ZnO基薄膜及其阻变式存储器的研制
摘要
在众多的新型非挥发性存储器中,阻变式存储器(RRAM)因具有简单的结构、优秀的尺寸可缩小性、较小的编程电流、较低的功耗、较高的读写速度以及与传统的CMOS工艺兼容性好等优点,被认为是下一代非挥发性存储器的有利竞争者之一。本文围绕如何改善基于ZnO半导体材料的RRAM器件的阻变开关性能展开研究,主要内容如下：
1、用射频磁控溅射在石英衬底上沉积了ZnO薄膜,研究了不同的氧气流量对薄膜晶体结构和光学性能的影响,并在此基础上,研究了不同的ZnO沉积温度对Ag/ZnO/ITO结构RRAM器件性能的影响。结果表明,氧气流量为25SCCM、氩气流量为30SCCM、沉积温度为400℃时,器件具有较好的阻变性能,阻值开关比达到30倍,操作电压在2V以下,操作电流为200μA左右。
2、在硅衬底上用磁控溅射制备了Ag/ZnO/Zn/Pt结构RRAM器件。首次采用了在金属底电极和ZnO功能层之间沉积Zn缓冲层的方法,提高了ZnO薄膜的结晶质量。系统的研究了不同的ZnO沉积温度、不同的Zn缓冲层厚度以及不同的ZnO退火温度对器件阻变开关性能的影响。结果表明,20nm的Zn缓冲层厚度、400℃的衬底沉积温度和ZnO330℃退火条件下,器件的阻变开关性能较好,阻值开关比达到1×103,相应的阻值转变也较稳定。正向和负向的阂值电压非常集中,都保持在±1V之间。测得低阻态时电阻值不随Ag电极尺寸的变化而改变,因而器件的开关机理是由局域的导电细丝的形成和断裂导致的。
3、在硅衬底上制备了ZnO掺Ga薄膜的Ag/GZO/ZnO/Pt结构RRAM器件。与本征ZnO基Ag/ZnO/Zn/Pt器件相比,增大了器件的阻值开关比,提高了器件在高低阻态转换过程中的稳定性,说明有效地掺杂可以起到提高阻变存储器性能的作用。系统的研究了GZO薄膜的退火温度、ZnO缓冲层厚度和GZO沉积温度对器件性能的影响。结果表明,ZnO缓冲层厚度为15nm、GZO薄膜的退火温度为330℃、沉积温度为400℃时,器件的阻变开关性能较好,阻值天关比达到1×104,器件的开关阈值电压都保持在±1V之间,高低态阻值的转变也十分稳定。
Among various new non-volatile memories, resistive random access memory (RRAM) regarded as next-generation nonvolatile memory devices in the storage field has been widely investigated due to its simple structure, excellent scalability, low operation current, low power consumption, high speed, and well compatibility with complementary metal oxide semiconductor (CMOS) technology. In this thesis, we focus on improving the switching performance of ZnO-RRAM devices. The main contents are as follows:
The ZnO thin films were deposited on quartz substrates by radio frequency magnetron sputtering. The effects of sputtering oxygen gas flow on the structure and optical properties of ZnO thin films were investigated. Then the performances of RRAM devices depend on different substrate temperature were also studied. The results reveal that when oxygen flow is25SCCM, argon flow is30SCCM and ZnO thin films grow at400℃, the ZnO-RRAM devices have better switching performance. The ratio of high resistance state to low resistance state is50. The operation voltages and operation currents are very low, which are2V and200μA, respectively.
The ZnO-RRAM devices were prepared on Si substrates by radio frequency magnetron sputtering. We originally grew a Zn buffer layer between the ZnO thin film and metal bottom electrodes (BE). Through this method, we improved the quality of the ZnO films. Then the performance of ZnO-RRAM devices as a function of ZnO substrate temperature, the thickness of Zn buffer layer, and ZnO annealing temperature were systematically investigated. The results exhibit that the RRAM devices based on ZnO film grown at400℃, the Zn buffer layer at20nm, and the ZnO film annealed at330℃have better performance. The ratio of high resistance state to low resistance state is1X103. The resistive switch became more stable. The threshold voltages of OFF state and ON state were very uniform, which maintained at±1V. Then the effects of top electrode size were studied, we found that the conductive filament formation and rupture controlled by electrochemical redox-reaction are proposed to explain the resistive switching phenomenon.
The resistive switching properties of GZO-RRAM devices fabricated on Si substrates were systematically studied. By comparing the data with ZnO-RRAM, we found the memory window is bigger and the switch became more stable. It reveals that effective doping can improve the performance of RRAM device. The effects of GZO substrate temperature, the thickness of ZnO buffer layer, and GZO annealing temperature on GZO-RRAM devices were investigated. The results show that the GZO-RRAM devices based on GZO film grown at400℃, the ZnO buffer layer at15run and the GZO film annealed at330℃had better performance. The ratio of high resistance state to low resistance state is1X104. The threshold voltages of OFF state and ON state were maintained at±1V, and resistance switching is very uniform.
1、用射频磁控溅射在石英衬底上沉积了ZnO薄膜,研究了不同的氧气流量对薄膜晶体结构和光学性能的影响,并在此基础上,研究了不同的ZnO沉积温度对Ag/ZnO/ITO结构RRAM器件性能的影响。结果表明,氧气流量为25SCCM、氩气流量为30SCCM、沉积温度为400℃时,器件具有较好的阻变性能,阻值开关比达到30倍,操作电压在2V以下,操作电流为200μA左右。
2、在硅衬底上用磁控溅射制备了Ag/ZnO/Zn/Pt结构RRAM器件。首次采用了在金属底电极和ZnO功能层之间沉积Zn缓冲层的方法,提高了ZnO薄膜的结晶质量。系统的研究了不同的ZnO沉积温度、不同的Zn缓冲层厚度以及不同的ZnO退火温度对器件阻变开关性能的影响。结果表明,20nm的Zn缓冲层厚度、400℃的衬底沉积温度和ZnO330℃退火条件下,器件的阻变开关性能较好,阻值开关比达到1×103,相应的阻值转变也较稳定。正向和负向的阂值电压非常集中,都保持在±1V之间。测得低阻态时电阻值不随Ag电极尺寸的变化而改变,因而器件的开关机理是由局域的导电细丝的形成和断裂导致的。
3、在硅衬底上制备了ZnO掺Ga薄膜的Ag/GZO/ZnO/Pt结构RRAM器件。与本征ZnO基Ag/ZnO/Zn/Pt器件相比,增大了器件的阻值开关比,提高了器件在高低阻态转换过程中的稳定性,说明有效地掺杂可以起到提高阻变存储器性能的作用。系统的研究了GZO薄膜的退火温度、ZnO缓冲层厚度和GZO沉积温度对器件性能的影响。结果表明,ZnO缓冲层厚度为15nm、GZO薄膜的退火温度为330℃、沉积温度为400℃时,器件的阻变开关性能较好,阻值天关比达到1×104,器件的开关阈值电压都保持在±1V之间,高低态阻值的转变也十分稳定。
Among various new non-volatile memories, resistive random access memory (RRAM) regarded as next-generation nonvolatile memory devices in the storage field has been widely investigated due to its simple structure, excellent scalability, low operation current, low power consumption, high speed, and well compatibility with complementary metal oxide semiconductor (CMOS) technology. In this thesis, we focus on improving the switching performance of ZnO-RRAM devices. The main contents are as follows:
The ZnO thin films were deposited on quartz substrates by radio frequency magnetron sputtering. The effects of sputtering oxygen gas flow on the structure and optical properties of ZnO thin films were investigated. Then the performances of RRAM devices depend on different substrate temperature were also studied. The results reveal that when oxygen flow is25SCCM, argon flow is30SCCM and ZnO thin films grow at400℃, the ZnO-RRAM devices have better switching performance. The ratio of high resistance state to low resistance state is50. The operation voltages and operation currents are very low, which are2V and200μA, respectively.
The ZnO-RRAM devices were prepared on Si substrates by radio frequency magnetron sputtering. We originally grew a Zn buffer layer between the ZnO thin film and metal bottom electrodes (BE). Through this method, we improved the quality of the ZnO films. Then the performance of ZnO-RRAM devices as a function of ZnO substrate temperature, the thickness of Zn buffer layer, and ZnO annealing temperature were systematically investigated. The results exhibit that the RRAM devices based on ZnO film grown at400℃, the Zn buffer layer at20nm, and the ZnO film annealed at330℃have better performance. The ratio of high resistance state to low resistance state is1X103. The resistive switch became more stable. The threshold voltages of OFF state and ON state were very uniform, which maintained at±1V. Then the effects of top electrode size were studied, we found that the conductive filament formation and rupture controlled by electrochemical redox-reaction are proposed to explain the resistive switching phenomenon.
The resistive switching properties of GZO-RRAM devices fabricated on Si substrates were systematically studied. By comparing the data with ZnO-RRAM, we found the memory window is bigger and the switch became more stable. It reveals that effective doping can improve the performance of RRAM device. The effects of GZO substrate temperature, the thickness of ZnO buffer layer, and GZO annealing temperature on GZO-RRAM devices were investigated. The results show that the GZO-RRAM devices based on GZO film grown at400℃, the ZnO buffer layer at15run and the GZO film annealed at330℃had better performance. The ratio of high resistance state to low resistance state is1X104. The threshold voltages of OFF state and ON state were maintained at±1V, and resistance switching is very uniform.
引文
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