Wet thermal annealing effect on TaN/HfO2/Ge metal-oxide-semiconductor capacitors with and without a GeO2 passivation layer

Wet thermal annealing effects on the properties of TaN/HfO2/Ge metal-oxide-semiconductor(MOS) structures with and without a GeO2 passivation layer are investigated.The physical and the electrical properties are characterized by X-ray photoemission spectroscopy,high-resolution transmission electron microscopy,capacitance-voltage(C-V) and current-voltage characteristics.It is demonstrated that wet thermal annealing at relatively higher temperature such as 550℃ can lead to Ge incorporation in HfO2 and the partial crystallization of HfO2,which should be responsible for the serious degradation of the electrical characteristics of the TaN/HfO2/Ge MOS capacitors.However,wet thermal annealing at 400℃ can decrease the GeO x interlayer thickness at the HfO2/Ge interface,resulting in a significant reduction of the interface states and a smaller effective oxide thickness,along with the introduction of a positive charge in the dielectrics due to the hydrolyzable property of GeO x in the wet ambient.The pre-growth of a thin GeO2 passivation layer can effectively suppress the interface states and improve the C-V characteristics for the as-prepared HfO2 gated Ge MOS capacitors,but it also dissembles the benefits of wet thermal annealing to a certain extent.     

Performance improvement of charge trap flash memory by using a composition-modulated high-k trapping layer

A composition-modulated （HfO2）x（Al2O3）1-x charge trapping layer is proposed for charge trap flash memory by controlling the A1 atom content to form a peak and valley shaped band gap. It is found that the memory device using the composition-modulated （HfO2）x（Al2O3）l-x as the charge trapping layer exhibits a larger memory window of 11.5 V, improves data retention even at high temperature, and enhances the program/erase speed. Improvements of the memory characteristics are attributed to the special band-gap structure resulting from the composition-modulated trapping layer. Therefore, the composition-modulated charge trapping layer may be useful in future nonvolatile flash memory device application.     

镧系元素掺杂TiO_2的电子和光学特性的第一性原理计算

基于密度泛函理论的第一性原理局部密度近似法,结合Hubbard U校正(LDA+U),研究了镧系元素掺杂的锐钛矿型TiO_2的取代能、热力学电荷跃迁能级和光学性质.除La之外的所有镧系元素,在掺杂时向主带隙中引入杂质态.所得取代能表明了镧系元素掺杂TiO_2的可行性.同时预测了最佳掺杂比例约为3%,由Ce、Nd、Sm、Gd或Tm掺杂引入的掺杂能级具有负U特性.另外,所得热力学跃迁能级预测了Lu在主带隙内不发生电荷跃迁.算出的光吸收系数表明镧系元素掺杂可使TiO_2具有可见光吸收性能.     

纳米YAG∶Ce3+, Mn+(Mn+=Ca2+, Gd3+)荧光粉的结构与发光性能

当前商用白光LED器件中YAG∶Ce3+荧光粉的单一黄光发射,导致其缺乏红光限制了器件的应用和发展,在YAG∶Ce3+中掺杂其他离子是解决该问题的有效途径之一。采用溶胶凝胶法制备了系列单掺Ce3+,Ca2+和Gd3+的YAG纳米荧光粉。研究了离子掺杂量对荧光粉的物相、结构、形貌、粒度、发光性能及量子效率的影响,分析了发光机理。结果表明：制备的纳米荧光粉粒径为100～200 nm。Ce3+和Gd3+掺杂时均得到YAG纯相,但晶体结构膨胀,晶面衍射峰向小角度方向移动。样品结晶度随Ce3+和Ca2+(<0.025 mol)掺杂量增大变化不明显,随Gd3+则呈现逐步降低趋势。三种离子掺杂量增大时,Ce3+的晶格能上升,5d能级晶体场劈裂加剧;Gd系列荧光粉激发和发射光谱随掺杂量的增大发生红移,Ce和Ca系列则因掺杂量小表现不明显。荧光粉发光强度随Ce3+掺杂量上升先增大后减小,最佳掺杂量为0.06 mol;随Gd3+掺杂量增加逐步降低;随Ca2+掺杂量增大则急剧下降,0.03 mol掺杂量时荧光强度几乎为零,YAG晶体结构破坏,生成YAM和YAP相。研究的开展,将对后续纳米YAG荧光粉及其相关功能材料的进一步开发使用提供一定的理论依据和实践参考。     

紫外激发Ba_2SiO_4∶Gd~(3+),Tb~(3+)的发光性能

采用高温固相法合成了可被紫外光激发的Ba_2SiO_4∶Gd~(3+),Tb~(3+)荧光粉。考察了激活离子掺杂量等因素对发光性能的影响。通过X射线衍射(XRD)、荧光(FL)光谱和荧光寿命曲线对所合成样品的结构和发光性能进行表征,研究了Gd~(3+)和Tb~(3+)的特征吸收波长激发Ba_2SiO_4∶Gd~(3+),Tb~(3+)的发光性能。在275 nm(Gd~(3+):8S7/2→6IJ)激发下,检测到了Tb~(3+)的特征发射。通过对比不同Tb~(3+)掺杂量下Gd~(3+):~6P_(7/2)能级的衰减曲线,发现随着Tb~(3+)掺杂浓度的增加,该能级的荧光寿命不断缩短,表明样品中存在Gd~(3+)→Tb~(3+)的能量传递,传递方式为无辐射共振能量传递。在244 nm(Tb~(3+):4f~8→4f~75d~1)激发下,Gd~(3+)的掺入使得Tb~(3+)的~5D_3能级的发射逐渐减弱,5D4能级的发射增强。Gd~(3+)的掺入使得544 nm(~5D_4→~7F_5)处的特征发射增强了59%~128%,结合荧光衰减曲线得出Gd~(3+)的掺入对Tb~(3+)能级中~5D_3→~5D_4与~7F_6→~7F_0交叉驰豫有促进作用。     

掺杂对金属-MoS_2界面性质调制的第一性原理研究

采用基于密度泛函理论的第一性原理赝势平面波方法,计算了卤族元素掺杂对金属-MoS_2界面性质的影响,包括缺陷形成能、电子能带结构、差分电荷密度以及电荷布居分布.计算结果表明:卤族元素原子倾向于占据单层MoS_2表面的S原子位置;对于单层MoS_2而言,卤族元素的掺杂将在禁带中引入杂质能级以及导致费米能级位置的移动.对于金属-MoS_2界面体系,结合Schottky-Mott模型,证明了卤族元素的掺杂可以有效地调制金属-MoS_2界面间的肖特基势垒高度.发现F和Cl原子的掺杂将会降低体系的肖特基势垒高度.相比之下,Br和I原子的掺杂却增大了体系的肖特基势垒高度.通过差分电荷密度和布居分布的分析,阐明了肖特基势垒高度的被调制是因为电荷转移形成的界面偶极矩的作用导致.研究结果解释了相关实验现象,并给二维材料的器件化应用提供了调节手段.     

Effects of different dopants on switching behavior of HfO_2-based resistive random access memory

In this study the effects of doping atoms(Al, Cu, and N) with different electro-negativities and ionic radii on resistive switching of HfO2-based resistive random access memory(RRAM) are systematically investigated. The results show that forming voltages and set voltages of Al/Cu-doped devices are reduced. Among all devices, Cu-doped device shows the narrowest device-to-device distributions of set voltage and low resistance. The effects of different dopants on switching behavior are explained with deferent types of CFs formed in HfO2 depending on dopants: oxygen vacancy(Vo) filaments for Al-doped HfO2 devices, hybrid filaments composed of oxygen vacancies and Cu atoms for Cu-doped HfO2 devices,and nitrogen/oxygen vacancy filaments for N-doped HfO2 devices. The results suggest that a metal dopant with a larger electro-negativity than host metal atom offers the best comprehensive performance.     

掺杂PPQ薄膜的电致发光及电场调制

从掺杂PPQ薄膜单层器件的电致发光光谱在掺杂前后的变化。说明掺杂PPQ薄膜中存在着基质分子和掺杂分子间的能量传递，其电致发光光谱随加电场变化说明电场对PPQ薄膜的电致发光具有调制作用。用一个由单链模型扩展到包括杂质和外场的Hamiltonian进行数值求解。结果表明：在PPQ和TPL分子之间有效的能量传递是源于它们之间的是荷转移，且随着外加电压的变化，其电致发光谱峰位的移动与掺杂前后系统总量的改变及发光强度与掺杂后转移的电荷数之间分别存在对应关系，这一模型很好地解释了电场对PPQ薄膜电致发光的调制作用。     

纳米Gd2O3:Eu3+中Judd-Ofelt参数的实验确定

报道用Judd-Ofelt理论研究立方相纳米晶Gd2O3:Eu3+材料在77K下的光谱性质.以几乎不受周围晶场环境影响的5D0→7F1跃迁为参考，利用5D0→7F2和5D0→7F4跃迁，从实验上确定强度参数Ωλ(λ＝2，4).发现纳米Gd2O3:Eu3+材料晶场强度参数Ωλ随纳米晶粒径的变化而改变,与体材料相比有显著的不同.随微晶粒径减小，发射能级5D0的寿命变短、量子效率降低.这是因为微晶粒径越小，量子限域效应越强，表体比越大，在无序体调制的表面上表面缺陷作用增强而引起的.对电荷(Eu3+-O2-)迁移态和多声子过程另外两种无辐射通道也进行讨论. 关键词： 纳米Gd2O3:Eu3+ 强度参数 辐射与无辐射弛豫 量子效率     

稀土（Tb，Gd）掺杂多孔硅的光致发光性能研究

用电化学方法对多孔硅薄膜进行了稀土（Tb，Gd）离子的化学掺杂.利用荧光分光光度计测试了样品的光致发光特性.用扫描电子显微镜研究了薄膜的表面形貌.用卢瑟福背散射谱分析了稀土离子在多孔硅薄膜中的分布情况.结果表明，Tb的掺入显著增强了多孔硅的发光强度，并且发光峰位出现蓝移.这是由于Tb³⁺的4f能级⁵D_{4—⁷F3，⁵D4—⁷F关键词： 多孔硅 稀土掺杂 光致发光}     

铈掺杂高钆镥氧化物玻璃制备和光谱性能

实验中采用高温熔融法制备了一系列高钆镥硼硅酸盐新型玻璃体系样品,研究了这种新型玻璃体系的玻璃形成区,测量了样品的玻璃稳定性和密度。结果表明,玻璃体系的玻璃形成区较广,玻璃稳定性良好（析晶温度与转变温度的差为262 ℃）,且玻璃样品的密度达到5 g/cm3。以此种玻璃体系作为基质掺入Ce3+离子,测量其透过光谱、激发光谱、发射光谱、X射线激发发射光谱以及Gd3+离子的衰减时间。结果表明,玻璃的透过性能适合Ce3+离子的掺杂,并且Gd2O3和Lu2O3对闪烁体发光都具有积极的影响,同时研究了Gd3+离子和Ce3+离子的能量传递机理及最佳能量传递掺杂摩尔比。从玻璃的物理性能和光谱性能考虑,这种闪烁玻璃系统具有广泛应用于高能物理材料中的一定潜力。     

Infrared spectra study of Nd1.85−xRxCe0.15CuO4±δ (R = Gd and Sm) single crystals

The X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectra, and resistivity ρ are measured on Nd_1.85?xR_xCe_0.15CuO_4±δ (R = Gd and Sm) single crystals. From the XRD and FTIR spectra studies, the lattice constant c are found to decrease faster for Gd doping than that for Sm doping with increasing doping concentration x. Upon Gd doping, all the transmission peaks shift to high frequency but nearly unchanged with increasing Sm doping content. The volume of the unit cell observed through XRD and FTIR spectra decreases faster for Gd doping than that for Sm doping. Furthermore, for Gd doping the superconducting T_c decreases rapidly with increasing the doping concentration, while the T_c decreases slowly for Sm doping with increasing Sm content, which is found to be very well consistent with the evolution of the volume of the unit cell for two series.     

HfO2中ZrO2含量对266nm HfO2/SiO2多层膜反射率的影响

用两种不同纯度的HfO2材料与同一纯度的SiO2材料组合,沉积Λ／4规整膜系(HL)^11H形成266nm的紫外反射镜,发现反射率相差0．7％左右。用X光电子能谱法分析了高反膜中表层HfO2中的成分,发现ZrO2的含量相差一个数量级左右。为确定形成这种差别的原因,用辉光放电质谱法测定了这两种HfO2材料中锆(Zr)及其钛(Ti)、铁(Fe)的含量,发现Zr是其中的最主要的杂质,两种HfO2材料中Zr含量有一个数量级的差别。说明在266nm波段,HfO2中ZrO2的含量会对HfO2／SiO2高反膜的反射率造成影响。根据HfO2单层膜的光谱曲线,推算出了这两种材料的消光系数的差别,并用Tfcalc膜系设计软件进行理论和镀制结果的模拟,得到与实验测试一致的结果。     

Enhanced laser induced damage threshold of dielectric antireflection coatings by the introduction of one interfacial layer

A new method for increasing laser induced damage threshold (LIDT) of dielectric antireflection (AR) coating is proposed. Compared with AR film stack of H2.5L (H:HfO2, L:SiO2) on BK7 substrate, SiO2 interfacial layer with four quarter wavelength optical thickness (QWOT) is deposited on the substrate before the preparation of H2.5L film. It is found that the introduction of SiO2 interfacial layer with a certain thickness is effective and flexible to increase the LIDT of dielectric AR coatings. The measured LIDT is enhanced by about 50%, while remaining the low reflectivity with less than 0.09% at the center wavelength of 1064 nm. Detailed mechanisms of the LIDT enhancement are discussed.     

Interfacial electronic structure at a metal–phthalocyanine/graphene interface:Copper–phthalocyanine versus iron–phthalocyanine

The energy level alignment of CuPc and FePc on single-layer graphene/Ni(111)(SLG/Ni)substrate was investigated by using ultraviolet and X-ray photoelectron spectroscopy(UPS and XPS).The highest occupied molecular orbitals(HOMOs)in a thick layer of CuPc and FePc lie at 1.04 eV and 0.90 eV,respectively,below the Fermi level of the SLG/Ni substrate.Weak adsorbate–substrate interaction leads to negligible interfacial dipole at the CuPc/SLG/Ni interface,while a large interfacial dipole(0.20 eV)was observed in the case of FePc/SLG/Ni interface,due to strong adsorbate–substrate coupling.In addition,a new interfacial electronic feature was observed for the first time in the case of FePc on SLG/Ni substrate.This interfacial state can be attributed to a charge transfer from the SLG/Ni substrate to unoccupied orbitals of FePc.     

YTaO4 : Eu,Gd的合成及其发光

采用高温固相反应合成了Y_1-x-yEu_xGd_yTaO₄荧光体,经过XRD证明产物为纯相的M'型YTaO₄结构。通过对样品的光谱测试表明,TaO^3-₄将吸收的能量传递给Eu³⁺,起着一定的敏化作用。掺入少量Gd³⁺对YTaO₄ : Eu的发光有一定的增强作用。用147 nm的真空紫外光激发样品时,样品具有较强的荧光发射,其主发射峰位于612 nm,具有较好的色纯度。     

均苯三甲酸铽掺杂(钇、钆)配合物的合成及荧光性质

以均苯三甲酸(H₃BTC)为配体,用水热法合成了系列稀土掺杂发光配合物,通过元素分析,EDTA滴定,红外光谱等确定了其组成为Tb_(1-x)Ln_xBTC·0.5H₂O(Ln=Y,Gd,x=0,0.1,0.3,0.5,0.7,0.9)。研究了配合物的荧光性质。该类配合物均能发出Tb3+的特征荧光,并且不发光的Y3+和Gd3+的掺入使配合物的荧光强度得到了增强,这可能是由于分子内能量传递的结果。Tb3+受到敏化作用而使荧光增强,但发射峰的位置基本上没有发生变化。在Tb3+的4个发射峰中5D₄→7F₅(544nm)处的发射峰强度最强,并在此条件下确定了掺杂离子的最佳掺入量,当Tb3+∶Y3+=0.5∶0.5, Tb3+∶Gd3+=0.3∶0.7时Tb_(1-x)Ln_xBTC·0.5H₂O(Ln=Y,Gd)的荧光强度最强。同时发现在最佳掺入量条件下Gd3+对Tb3+的敏化程度大于Y3+对Tb3+的敏化程度。     

BaO掺杂对单畴GdBCO超导块材性能的影响(二)

为了有效地抑制Gd BCO超导块材在生长过程中出现的Gd/Ba替换现象,在前期工作的基础上,本文采用顶部籽晶熔渗生长工艺,通过在固相先驱粉中添加不同含量的Ba O粒子成功地制备出了一系列高性能的单畴Gd BCO超导块材,并且对样品的微观形貌以及临界电流密度进行了研究和分析.结果表明,随着BaO掺杂量的增加,样品中的Gd_(1+x)Ba_(2-x)Cu_3O_(7-δ)固溶体(Gd123ss)相呈现出减少的趋势,并生成了纳米量级的Gd123ss,这对GdBCO超导样品中存在的Gd/Ba替换起到了很好的抑制作用,使得样品中的GdBa_2Cu_3O_(7-δ)(Gd123)超导相有所增加;同时当样品中BaO的添加量在2 wt%—4 wt%之间时,样品的临界电流密度在一定程度上得到了有效提高.     

纳米晶Gd2O3：Eu^3＋的制备及发光性能

采用低温燃烧合成法制备了Gd2O3：Eu^3＋纳米晶。用X射线衍射仪（XRD）、高分辨透射电子显微镜（HRTEM）和荧光光谱仪分别对样品的结构、形貌和发光性能进行了研究。结果表明，改变甘氨酸与稀土离子的比例（G／M）、退火温度可以制备出不同结构和晶粒尺寸的Gd2O3：Eu^3＋纳米晶。在退火温度为800℃，G／M等于0．83和1．0时，均得到了纯立方相的Gd2O3：Eu^3＋纳米晶，随着G／M的增加，Gd2O3：Eu^3＋从立方相逐渐向单斜相转变。粉末的晶粒尺寸随着退火温度的增高而增大，晶粒尺寸在10-30nm之间。立方相的Gd2O3：Eu^3＋纳米晶主发射峰位置在612nm（^5D^0→^7F2跃迁），激发光谱中电荷迁移态发生了红移。     

The specific oxidation mechanism in the initial stages of O2 adsorption on submonolayer Ba covered W(1 1 0) surface

The initial oxidation of a polarized 0.35-ML Ba-covered W(1 1 0) surface has been investigated in detail by high-resolution photoemission spectroscopy using synchrotron radiation. Upon small exposures (?0.15 L) to O₂, both interfacial W 4f (Ba-coordinated W) and Ba 4d core levels shift simultaneously toward smaller binding energies and then fix during 0.15-0.25 L, finally disappear at 0.6 L. The concurrent negative shifts of both interfacial W 4f and Ba 4d peaks can be attributed to be a consequence of the increased occupancy of 5d states. This explanation is supported by the variations of 5d stats in valence band spectra upon the initial oxidation. Our results clearly demonstrate that charge rearrangement is the dominant effect in the surface reactivity of our oxidized surface. We also found that this charge redistribution is associated with a structural change during oxidation, which is in contrary to previous studies of alkali-metal promotion. That is, oxygen is first chemisorbed atop the polarized Ba adlayer, then incorporates beneath Ba adatoms to form a covalent Ba-O-W complex upon further dosage, and reacts strongly with the Ba overlayer to become an ionic Ba⁺²O⁻² surface dipole layer at 0.6 L.