HfO_2中影响电荷俘获型存储器的氧空位特性第一性原理研究

随着器件尺寸进一步等比例缩小,高k材料HfO2作为俘获层的电荷俘获型存储器展现了较好的耐受性和较强的存储能力,且工艺相对简单,与传统半导体工艺完全兼容,因此得到了广泛的研究.为研究HfO2中氧空位引入的缺陷能级对电荷俘获型存储器存储特性的影响,运用第一性原理计算分析了HfO2中的氧空位缺陷.通过改变缺陷超胞中的电子数模拟器件的写入和擦除操作,发现氧空位对电荷的俘获基本上不受氧空位之间距离的影响,而氧空位个数则影响对电子的俘获,氧空位数多,俘获电子的能力就强.此外,四价配位的氧空位俘获电子的能力比三价配位的氧空位大.态密度分析发现四价配位的氧空位引入深能级量子态数大,并且受氧空位之间的距离影响小,对电子的俘获概率大.结果表明,HfO2中四价配位的氧空位缺陷有利于改善电荷俘获型存储器的存储特性.     

分子包埋纳米粒子薄膜阻变特性研究进展

有机分子包埋纳米粒子阻变薄膜是信息存储领域的研究热点之一,本文从器件电极、介质层结构、纳米粒子种类、阻变机理和柔性弯折等方面,综述了其近年来的研究进展.电极/分子及分子/纳米粒子界面性质对器件阻变特性影响较大,但影响规律及界面调控机理仍待探究;分子结构与纳米粒子的种类、尺度及分布可改变膜内界面性质进而影响阻变特性;器件阻变机理主要包括导电细丝、电荷俘获与释放和电荷转移三种,其中导电细丝又分金属、氧空位和碳细丝.分子包埋纳米粒子薄膜阻变研究现多停留在小规模和静态器件方面,下一步应从连续卷绕制备、纳米粒子分布精确控制和耐弯扭特性等方面深入研究,为实现大面积、低成本、高柔性阻变存储器奠定基础.     

DFT方法研究掺杂氮化硅对SONOS器件保持性能的作用

可通过对氮化硅层掺杂来改变俘获电荷的缺陷种类和数量的方法，改善SONOS非挥发性存储器件的保持性能.建立无定形氮化硅和氧、硫、磷、氟或氯掺杂氮化硅中缺陷的簇模型；根据第一性原理的密度泛函理论(DFT)，对缺陷的簇模型结构优化并计算能量，得到缺陷俘获电荷过程的能量变化.发现缺陷俘获电子的能力比俘获空穴的能力好，电子释放过程应对温度敏感，而空穴释放过程主要由隧穿机理控制.预测与氧氮化硅一样，硫或磷掺杂氮化硅代替氮化硅作为SONOS器件的电荷储存层，可改善器件的保持性能.     

ZnO电子传输层对于反型结构聚合物太阳电池光浴效应的影响

采用金属氧化物电子传输层(ETL)的聚合物光伏器件在制备完成之初通常性能表现低下, J-V曲线呈异常“S”形. 当器件受白光持续照射后, 该不良状况会逐渐好转, 此过程称为光浴(light-soaking). 光浴现象普遍被认为是ETL界面问题所致. 从器件结构着手, 研究了ZnO 纳米颗粒ETL相邻的两个界面在光浴问题上的作用. 制备了功能层相同的(电极除外)正型、反型器件及复合ETL结构器件, 发现光浴现象仅出现于包含ZnO/ITO界面的反型器件中, 证明该界面是导致光浴现象的主要原因. 分析认为: ZnO颗粒表面O₂吸附形成的电子陷阱增加了ITO/ZnO势垒厚度, 使得光生电子无法逾越而成为空间电荷积累, 从而导致器件初始性能不佳. 器件经光照后, ETL内部受激而生的空穴电子对填补了ZnO缺陷, 提升了ETL的电荷选择性并减小了界面势垒厚度, 被束缚的光生电子得以隧穿至ITO电极, 反型器件性能最终得以改善.     

尺寸调控SnO_2量子点的阻变性能及调控机理

零维SnO_2量子点因具有优异的物理化学稳定性、高电子迁移率和能带结构可调等特性,是阻变存储器中阻变功能材料的良好选择,受到了研究者的广泛关注.本文采用溶剂热法制备了尺寸为2.51 nm,2.96 nm和3.53 nm的SnO_2量子点,在较小尺寸范围内证明了SnO_2量子点能带结构随尺寸离散化的量子尺寸效应;并基于其量子尺寸效应,实现了对SnO_2量子点阻变存储器开关电压的有效调控.研究表明,尺寸为3.53 nm的SnO_2量子点具有较低的开关电压(-2.02 V/3.08 V)与较大的阻变开关比( 10~4),器件在经过2 × 10~4次的耐久性测试后,阻变性能变化率小于5%,具有较好的稳定性与保持性.基于库仑阻塞效应,SnO_2量子点内部缺陷势阱作为俘获中心对电子的自俘获/脱俘作用,是其实现阻变效应的原因;此外,SnO_2量子点与ITO,Au界面肖特基势垒高度的有效控制则是精准调控其阻变开关电压的关键.以上工作揭示了SnO_2量子点在阻变存储领域的巨大应用潜力和商业化应用价值,为阻变存储器的发展提供了一项新的选择.     

双电子传输层结构硫硒化锑太阳电池的界面特性优化

硫硒化锑薄膜太阳电池因其制备方法简单、原材料丰富无毒、光电性质稳定等优点,成为了光伏领域的研究热点.经过近几年的发展,硫硒化锑太阳电池的光电转换效率已经突破10%,极具发展潜力.本文针对硫硒化锑太阳电池中n/i界面引起的载流子复合进行了深入研究.发现硫硒化锑太阳电池的界面特性会受到界面电子迁移能力和能带结构两方面的影响.界面电子迁移率的提高能使电子更有效地传输至电子传输层,实现器件短路电流密度和填充因子的有效提升.在此基础上,引入ZnO/Zn_1-xMg_xO双电子传输层结构能够进一步优化硫硒化锑太阳电池性能.其中,Zn_1-xMg_xO能级位置的改变可以同时调节界面和吸光层的能级分布,在Zn_1-xMg_xO导带能级为-4.2 eV,对应Mg含量为20%时,抑制载流子复合的效果最为明显,硫硒化锑太阳电池也获得了最佳的器件性能.在去除缺陷态的理想情况下,双电子传输层结构硫硒化锑太阳电池在600 nm厚时获得了20.77%的理论光电转换效率,该研究结果为硫硒化锑太阳电池...     

电荷俘获存储器的过擦现象

基于密度泛函理论的第一性原理平面波超软赝势方法和VASP软件对电荷俘获存储器过擦现象进行了分析研究.通过形成能的计算,确定了含有氮空位缺陷的Si3N4和含有间隙氧缺陷的Hf O2作为研究的对象;俘获能的计算结果表明两种体系对电子的俘获能力比对空穴的大,因而对两体系擦写载流子确定为电子.分别计算了Hf O2和Si3N4擦写前后的能量、擦写前后电荷分布变化、吸附能和态密度,以说明过擦的微观机理.对能量和擦写电荷变化的研究,表明Si3N4相比于Hf O2,其可靠性较差,且Si3N4作为俘获层,在一个擦写周期后,晶胞中电子出现减少现象;界面吸附能的研究表明,Si3N4相比于Hf O2在缺陷处更容易与氧进行电子交换;最后,通过对态密度的分析表明Si3N4和Hf O2在对应的缺陷中均有缺陷能级俘获电子,前者为浅能级俘获,后者为深能级俘获.综上分析表明,Si3N4在氮空位的作用下,缺陷附近原子对电子的局域作用变弱,使得Si3N4作为俘获层时,材料本身的电子被擦出,使得擦操作时的平带偏移电压增大,导致存储器发生过擦.本文的研究结果揭示了过擦的本质,对提高电荷俘获存储器的可靠性以及存储特性有着重要的指导意义.     

La1-xPrxMnO3(x=0.1,0.2)薄膜庞磁电阻性质的研究

一种新的庞磁电阻氧化物薄膜La1-xPrxMnO3(x=0.1,0.2)薄膜用脉冲激光沉积(PLD)方法生长在(100)SrTiO3单晶基底上.XRD结果显示薄膜具有很好的外延单晶取向.电输运和磁性质的研究表明薄膜具有显著的庞磁电阻效应(CMR)效应,其中磁电阻比率达95%(在5T的磁场下).X射线光电子能谱(XPS)的结果表明薄膜体系中Pr离子的价态为+4价,因此该薄膜很可能是电子掺杂的庞磁电阻体系.     

MgO单晶势垒磁性隧道结的第一性原理计算和实验研究

在MgO单晶势垒磁性隧道结中发现的室温高隧穿磁电阻现象,是近些年自旋电子学以及磁性隧道结磁电阻材料研究中的又一重大突破.本文主要评述和介绍2001年以来MgO单晶势垒磁性隧道结第一性原理计算和实验上的重要进展,以及介绍利用Layer-KKR第一性原理计算方法研究的Fe(001)/MgO/Fe、Fe(001)/FeO/MgO/Fe、Fe(001)/Mg/MgO/Fe、Fe(001)/Co/MgO/Co/Fe和Fe(001)[MgO/Fe/MgO/Fe等基于单晶MgO(001)单势垒及双势垒磁性隧道结材料的电子结构和自旋相关输运性质研究的最新进展.这些第一性原理定量计算的结果,不仅从物理上增强了对MgO单晶势垒磁性隧道结的电子结构和自旋相关输运特性的了解,而且对于研究新型室温磁电阻隧道结材料及其在自旋电子学器件中的广泛应用,具有一定的参考价值.     

嵌入Ag纳米颗粒层的DNA忆阻器

构建了具有“Al/DNA-CTMAB/Ag NPs/DNA-CTMAB/ITO”结构的有机忆阻器件, 并对其电流-电压 (I-V)曲线进行测量. 结果表明, 嵌入Ag纳米颗粒层, 不仅可以增强器件的导电性, 而且忆阻特性也显著提高. 当颗粒粒径在15–20 nm范围时, 开-关电流比I_ON/I_OFF能够达到10³. 器件的I-V特性受扫描电压幅值V_A的影响, 随着V_A的增大, 高阻态的电流变化较小, 而低阻态的电流明显增大, 开(或关)电压V_SET (V_RESET)和I_ON/I_OFF增加. 实验还发现, 器件高低阻状态的相互转换取决于外加电场的方向, 说明该忆阻器具有极性.     

Unipolar resistive switching properties of amorphous Pr0.7Ca0.3MnO3 films grown on a Pt/Ti/SiO2/Si substrate

Amorphous Pr_0.7Ca_0.3MnO₃ (APCMO) films were grown on a Pt/Ti/SiO₂/Si (Pt–Si) substrate at temperatures below 500 °C and the Pt/APCMO/Pt–Si device showed unipolar resistive switching behavior. Conduction behavior of the low resistance state (LRS) of the Pt/APCMO/Pt–Si device followed Ohm's law, and the resistance in LRS was independent of the size of the device, indicating that the conduction behavior in LRS can be explained by the presence of the conductive filaments. On the other hand, the resistance in the high resistance state (HRS) decreased with increasing the device size, and the conduction mechanism in the HRS was explained by Schottky emission.     

Analysis of the resistive switching behaviors of vanadium oxide thin film

We demonstrate the polarization of resistive switching for a Cu/VOx/Cu memory cell.The switching behaviors of Cu/VOx/Cu cell are tested by using a semiconductor device analyzer(Agilent B1500A),and the relative micro-analysis of I-V characteristics of VOx/Cu is characterized by using a conductive atomic force microscope(CAFM).The I-V test results indicate that both the forming and the reversible resistive switching between low resistance state(LRS) and high resistance state(HRS) can be observed under either positive or negative sweep.The CAFM images for LRS and HRS directly exhibit evidence for the formation and rupture of filaments based on positive or negative voltage.The Cu/VOx/Cu sandwiched structure exhibits reversible resistive switching behavior and shows potential applications in the next generation of nonvolatile memory.     

Nonvolatile Resistive Switching and Physical Mechanism in LaCrO_3 Thin Films

Polycrystalline LaCrO_3(LCO) thin films are deposited on Pt/Ti/SiO_2/Si substrates by pulsed laser deposition and used as the switching material to construct resistive random access memory devices. The unipolar resistive switching(RS) behavior in the Au/LCO/Pt devices exhibits a high resistance ratio of ~104 between the high resistance state(HRS) and low resistance state(LRS) and exhibits excellent endurance/retention characteristics.The conduction mechanism of the HRS in the high voltage range is dominated by the Schottky emission, while the Ohmic conduction dictates the LRS and the low voltage range of HRS. The RS behavior in the Au/LCO/Pt devices can be understood by the formation and rupture of conducting filaments consisting of oxygen vacancies,which is validated by the temperature dependence of resistance and x-ray photoelectron spectroscopy results.Further analysis shows that the reset current I_R and reset power P_R in the reset processes exhibit a scaling law with the resistance in LRS(R_0), which indicates that the Joule heating effect plays an essential role in the RS behavior of the Au/LCO/Pt devices.     

Effect of AlN layer on the resistive switching properties of TiO2 based ReRAM memory devices

The present study reports the resistive switching behaviour in Titanium Dioxide (TiO₂) material, with possible implementations in non volatile memory device. The Cu/TiO₂/Pt memory device exhibit uniform and stable bipolar resistive switching behaviour. The current-voltage (I-V) analysis shows two discrete resistance states, the High Resistance State (HRS) and the Low Resistance State (LRS). The effect of an additional AlN layer in the resistive memory cell is also investigated. The Cu/TiO₂/AlN/Pt device shows a multilevel (tri-state) resistive switching. Multilevel switching is facilitated by ionic and metallic filament formation, and the nature of the formed filaments is confirmed by performing a resistance vs. temperature measurement. The bilayer device shows improved reliability over the single layer device. The formation of high thermal conductive interfacial oxy-nitride (AlON) layer is the main reasons for the enhancement of resistive switching properties in Cu/TiO₂/AlN/Pt cell. The performance of device was measured in terms of endurance and retention, which exhibits good endurance over 10⁵ cycles and long retention time of 10⁵ s at 125 °C. The above result suggests the feasibility of Cu/TiO₂/AlN/Pt devices for multilevel non volatile ReRAM application.     

Intrinsic memory characteristic of polycrystalline ZnTe film originating from Mott variable range hopping conduction

The resistive switching characteristics of Au/ZnTe/ITO structure with polycrystalline ZnTe film as resistive switching layer is investigated. Macroscopically, 100 bipolar switching cycles under the direct current (dc) voltages were carried out and the conduction states can retain for several hours. Microscopically, reading and writing operations can be achieved on ZnTe film with Au top electrode replaced by conductive Atomic Force Microscopy (c-AFM) tip. The I–V characteristic in low resistance state (LRS) is linear in the whole range of voltage. The I–V characteristic in high resistance state (HRS) is linear in the low voltage while it obeys Schottky emission in the high voltage, and Schottky barrier height is symmetric in the positive and negative voltage. During linear I–V characteristic voltage range, the electrons transport between adjacent point defects via Mott variable range hopping. The higher hopping distance and higher activation energy in HRS contribute to the higher resistance value in HRS compared with LRS. Impedance spectroscopy in HRS and LRS both behave as a semicircle, which accords with the semiconductor-like characteristic of conductive point defects. Photoluminescence (PL) spectroscopy indicates the decisive role of deep level defects in conduction. This study confirms the intrinsic resistive switching characteristic of ZnTe film and provides a new choice for intrinsic non-oxides material in nonvolatile memory application.     

Bipolar resistive switching in BiFe_(0.95)Zn_(0.05)O_3 films

Bipolar resistive switching is studied in BiFe0.95Zn0.05O3 films prepared by pulsed laser deposition on （001） SrTiO3 substrate, with LaNiO3 as the bottom electrode, and Pt as the top electrode. Multiple steps of resistance change are ob- served in the resistive switching process with a slow voltage sweep, indicating the formation/rupture of multiple conductive filaments. A resistive ratio of the high resistance state （HRS） to the low resistance state （LRS） of over three orders of mag- nitude is observed. Furthermore, the conduction mechanism is confirmed to be space-charge-limited conduction with the Schottky emission at the interface with the top Pt electrodes in the HRS, and Ohmic in the LRS. Impedance spectroscopy demonstrates a conductive ferroelectric/interfacial dielectric 2-layer structure, and the formation/rupture of the conductive filaments mainly occurs at the interfacial dielectric layer close to the top Pt electrodes.     

Coexistence of nonvolatile unipolar and volatile threshold resistive switching in the Pt/LaMnO3/Pt heterostructures

Coexistence of nonvolatile unipolar and volatile threshold resistive switching is observed in the Pt/LaMnO₃ (LMO)/Pt heterostructures. The nonvolatile unipolar memory is achieved by applying a negative bias, while the volatile threshold resistive switching is obtained under a positive bias. Additionally, the pristine low resistance state (LRS) could be switched to high resistance state (HRS) by the positive voltage sweeping, which is attributed to the conduction mechanism of Schottky emission. Subsequently, the insulator-to-metal transition in the LMO film due to formation of ferromagnetic metallic phase domain contributes to the volatile threshold resistive switching. However, the nonvolatile unipolar switching under the negative bias is ascribed to the formation/rupture of oxygen-vacancy conducting filaments. The simultaneously controllable transition between nonvolatile and volatile resistance switching by the polarity of the applied voltage exhibits great significance in the applications of in-memory computing technology.     

Bipolar switching properties of amorphous TiO2 thin film grown on TiN/Si substrate

Pt/TiO₂/TiN device with the amorphous TiO₂ film grown at room temperature under an oxygen partial pressure of 1.0 mTorr showed reliable bipolar switching behavior. During the electroforming process, a large number of oxygen vacancies formed in the TiO₂ film and accumulated at the Pt/TiO₂ interface. The barrier height of the Schottky contact of the Pt/TiO₂ interface was reduced owing to the presence of these oxygen vacancies, resulting in the low-resistance state (LRS). Moreover, oxygen ions diffused into the TiN electrode during the electroforming and set processes. On the other hand, the oxygen ions in the TiN electrode diffused out and reacted with oxygen vacancies in the TiO₂ film during the reset process, and the device changed from the LRS to the high-resistance state (HRS). Conduction in the LRS and HRS can be attributed to Ohmic conduction and the trap controlled space charged limited mechanism, respectively.     

Ti/HfO2/Pt阻变存储单元中的氧空位聚簇分布

为了研究阻变存储器导电细丝的形成位置和分布规律, 使用X射线光电子能谱研究了Ti/HfO₂/Pt阻变存储器件单元中Hf 4f的空间分布, 得到了阻变层的微结构信息. 通过I-V测试, 得到该器件单元具有典型的阻变特性; 通过针对Hf 4f的不同深度测试, 发现处于低阻态时, 随着深度的增加, Hf⁴⁺化学组分单调地减小; 而处于高阻态和未施加电压前, 该组分呈现波动分布; 通过Hf⁴⁺在高阻态和低阻态下组分含量以及电子能损失谱分析, 得到高阻态下Hf⁴⁺组分的平均含量要高于低阻态; 另外, 高阻态和低阻态下的O 1s谱随深度的演变也验证了Hf⁴⁺的变化规律. 根据实验结果, 提出了局域分布的氧空位聚簇可能是造成这一现象的原因. 空位簇间的链接和断裂决定了导电细丝的形成和消失. 由于导电细丝容易在氧空位缺陷聚簇的地方首先形成, 这一研究为导电细丝的发生位置提供了参考.     

Nonvolatile bipolar resistance switching effects in multiferroic BiFeO3 thin films on LaNiO3-electrodized Si substrates

We report on reversible bipolar resistance switching effects in multiferroic BiFeO₃ thin films without electroforming. The BiFeO₃ thin films with (110) preferential orientation were prepared on LaNiO₃-electrodized Si substrates with a Pt/BiFeO₃/LaNiO₃ device configuration. The resistance ratio of high resistance state (HRS) to low resistance state (LRS) of the devices was as high as three orders of magnitude. The dominant conduction mechanisms of LRS and HRS were dominated by ohmic behavior and trap-controlled space charge limited current, respectively. The resistance switching mechanism of the devices was discussed using a modified Schottky-like barrier model taking into account the movement of oxygen vacancies.