氮流量对TaN薄膜微结构及性能的影响

采用反应直流磁控溅射法在Al2O3陶瓷基片上制备TaN薄膜,研究了氮流量(N2/(N2+Ar))对TaN薄膜微结构及性能的影响。结果表明,随氮流量的增大,TaN薄膜的氮含量、电阻率、方阻以及TCR的绝对值逐渐增大,而沉积速率逐渐降低。当N2流量较低(2%～4%)时,TaN薄膜中主要含有电阻率和TCR绝对值较低的六方Ta2N相(hcp),薄膜的电阻率在344μΩ.cm到412μΩ.cm范围内,薄膜的TCR绝对值约为几十ppm/℃。当氮气流量较高(5%～6%)时,薄膜中Ta2N相消失,薄膜中主要含有TCR绝对值较大的体心四方结构(bct)的TaN和四方结构(bct)的Ta3N5相,薄膜的电阻率在940μΩ.cm到1030μΩ.cm范围内,薄膜的TCR绝对值约为几百ppm/℃。     

退火处理对N掺杂Al:ZnO薄膜结构及性能的影响

采用射频磁控溅射方法, 常温条件下以N₂作为N掺杂源, 在玻璃基底制备了N掺杂Al:ZnO薄膜。在真空氛围下对样品进行了不同温度的退火处理15 min。通过X射线衍射、霍尔效应测试、紫外-可见光谱和X射线光电子能谱 (XPS) 仪分析了退火对样品结构和光电性能的影响。结果表明真空400℃退火15 min时成功制备出性能优异的p型ZnO薄膜, 其空穴载流子浓度为3.738×10²⁰cm^-3, 电阻率为1.299×10^-2Ω·cm, 样品可见光透射率达到了85%以上。XPS分析说明No受主缺陷的含量大于 (N₂)_o施主缺陷导致薄膜实现了p型转变。     

粉末表面氧化对二氧化铀芯块烧结性能的影响

用SEM、XRD、BET和DSC TG、热膨胀仪等观察了UO₂粉末的形貌结构并研究粉末氧化前后的烧结性能,分析了UO₂粉末表面预氧化对二氧化铀芯块烧结性能的影响。结果表明,240℃×8 h是UO₂粉末预氧化表面改性的最佳工艺;粉末改性后表层为UO_2+x和少量U₃0₇,改性粉末压坯在氩气气氛中开始发生收缩的温度降低了530-600℃,平均线收缩率提高了1倍;在本氩气保护条件下,热膨胀试验后芯块的密度从8.52 g/cm³提高到9.44 g/cm³。采用本改性粉末,在1300℃×5 h/N2+5%CO₂-1500℃×1 h/H₂批试烧结,其密度达10.26 g/cm³,O/U比为2.013。     

环氧耐磨绝缘防腐涂料制备及应用研究

以双酚A树脂和腰果酚改性胺树脂为基料,添加氧化铝微粉、碳化硅、氧化铁红等耐磨防腐填料,通过试验室模拟加速试验测试,获得环氧耐磨绝缘防腐涂料。该涂料在碳钢表面附着力大于6 MPa;750 g/1 000 r条件下涂层表面磨蚀失重低于30 mg;涂层表面电阻率高于8.04×10¹⁰ Ω,绝缘性好;耐盐雾测试1 000 h后,3个样板涂层表面都未起泡、未锈蚀、未脱落;在0.01 Hz低频阻抗(|Z|_{0.01 Hz})条件下进行电化学交流阻抗值测试,经过1 000 h的耐盐雾性能测试后,其化学交流阻抗值由测试前的1.38×10⁹ Ω·cm²下降为测试后的8.11×10⁷ Ω·cm²以上,涂层具有较高的阻抗值和较好的保护性能,防腐性能良好。同时该涂料应用于嘉兴轻轨试验段轨道防腐绝缘防护,经测试该产品可使轨道电阻由裸轨的15 Ω·km增加到26.25 Ω·km,证明该产品绝缘性能优异。     

(Ti,Ta)N三元薄膜的制备和表征

在用真空阴极弧制备TiN和TaN两种薄膜的基础上,采用两个独立的金属弧源同时放电的方法成功制备出(Ti,Ta) N三元薄膜。通过X射线衍射、X射线光电子能谱、原子力显微镜对TiN、TaN和(Ti,Ta) N薄膜的微结构、化学组分、表面形貌进行了比较分析,发现制备的(Ti,Ta) N三元薄膜是以立方结构为主的固溶体相构成,另外还存在单斜结构的Ta₃N₅相。与两种二元薄膜相比,其XRD图谱的衍射峰显著变宽,择优取向(200)的择优程度进一步加强。三元薄膜表面的Ti:Ta:N比为0.46:0.34:1,晶粒大小为纳米尺度。     

La掺杂Hf0.5Zr0.5O2薄膜铁电性能研究

铪基氧化物薄膜在超薄膜厚下仍具有优良的铁电性能,非常适用于高密度集成的铁电存储。La掺杂铪基薄膜拥有极为优异的循环写擦特性,但其剩余极化强度(2Pr≤35μC/cm²)还有待进一步提高。本研究采用原子层沉积(ALD)制备La掺杂的Hf_0.5Zr_0.5O₂薄膜(HZLO),通过快速热退火(RTA)对样品进行500℃、550℃和600℃的热处理,研究La掺杂及退火温度对TiN/HZLO/TiN/W结构铁电性能的影响。研究表明,La掺杂促进薄膜四方相转变为正交相,剩余极化强度(49.8μC/cm²)获得极大提高。此外,La掺杂还降低了器件矫顽场(～1.25 MV/cm)并改善矫顽电场对称性。随着退火温度升高至550℃,正交相占比升高至～77%,剩余极化强度高达49.8μC/cm²,而进一步升高退火温度至600℃,正交相、四方相和立方相朝着单斜相转变,器件剩余极化强度降低。     

超薄α-Ta(N)/TaN双层扩散阻挡层的微观结构与热稳定性

提出利用真空室残余的低浓度N原子制备超薄α-Ta(N)/TaN双层扩散阻挡层的方法,有效地避免了异质元素的引入和高N含量导致的高电阻率。用四点探针(FPP)、X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)进行薄膜电性能和微结构的表征,分析结果表明,利用低浓度氮化工艺,能调控超薄金属Ta膜的相结构,从而获得低阻α-Ta(N)/TaN双层Cu扩散阻挡层结构。高温退火的实验结果证明,此超薄结构具有高的热稳定性,失效温度达600℃。     

氢化及沉积温度对掺铝ZnO透明导电薄膜性能影响

采用射频磁控溅射方法在玻璃衬底上制备了掺铝ZnO透明导电薄膜(AZO)。为了降低AZO薄膜的电阻率, 采用在溅射气氛中通入一定比例H₂的方法对AZO薄膜进行氢化处理, 并研究了溅射气氛中H₂含量及衬底温度对AZO薄膜氢化效果的影响。结果表明: 在低温条件下, 氢化处理能有效降低AZO薄膜的电阻率; 在衬底温度为100℃的低温条件下, 通过调节溅射气氛中H₂的比例, 制备了电阻率为6.0×10^-4 Ω·cm的高质量氢化AZO薄膜, 该电阻值低于同等条件下未氢化AZO薄膜电阻值的1/3; 但随着衬底温度的升高, 氢化处理对薄膜电学性能的改善效果逐渐减弱。     

快速热退火对原子层淀积铂纳米颗粒的影响

以（MeCp）Pt（CH3）3和O₂为反应源,采用原子层淀积（ALD）技术在A1₂O₃衬底上制备Pt纳米颗粒,研究了在氮气中快速热退火对Pt纳米颗粒的特性的影响。结果表明,随着退火温度从700℃升高到900℃,Pt纳米颗粒尺寸逐渐增大,颗粒之间分离愈加清晰,形貌趋向球形,但颗粒密度稍有降低。随着在800℃退火时间从15 s增加到60 s,Pt纳米颗粒的尺寸逐渐增大,尺寸分布变得更加弥散,颗粒的密度逐渐降低;其中退火15 s后的Pt纳米颗粒密度高（9.29×10cm-2）、分布均匀、分离清晰。900℃退火后在Pt纳米颗粒中出现部分氧化态的Pt原子,其原因可能是在高温下Pt纳米颗粒与A1₂O₃薄膜之间发生了界面化学反应。     

Ti6Al4V钛合金渗碳层在HF中的腐蚀行为

用真空感应渗碳方法对Ti6Al4V钛合金进行高速渗碳,研究了渗碳层在HF溶液中的腐蚀行为。对腐蚀前后渗碳层的相结构和形貌的分析发现：对Ti6Al4V钛合金高速渗碳后,在表面生成一层TiC和CTi_0.42V_1.58复合化合物相的渗碳层。因为表面有渗碳层,Ti6Al4V钛合金在浓度为0.2%的HF中?泡其腐蚀速率从4.65×10^-10 g·m^-2·h^-1降低到3.3×10^-10 g·m^-2·h^-1。电化学腐蚀测试结果表明,其自腐蚀电位从未渗碳时的-0.94 V升高到-0.68 V,腐蚀电流密度从4.10 mA·cm^-2降至1.65 mA·cm^-2,极化电阻从6.36 Ω·cm²增大到15.8 Ω·cm²,R_t从0.2 Ω·cm²增大到5.7 Ω·cm²。渗碳层具有n型半导体特性,未渗碳样品具有p型半导体特性。Ti6Al4V钛合金渗碳后,在腐蚀过程中电子转移的阻力增大,使耐蚀性提高。F^-对Ti6Al4V钛合金渗碳层的腐蚀机理,主要是析氢腐蚀。     

The effect of rapid thermal annealing on structural and electrical properties of TiB2 thin films

This work reports on the effect of post-deposition rapid thermal annealing on the structural and electrical properties of deposited TiB₂ thin films. The TiB₂ thin films, thicknesses from 9 to 450 nm, were deposited by e-beam evaporation on high resistivity and thermally oxidized silicon wafers. The resistivity of as-deposited films varied from 1820 μΩ cm for the thinnest film to 267 μΩ cm for thicknesses greater than 100 nm. In the thickness range from 100 to 450 nm, the resistivity of TiB₂ films has a constant value of 267 μΩ cm.

A rapid thermal annealing (RTA) technique has been used to reduce the resistivity of deposited films. During vacuum annealing at 7 × 10⁻³ Pa, the film resistivity decreases from 267 μΩ cm at 200 °C to 16 μΩ cm at 1200 °C. Heating cycles during RTA were a sequence of 10 s. According to scanning tunneling microscopy analysis, the decrease in resistivity may be attributed to a grain growth through polycrystalline recrystallization, as well as to an increase in film density.

The grain size and mean surface roughness of annealed films increase with annealing temperature. At the same time, the conductivity of the annealed samples increases linearly with grain size. The obtained results show that RTA technique has a great potential for low resistivity TiB₂ formation.     

Direct liquid injection metal-organic chemical vapor deposition of HfO2 thin films using Hf(dimethylaminoethoxide)4

Hf(OCH₂CH₂NMe₂)₄, [Hf(dmae)₄] (dmae=dimethylaminoethoxide) was synthesized and used as a chemical vapor deposition precursor for depositing Hf oxide (HfO₂). Hf(dmae)₄ is a liquid at room temperature and has a moderate vapor pressure (4.5 Torr at 80 °C). It was found that HfO₂ film could be deposited as low as 150 °C with carbon level not detected by X-ray photoelectron spectroscopy. As deposited film was amorphous but when the deposition temperature was raised to 400 °C, X-ray diffraction pattern showed that the film was polycrystalline with weak peak of monoclinic (020). Scanning electron microscope analysis indicated that the grain size was not significantly changed with the increase of the annealing temperature. Capacitance–voltage measurement showed that with the increase of annealing temperature, the effective dielectric constant was increased, but above 900 °C, the effective dielectric constant was decreased due to the formation of interface oxide. For 500 Å thin film, the dielectric constant of HfO₂ film annealed at 800 °C was 20.1 and the current–voltage measurements showed that the leakage current density of the HfO₂ thin film annealed at 800 °C was 2.2×10⁻⁶ A/cm² at 5 V.     

石墨在固相剪切碾磨力场下的片层剥离及与PVC的纳米复合

采用固相剪切复合技术成功制备石墨-聚氯乙烯(PVC)复合粉体, 实现了石墨的片层剥离和在PVC基体中的纳米分散及对PVC的抗静电改性。通过XRD、 SEM、 TEM等表征了石墨-PVC/PVC复合材料的结构, 研究了其抗静电性能。结果表明, 石墨的片层厚度约20 nm, 径厚比超过10。固相剪切碾磨技术制备的石墨-PVC/PVC复合材料的导电性能有较大提高。在石墨质量分数为2%时, 表面电阻率为4.6×10⁷ Ω·cm, 已达到了抗静电材料的要求, 实现了低填充。在石墨质量分数为10%时, 表面电阻率达到最低的4.1×10⁴ Ω·cm。     

Enhanced ferroelectric properties of multilayer SrBi2Ta2O9/SrBi2Nb2O9 thin films for NVRAM applications

Ferroelectric SrBi₂Ta₂O₉/SrBi₂Nb₂O₉ (SBT/SBN) multilayer thin films with various stacking periodicity were deposited on Pt/TiO₂/SiO₂/Si substrate by pulsed laser deposition technique. The X-ray diffraction patterns indicated that the perovskite phase was fully formed with polycrystalline structure in all the films. The Raman spectra showed the frequency of the O–Ta–O stretching mode for multilayer and single layer SrBi₂(Ta_0.5Nb_0.5)₂O₉ (SBNT) samples was 827–829 cm⁻¹, which was in between the stretching mode frequency in SBT (813 cm⁻¹) and SBN (834 cm⁻¹) thin films. The dielectric constant was increased from 300 (SBT) to 373 at 100 kHz in the double layer SBT/SBN sample with thickness of each layer being 200 nm. The remanent polarization (2P_r) for this film was obtained 41.7 μC/cm², which is much higher, compared to pure SBT film (19.2 μC/cm²). The coercive field of this double layer film (67 kV/cm) was found to be lower than SBN film (98 kV/cm).     

Gd对Mg-x Gd-1Er-1Zn-0.6Zr合金显微组织和腐蚀行为的影响EI北大核心CSCD

采用重力铸造法制备Gd含量分别为7%(质量分数,下同),9%和11%的Mg-x Gd-1Er-1Zn-0.6Zr合金,利用光学显微镜、扫描电镜和X射线衍射仪等研究合金的显微组织,通过开路电位、动电位极化和电化学阻抗测试等方法研究合金在3.5%NaCl溶液中的腐蚀行为。结果表明:当Gd含量从7%增至11%时,开路电位峰值时间从1609 s降为851 s,电荷转移电阻从588.5Ω降至31.9Ω,腐蚀电流密度从2.21×10^(-5)A/cm^(2)增至3.97×10^(-5)A/cm^(2),说明随着Gd含量的增加,合金耐蚀性下降,这主要归因于第二相的微电偶腐蚀效应和腐蚀屏障效应共同作用。当Gd含量从7%增至11%时,(Mg,Zn)_(3)(Gd,Er)相体积分数从1.9%增至5.2%,并从沿晶界不连续分布转变为半连续分布,层片状LPSO相体积分数从11.7%增至26.7%,并沿着晶界贯穿晶粒内部,(Mg,Zn)_(3)(Gd,Er)相和层片状LPSO相体积分数的增加导致合金耐腐蚀性能下降,但大量细小层状LPSO相也能阻止腐蚀扩展,使得Gd含量为11%的合金在8~24 h内腐蚀速率增长减缓。     

Investigation of stress behaviors and mechanism of void formation in sputtered TiSix films

We have investigated the stress behaviors and a mechanism of void formation in TiSi_x films during annealing. TiSi_x thin films were prepared by DC magnetron sputtering using a TiSi_2.1 target in the substrate temperature range of 200–500 °C. The as-deposited TiSi_x films at low substrate temperature (<300 °C) have an amorphous structure with low stress of 1×10⁸ dynes/cm². When the substrate temperature increases to 500 °C, the as-deposited TiSi_x film has a mixture of C49 and C54 TiSi₂ phase with stress of 8×10⁹ dynes/cm². No void was observed in the as-deposited TiSi_x film. Amorphous TiSi_x film transforms to C54 TiSi₂ phase with a random orientation of (311) and (040) after annealing at 750 °C. The C49 and C54 TiSi₂ mixture phase transforms to (040) preferred C54 TiSi₂ phase after annealing over 650 °C. By increasing substrate temperature, the transformation temperature for C54 TiSi₂ can be reduced, resulting in relieved stress of TiSi₂ film. The easy nucleation of the C54 phase was attributed to an avoidance of amorphous TiSi_x phase. We found that amorphous TiSi_x→C54 TiSi₂ transformation caused higher tensile stress of 2×10¹⁰ dynes/cm², resulting in more voids in the films, than C49→C54 transformation. It was observed that void formation was increased with thermal treatment. The high tensile stress caused by volume decreases in the silicide must be relieved to retard voids and cracks during C54 TiSi₂ formation.     

Characterization of fluorine-doped silicon dioxide film by Raman spectroscopy

We have measured Raman spectra of fluorine-doped SiO₂ (SiOF) films and quartz glass. From a comparison between Raman spectra of the SiO₂ film and quartz glass, it has been found that the SiO₂ film is under compressive stress and that it has more threefold ring defects than quartz glass. Raman bands from threefold and fourfold ring defects in SiOF films become week as the fluorine/oxygen (F/O) ratio increases and as the stress decreases. The decrease of intensities of these Raman bands shows that ring defects in SiOF films decrease as the F/O ratio increases and as the stress decreases. The triply degenerated ω₄ mode at 460 cm⁻¹ becomes sharp as the F/O ratio increases and as the stress decreases. Furthermore, the peak-frequency of ω₁ mode around 820 cm⁻¹ decreases with a decrease of stresses whereas that of ω₃ mode around 1065 cm⁻¹ increases. These results can be well understood in terms of a decrease of O-Si-O bonding angle caused by relaxation of stresses.     

溅射功率对TaN薄膜电阻电性能的影响

本文利用直流反应磁控溅射技术,通过调节溅射功率于200℃、3％的氮分压条件在Al2O3基片上沉积了一系列TaN薄膜,并使用光刻工艺制备出相应的TaN薄膜电阻,研究了溅射功率对TaN薄膜电阻率、电阻温度系数（TCR）和功率容量的影响。实验结果表明：当溅射功率从200W增大到1000W,TaN薄膜电阻率逐渐减小,TCR绝对值从几百ppm／℃降为几十ppm／℃,功率容量呈现逐渐增大趋势。     

New transparent conducting MgIn2O4---Zn2In2O5 thin films prepared by magnetron sputtering

New materials for a transparent conducting oxide film are demonstrated. Highly transparent Zn₂In₂O₅ films with a resistivity of 3.9 × 10⁻⁴ Ω cm were prepared on substrates at room temperature using a pseudobinary compound powder target composed of ZnO (50 mol.%) and In₂O₃ (50 mol.%) by r.f. magnetron sputtering. MgIn₂O₄---Zn₂In₂O₅ films were prepared using MgIn₂O₄ targets with a ZnO content of 0–100 wt.%. The resistivity of the deposited films gradually decreased from 2 × 10⁻³ to 3.9 × 10⁻⁴ Ω cm as the Zn/(Mg + Zn) atomic ratio introduced into the films was increased. The greatest transparency was obtained in a MgIn₂O₄ film. The optical absorption edge of the films decreased as the Zn/(Mg + Zn) atomic ratio was increased, corresponding to the bandgap energy of their materials. It was found that the resistance of the undoped Zn₂In₂O₅ films was more stable than either the undoped MgIn₂O₄, ZnO or In₂O₃ films in oxidizing environments at high temperatures.