋กœ ์„ค๋ช…๋  ์ˆ˜ ์žˆ๋‹ค [30,31,32]. ์ด๋Š” ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์—์„œ Hf:Zr์˜ ๋น„์œจ์ด 5:5 ์ผ ๋•Œ์— ๊ฐ•์œ ์ „์„ฑ์ด ๋šœ๋ ท์ด ๋‚˜ํƒ€๋‚˜๊ณ  3:7 โ€“ 2:8์˜ ๋น„์œจ์—์„œ ์ „๊ณ„ ์œ ๋„ ๊ฐ•์œ ์ „์„ฑ์ด ๋ฐœํ˜„๋˜๋Š” ๊ฒฐ๊ณผ์™€๋„ ์ผ์น˜ํ•œ๋‹ค. ์ฆ‰, nanolaminate ์ƒ˜ํ”Œ์—์„œ์˜ ์‚ฐํ™”ํ•˜ํ”„๋Š„๊ณผ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋‘๊ป˜์˜ ๋น„์œจ์ด ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์—์„œ์˜ ์›์†Œ ๋น„์œจ๊ณผ ์œ ์‚ฌํ•œ ํšจ๊ณผ๋ฅผ ๊ฐ€์ง„๋‹ค๋Š” ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค.

ํ•œํŽธ, ์‚ผ์ค‘์ธต ๊ตฌ์กฐ๋ฅผ ๊ฐ€์ง€๋Š” ์ƒ˜ํ”Œ ์ค‘ ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„/์‚ฐํ™”ํ•˜ํ”„๋Š„์˜ ์ ์ธต ๊ตฌ์กฐ๋ฅผ ๊ฐ€์ง€๋Š” ์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ์—๋Š” ํŠนํžˆ ๋งค์šฐ ํฅ๋ฏธ๋กœ์šด ํŠน์„ฑ์„ ๋ณด์˜€๋‹ค. ๊ทธ๋ฆผ 3(c)๋Š” ๋‹ค์–‘ํ•œ ์‚ฐํ™”ํ•˜ํ”„๋Š„:์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋‘๊ป˜ ๋น„์œจ์„ ๊ฐ€์ง€๋Š” ์‚ผ์ค‘์ธต ๊ตฌ์กฐ์—์„œ์˜ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ๊ณก์„ ์„ ๋ณด์—ฌ์ค€๋‹ค. ํŠน์ดํ•˜๊ฒŒ๋„ ์‚ฐํ™”ํ•˜ํ”„๋Š„: ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋‘๊ป˜ ๋น„์œจ์ด 6.6 nm: 2.2 nm๋กœ ์ผ๋ฐ˜์ ์œผ๋กœ monoclinic phase๊ฐ€ ์šฐ์„ธํ•˜๊ฒŒ ํ˜•์„ฑ๋  ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋˜๋Š” ์กฐ์„ฑ ๋ฒ”์œ„์—์„œ๋„ olive green ์ƒ‰์˜ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ๊ณก์„ ์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด 15 ยตC/cm2 ์ด์ƒ์˜ ๋†’์€ ๊ฐ’์„ ๊ฐ€์ง€๊ณ  ์žˆ์Œ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ์ด๋Š” ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์ด๋‚˜ ํ•ด๋‹น ์—ฐ๊ตฌ์˜ ๋‹ค๋ฅธ nanolaminate ์ƒ˜ํ”Œ๊ณผ ๋น„๊ตํ–ˆ์„ ๋•Œ ์ด๋ก€์ ์œผ๋กœ ๋†’์€ ๊ฒฐ๊ณผ์ด๋‹ค. ๊ทธ๋ฆผ 3(d)์— ๋‹ค์–‘ํ•œ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ธต์˜ ๋‘๊ป˜์˜ ์ƒ๋Œ€์  ๋น„์œจ์— ๋Œ€ํ•ด์„œ ๋ฐœํ˜„๋˜๋Š” ์ž”๋ฅ˜๋ถ„๊ทน 2๋ฐฐ (2Pr)์˜ ๊ฐ’์„ ๋‹ค์–‘ํ•œ ์ด์ค‘์ธต ๋ฐ ์‚ผ์ค‘์ธต ๊ตฌ์กฐ์™€ ๊ณ ์šฉ์ฒด (SS) ์ƒ˜ํ”Œ์— ๋Œ€ํ•ด์„œ ์ •๋ฆฌํ•œ ๊ฒฐ๊ณผ์ด๋‹ค. ๋‹ค๋ฅธ ์ƒ˜ํ”Œ์— ๋น„ํ•ด์„œ ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„/์‚ฐํ™”ํ•˜ํ”„๋Š„์˜ ์‚ผ์ค‘์ธต ๊ตฌ์กฐ๊ฐ€ ๊ฐ€์žฅ ๋„“์€ ์กฐ์„ฑ ๋ฒ”์œ„์—์„œ ์šฐ์ˆ˜ํ•œ 2Pr ๊ฐ’์„ ๋ณด์ž„์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค. ์ด๋Š” ๋„“์€ ์กฐ์„ฑ ์œˆ๋„์šฐ์—์„œ ์šฐ์ˆ˜ํ•œ ๊ฐ•์œ ์ „์„ฑ์ด ๋ฐœํ˜„๋œ๋‹ค๋Š” ๊ฒƒ์œผ๋กœ ์‹ค์ œ ์–‘์‚ฐ์— ๋„์ž…๋˜์—ˆ์„ ๋•Œ์— ๋„“์€ ๊ณต์ • ์œˆ๋„์šฐ๋ฅผ ํ™•๋ณดํ•  ์ˆ˜ ์žˆ์–ด ์‚ฐ์—…์ ์ธ ์ž ์žฌ์  ๊ฐ€์น˜๊ฐ€ ๋†’์€ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค. ๋ณธ ์—ฐ๊ตฌ ์ดํ›„์— Migita ๋“ฑ์˜ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ์—์„œ๋„ ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„/์‚ฐํ™”ํ•˜ํ”„๋Š„ ์‚ผ์ค‘์ธต ๊ตฌ์กฐ๊ฐ€ ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰์— ๋น„ํ•ด์„œ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์˜ ํ˜•์„ฑ์ด ์ด‰์ง„๋˜์–ด ์šฐ์ˆ˜ํ•œ ๊ฐ•์œ ์ „์„ฑ์„ ๋ฐœํ˜„ํ•  ์ˆ˜ ์žˆ์Œ์ด ๋ณด๊ณ ๋˜์—ˆ๋‹ค [33].

๊ทธ๋ฆผ 4(a)์™€ (b)๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„ ๋ฐ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์„ ์ตœํ•˜๋ถ€์ธต์œผ๋กœ ๋‘” nanolaminate ์ƒ˜ํ”Œ๋“ค์˜ ๋‹ค์–‘ํ•œ ํ•œ ์ธต์˜ ๋‘๊ป˜์— ๋Œ€ํ•ด์„œ ํ‰๊ฐ€๋œ ๋ถ„๊ทน-์ „๊ณ„ ์ด๋ ฅ ๊ณก์„ ์„ ๋ณด์—ฌ์ฃผ๋ฉฐ, ์—ฌ๊ธฐ์—์„œ ์ถ”์ถœ๋œ 2Pr๊ฐ’์„ ํ•œ ์ธต์˜ ๋‘๊ป˜์— ๋Œ€ํ•ด์„œ ์ •๋ฆฌํ•œ ๊ฒƒ์ด ๊ทธ๋ฆผ 4(c)์ด๋‹ค. ๊ทธ๋ฆผ 4(d)๋Š” GIXRD ํŒจํ„ด์—์„œ monoclinic phase์—์„œ ๊ธฐ์ธํ•˜๋Š” diffraction peak๋“ค์˜ ์ƒ๋Œ€์ ์ธ ๋ฉด์  ๋ถ„์œจ์„ ๊ณ„์‚ฐํ•˜์—ฌ ํ•œ ์ธต์˜ ์›์ž์ธต์ฆ์ฐฉ๋ฒ• cycle์ˆ˜์˜ ํ•จ์ˆ˜๋กœ plotํ•œ ๊ฒฐ๊ณผ๋กœ monoclinic phase์˜ ์ƒ๋Œ€์ ์ธ ๋ถ„์œจ์ด ์–ด๋–ป๊ฒŒ ๋ณ€ํ™”ํ•˜๋Š”์ง€ ์ •์„ฑ์ ์œผ๋กœ ํ™•์ธ ๊ฐ€๋Šฅํ•˜๋‹ค. ๊ทธ๋ฆผ 4(a)์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด ์ตœํ•˜๋ถ€์ธต์ด ์‚ฐํ™”ํ•˜ํ”„๋Š„์ธ ๊ฒฝ์šฐ์—๋Š” ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ ๋ณ€ํ•  ๋•Œ์— ๋ฏธ์„ธํ•œ ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์˜ ๊ฐ์†Œ๊ฐ€ ๊ด€์ฐฐ๋˜์ง€๋งŒ ๊ทธ ๋ณ€ํ™”๋Š” ๋งค์šฐ ์ž‘์€ ํŽธ์ด๋‹ค. ํ•˜์ง€๋งŒ, ๊ทธ๋ฆผ 4(b)์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์„ ์ตœํ•˜๋ถ€์ธต์œผ๋กœ ๋‘” nanolaminate ์ƒ˜ํ”Œ์˜ ๊ฒฝ์šฐ์—๋Š” ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ 0.22 nm (ํ‘์ƒ‰ ๊ณก์„ ) ๋ฐ 0.55 nm (์ ์ƒ‰ ๊ณก์„ )์ธ ๊ฒฝ์šฐ์—๋Š” ์ž”๋ฅ˜๋ถ„๊ทน์ด ์•ฝ 20 ยตC/cm2 ์ •๋„๋กœ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ์ตœํ•˜์ธต์„ ๊ฐ€์ง„ nanolaminate ์ƒ˜ํ”Œ๊ณผ ๊ฑฐ์˜ ์œ ์‚ฌํ•œ ํŠน์„ฑ์„ ๋ณด์ด์ง€๋งŒ ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ 1.1 nm ์ด์ƒ์ธ ๊ฒฝ์šฐ์— ์ž”๋ฅ˜๋ถ„๊ทน ๊ฐ’์ด 12 ยตC/cm2 ์ •๋„๋กœ ๊ธ‰๊ฒฉํžˆ ๊ฐ์†Œํ•˜๋ฉฐ, ์ถ”๊ฐ€์ ์œผ๋กœ ํ•œ ์ธต์˜ ๋‘๊ป˜๊ฐ€ ์ฆ๊ฐ€ํ•  ๋•Œ์— ์ถ”๊ฐ€์ ์ธ ์ž”๋ฅ˜๋ถ„๊ทน์˜ ๊ฐ์†Œ ๋˜ํ•œ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค. ๊ทธ๋ฆผ 4(a)์™€ (b)๋ฅผ ๋น„๊ตํ•˜์˜€์„ ๋•Œ์— ์ตœํ•˜์ธต ๋ฌผ์งˆ์˜ ํšจ๊ณผ๊ฐ€ ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒƒ์€ ์•ฝ 1.1 nm ์ด์ƒ์˜ ๋‘๊ป˜์˜ ์ž„๊ณ„๊ฐ’์„ ๋„˜๊ฒผ์„ ๋•Œ์ธ ๊ฒƒ์„ ์•Œ ์ˆ˜ ์žˆ๋‹ค. ํ•˜๋ถ€ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ธต์ด monoclinic phase์˜ ํ˜•์„ฑ์„ ์ด‰์ง„์‹œํ‚ค๋Š” ๊ฒƒ์„ ์•ž์„œ ์„ค๋ช…ํ•œ ๊ฒƒ์ฒ˜๋Ÿผ ์›์ž์ธต์ฆ์ฐฉ๋ฒ• ๋„์ค‘์— ๋‚˜ํƒ€๋‚˜๋Š” ๊ฒฐ์ •ํ™”๋„๋ฅผ ์ฆ๊ฐ€์‹œํ‚ค๋Š” ๊ฒƒ๊ณผ ์ƒ๋ถ€์— ํ˜•์„ฑ๋˜๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„ ์ธต์— tensile strain์„ ์ƒ์„ฑํ•˜๊ธฐ ๋•Œ๋ฌธ์ผ ๊ฒƒ์ด๋ฏ€๋กœ, ์ด๋Ÿฌํ•œ ํšจ๊ณผ๋ฅผ ๋งŒ๋“œ๋Š” ์ž„๊ณ„ ๋‘๊ป˜๊ฐ€ 1.1 nm ์ด์ƒ์ธ ๊ฒƒ์œผ๋กœ ํŒ๋‹จ๋œ๋‹ค. ์ด ๋‘๊ป˜๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์˜ unit cell 2๊ฐœ ์ •๋„๋กœ ๋งค์šฐ ์–‡์€ ๋‘๊ป˜์— ํ•ด๋‹น๋œ๋‹ค. ๊ทธ๋ฆผ 4(d)์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด GIXRD ํŒจํ„ด์„ ๋ถ„์„ํ•˜๋ฉด ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ์ตœํ•˜๋ถ€์ธต์„ ๊ฐ€์ง€๋Š” nanolaminate์—์„œ ํ•œ์ธต์˜ ๋‘๊ป˜๋ฅผ ์ฆ๊ฐ€์‹œํ‚ฌ ๋•Œ์— monoclinic phase์˜ ์ƒ๋Œ€์ ์ธ ๋น„์œจ์ด ์ฆ๊ฐ€ํ•˜๋Š” ๊ฒฝํ–ฅ์ด ๋šœ๋ ท์ด ๊ด€์ฐฐ๋œ๋‹ค.

Park ๋“ฑ์˜ ์—ฐ๊ตฌ์—์„œ ๋ณด๊ณ ๋œ ๋˜ ๋‹ค๋ฅธ ํฅ๋ฏธ๋กœ์šด ๊ฒฐ๊ณผ๋Š” nanolaminate์—์„œ ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰๊ณผ ๋น„๊ตํ–ˆ์„ ๋•Œ์— ๋” ์šฐ์ˆ˜ํ•œ endurance๊ฐ€ ๋‹ฌ์„ฑ๋  ์ˆ˜ ์žˆ๋‹ค๋Š” ๊ฒฐ๊ณผ์˜€๋‹ค. ํŠนํžˆ, ๊ทธ๋ฆผ 5(a)์—์„œ ๋ณผ ์ˆ˜ ์žˆ๋“ฏ์ด ๋„“์€ ์กฐ์„ฑ ๋ฒ”์œ„์—์„œ ์šฐ์ˆ˜ํ•œ ๊ฐ•์œ ์ „์„ฑ์„ ๋ณด์ผ ์ˆ˜ ์žˆ๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„/์‚ฐํ™”ํ•˜ํ”„๋Š„ ์‚ผ์ค‘์ธต ๊ตฌ์กฐ์—์„œ ์šฐ์ˆ˜ํ•œ endurance๊ฐ€ ๊ด€์ฐฐ๋˜์—ˆ๋‹ค. Endurance๋Š” ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ตฌ์กฐ ๊ฐ•์œ ์ „์ฒด๋Š” ๋ฐ˜๋„์ฒด ์†Œ์ž์— ์ ์šฉํ–ˆ์„ ๋•Œ์— ํ˜„์žฌ ๊ฐ€์žฅ ๊ธฐ์ˆ ์ ์ธ ์ด์Šˆ๊ฐ€ ๋˜๋Š” ๋ฌธ์ œ๋ผ ํ•  ์ˆ˜ ์žˆ๋‹ค. Endurance๋Š” ์ „์ž ์†Œ์ž๋ฅผ ์–ผ๋งˆ๋‚˜ ๋งŽ์€ ํšŸ์ˆ˜๋งŒํผ ๋™์ž‘์‹œํ‚ฌ ์ˆ˜ ์žˆ๋Š”์ง€์™€ ์—ฐ๊ด€๋˜๋Š” ์ง€ํ‘œ๋กœ ๊ฐ•์œ ์ „์ฒด ์†Œ์žฌ์˜ ๊ฒฝ์šฐ์—๋Š” ์Šค์œ„์นญ ํšŸ์ˆ˜๊ฐ€ ์—ฌ๊ธฐ์— ์—ฐ๊ด€์ด ๋œ๋‹ค. ๋ฌผ๋ก , ์‹ค์ œ ํŠธ๋žœ์ง€์Šคํ„ฐ์˜ ๊ฒŒ์ดํŠธ ์Šคํƒ์œผ๋กœ ์ ์šฉ๋˜์—ˆ์„ ๊ฒฝ์šฐ์—๋Š” ์‹ค๋ฆฌ์ฝ˜ ์ฑ„๋„๊ณผ์˜ ๊ณ„๋ฉด์˜ ํŠน์„ฑ์ด ๋” criticalํ•œ ์š”์†Œ๊ฐ€ ๋  ์ˆ˜ ์žˆ์ง€๋งŒ ๊ธˆ์†/๊ฐ•์œ ์ „์ฒด/๊ธˆ์† ์บํŒจ์‹œํ„ฐ ๊ตฌ์กฐ์—์„œ๋„ ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ตฌ์กฐ ๊ฐ•์œ ์ „์ฒด ํŠน์œ ์˜ ๋†’์€ Ec ๊ฐ’์œผ๋กœ ์ธํ•ด์„œ ์ƒ๋Œ€์ ์œผ๋กœ ๋‚ฎ์€ ํšŸ์ˆ˜์—์„œ endurance failure๊ฐ€ ๊ด€์ฐฐ๋˜๊ณ ๋Š” ํ•œ๋‹ค. Failure mechanism์€ ์ฃผ๋กœ ๋ˆ„์„ค์ „๋ฅ˜์˜ ๊ธ‰๊ฒฉํ•œ ์ฆ๊ฐ€๋กœ ์ธํ•œ hard breakdown์˜ ํ˜•ํƒœ๋กœ ๋‚˜ํƒ€๋‚˜๋ฉฐ ์ด๋Š” ์‚ฐ์†Œ ๊ณต๊ณต ๋“ฑ์˜ drift์™€ accumulation์ด ์ฃผ์š” ์›์ธ์œผ๋กœ ๋ฐ›์•„๋“ค์—ฌ์ง€๊ณ  ์žˆ๋‹ค. ๊ทธ๋ฆผ 5(b)์— ์„ ํ–‰์—ฐ๊ตฌ์—์„œ ๋ณด๊ณ ๋œ ๋‹ค์–‘ํ•œ ๋„ํŽ€ํŠธ๋กœ ๋„ํ•‘๋œ ์‚ฐํ™”ํ•˜ํ”„๋Š„ ๋ฐ•๋ง‰๊ณผ nanolaminate ์ƒ˜ํ”Œ์˜ endurance์™€ Pr ๊ฐ’์ด ์ •๋ฆฌ๋˜์–ด ์žˆ์œผ๋ฉฐ, ์‚ผ์ค‘์ธต ๊ตฌ์กฐ์—์„œ ๊ด€์ฐฐ๋œ 1010ํšŒ์˜ endurance๋Š” ๋ณด๊ณ ๋œ ์ตœ๊ณ  ์ˆ˜์ค€์— ๊ฐ€๊นŒ์šด ๊ฐ’์ž„์„ ํ™•์ธํ•  ์ˆ˜ ์žˆ๋‹ค.

ํ‘œ 1์—์„œ๋Š” ์‚ฐํ™”ํ•˜ํ”„๋Š„/์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ nanolaminate ์ƒ˜ํ”Œ์— ๋Œ€ํ•ด ์—ฌ๋Ÿฌ ์„ ํ–‰ ์—ฐ๊ตฌ์—์„œ ๊ด€์ฐฐํ•œ ๋‚ด์šฉ์„ ์š”์•ฝํ•œ ๊ฒƒ์œผ๋กœ, ์ƒ˜ํ”Œ์˜ ์ข…๋ฅ˜ ๋ฐ ์ œ์ž‘ ๋ฐฉ๋ฒ•, ๊ฐ•์œ ์ „ ํŠน์„ฑ ๋“ฑ์— ๊ด€ํ•œ ์ •๋ณด๋ฅผ ํฌํ•จํ•œ๋‹ค.

3. ๊ฒฐ๋ก  ๋ฐ ์ „๋ง

๋ณธ ๋ฆฌ๋ทฐ์—์„œ ์‚ดํŽด๋ณด์•˜๋“ฏ์ด ์‚ฐํ™”ํ•˜ํ”„๋Š„, ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„ ๋“ฑ ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ตฌ์กฐ ์‚ฐํ™”๋ฌผ๋กœ ๊ตฌ์„ฑ๋œ nanolaminate ๋Š” ๊ณ ์šฉ์ฒด ์ค‘์‹ฌ์˜ ๊ธฐ์กด ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ตฌ์กฐ ๊ฐ•์œ ์ „์ฒด ์—ฐ๊ตฌ์— ์ธ๊ณต์ ์ธ ์‹ ์†Œ์žฌ๋กœ์จ ํ–ฅ์ƒ๋œ ๊ฐ•์œ ์ „์„ฑ์„ ๋ฐœํ˜„ํ•˜์—ฌ ๋ฐ˜๋„์ฒด ๋ฐ ์—๋„ˆ์ง€ ์‘์šฉ ์†Œ์ž์˜ ํŠน์„ฑ์„ ํ–ฅ์ƒํ•  ์ˆ˜ ์žˆ๋Š” ๋ฏธ๋ž˜ ์œ ๋ง ์†Œ์žฌ๋กœ ๊ด€์‹ฌ์„ ์–ป๊ณ  ์žˆ๋‹ค. 2014๋…„ ์ฒ˜์Œ ๋ฐœ๊ฒฌ๋œ ์ดํ›„ ์ด 7์—ฌ๋…„์˜ ์งง์€ ์—ญ์‚ฌ๋กœ ์ธํ•ด ์•„์ง๊นŒ์ง€ ๋ณด๊ณ ๋œ ์‹คํ—˜ ๊ฒฐ๊ณผ์˜ ์ˆ˜๋Š” ๋‹ค์†Œ ์ ์€ ํŽธ์ด๋‚˜ ์†Œ์ˆ˜์˜ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋ฅผ ํ†ตํ•ด ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰๊ณผ ์ฐจ๋ณ„ํ™”๋œ ํŠน์ง•์ด ์žฌํ˜„์„ฑ ์žˆ๊ฒŒ ๊ด€์ฐฐ๋˜๋Š” ๊ฒƒ์€ ๊ณ ๋ฌด์ ์ธ ๊ฒฐ๊ณผ๋ผ ํ•  ์ˆ˜ ์žˆ๋‹ค. ํŠนํžˆ, ์ž”๋ฅ˜๋ถ„๊ทน์˜ ์ธก๋ฉด์—์„œ ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰๊ณผ ๋น„๊ตํ•˜์—ฌ ์•ฝ 20-30%์˜ ์ •๋Ÿ‰์ ์ธ ํ–ฅ์ƒ์ด ๊ฐ€๋Šฅํ•˜์˜€์œผ๋ฉฐ, ๊ฐ•์œ ์ „์„ฑ์ด ์œ ๋„๋˜๋Š” ์กฐ์„ฑ ๋ฒ”์œ„๋ฅผ ํฌ๊ฒŒ ์ฆ๊ฐ€์‹œ์ผœ ์‹ค์ œ ์–‘์‚ฐ๋˜๋Š” ๊ณต์ •์— ์ ์šฉ๋˜์—ˆ์„ ๋•Œ์— ๊ณต์ • ์œˆ๋„์šฐ๋ฅผ ์ถฉ๋ถ„ํžˆ ํ™•๋ณดํ•  ์ˆ˜ ์žˆ๋Š” ์žฅ์ ์„ ๊ฐ€์กŒ๋‹ค. ๋˜ํ•œ, endurance ์ธก๋ฉด์—์„œ๋„ ๊ณ ์šฉ์ฒด ๋ฐ•๋ง‰ ๋Œ€๋น„ ์•ฝ 1 order ์ •๋„์˜ ์‹ ๋ขฐ์„ฑ ํ–ฅ์ƒ์„ ๊ด€์ฐฐํ•  ์ˆ˜ ์žˆ์—ˆ๋‹ค.

ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ฐ•์œ ์ „์ฒด ์ž์ฒด์˜ ์—ฐ๊ตฌ ์—ญ์‚ฌ๋„ 10์—ฌ๋…„์œผ๋กœ ๋งค์šฐ ์งง์€ ํ˜„์‹ค์—์„œ ๊ฐ•์œ ์ „์„ฑ ๊ฒฐ์ •์ƒ์ด ํ˜•์„ฑ๋˜๋Š” ์ž์„ธํ•œ ๋ฉ”์ปค๋‹ˆ์ฆ˜ ๋“ฑ์„ ์•„์ง๊นŒ์ง€ ์ •ํ™•ํžˆ ์ดํ•ดํ•˜๊ณ  ์žˆ์ง€ ๋ชปํ•˜๊ธฐ ๋•Œ๋ฌธ์— ํ˜„์žฌ์—๋„ ์žฌ๋ฃŒ๊ณตํ•™ ์ธก๋ฉด์—์„œ ์—ฐ๊ตฌ๋˜๊ณ  ์ดํ•ด๋˜์–ด์•ผ ํ•  ๋ถ€๋ถ„์ด ๋งค์šฐ ๋งŽ์€ ๊ฒƒ์œผ๋กœ ์—ฌ๊ฒจ์ง€๊ณ  ์žˆ๋‹ค. ํŠนํžˆ, ์ง€๊ธˆ๊นŒ์ง€์˜ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋ฅผ ์ข…ํ•ฉํ•ด ๋ณด์•˜์„ ๋•Œ ๋‹จ์ผ์ธต์œผ๋กœ๋Š” ๊ฐ•์œ ์ „์„ฑ ์œ ๋„๊ฐ€ ์–ด๋ ค์šด ์‚ฐํ™”ํ•˜ํ”„๋Š„์ด๋‚˜ ์‚ฐํ™”์ง€๋ฅด์ฝ”๋Š„์ด ์ธ๊ณต์ ์œผ๋กœ ํ˜•์„ฑ๋œ ์ ์ธต ๊ตฌ์กฐ์—์„œ ๊ฐ•์œ ์ „์„ฑ ํ˜น์€ ์ „๊ณ„ ์œ ๋„ ๊ฐ•์œ ์ „์„ฑ์ด ๋ฐœํ˜„๋˜๋Š” ๊ฒƒ์€ ํ•™๋ฌธ์ ์œผ๋กœ ๋งค์šฐ ํฅ๋ฏธ๋กœ์šด ํ˜„์ƒ์ด๋ฉฐ, ํŽ˜๋กœ๋ธŒ์Šค์นด์ดํŠธ ๊ตฌ์กฐ ๊ฐ•์œ ์ „์ฒด์—์„œ ํ•œ ๋•Œ ๋‹ค์ˆ˜์˜ ์—ฐ๊ตฌ์ž๋“ค์— ๊ด€์‹ฌ์„ ํฌ๊ฒŒ ์–ป์—ˆ๋˜ nanolaminate์— ๋Œ€ํ•œ ํ•™๋ฌธ์  ์ดํ•ด๋ฅผ ์œ„ํ•œ ์—ฐ๊ตฌ์™€ ํŠน์„ฑ ํ–ฅ์ƒ์€ ์œ„ํ•œ engineering์ด ๋ณธ ์‹œ์Šคํ…œ์—์„œ๋„ ํ™œ๋ฐœํ•˜๊ฒŒ ์ด๋ฃจ์–ด์งˆ ์ˆ˜ ์žˆ์„ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค.

ํŠนํžˆ, ์•„์ง๊นŒ์ง€ ํ”Œ๋ฃจ์˜ค๋ผ์ดํŠธ ๊ธฐ๋ฐ˜ nanolaminate์—์„œ ๊ฐ•์œ ์ „์„ฑ ๋ฐ ๋ฐ˜๊ฐ•์œ ์ „์„ฑ์— ์˜ํ–ฅ์„ ์ค„ ์ˆ˜ ์žˆ๋Š” ์ž ์žฌ์  ์š”์ธ์œผ๋กœ ํŒ๋‹จ๋˜๋Š” electrostatic coupling์ด๋‚˜ strain ๋“ฑ์˜ ํšจ๊ณผ์— ๋Œ€ํ•œ ์—ฐ๊ตฌ๋Š” ๊ฑฐ์˜ ์ „๋ฌดํ•œ ์ƒํ™ฉ์ด๋ผ ํ•  ์ˆ˜ ์žˆ๋‹ค. ์ด๋Š” ์ง€๊ธˆ๊นŒ์ง€ ์ง„ํ–‰๋œ ์—ฐ๊ตฌ๋“ค์ด ๋Œ€๋ถ€๋ถ„ ์›์ž์ธต์ฆ์ฐฉ๋ฒ• ๋“ฑ์— ๊ธฐ๋ฐ˜ํ•œ ๋‹ค๊ฒฐ์ •์งˆ ๋ฐ•๋ง‰์—์„œ ์ด๋ฃจ์–ด์ ธ ๋ฌผ๋ฆฌ์  ๋ฉ”์ปค๋‹ˆ์ฆ˜ ์—ฐ๊ตฌ์— ํ•œ๊ณ„๊ฐ€ ์žˆ๋Š” ๊ฒƒ์œผ๋กœ ์ดํ•ด๋˜๋ฉฐ, ํ˜„์žฌ ํ™œ๋ฐœํžˆ ์—ฐ๊ตฌ๋˜๊ธฐ ์‹œ์ž‘ํ•œ ์—ํ”ผํƒ์…œ ๋ฐ•๋ง‰์— ๋Œ€ํ•œ ๊ธฐ์ˆ  ๊ฐœ๋ฐœ์„ ๋ฐ”ํƒ•์œผ๋กœ ๋ฉ”์ปค๋‹ˆ์ฆ˜ ์ดํ•ด์— ๋Œ€ํ•ด ๋”์šฑ ํ™œ๋ฐœํ•œ ์—ฐ๊ตฌ๊ฐ€ ์ง„ํ–‰๋  ์ˆ˜ ์žˆ์„ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค. Nanolaminate ๊ตฌ์กฐ๋ฅผ ์ด์šฉํ•˜๋Š” ์—ฐ๊ตฌ ์—ญ์‹œ ์•„์ง๊นŒ์ง€๋Š” ์†Œ์ˆ˜ ์—ฐ๊ตฌ ๊ทธ๋ฃน์— ์˜ํ•œ ๋ณด๊ณ ์— ๊ทธ์น˜๊ณ  ์žˆ๋Š” ์ƒํ™ฉ์ด์ง€๋งŒ, ์‹ค์ œ ๋ฐ˜๋„์ฒด ์†Œ์ž๋กœ ํ™œ์šฉ ๊ฐ€๋Šฅํ•œ FeFET์™€ ๊ฐ™์€ ์†Œ์ž์˜ gate oxide์— ๋„์ž…๋œ ์—ฐ๊ตฌ ๊ฒฐ๊ณผ๋Š” ์•ž์œผ๋กœ ๊ด€๋ จ๋œ ์—ฐ๊ตฌ๊ฐ€ ๋” ํ™œ๋ฐœํžˆ ์ง„ํ–‰๋  ์ˆ˜ ์žˆ๋Š” ์‹œ๋ฐœ์ ์ด ๋  ์ˆ˜ ์žˆ์„ ๊ฒƒ์œผ๋กœ ๊ธฐ๋Œ€๋œ๋‹ค.

Acknowledgements

์ด ์„ฑ๊ณผ๋Š” 2021๋…„๋„ ์ •๋ถ€(๊ณผํ•™๊ธฐ์ˆ ์ •๋ณดํ†ต์‹ ๋ถ€)์˜ ์žฌ์›์œผ๋กœ ํ•œ๊ตญ์—ฐ๊ตฌ์žฌ๋‹จ์˜ ์ง€์›์„ ๋ฐ›์•„ ์ˆ˜ํ–‰๋œ ์—ฐ๊ตฌ์ž„(No. 2020R1C1C1008193).

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Figures and Table

Fig. 1.

Analyses of ZrO2/HfO2 and HfO2/ZrO2 bilayer thin films: (a) GIXRD patterns, (b) P-E hysteresis curves and (c) I-E curves of Z1.5H6, Z3H6, Z6H6 and H6Z6 thin films. (Reproduced from Y. Lu, J. Shieh and F. Tsai, Acta Materialia 115, 68-75, 2016. [22] with the permission of Elsevier)

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-12-849f1.jpg
Fig. 2.

Polarization scans collected after electrical cycling from the (4 nm HfO2/4 nm ZrO2), (2 nm HfO2/2 nm ZrO2) ร— 2, and (1 nm HfO2/1 nm ZrO2) ร— 4 nanolaminates and the HfZrO4 solid solution deposited at 285 ยฐC (aโˆ’d) and 260 ยฐC (eโˆ’h). (Reproduced from S. L. Weeks, A. Pal, V. K. Narasimhan, K. A. Littau and T. Chiang, ACS applied materials & interfaces 9 (15), 13440-13447, 2017. [23] with the permission of 2017 American Chemical Society.)

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-12-849f2.jpg
Fig. 3.

Polarization-electric field (P-E) curves of the nanolaminate samples with (a) 40:40 and (b) 20:60 HfO2:ZrO2 ALD cycle number ratios, respectively. (c) P-E curves of the HZH samples with various HfO2:ZrO2 ALD cycle number ratios. (d) Change in 2Pr as a function of the ZrO2 fraction for HZ, ZH, HZH, and ZHZ samples as well as solid solution (SS) films. (Reproduced from M. H. Park, H. J. Kim, G. Lee, J. Park, Y. H. Lee, Y. J. Kim, T. Moon, K. D. Kim, S. D. Hyun and H. W. Park, Applied Physics Reviews 6 (4), 041403, 2019. [21] with the permission of AIP Publishing.)

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-12-849f3.jpg
Fig. 4.

P-E curves of the (a) HfO2- and (b) ZrO2-startingnanolaminates. Changes in the (c) 2Pr and (d) (Im(-111)+Im(111))/(Im(-111)+Im(111)+Io(111)) as functions of the ALD cycle number per single layer for before wake-up (before) and after wake-up (after). Ix(hkl) stands for the areal intensity of diffraction peak from the (hkl) plane of x-phase. o(111) peak can be an overlap of o(111) and t(011) diffraction peak, but it was written as o(111) for the sake of convenience. (Reproduced from M. H. Park, H. J. Kim, G. Lee, J. Park, Y. H. Lee, Y. J. Kim, T. Moon, K. D. Kim, S. D. Hyun and H. W. Park, Applied Physics Reviews 6 (4), 041403, 2019. [21] with the permission of AIP Publishing.)

../../Resources/kim/KJMM.2021.59/kjmm-2021-59-12-849f4.jpg
Fig. 5.

(a) Endurance test results of the HZH samples with various HfO2:ZrO2 atomic layer deposition cycle ratio (30:50, 40:40. 50:30, and 60:20). The bipolar rectangular fatigue pulse height and frequency were 2.5 MV/cm and 100 kHz, respectively. (b) Endurance-Pr diagram for the various reported results. (Reproduced from M. H. Park, H. J. Kim, G. Lee, J. Park, Y. H. Lee, Y. J. Kim, T. Moon, K. D. Kim, S. D. Hyun and H. W. Park, Applied Physics Reviews 6 (4), 041403, 2019. [21] with the permission of AIP Publishing.)

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Table 1.

Summary of ferroelectric properties on HfO2/ZrO2 nanolaminate samples experimentally observed from ref. [21-23, 33-36].

Sample HfO2/ZrO2 layer (upper/lower layer) Deposition Method / Temperature [ยฐC] Thickness [nm] Electrode (top / bottom) Remanent polarization (2Pr) [ฮผC/cm2] Coercive field (+Ec,/ -Ec) [MV/cm] Endurance [cycle] Ref.
MFM HfO2 2.75 nm / ZrO2 3.3 nm / HfO2 2.75 nm ALD / 280 8.8 (Pt/TiN) / TiN 42 1 / -1 109 [21]
MFM HfO2 1.65 nm / ZrO2 5.5 nm / HfO2 1.65 nm ALD / 280 8.8 (Pt/TiN)/ TiN 26 0.75 / -0.5 1010 [21]
MFM ZrO2 6 nm / HfO2 6 nm ALD / 150 12 (Au/Ni)/(Pt/Ti) 30 2.1 / -1.5 [22]
MFM 4*(ZrO2 1 nm / HfO2 1 nm) ALD / 285 8 TiN / TiN 50 1.2 / -1.2 [23]
MFM 4*(ZrO2 1.5 nm / HfO2 1.5 nm) RF sputtering / 12 TaN / TaN 35 1 / -1 [23]
MFM ZrO2 3 nm / HfO2 3 nm ALD / 260 6 TiN / TiN 24.5 1.2 / -1.1 [34]
MFM 6*(ZrO2 1 nm / HfO2 1 nm) ALD / 250 12 TiN / TIN 35.4 3 / -3 109 [35]
MFM 5*(ZrO2 1 nm / HfO2 1 nm) ALD / 250 10 W / W 20 0.8 / -0,8 [36]