Effect of RuO2 electrode on laser-MBE prepared HfO2 gate dielectrics

In this paper, we report our recent study of the effect of RuO₂ as an alternative top electrode for pMOS devices to overcome the serious problems of polysilicon (poly-Si) gate depletion, high gate resistance and dopant penetration in the trend of down to 50 nm devices and beyond. The conductive oxide RuO₂, prepared by RF sputtering, was investigated as the gate electrode on the Laser MBE (LMBE) fabricated HfO₂ for pMOS devices. Structural, dielectric and electric properties were investigated. RuO₂/HfO₂/n-Si capacitors showed negligible flatband voltage shift (<10 mV), very strong breakdown strength (>10 MV cm⁻¹). Compared to the SiO₂ dielectric with the same EOT value, RuO₂/HfO₂/n-Si capacitors exhibited at least 4 orders of leakage current density reduction. The work function value of the RuO₂ top electrode was calculated to be about 5.0 eV by two methods, and the effective fixed oxide charge density was determined to be 3.3 × 10¹² cm⁻². All the results above indicate that RuO₂ is a promising alternative gate electrode for LMBE grown HfO₂ gate dielectrics.     

Investigation of atomic vapour deposited TiN/HfO2/SiO2 gate stacks for MOSFET devices

HfO₂ films were grown by atomic vapour deposition (AVD) on SiO₂/Si (1 0 0) substrates. The positive shift of the flat band voltage of the HfO₂ based metal-oxide-silicon (MOS) devices indicates the presence of negative fixed charges with a density of 5 × 10¹² cm⁻². The interface trap charge density of HfO₂/SiO₂ stacks can be reduced to 3 × 10¹¹ eV⁻¹ cm⁻² near mid gap, by forming gas annealing. The extracted work function of 4.7 eV preferred the use of TiN as metal gate for PMOS transistors. TiN/HfO₂/SiO₂ gate stacks were integrated into gate-last-formed MOSFET structures. The extracted maximum effective mobility of HfO₂ based PMOS transistors is 56 cm²/Vs.     

氮气或氧气气氛退火的氧化铪材料电荷泄漏情况研究

本文中, 使用开尔文探针显微镜,研究了不同退火气氛(氧气或氮气)情况下氧化铪材料的电子和空穴的电荷保持特性。与氮气退火器件相比,氧气退火可以使保持性能变好。横向扩散和纵向泄露在电荷泄露机制中都起了重要的作用。 并且,保持性能的改善与陷阱能级深度有关。氮气和氧气退火情况下,氧化铪存储结构的的电子分别为0.44 eV, 0.49 eV,空穴能级分别为0.34 eV, 0.36 eV。 最后得到,不同退火气氛存储器件的电学性能也与KFM结果一致。对于氧化铪作为存储层的存储器件而言,对存储特性的定性和定量分析,陷阱能级,还有泄漏机制研究是十分有意义的。     

超薄SiO2/HfO2双层栅介质的时变击穿特性和击穿机制的研究

The characteristics of TDDB （time-dependent dielectric breakdown） and SILC （stress-induced leakage current） for an ultra-thin SiO2/HfO2 gate dielectric stack are studied. The EOT （equivalent-oxide-thickness） of the gate stack （Si/SiO2/HfOz/TiN/TiA1/TiN/W） is 0.91 am. The field acceleration factor extracted in TDDB experi- ments is 1.59 s.cm/MV, and the maximum voltage is 1.06 V when the devices operate at 125 ℃ for ten years. A detailed study on the defect generation mechanism induced by SILC is presented to deeply understand the break- down behavior. The trap energy levels can be calculated by the SILC peaks： one S1LC peak is most likely to be caused by the neutral oxygen vacancy in the HfO2 bulk layer at 0.51 eV below the Si conduction band minimum; another SILC peak is induced by the interface traps, which are aligned with the silicon conduction band edge. Fur- thermore, the great difference between the two SILC peaks demonstrates that the degeneration of the high-k layer dominates the breakdown behavior of the extremely thin gate dielectric.     

Comparative study of AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors with Al2O3 and HfO2 gate oxide

AlGaN/GaN metal-oxide-semiconductor heterostructure field-effect transistors (MOSHFETs) with Al₂O₃ gate oxide which was deposited by atomic layer deposition (ALD) were fabricated and their performance was then compared with that of AlGaN/GaN MOSHFETs with HfO₂ gate oxide. The capacitance (C)-voltage (V) curve of the Al₂O₃/GaN MOS diodes showed a lower hysteresis and lower interface state density than the C-V curve of the HfO₂/GaN diodes, indicating better quality of the Al₂O₃/GaN interface. The saturation of drain current in the I_D-V_GS relation of the Al₂O₃ AlGaN/GaN MOSHFETs was not as pronounced as that of the HfO₂ AlGaN/GaN MOSHFETs. The gate leakage current of the Al₂O₃ MOSHFET was five to eight orders of magnitude smaller than that of the HfO₂ MOSHFETs.     

Impact of the TiN electrode deposition on the HfO2 band gap for advanced MOSFET gate stacks

The impact of the deposition of a TiN electrode on the high-k oxide HfO₂ has been investigated, focussing on the dielectric band gap. After the gate elaboration, a non-destructive approach combining Spectroscopic Ellipsometry (SE), Reflection Electron Energy Loss Spectroscopy (REELS) and X-ray Photoelectron Spectroscopy (XPS) was developed to probe the buried metal/high-k interface. The overall optical band gap is 5.9 ± 0.1 eV with no change after the metal gate deposition. A local reduction of 1 eV is measured near the TiN layer, due to N diffusion at the interface creating N 2p states at the top of the HfO₂ valence band. Increased disorder and defects are identified in the high-k after gate elaboration by XPS, REELS and SE.     

Annealing effect on the metal gate effective work function modulation for the Al/TiN/SiO2/p-Si structure

In this work, the thermal annealing effect on the metal gate effective work function (EWF) modulation for the Al/TiN/SiO₂/p-Si(1 0 0) structure was investigated. Compared with the sample of TiN/SiO₂/p-Si(1 0 0) structure, for the sample additionally capped with Al the flat band voltage has a very obvious shift as large as 0.54 V to the negative direction after forming gas annealing. It is also revealed that the thermal budget can effectively influence both the EWF of the gate electrode and the thickness of the gate dielectric layer when a post annealing at 600 °C with different soak times was applied to the samples with Al cap. Material characterization indicates that the diffusion of Al and the formation of Al oxide during annealing should be responsible for all the phenomena. The interface trap density Dit calculated from the high-frequency C-V and the laser-assisted high-frequency C-V curves show that the introduction of Al does not cause reliability problem in the Al/TiN/SiO₂/p-Si structure.     

Physical and electrical characterization of polysilicon vs. TiN gate electrodes for HfO2 transistors

The effects of pre-deposition substrate treatments and gate electrode materials on the properties and performance of high-k gate dielectric transistors were investigated. The performance of O₃ vs. HF-last/NH₃ pre-deposition treatments followed by either polysilicon (poly-Si) or TiN gate electrodes was systematically studied in devices consisting of HfO₂ gate dielectric produced by atomic layer deposition (ALD). High-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) using X-ray spectra and Electron Energy Loss Spectra (EELS) were used to produce elemental profiles of nitrogen, oxygen, silicon, titanium, and hafnium to provide interfacial chemical information and to convey their changes in concentration across these high-k transistor gate-stacks of 1.0–1.8 nm equivalent oxide thickness (EOT). For the TiN electrode case, EELS spectra illustrate interfacial elemental overlap on a scale comparable to the HfO₂ microroughness. For the poly-Si electrode, an amorphous reaction region exists at the HfO₂/poly-Si interface. Using fast transient single pulse (SP) electrical measurements, electron trapping was found to be greater with poly-Si electrode devices, as compared to TiN. This may be rationalized as a result of a higher density of trap centers induced by the high-k/poly-Si material interactions and may be related to increased physical thickness of the dielectric film, as illustrated by HAADF-STEM images, and may also derive from the approximately 0.5 nm larger EOT associated with polysilicon electrodes on otherwise identical gate stacks.     

掺氮氧化铪的光学特性研究

掺氮氧化铪是半导体工业非常重要的材料。在本论文中,我们利用Hf[N(C₂H₅)(CH₃)]₄ 和 H₂O₂作为原子层淀积的前驱体,制备了二氧化铪材料。然后,我们使用快速热退火的办法,在不同温度下,对二氧化铪进行了氮掺杂工艺。我们对掺氮二氧化铪的组分,跟硅界面的稳定性以及薄膜材料的光学特性随退火温度的变化进行了细致的研究。研究发现,随着退火温度的提高,二氧化铪薄膜材料的氮组分从1.41% 上升至 7.45%,相应的,薄膜材料的禁带宽度从5.82 eV 降低为 4.94 eV。     

环境温度对HfO2铁电存储器的质子辐照效应影响研究

基于HfO₂的铁电随机存取存储器(FeRAM)具有功耗低、存取速度快,易于小型化,抗干扰能力强等优势,在航天航空领域有广袤的发展空间。然而,FeRAM在太空环境下的抗辐照性能尚未得到全面的研究。研究了W/TiN/Hf0.5Zr0.5O₂(HZO)/TiN铁电存储器在常温和高温环境下经5 MeV质子辐照后的电学特性和铁电畴结构变化。通过电学和压电响应力显微镜(PFM)手段表征发现,在常温质子辐照后,电容器的介电常数(ε_r)和剩余极化强度(P_r)值均增大,器件的铁电性能提升,常温高注量质子辐照有利于存储器在太空环境中工作,但随着辐照时环境温度升高,HZO存储器的铁电性能下降,漏电流增大,铁电存储器的各项性能明显退化。     

A low gate leakage current and small equivalent oxide thickness MOSFET with Ti/HfO2 high-k gate dielectric

Annealing effects on electrical characteristics and reliability of MOS device with HfO₂ or Ti/HfO₂ high-k dielectric are studied in this work. For the sample with Ti/HfO₂ higher-k dielectric after a post-metallization annealing (PMA) at 600 °C, its equivalent oxide thickness value is 7.6 Å and the leakage density is about 4.5 × 10⁻² A/cm². As the PMA is above 700 °C, the electrical characteristics of MOS device would be severely degraded.     

A comparative study of depth profiling of interface states using charge pumping and low frequency noise measurement in SiO2/HfO2 gate stack nMOSFETs

Charge pumping and low frequency noise measurements for depth profiling have been studied systematically using a set of gate stacks with various combinations of IL and HfO₂ thicknesses. The distribution of generated traps after HCI and PBTI stress was also investigated. The drain-current power spectral density made up all of the traps of IL in 0 < z < T_IL and the traps of HfO₂ in T_IL < z < T_HK. The traps near the Si/SiO₂ interface dominated the 1/f noise at higher frequencies, which is common in SiO₂ dielectrics. For the HfO₂/SiO₂ gate stack, however, the magnitude of the 1/f noise did not significantly change after HCI and PBTI because of more traps in the bulk HfO₂ film than at the bottom of the interface.     

二氧化铪材料中Cu的最佳迁移路径

The movement of Cu in a HfO2-based resistive random access memory （RRAM） device is investigated in depth by first-principle calculations. Thermodynamics analysis shows that the dominant motion of Cu tends to be along the [001] orientation with a faster speed. The migration barriers along different routes are compared and reveal that the [001] orientation is the optimal migration route of Cu in HfO2, which is more favorable for Cu transportation. Furthermore, the preferable HfOz growth orientation along [100], corresponding to Cu migration along [001], is also observed. Therefore, it is proposed that the HfO2 material should grow along [100] and the operating voltage should be applied along [001], which will contribute to the improvement of the response speed and the reduction of power consumption of RRAM.     

Epitaxial anatase HfO2 on high-mobility substrate for ultra-scaled CMOS devices

On the basis of ab initio simulations, the formation of an epitaxial phase that has the anatase structure has been proposed as the microscopic mechanism responsible for the preferential orientation of monoclinic HfO₂ films on the high-mobility (0 0 1) oriented Ge and GaAs substrates. In fact, the oriented monoclinic structure follows the in-plane axis of the anatase phase as proved by X-ray scattering measurements. The fact that epitaxial HfO₂ anatase has no bulk counterpart is explained by our calculations as due to the unfavorable Helmholtz free energy of anatase phase when the condition of epitaxy is released.     

Effect of fluorinated silicate glass passivation layer on electrical characteristics and dielectric reliabilities for the HfO2/SiON gate stacked nMOSFET

The superior characteristics of the fluorinated hafnium oxide/oxynitride (HfO₂/SiON) gate dielectric are investigated comprehensively. Fluorine is incorporated into the gate dielectric through fluorinated silicate glass (FSG) passivation layer to form fluorinated HfO₂/SiON dielectric. Fluorine incorporation has been proven to eliminate both bulk and interface trap densities due to Hf-F and Si-F bonds formation, which can strongly reduce trap generation as well as trap-assisted tunneling during subsequently constant voltage stress, and results in improved electrical characteristics and dielectric reliabilities. The results clearly indicate that the fluorinated HfO₂/SiON gate dielectric using FSG passivation layer becomes a feasible technology for future ultrathin gate dielectrics applications.     

Wideband frequency and in situ characterization of ultra thin ZrO2 and HfO2 films for integrated MIM capacitors

High-κ dielectrics are promising candidates to increase capacitor integration densities but their properties depend on manufacturing process and frequency because relaxation and resonance mechanisms occur. Complementary characterization protocols are needed to analyze high-κ insulator behaviour from DC to microwave frequencies. The extraction of Plasma Enhanced Atomic Layer Deposition HfO₂ and ZrO₂ complex permittivity was performed up to 5 GHz using dedicated test vehicles allowing an in situ characterization as a function of dielectric thickness. The measurement procedure was thus validated, highlighting the potentiality of these two dielectrics to cover a wide range of frequencies.     

插层Al2O3对氧化铪基忆阻器的性能优化及多值特性研究

近年来,氧化铪基忆阻器因其优异的阻变性能及与CMOS工艺兼容等特点而被广泛研究。然而,氧化铪基忆阻器仍存在以下问题:1) 器件良率、可靠性、均一性不足;2) Set和Reset 过程中电流突变,导致多值特性较差。为实现氧化铪基忆阻器的性能优化及多值特性,文章在HfO₂表面生长一层1~5 nm Al₂O₃,构造Al₂O₃/HfO₂双介质层忆阻器,并对HfO₂和Al₂O₃的厚度进行优化,最终得到性能显著提升的Al₂O₃/HfO₂双介质层多值忆阻器。该器件呈现出保持性良好的10个不同电阻态(1×10⁴ s@85℃)。由于氧离子在Al₂O₃层的迁移率更低,限制了氧空位细丝生长速率及宽度,且Al₂O₃具有热增强作用,使氧空位分布更均匀,促使氧空位细丝生成/断裂过程由突变转为渐变。该工作为进一步实现氧化铪基忆阻器的性能优化及多值特性提供了参考。     

Study on electrical characteristics and reliability of fluorinated HfO2 for HKMG

The dielectric properties and reliability of fluorinated HfO₂ have been studied. The fluorinated HfO₂ dielectric treated by NF₃ plasma showed improved dielectric characteristics but resulted in interfacial layer (IL) regrowth during the fluorine plasma treatment process, which led to an oxide capacitance reduction and poor electrical characteristics. Through the analysis of chemical composition and electrical characteristics, it has been revealed that the Hf-O bonds in HfO₂ layer were converted to Hf-F bonds by the plasma treatment and then the dissociated oxygen diffused to the IL. In order to suppress the IL regrowth, newly fluorinated HfO₂ has been developed. Reliability of fluorinated HfO₂ dielectric was sharply improved without a decrease in the oxide capacitance at fluorine plasma treatment conditions of low power and temperature.     

Changes in effective work function of HfxRu1−x alloy gate electrode

Effective work function (?_m,eff) values of Hf_x Ru_1−x alloy gate electrodes on SiO₂ metal-oxide-semiconductor (MOS) capacitors were carefully examined to assess whether the ?_m,eff was determined by the crystalline structure or the composition of the Hf_xRu_1−x alloy. X-ray diffraction results indicated that the crystalline structures of Hf_xRu_1−x alloy were divided into hexagonal-Ru, cubic-HfRu or hexagonal-Hf with the increase of Hf content. The ?_m,eff values could be controlled continuously from 4.6 to 4.0 eV by changing the Hf content. The experimental ?_m,eff value showed a good agreement with theoretical results considering the compositional ratio of pure Hf and Ru. These results suggest that the ?_m,eff of Hf_xRu_1−x alloy gates on SiO₂ MOS capacitors is dominantly determined by the Hf_xRu_1−x composition rather than the crystalline structure.     

Atomic-layer-deposited Al2O3 and HfO2 on GaN: A comparative study on interfaces and electrical characteristics

Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ films were deposited on n-type GaN using atomic layer deposition (ALD). The interfacial layer of GaON and HfON was observed between HfO₂ and GaN, whereas the absence of an interfacial layer at Al₂O₃/GaN was confirmed using X-ray photoelectron spectroscopy and transmission electron microscopy. The dielectric constants of Al₂O₃, HfO₂, and composite HfO₂/Al₂O₃ calculated from the C-V measurement are 9, 16.5, and 13.8, respectively. The Al₂O₃ employed as a template in the composite structure has suppressed the interfacial layer formation during the subsequent ALD-HfO₂ and effectively reduced the gate leakage current. While the dielectric constant of the composite HfO₂/Al₂O₃ film is lower than that of HfO₂, the composite structure provides sharp oxide/GaN interface without interfacial layer, leading to better electrical properties.