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HfOX忆阻器因其低操作电压、良好的耐受性及循环特性等优异性能, 使其成为下一代非易失性存储器最有前景的候选者之一. 然而, 由于HfOX薄膜内氧空位导电细丝的形成和断裂的随机性, 器件阈值电压分布较为分散, 整体稳定性较差, 因此, 通过调控氧空位来提高HfOX器件的稳定性具有重要的研究意义. 本研究采用磁控溅射法制备了不同氩氧比的三组器件, 均表现出双极性阻变特性. 在三种不同氩氧比的W/HfOX/Pt 器件中, 氩氧比为45∶5的器件展现出最优的综合性能: I-V循环超过200次、开关比~103、在104 s内具有优异的数据保持特性且阈值电压分布集中, 表明器件稳定性显著提高. 通过构建氧空位调控与导电细丝演变的物理模型, 揭示了氧空位浓度对阻变机理的影响机制. 本研究明确了氧空位的调控HfOX忆阻器性能的关键作用, 为发展高性能、高可靠性的阻变存储器提供了有效途径.HfOX memristors have emerged as one of the most promising candidates for next-generation non-volatile memory due to their low operating voltage, excellent endurance, and cycling characteristics. However, the randomness in the formation and rupture of oxygen vacancy conductive filaments within HfOX thin films leads to a relatively dispersed threshold voltage distribution and poor stability. Therefore, improving the stability of HfOX devices by modulating oxygen vacancies is of significant research importance. In this study, three groups of W/HfOX/Pt devices are prepared using magnetron sputtering with argon-to-oxygen ratios of 30∶20, 40∶10 and 45∶5, respectively. XPS results indicate that the 45∶5 device has the highest oxygen vacancy concentration (25.59%). All of three groups exhibit bipolar resistive switching behavior. Of the three W/HfOX/Pt devices, the device with the argon-to-oxygen ratio of 45:5 demonstrates the best overall performance: over 200 I-V cycles, a switching ratio of ~103, excellent data retention within 104 s, and a concentrated threshold voltage distribution. Analysis of the conduction mechanisms reveals that the device follows a space-charge-limited current (SCLC) mechanism in the high-resistance state and exhibits Ohmic conduction behavior in the low-resistance state. In the initial state, there is a high density of oxygen vacancies near the nucleation region of the conductive filament, which can shorten the effective migration path of oxygen vacancies. Under an applied electric field, negatively charged oxygen ions migrate toward the top electrode, while oxygen vacancies gradually accumulate from the bottom electrode to the top electrode, leading to the formation of continuous conductive filaments. A higher oxygen vacancy concentration facilitates the development of robust and structurally more stable conductive filaments, thereby enhancing the uniformity of resistive switching and device reliability. This study reveals the critical role of oxygen vacancy modulation in the performance of HfOX memristors and provides an effective pathway for developing high-performance and highly reliable resistive random-access memory.
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Keywords:
- memristor /
- HfOX thin film /
- oxygen vacancy /
- conductive filament
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图 3 HfOX薄膜的SEM图像 (a) 表面图; (b) 截面图
Fig. 3. SEM images of the HfOX thin films: (a) Surface diagrams; (b) cross-sectional view.
图 4 HfOX薄膜的XPS能谱 (a)—(c) 氩氧比为(a) 30∶20, (b) 40∶10, (c) 45∶5条件下Hf 4f核心能级谱图; (d)—(f) 氩氧比为(d) 30∶20, (e) 40∶10, (f) 45∶5条件下O 1s核心能级谱图
Fig. 4. XPS spectra of the HfOX thin films: (a)–(c) Hf 4f core level spectrum with argon-to-oxygen ratios of (a) 30∶20, (b) 40∶10, (c) 45∶5; (d)–(f) O 1s core level spectrum with argon-to-oxygen ratios of (d) 30∶20, (e) 40∶10, (f) 45∶5.
图 5 W/HfOX/Pt忆阻器的I-V特性曲线 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 5. I-V characteristic curves of the W/HfOX/Pt memristor: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 6 W/HfOX/Pt忆阻器在不同限制电流ICC下的I-V特性 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 6. I-V characteristics of the W/HfOX/Pt memristor under different current compliance values: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 7 W/HfOX/Pt忆阻器的阈值电压统计分布 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 7. Statistical distribution of threshold voltage of W/HfOX/Pt memristors: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 8 W/HfOX/Pt忆阻器循环耐受性 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 8. Cycling endurance of the W/HfOX/Pt memristor: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 9 W/HfOX/Pt忆阻器的数据保持特性 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 9. Data retention characteristics of the W/HfOX/Pt memristor: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 10 W/HfOX/Pt忆阻器的脉冲响应时间(图中黑色曲线为设置电压, 红色曲线为器件在电脉冲下测试的电流值) (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 10. Pulse response time of the W/HfOX/Pt memristor: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 11 W/HfOX/Pt忆阻器连续周期的脉冲循环 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 11. Pulse cycles of the W/HfOX/Pt memristor in continuous periods: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
图 12 W/HfOX/Pt忆阻器的导电拟合机制 (a) 30∶20器件正扫描区I-V曲线的双对数拟合结果; (b) 40∶10器件正扫描区I-V曲线的双对数拟合结果; (c) 45∶5器件正扫描区I-V曲线的双对数拟合结果
Fig. 12. Conductive fitting mechanism of the W/HfOX/Pt memristor: (a) Double logarithmic fitting results of the I-V curve in the positive scanning region of the device with a ratio of 30∶20; (b) double logarithmic fitting results of the I-V curve in the positive scanning region of the device with a ratio of 40∶10; (c) double logarithmic fitting results of the I-V curve in the positive scanning region of the device with a ratio of 45∶5.
图 13 W/HfOX/Pt忆阻器阻变机制示意图 (a) 30∶20器件; (b) 40∶10器件; (c) 45∶5器件
Fig. 13. Schematic diagrams of the resistive switching mechanism of the W/HfOX/Pt memristor: (a) The device with a ratio of 30∶20; (b) the device with a ratio of 40∶10; (c) the device with a ratio of 45∶5.
表 1 HfOX忆阻器与各类忆阻器电学性能的对比
Table 1. . Comparison of electrical performance between HfOX memristors and various types of memristors.
RRAM structure VSet/VReset Endurance Retention time ON/OFF ratio Response time Ref. Ti/hBN/Au 1.73/–0.85 V 200 — ＞50 120/120 ps [18] Cu/A1 OX/A1 2.11/–1.1 V 50 ~104 ~105 — [48] Al/WOX/ITO 0.65/–3.1 V 100 — ~103 — [49] Ti/ZrO2/Pt 2.5/–2 V 100 ＞104 ＞10 250/250 ns [50] Pt/HfO2/TiO2/ITO 0.7/–0.5 V 100 ~104 ＞10.6 — [51] Ag/BP/HfO2/Pt 1.4/–0.54 V ＞100 — ~102 — [52] W/HfOX/Pt(45∶5) 0.91/–1.84 V 200 ＞104 ~103 70/130 μs This work 
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