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大数据、物联网和人工智能的快速发展对存储芯片、逻辑芯片和其他电子元器件的性能提出了越来越高的要求. 本文介绍了HfO 2基铁电薄膜的铁电性起源, 通过掺杂元素改变晶体结构的对称性或引入适量的氧空位来降低相转变的能垒可以增强HfO 2基薄膜的铁电性, 在衬底和电极之间引入应力、减小薄膜厚度、构建纳米层结构和降低退火温度等方法也可以稳定铁电相. 与钙钛矿氧化物铁电薄膜相比, HfO 2基铁电薄膜具有与现有半导体工艺兼容性更强和在纳米级厚度下铁电性强等优点. 铁电存储器件理论上可以达到闪存的存储密度, 读写次数超过10 10次, 同时具有读写速度快、低操作电压和低功耗等优点. 此外, 还总结了HfO 2基薄膜在负电容晶体管、铁电隧道结、神经形态计算和反铁电储能等方面的主要研究成果. 最后, 讨论了HfO 2基铁电薄膜器件当前面临的挑战和未来的机遇.The rapid developments of big data, the internet of things, and artificial intelligence have put forward more and more requirements for memory chips, logic chips and other electronic components. This study introduces the ferroelectric origin of HfO 2-based ferroelectric film and explains how element doping, defects, stresses, surfaces and interfaces, regulate and enhance the ferroelectric polarization of the film. It is widely accepted that the ferroelectricity of HfO 2-based ferroelectric film originates from the metastable tetragonal phase. The ferroelectricity of the HfO 2-based film can be enhanced by doping some elements such as Zr, Si, Al, Gd, La, and Ta, thereby affecting the crystal structure symmetry. The introduction of an appropriate number of oxygen vacancy defects can reduce the potential barrier of phase transition between the tetragonal phase and the monoclinic phase, making the monoclinic phase easy to transition to tetragonal ferroelectric phase. The stability of the ferroelectric phase can be improved by some methods, including forming the stress between the substrate and electrode, reducing the film thickness, constructing a nanolayered structure, and reducing the annealing temperature. Compared with perovskite oxide ferroelectric thin films, HfO 2-based films have the advantages of good complementary-metal-oxide-semiconductor compatibility and strong ferroelectricity at nanometer thickness, so they are expected to be used in ferroelectric memory. The HfO 2-based 1T1C memory has the advantages of fast reading and writing speed, more than reading and writing 10 12times, and high storage density, and it is the fast reading and writing speed that the only commercial ferroelectric memory possesses at present. The 1T ferroelectric field effect transistor memory has the advantages of non-destructive reading and high storage density. Theoretically, these memories can achieve the same storage density as flash memory, more than reading 10 10times, the fast reading/writing speed, low operating voltage, and low power consumption, simultaneously. Besides, ferroelectric negative capacitance transistor can obtain a subthreshold swing lower than 60 mV/dec, which greatly reduces the power consumption of integrated circuits and provides an excellent solution for further reducing the size of transistors. Ferroelectric tunnel junction has the advantages of small size and easy integration since the tunneling current can be largely adjusted through ferroelectric polarization switching. In addition, the HfO 2-based field effect transistors can be used to simulate biological synapses for applications in neural morphology calculations. Moreover, the HfO 2-based films also have broad application prospects in antiferroelectric energy storage, capacitor dielectric energy storage, memristor, piezoelectric, and pyroelectric devices, etc. Finally, the current challenges and future opportunities of the HfO 2-based thin films and devices are analyzed.
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掺杂元素 掺杂浓度 结构 沉积方法 薄膜厚度/nm 沉积温度/℃ 退火 电场/(MV·cm–1) 2Pr/(μC·m–2) 2Ec/(MV·cm–1) 极化翻转次数/cycle Si[37] 4.4 mol% TiN/Si:HfO2/TiN ALD 9 N/A 800 ℃, N2 4.5 48 1.74 N/A Zr[38] 50 at% W/Zr:HfO2/W ALD 10 250 700 ℃, N2, 5 s 3.5 65 2.4 104at3.0 MV cm–1 Y[28] 5.2 mol% TiN/Y:HfO2/TiN ALD 10 N/A 600 ℃, N2, 20 s 4.5 48 2.4 N/A Gd[39] 3.4 cat% TaN/Gd:HfO2/TaN ALD 10 300 800 ℃, N2, 20 s — 70 N/A 105at4.0 MV cm–1 Al[40] 6.4 mol% W/TiN/Al:HfO2/Si ALD 10 280 700 ℃, N2, 10 s 8 100 9.5 106at8.0 MV cm–1 La[41] 10.0 cat% TiN/La:HfO2/TiN ALD 12 280 800 ℃, N2, 20 s 4.5 55 2.8 5×105at 4 MV cm–1 Sr[42] 9.9 mol% TiN/Sr:HfO2/TiN ALD 10 300 800 ℃, N2, 20 s 3.5 46 $ \sim $3.2 106at3.0 MV cm–1 Ta[43] 16 at% Pt/Ta:HfO2/Pt/Ti PVD 60 500 No anneal 1.25 106 1.6 107at0.8 MV cm–1 非掺杂[44] N/A TiN/HfO2/TiN PEALD 8 N/A 600 ℃, Ar, 30 s 3.125 26 2.4 > 108at2.5 MV cm–1 对照[45] Pb(Zr0.53Ti0.47)O3 PLD 500 650 650 ℃, O2, 15 min N/A 151 0.14 1×1010 对照[46] BiFeO3 CSD 525 N/A 650 ℃, N2 N/A 142 1.0 106at0.4 MV cm–1 材料 类型 厚度/nm 电场/(MV·cm–1) ESD/(J·cm–3) η/% Ref. Hf0.5Zr0.5O2 铁电 9.2 4.9 55 57 [22] Ta2O5/Hf0.5Zr0.5O2 介电/反铁电 25 7 100 >95 [148] Hf0.5Zr0.5O2/Hf0.25Zr0.75O2 铁电/反铁电 10 6 71.95 57.8 [149] Hf0.3Zr0.7O2 反铁电 9.2 4.35 45 51 [22] Si:Hf0.5Zr0.5O2 反铁电 10 4 53 82 [147] Al:Hf0.5Zr0.5O2 反铁电 10 5 52 80 [147] La:Hf0.5Zr0.5O2 反铁电 10 4 50 70 [53] Al2O3 线性 5 — 50 — [150] BiFeO3 铁电 $ \sim $40 — 3.2 — [146] BaTiO3 铁电 $ \sim $300 2.6 28.5 75 [145] Pb(Zr0.52Ti0.48)O3 铁电 350 1.13 15.6 58.8 [151] La:PbZrO3 反铁电 103 1 17.3 80.8 [152] PVDF-HFP 铁电 104 7.9 31.2 — [153] -
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