Characteristics of the NO dielectric film with low pressure chemical vapor deposition in-situ nitridation

We investigated the formation of the thin NO dielectric films by in-situ nitridation of native oxide, and subsequent deposition of silicon nitride in the low pressure chemical vapor deposition systems for the application to the capacitors in high density dynamic random access memory. The native oxide was nitrided at elevated temperatures of 690 or 780°C in the flowing ammonia gas atmosphere, and nitride was deposited by flowing silane gas additionally immediately after the nitridation process. By in-situ nitridation process, we could obtaine 5 and 4.5 nm thick (equivalent oxide thickness) nitride/oxide (NO) dielectric films. These films were characterized to be electrically more reliable than the conventional oxide/nitride/oxide (ONO) films of the same equivalent oxide thickness. The nitrided NO films also showed lower leakage current and higher breakdown voltage than conventional ONO films. We obtained electrically most reliable NO films by loading the wafer at 400°C and nitriding the native oxide at 780°C.     

Impurity barrier properties of reoxidized nitrided oxide films foruse with P+-doped polysilicon gates

The ability of thin reoxidized nitrided oxide (ONO) gate dielectrics formed by rapid thermal processing to act as a barrier to boron penetration resulting from p⁺ poly gate processing are investigated. Measurements comparing the threshold voltage instability of capacitors fabricated with BF₂ implanted poly gates subjected to various postgate thermal cycles have been performed. The ONO gate dielectrics are found to be an excellent impurity barrier to boron diffusion, even in the presence of fluorine. The extent of the nitridation is also found to affect the diffusion barrier properties, with the highest temperature nitridations forming the best barriers. Reoxidation of the nitrided films reduces the barrier properties somewhat, but improvement is still observed over SiO₂     

Oxide thickness dependence of nitridation effects on TDDB characteristics

Wet oxide thicknesses dependence of nitridation effects on electrical characteristics, charge trapping properties and TDDB (Time Dependent Dielectric Breakdown) characteristics have been investigated. It is found that the difference of conduction current between the wet and nitrided wet oxide increases with increasing oxide thickness both for negative and positive bias to the gate until constant current stress is applied. After the stress, with decreasing oxide thickness both in wet and nitrided wet oxide leakage current increases. Up to 60 Å no difference was observed between the wet and nitrided wet oxide but at 50 Å nitrided wet oxide has less increase of current comparing to the wet oxide for the same stress. In wet oxide with increasing stress current density initial hole trap decreases but electron trap increases whereas in nitrided wet oxide has less initial hole trap and also electron trap is less comparing to the wet oxide. Both in wet and nitrided wet oxide for negative bias stress, time to 50 % breakdown decreases with decreasing thickness but at 50 Å a turn-around effect was observed due to nitridation i.e., the 50 % breakdown time is greater for nitrided wet oxide comparing to the wet oxide. On the contrary, for positive bias stress 50 % breakdown time increases with decreasing oxide thickness both in wet and nitrided wet oxide. For positive bias also a turn-around effect is observed at 50 Å i.e., 50% breakdown time is less in nitrided wet oxide comparing to the wet oxide. The improved reliability of nitrided wet oxide at the thin region of 50 Å seems to be due to the increase of more Si---N bond to the interface of oxide and Si comparing to the thick oxide of above 60 Å for the same nitridation conditions.     

氮化H_2-O_2合成薄栅氧抗辐照特性

对氮化 H2 - O2 合成薄栅氧抗辐照性能进行了研究 ,将 H2 - O2 合成和氮氧化栅两种技术结合起来 ,充分利用两者的优点制成三层结构的 Sandwich栅 ,对比常规氧化、H2 - O2 合成氧化和氮化 H2 - O2 合成氧化三种方式及不同退火条件 ,得出氮化 H2 - O2 合成氧化方法抗辐照性能最佳 ,采用硅化物工艺加快速热退火是未来抗辐照工艺发展的趋势 ;并对氮化 H2 - O2 合成栅的抗辐照机理进行了研究     

利用电导技术研究快速热氮化二氧化硅与硅界面的性质

本文介绍了尼科里安-科兹伯格(Nicollian-Goetzberger)电导技术及其基本原理,建立了采用双相锁相放大器的测试系统,利用它测量了常规热氮化和快速热氮化SiO_2薄膜与Si衬底的界面性质,包括界面态密度,空穴俘获截面,表面势起伏,以及界面态时间常数等,并对它们进行了分析和讨论。研究结果表明:氮化会增加界面态的密度和平均时间常数,会增强表面势起伏,但只是轻微地改变空穴俘获截面.特别地,氮化还导致界面态密度在禁带中央以下0.2-0.25eV处出现峰值以及削弱了空穴俘获截面对能带能量的依赖关系.利用一个阵列模型,可以较好地模拟表面势起伏的标准偏差并可由此推断表面势起伏是由长波形式的界面态电荷非均匀性所引起.这个结果和氮化会导致高密度氧化层电荷的事实相一致.而以上所有界面态的性质,都与氮化的时间和温度有关.     

Thermal Nitridation of Si and SiO/sub 2/ for VLSI

This paper presents an extensive review of our work on thermal nitridation of Si and SiO/sub 2/. High-quality ultrathin films of silicon nitride and nitrided-oxide (nitroxide) have been thermally grown in ammonia atmosphere in a cold-wall RF-heated reactor and in a lamp-heated system. The growth kinetics and their dependence on processing time and temperature have been studied from very short to long nitridation times. The kinetics of thermal nitridation of SiO/sub 2/ in ammonia ambient have also been studied. In nitroxide, nitrogen-rich layers are formed at the surface and interface at a very early stage of the nitridation. Then the nitridation reaction mainly goes on in the bulk region with the surface and near interface nitrogen content remaining fairly constant. Our results also indicate the formation of an oxygen-rich layer at the interface underneath the nitrogen-rich layer whose thickness increases slowly with nitridation time. The nitride and nitroxide films were analyzed using Auger electron spectroscopy, grazing angle Rutherford backscattering, and etch rate measurements. MIS devices were fabricated using these films as gate insulators and were electrically characterized using I-V, C-V, time-dependent breakdown, trapping, and dielectric breakdown techniques. Breakdown, conduction, and C -V measurements on metal-insulator semiconductor (MIS) structures fabricated with these films show that very thin thermal silicon nitride and nitroxide films can be used as gate dielectrics for future highly scaled-dowm VLSI devices. The electrical characterization results also indicate extremely low trapping in the nitride films. The reliability of ultrathin nitride was observed to be far superior to SiO/sub 2/ and nitroxide due to its much less trapping. Studies show that the interface transition from nitride to silicon is almost abrupt and the morphology and roughness of the interface are comparable to the SiO/sub 2/-Si interfaces.     

Thermal nitridation of Si and SiO2for VLSI

This paper presents an extensive review of our work on thermal nitridation of Si and SiO2. High-quality ultrathin films of silicon nitride and nitrided-oxide (nitroxide) have been thermally grown in ammonia atmosphere in a cold-wall RF-heated reactor and in a lamp-heated system. The growth kinetics and their dependence on processing time and temperature have been studied from very short to long nitridation times. The kinetics of thermal nitridation of SiO2in ammonia ambient have also been studied. In nitroxide, nitrogen-rich layers are formed at the surface and interface at a very early stage of the nitridation. Then the nitridation reaction mainly goes on in the bulk region with the surface and near interface nitrogen content remaining fairly constant. Our results also indicate the formation of an oxygen-rich layer at the interface underneath the nitrogen-rich layer whose thickness increases slowly with nitridation time. The nitride and nitroxide films were analyzed using Auger electron spectroscopy, grazing angle Rutherford backscattering, and etch rate measurements. MIS devices were fabricated using these films as gate insulators and were electrically characterized usingI - V, C - V, time-dependent breakdown, trapping, and dielectric breakdown techniques. Breakdown, conduction, andC-Vmeasurements on metal-insulator semiconductor (MIS) structures fabricated with these films show that very thin thermal silicon nitride and nitroxide films can be used as gate dielectrics for future highly scaled-down VLSI devices. The electrical characterization results also indicate extremely low trapping in the nitride films. The reliability of ultrathin nitride was observed to be far superior to SiO2and nitroxide due to its much less trapping. Studies show that the interface transition from nitride to silicon is almost abrupt and the morphology and roughness of the interface are comparable to the SiO2-Si interfaces.     

Wet chemical nitridation of (100)GaAs surface: Effect on electrical parameters of surface-barrier Au-Ti/GaAs structures

The influence exerted by wet chemical nitridation of the (100)GaAs substrate surface in hydrazinesulfide solutions before fabrication of barrier contacts on the parameters of surface-barrier Au-Ti/GaAs structures has been studied. The structures fabricated on nitrided substrates are characterized by lower reverse currents and higher breakdown voltages. The barrier height in structures of this kind is 0.71±0.02 eV, and the ideality factor, 1.06±0.01. The observed improvement in the electrical parameters of the structures is due to replacement of the natural oxide layer on the substrate surface by a thin coherent GaN film.     

Process dependence of interface state generation due to irradiation and hot carrier stress in rapid thermally nitrided thin gate oxides

A study of the effects of nitridation time and temperature on the interface state generation in MOS devices with thin rapid thermally nitrided gate oxides is reported. A different process dependence was observed for interface state generation caused by X-ray irradiation and hot carrier stress. The discrepancy is explained using the structural changes at the interface during nitridation and some of the earlier defect generation models.<>     

Characteristics of thermally nitrided silicon dioxide film and plasma enhancement

After reviewing characteristics of thermally nitrided silicon dioxide films, plasma enhanced nitridation is described. The plasma technique makes possible reduction of the nitridation temperature by activating reaction species. Silicon dioxide films of about 10 nm thickness were nitrided in ammonia gas plasma, for example, at 1000‡C and at a pressure of 40 Pa. From the results of the AES depth profiles and the N_ss distribution, good dielectric and interfacial properties have been obtained via plasma nitridation. The plasma nitroxide films are useful for gate insulators of small MOSFETs in future VLSI.     

Effects of N distribution on charge trapping and TDDBcharacteristics of N2O annealed wet oxide

Wet pyrogenic oxide of different thicknesses was annealed in N₂O ambient and the N concentration in the films was studied by using SIMS (secondary ion mass spectroscopy). It was found that for a certain annealing time and temperature, the N concentration (at %) increases with decreasing wet oxide thickness and the location of the peak of N is observed near the interface of nitrided oxide and Si substrate. On the contrary, after nitridation the concentration of H is higher in the thicker wet oxide of thickness 100 Å and also does not change much from the surface to the interface. For the thinner wet oxide of thickness 40 Å, the concentration of H is less and decreases toward the interface. Gate dielectrics were characterized using high-frequency and quasi-static measurements. After a constant current stress, a large distortion was observed for the N₂O annealed wet oxide of 98 Å whereas for the N₂O annealed wet oxide of 51 Å the distortion was small. With increasing stressing time, hole trap is followed by electron trapping for the wet oxide of 98 Å whereas for the N₂O annealed wet oxide of 51 Å, hole trapping increases a little at the beginning and then saturates. From the TDDB characteristics, a longer t_BD was observed for N₂O annealed wet oxide of 51 Å compared to 98 Å. From the experimental results, it can be suggested that the improved reliability of thin gate oxide is due to the large amount of N concentration near the interface only. Hence for the device fabrication process, if the wet oxide is nitrided in N₂O ambient, the reliability of gate oxide will be improved in the ultrathin region     

Effect of rapid thermally nitrided titanium films contacting silicided and nonsilicided junctions

The effect of rapid thermally nitrided titanium films contacting silicided (titanium disilicided) and nonsilicided junctions has been studied in the temperature range of 800 to 900°C. The rapid thermal nitridation of titanium films used as diffusion barriers between aluminum and silicon, has a major impact on shallow junction complementary metal oxide semiconductor technologies. During the process of rapid thermal nitridation, the dopants in the junctions undergo a redistribution and affect the electrical properties of shallow junction structures. This work focuses on using novel contact resistance structures to measure the variation in electrical parameters for rapid thermally nitrided titanium films annealed at different temperatures. The self-aligned silicide (salicide) junctions in this study were formed using rapid thermally annealed titanium films. Electrical contact resistance testers were used to measure the interface contact resistance between the salicide and silicon, as well as between the metal and the salicide. The results show that the interface contact resistance to the p⁻ diffused salicided junctions increases with rapid thermal nitridation of the additional titanium film, whereas the interface contact resistance to the n⁻ diffused salicided junction shows a decrease. Further, as a function of the rapid thermal annealing temperature (for fixed titanium thickness), the nonsalicided diffusions show an increase in the interface contact resistance. The boron profiles at the TiSi₂/Si interface obtained using secondary ion mass spectroscopy show an excellent qualitative agreement with the electrical results for each of the conditions discussed. The films were also characterized using Rutherford back-scattering spectrometry and transmission electron microscopy and the results show good agreement with the measured variation in electrical parameters. These results also show that as the anneal temperature is increased, the TiN thickness increases, further the change in the silicide/silicon interface position with the nitridation of the additional titanium layer was verified. This work was carried out when the author was working at AT&T Bell Labs     

Direct nitridation of high-k metal oxide thin films using argon excimer sources

Reported, for the first time, is the formation of metal oxynitride thin films via direct nitridation of the metal oxide films by active nitrogen species generated from molecular nitrogen with argon excimer sources. Preliminary results on TaO/sub x/N/sub y/ thin films formed from 9 nm Ta/sub 2/O/sub 5/ films have exhibited excellent electrical properties with three orders magnitude lower leakage current density being achieved and 25% higher accumulation capacitance being obtained. The nitridation process for a specific film thickness can be optimised by adjusting the VUV irradiation time to achieve both increased accumulation capacitance and improved leakage property, without the need for the use of H/sub 2/O, NH/sub 3/ or high temperature substrate heating.     

Effect of thermally nitrided SiO2thickness on MIS characteristics

The flatband voltage of metal-insulator-semiconductor (MIS) structures with thermally nitrided SiO2(nitroxide) insulators has been studied as a function of the nitroxide thickness in the range of 10-60 nm, for different nitridation conditions. The most striking result is that 10-nm nitroxide films are far less susceptible than thicker ones to the degradation of the electrical properties of the starting SiO2films induced by nitridation, as revealed by a negative shift of the flatband voltage. For nitridation cycles at relatively low temperatures (900° 120 min or 1000°C 60 min) the shift in the 10-nm films is practically negligible.     

Short-channel MOSFETs with oxynitride gate dielectrics fabricated using multiple rapid thermal processing

Short-channel MOSFETs with superior thin gate dielectrics have been successfully fabricated using multiple reactive rapid thermal processing of thermal oxides. The gate dielectrics are produced by rapid thermal nitridation (RTN) of thin thermal oxides in pure NH/sub 3/ ambient followed by rapid thermal reoxidation (RTO) in O/sub 2/ ambient. Devices fabricated with RTO/RTN gate dielectrics exhibit improved hot electron induced degradation compared to those fabricated with pure oxides. In addition, the subthreshold leakage current level of RTO/RTN devices is as good as for standard oxide devices.<>     

Enhanced negative substrate bias degradation in nMOSFETs with ultrathin plasma nitrided oxide

The degradation induced by substrate hot electron (SHE) injection in 0.13-/spl mu/m nMOSFETs with ultrathin (/spl sim/2.0 nm) plasma nitrided gate dielectric was studied. Compared to the conventional thermal oxide, the ultrathin nitrided gate dielectric is found to be more vulnerable to SHE stress, resulting in enhanced threshold voltage (V/sub t/) shift and transconductance (G/sub m/) reduction. The severity of the enhanced degradation increases with increasing nitrogen content in gate dielectric with prolonged nitridation time. While the SHE-induced degradation is found to be strongly related to the injected electron energy for both conventional oxide , and plasma-nitrided oxide, dramatic degradation in threshold voltage shift for nitrided oxide is found to occur at a lower substrate bias magnitude (/spl sim/-1 V), compared to thermal oxide (/spl sim/-1.5 V). This enhanced degradation by negative substrate bias in nMOSFETs with plasma-nitrided gate dielectric is attributed to a higher concentration of paramagnetic electron trap precursors introduced during plasma nitridation.     

Process dependency of radiation hardness of rapid thermalreoxidized nitrided gate oxides

The radiation hardness of MOS capacitors with various reoxidized nitrided oxide (RNO) structures was studied by changing the duration of rapid thermal processes during sample preparation and by applying irradiation-then-anneal (ITA) treatments on samples after preparation. It was found that the initial flatband voltage and midgap interface trap density of MOS capacitors exhibit turnaround dependency on the total time of nitridation and reoxidation processes. For samples with nitrided oxide (NO) structures, the radiation-induced variations of the above parameters are also turnaround-dependent on nitridation time. However, when the reoxidation process is performed, the radiation hardness for all samples is gradually improved with increasing reoxidation time no matter when the nitridation time. The most radiation-hard process for RNO structures is suggested. Finally, it was found that when ITA treatments are applied on samples after preparation, their radiation hardness is much improved     

Electrical and physical characteristics of thin nitrided oxides prepared by rapid thermal nitridation

Ultrathin oxides (5-12 nm) were nitrided by lamp-heated rapid thermal annealing in ammonia at temperatures of 900-1150°C for 5-300 s. Elemental depth profiles were measured by Auger electron spectroscopy (AES) and secondary ion mass spectroscopy (SIMS). Both the nitrogen concentration measured by AES and the hydrogen one measured by SIMS for a nitrided oxide are found to increase monotonically as nitridation proceeds. The AES depth profiles of oxygen show that the Si-SiO2interface does not move during nitridation. Dependences of midgap interface state density (D_{it}_{m}) and fixed charge density (Nf) on nitridation temperature and on oxide thickness were studied. For a given temperature, bothD_{it}_{m}and (Nf) are found to show turnarounds as nitridation time increases in a similar manner: at first both increase, reach respective maxima at a certain nitridation timet_{max}, and then decrease gradually. The (D_{it}_{m}) and (Nf) increase more rapidly and thet_{max}is shorter as the nitridation temperature is raised or the oxide film is thinner. The maximum ofD_{it}_{m}increases as the oxide film is thinner. A two-step model is newly proposed to explain the turn-around behaviors ofD_{it}_{m}and Nf: the first step is defect formation as a result of nitrogen incorporation and the second step is reduction of the defects by an annealing-type process. The simulation reproduces the turnaround behaviors very well.     

钙钛矿氧化物薄膜和异质结的外延生长与物性研究

用激光分子束外延，原子尺度控制的外延生长出多种钙钛矿氧化物薄膜和异质结．原子力显微镜和高分辨透射电镜测量结果表明，薄膜与异质结的表面和界面均达到原子尺度的光滑．制备出在可见光波段透过率大于85％的导电氧化物薄膜；物性研究结果表明，随着含氧量的不同，BaTiO3薄膜具有绝缘体、半导体和导体的不同特性。BaTiO3／SrTiO3超晶格的光学非线性效应比BaTiO3体材增大23倍．首次在La0．9Sr0．1MnO3／SrNb0．01Ti0.99O3(LSMO／SNTO)异质结上，观测到全氧化物p-n结电流和电压的磁调制与正磁电阻效应。在255K条件下，当外加磁场分别为5和1000Oe时，LSMO／SNTO p-n结的磁电阻变化率R／RO达到：46．7％和83．4％；在外加磁场为3T时，在100K条件下，在LSMO／SNTO多层p-n异质结上观测515％的正磁电阻变化率。     

氮化时间对RF-MBE法生长InN薄膜晶体结构的影响

采用射频等离子体分子束外延(RF-MBE)技术在蓝宝石(Al2O3)衬底上外延生长了InN薄膜,在生长之前对其进行不同时间的氮化处理.通过扫描电子显微镜(SEM)和X射线衍射(XRD)对薄膜的形貌和结构进行了表征,发现氮化时间小于60 min时获得的InN薄膜的晶体结构为多晶且表面粗糙,而氮化时间为60 min及120 min时获得的InN薄膜为单晶结构,表面粗糙度有所下降.分析表明,氮化时间对InN薄膜的晶体结构有很重要的影响.