Electron trapping properties at HfO_2/SiO_2 interface,studied by Kelvin probe force microscopy and theoretical analysis

Electron trapping properties at the HfO_2/SiO_2 interface have been measured through Kelvin Probe force microscopy,between room temperature and 90 ℃.The electron diffusion in HfO_2 shows a multiple-step process.After injection,electrons diffuse quickly toward the HfO_2/SiO_2 interface and then diffuse laterally near the interface in two sub-steps:The first is a fast diffusion through shallow trap centers and the second is a slow diffusion through deep trap centers.Evolution of contact potential difference profile in the fast lateral diffusion sub-step was simulated by solving a diffusion equation with a term describing the charge loss.In this way,the diffusion coefficient and the average life time at different temperatures were extracted.A value of 0.57 eV was calculated for the activation energy of the shallow trap centers in HfO_2.     

γ射线作用下氧化铪基MOS结构总剂量效应研究

使用原子层淀积方法得到了7.8 nm厚度的HfO₂薄膜并通过直接溅射金属铝电极得到了Al/HfO₂/Si MOS电容结构,测量得到了HfO₂基MOS结构在60Co γ射线辐照前后的电容-电压特性,使用原子力显微镜得到了HfO₂薄膜在辐照前后的表面微观形貌,使用X射线光电子能谱方法测量得到了HfO₂薄膜在辐照前后的化学结构变化。研究发现,使用原子层淀积方法制备的HfO₂薄膜表面质量较高;γ射线辐照在HfO₂栅介质中产生了数量级为1012 cm-2的负的氧化层陷阱电荷;HfO₂薄膜符合化学计量比,介质内部主要的缺陷为氧空位且随着辐照剂量的增加而增加,说明辐照在介质中引入了陷阱从而导致MOS结构性能的退化。     

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.     

原子层沉积Al2O3/n-GaN MOS结构的电容特性

利用原子层沉积技术制备了具有圆形透明电 极的Ni/Au/Al₂O₃/n-GaN金属-氧化物-半导体结构, 研究了紫外光照对样品电容特性及深能级界面态的影响, 分析了非理想样品积累区电容随偏压增加而下降的物理起源. 在无光照情形下, 由于极长的电子发射时间与极慢的少数载流子热产生速率, 样品的室温电容-电压扫描曲线表现出典型的深耗尽行为, 且准费米能级之上占据深能级界面态的电子状态保持不变. 当器件受紫外光照射时, 半导体耗尽层内的光生空穴将复合准费米能级之上的深能级界面态电子, 同时还将与氧化层内部的深能级施主态反应. 非理想样品积累区电容的下降可归因于绝缘层漏电导的急剧增大, 其诱发机理可能是与氧化层内的缺陷态及界面质量有关的“charge-to-breakdown”过程. 关键词： 原子层沉积 2O₃/n-GaN')" href="#">Al₂O₃/n-GaN 金属-氧化物-半导体结构 电容特性     

Atomic-layer-deposited Al_2O_3 and HfO_2 on InAlAs: A comparative study of interfacial and electrical characteristics

Al_2O_3 and HfO_2 thin films are separately deposited on n-type InAlAs epitaxial layers by using atomic layer deposition(ALD).The interfacial properties are revealed by angle-resolved x-ray photoelectron spectroscopy(AR-XPS).It is demonstrated that the Al_2O_3 layer can reduce interfacial oxidation and trap charge formation.The gate leakage current densities are 1.37×10~6 A/cm~2 and 3.22×10~6 A/cm~2 at+1V for the Al_2O_3/InAlAs and HfO_2/InAlAs MOS capacitors respectively.Compared with the HfO_2/InAlAs metal-oxide-semiconductor(MOS) capacitor,the Al_2O_3/InAlAS MOS capacitor exhibits good electrical properties in reducing gate leakage current,narrowing down the hysteresis loop,shrinking stretch-out of the C-V characteristics,and significantly reducing the oxide trapped charge(Q_(ot)) value and the interface state density(D_(it)).     

Growth and characterization of MOMBE grown HfO2

HfO₂ dielectric layers were grown directly on the p-type Si (1 0 0) by metalorganic molecular beam epitaxy (MOMBE). Hafnium tetra-butoxide was used as a Hf precursor and pure oxygen was introduced to form an oxide layer. The properties of the layers with different thicknesses were evaluated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HRTEM), and capacitance–voltage (C–V) and current–voltage (I–V) analyses. XRD and HRTEM results showed that the HfO₂ films thinner than 12 nm were amorphous while the films thicker than 12 nm began to crystallize in the tetragonal and the monoclinic phases. The XPS spectra of O 1s show that the O---Si binding energies shifted to the lower binding energy with increasing the HfO₂ layer thickness. Moreover, the snap back phenomenon is observed in accumulation capacitance. These changes are believed to be linked with the decomposition of SiO and the crystallization of HfO₂ layer during the film growth.     

阻变存储器复合材料界面及电极性质研究

采用基于密度泛函理论的第一性原理对比研究了Cu（111）/HfO₂（001）,Cu（111）/HfO₂（010）,Cu（111）/HfO₂（100）三种复合材料界面模型的失配率、界面束缚能、电荷密度、电子局域函数以及差分电荷密度. 计算结果表明：Cu（111）/HfO₂（010）失配率最小,界面束缚能最大,界面体系相对最稳定;对比电荷密度及电子局域函数图显示,只有HfO₂（010）方向形成的复合材料体系出现了垂直Cu电极方向完整连通的电子通道,表明电子在此方向上具有局域性、连通性,与阻变存储器（RRAM）器件导通方向一致;差分电荷密度图显示,Cu（111）/HfO₂（010）复合材料体系界面处存在电荷密度分布重叠的现象,界面处有电子的相互转移、成键的存在;进一步计算了Cu（111）/HfO₂（010）体系距离界面不同位置的间隙Cu原子形成能,表明越靠近界面Cu原子越容易进入HfO₂ 体内,在外加电压下易发生电化学反应,从而导致Cu导电细丝的形成与断裂. 研究结果可为RRAM存储器的制备及性能的提高提供理论指导和设计工具. 关键词： 阻变存储器 复合材料 界面 电子通道     

溶胶凝胶法制备以HfO2为绝缘层和ZITO为有源层的高迁移率薄膜晶体管

采用溶胶凝胶法制备了h-k氧化铪HfO₂薄膜, 经500℃退火后, 获得了高透过率、表面光滑、低漏电流和相对高介电常数的HfO₂薄膜. 并采用氧化铪作为绝缘层和锌铟锡氧化物作为有源层成功地制备了底栅顶接触结构薄膜晶体管器件. 获得的薄膜晶体管器件的饱和迁移率大于100 cm²·V^-1·s^-1, 阈值电压为-0.5 V, 开关比为5×10⁶, 亚阈值摆幅为105 mV/decade. 表明采用溶胶凝胶制备的薄膜晶体管具备高的迁移率, 其迁移率接近低温多晶硅薄膜晶体管的迁移率.     

Crystallization behaviors of ultrathin Al-doped HfO_2 amorphous films grown by atomic layer deposition

In this work, ultrathin pure HfO_2 and Al-doped HfO_2films(about 4-nm thick) are prepared by atomic layer deposition and the crystallinities of these films before and after annealing at temperatures ranging from 550℃ to 750℃ are analyzed by grazing incidence x-ray diffraction. The as-deposited pure HfO_2 and Al-doped HfO_2 films are both amorphous. After550-℃ annealing, a multiphase consisting of a few orthorhombic, monoclinic and tetragonal phases can be observed in the pure HfO_2 film while the Al-doped HfO_2 film remains amorphous. After annealing at 650℃ and above, a great number of HfO_2 tetragonal phases, a high-temperature phase with higher dielectric constant, can be stabilized in the Al-doped HfO_2 film. As a result, the dielectric constant is enhanced up to about 35. The physical mechanism of the phase transition behavior is discussed from the viewpoint of thermodynamics and kinetics.     

Time-dependent response of interface states determined by using differential isothermal transient spectroscopy

A method based on the differential analysis of the isothermal transients is proposed to study the dynamical properties of the charging and discharging of interface states, and several possibilities of using this method are shown. The results obtained in SiO₂/Si and Si₃N₄/SiO₂/Si samples are in agreement with the existence of a spatial and energy distribution of interface states within the insulator. From the experimental data, the concentration of traps within the insulator at 35 Å is estimated to be 5×10⁹ cm^-2 eV^-1, with a tunneling cross section 10^-19 cm², at E_c-E ≈ 0.2 eV.     

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.     

十二烷二酸修饰TiO_2电子传输层改善钙钛矿太阳电池的电流特性

在经典的平面异质结钙钛矿太阳电池中,TiO_2致密层的电子传输性能一直是获得优异光伏性能的决定性因素之一.相较于spriro-OMe TAD等常见的空穴传输材料优异的空穴传输能力,作为电子传输材料的TiO_2的导电性较弱,无法形成良好的电荷匹配.为了解决这个问题,我们使用自组装的十二烷二酸(DDDA)单分子层来修饰TiO_2致密层的表面,TiO_2致密层的导电性能得到大幅提升,并且其能带结构得到优化,促进了电子传输,降低了电子积聚和载流子复合,使得电池的短路电流密度(JSC)从修饰前的20.34 mA·cm~(-2)提升至修饰后的23.28 mA·cm~(-2),进而使得电池在标准测量条件下的光电能量转换效率从14.17%提升至15.92%.同时还发现,通过DDDA修饰TiO_2致密层,所制备的器件的光稳定性显著提升,器件未封装暴露在AM 1.5光强100 mW·cm~(-2)的模拟太阳光下超过720 min,保持初始效率的71%以上且趋于稳定.     

基于Ni电极和ZrO_2/SiO_2/ZrO_2介质的MIM电容的导电机理研究

研究了基于Ni电极和原子层淀积的ZrO_2/SiO_2/ZrO_2对称叠层介质金属-绝缘体-金属(MIM)电容的电学性能.当叠层介质的厚度固定在14nm时,随着SiO_2层厚度从0增加到2nm,所得电容密度从13.1 fF/μm~2逐渐减小到9.3fF/μm~2,耗散因子从0.025逐渐减小到0.02.比较MIM电容的电流-电压(I-V)曲线,发现在高压下电流密度随着SiO_2厚度的增加而减小,在低压下电流密度的变化不明显,还观察到电容在正、负偏压下表现出完全不同的导电特性,在正偏压下表现出不同的高、低场I-V特性,而在负偏压下则以单一的I-V特性为主导.进一步对该电容在高、低场下以及电子顶部和底部注入时的导电机理进行了研究.结果表明,当电子从底部注入时,在高场和低场下分别表现出普尔-法兰克(PF)发射和陷阱辅助隧穿(TAT)的导电机理;当电子从顶部注入时,在高、低场下均表现出TAT导电机理.主要原因在于底电极Ni与ZrO_2之间存在镍的氧化层(NiO_x),且ZrO_2介质层中含有深浅两种能级陷阱(分别为0.9和2.3 eV),当电子注入的模式和外电场不同时,不同能级的陷阱对电子的传导产生作用.     

金衬底调控单层二硫化钼电子性能的第一性原理研究

基于密度泛函的第一性原理研究了金衬底对单层二硫化钼电子性能的调控作用. 从结合能、能带结构、电子态密度和差分电荷密度四个方面进行了深入研究. 结合能计算确定了硫原子层在界面的排布方式, 并指出这种吸附结构并不稳定. 能带结构分析证实了金衬底与单层二硫化钼形成肖特基接触, 并出现钉扎效应. 电子态密度分析表明金衬底并没有影响硫原子和钼原子之间的共价键, 而是通过调控单层二硫化钼的电子态密度增加其导电率. 差分电荷密度分析表明单层二硫化钼的导电通道可能在界面处产生. 研究结果可对单层二硫化钼晶体管的建模和实验制备提供指导.     

退火对EBE,IBS和ALD沉积HfO2薄膜的抗激光损伤性能影响

结合自身实验条件采用电子束蒸发(EBE)、离子束溅射(IBS)和原子层沉积(ALD)三种工艺制备了HfO2薄膜,对其进行退火实验,采用1064 nm Nd:YAG激光测定了即时沉积和退火后各HfO2薄膜的抗激光损伤能力。研究发现,ALD HfO2薄膜的激光损伤阈值最高,EBE HfO2薄膜次之,IBS HfO2薄膜的损伤阈值最低;300℃退火对各工艺薄膜抗激光损伤能力的影响均为负面,500℃退火则会显著降低ALD HfO2薄膜的抗激光损伤能力。     

硒化锑薄膜太阳电池的模拟与结构优化研究

采用wx-AMPS模拟软件对硒化锑(Sb_2Se_3)薄膜太阳电池进行建模仿真,将CdS, ZnO和Sn02的模型应用到Sb_2Se_3太阳电池的电子传输层中.结果显示,应用CdS和ZnO都能实现较高的器件性能,并发现电子传输层电子亲和势(Xe-ETL)的变化能够调节Sb_2Se_3太阳电池内部的电场分布,是影响器件性能的关键参数之一.过高或者过低的Xe-ETL都会使电池的填充因子降低,导致电池性能劣化.当Xe-ETL为4.2eV时,厚度为0.6μm的Sb_2Se_3太阳电池取得了最优的7.87%的转换效率.应用优化好的器件模型,在不考虑Sb_2Se_3层缺陷态的理想情况下,厚度为3μm的Sb_2Se_3太阳电池的转换效率可以达到16.55%(短路电流密度J_(SC)=34.88 mA/cm~2、开路电压V_(OC)=0.59 V、填充因子FF=80.40%).以上模拟结果表明,Sb_2Se_3薄膜太阳电池在简单的器件结构下就能够获得优异的光电性能,具有较高的应用潜力.     

Effects of oxygen flow rate on the properties of HfO2 layers grown by metalorganic molecular beam epitaxy

The investigations on the properties of HfO₂ dielectric layers grown by metalorganic molecular beam epitaxy were performed. Hafnium-tetra-tert-butoxide, Hf(C₄H₉O)₄ was used as a Hf precursor and pure oxygen was introduced to form an oxide layer. The grown film was characterized by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), and capacitance–voltage (C–V) and current–voltage (I–V) analyses. As an experimental variable, the O₂ flow rate was changed from 2 to 8 sccm while the other experimental conditions were fixed. The XPS spectra of Hf 4f and O 1s shifted to the higher binding energy due to the charge transfer effect and the density of trapped charges in the interfacial layer was increased as the oxygen flow rate increased. The observed microstructure indicated the HfO₂ layer was polycrystalline, and the monoclinic phases are the dominant crystal structure. From the C–V analyses, k = 14–16 and EOT = 44–52 were obtained, and the current densities of (3.2–3.3) × 10⁻³ A/cm² were measured at −1.5 V gate voltage from the I–V analyses.     

Ta和TaN底电极对原子层淀积HfO2介质MIM电性能的影响

以Ta,TaN为衬底,采用原子层淀积方法制备高介电常数HfO₂介质,比较研究了不同衬底电极对金属-绝缘体-金属（MIM）电容的性能影响.结果表明,采用TaN底电极能够获得较高的电容密度和较小的电容电压系数（VCC）,在1MHz下的其电容密度为7.47fF/μm²,VCC为356ppm/V²和493ppm/V,这归因于TaN底电极与HfO₂介质之间良好的界面特性.两种电容在3?V时漏电流为5×10^-8关键词： 高介电常数 MIM电容 2薄膜')" href="#">HfO₂薄膜 电极     

单层二硫化钼多相性质及相变的第一性原理研究

本文基于密度泛函的第一性原理,并引入范德瓦耳斯力修正,研究了单层二硫化钼2H,1T,ZT三种相的电学性质及相变原理.首先通过结构弛豫确定了三种相的几何结构,能带和态密度计算证实1T相具有金属性质,ZT相具有半导体性质,带隙为0.01 eV.然后结合变形势理论计算了2H和ZT相的迁移率,ZT相的迁移率高达104cm~2·V~(-1)·s~(-1),进一步拓展了单层二硫化钼的应用范围.最后通过对比三种相吸附锂原子结合能,计算2H-1T相变能量曲线,解释了引起二硫化钼相变的原因.本文的研究结果将对单层二硫化钼实验制备表征以及相关光电器件性能分析提供重要参考.     

Penetration of electronic states from silicon substrate into silicon oxide

The depth profiling of O 1s energy loss in silicon oxide near the SiO₂/Si interface was performed using extremely small probing depth. As a result, the energy loss of O 1s photoelectrons with threshold energy of 3.5 eV was found. This value of 3.5 eV is much smaller than the SiO₂ bandgap of 9.0 eV, but quite close to direct interband transition at Γ point in energy band structure of silicon. This can be explained by considering the penetration of electronic states from silicon substrate into silicon oxide up to 0.6 nm from the interface. In addition, the penetrating depth is larger than the thickness of the compositional transition layer.