VNbMoTaWCo高熵合金氮化物扩散阻挡层的制备及其热稳定性

利用直流磁控溅射镀膜机设置不同氮气流量参数,制备VNbMoTaWCoN_x薄膜,氮气流量为20%时,在洁净的硅基底上沉积厚度约为15 nm的VNbMoTaWCoN₂₀高熵合金氮化物薄膜,并在其上面再溅镀一层厚度约为50 nm的Cu膜,最终形成Cu/VNbMoTaWCoN₂₀/Si 三层复合结构。采用四点探针电阻测试仪(FPP)、X射线衍射仪(XRD)、原子力显微镜(AFM)、场发射扫描电镜(SEM)对三层复合结构500 ℃退火前后的方块电阻、物相结构、粗糙度以及表面形貌进行了分析表征,研究了VNbMoTaWCoN₂₀高熵合金氮化物薄膜作为扩散阻挡层的热稳定性。研究结果表明,当氮气流量占比为20%时,VNbMoTaWCo₂₀高熵合金氮化物薄膜为非晶态,且出现了微量纳米晶;此氮气流量占比下制备的薄膜表面平整光滑、致密度最佳、粗糙度数值最小。Cu/VNbMoTaWCoN₂₀/Si三层复合结构进行500 ℃退火8 h后,Cu膜的方块电阻仍然维持在较低的数值,即0.065 Ω/sq,虽然Cu膜发生团聚,但是并未检测到高阻态Cu-Si化合物。VNbMoTaWCoN₂₀高熵合金氮化物薄膜作为扩散阻挡层在500 ℃温度下退火8 h后,表现出了优异的热稳定性。     

不同氮气流量AlCrTaTiZr高熵合金氮化物薄膜扩散阻挡性能研究

目的 提高铜互连扩散阻挡层的失效温度。方法 采用磁控溅射方法制备了不同氮气流量下的Cu/AlCrTaTiZrNx/Si高熵合金薄膜体系,使用真空退火炉对Cu/AlCrTaTiZrNx/Si高熵合金薄膜体系分别进行600、700、800、900 ℃的真空退火,并利用扫描电子显微镜（SEM）、原子力显微镜（AFM）、X 射线衍射仪（XRD）以及透射电子显微镜（TEM）等表征手段对薄膜的组织结构、三维形貌等进行表征。结果 不通入氮气时,高熵合金薄膜为非晶状态。随着氮气流量的增加,薄膜的结晶性越来越好,薄膜为FCC结构。随着氮气流量的增加,高熵合金薄膜表面粗糙度呈现下降的趋势,在氮气流量为20%时,高熵合金氮化物薄膜的致密性最好。Cu/AlCrTaTiZrN20/Si薄膜体系的扩散阻挡层结构主要为非晶包裹的纳米晶结构。薄膜在800 ℃退火后,没有Cu-Si化合物存在,薄膜方阻为0.0937Ω/□;在900 ℃退火后,Cu/AlCrTaTiZrN20/Si薄膜体系中Si基体部分出现不规则五边形状的大颗晶粒Cu-Si化合物。结论 AlCrTaTiZrNx高熵合金氮化物薄膜的扩散阻挡性能随着氮气流量的增加,呈现先增加后降低的趋势。在氮气流量为20%时,高熵合金氮化物薄膜的扩散阻挡性能最优,800 ℃高温退火后仍发挥阻挡作用。     

AlCrTaTiZrMo高熵合金氮化物扩散阻挡层的制备与表征

目的 制备15 nm的(AlCrTaTiZrMo)N六元高熵合金氮化物薄膜,并对其扩散阻挡性能进行表征。方法 使用直流磁控溅射设备在单晶硅上沉积(AlCrTaTiZrMo)N高熵合金氮化物薄膜,然后在薄膜上沉积150 nm的Cu,形成Cu/(AlCrTaTiZrMo)N/Si结构。在600 ℃下,对该结构进行不同时间的退火处理,使用X射线衍射仪（XRD）、四探针测试仪（FPP）、原子力显微镜（AFM）和场发射扫描电子显微镜（FESEM）研究薄膜成分及退火时间对薄膜组织结构、表面形貌、方块电阻的影响,研究其扩散阻挡性。结果 高熵合金氮化物薄膜与基体Si和Cu的结合性较好。沉积态高熵合金氮化物薄膜为非晶结构,表面光滑平整,方块电阻阻值较低。在600 ℃下经1 h退火后,薄膜仍为非晶结构,表面发生粗化。随着退火时间增加,5 h退火后,结构中出现少量纳米晶,大部分仍为非晶,表面粗糙度增加。退火7 h后,结构没有发生变化,仍为非晶包裹纳米晶结构,Cu表面生成部分岛状物,方块电阻阻值仍然较低,且无Cu-Si化合物生成,证明(AlCrTaTiZrMo)N高熵合金氮化物薄膜在长时间退火处理后,仍能保持良好的铜扩散阻挡性。结论 15 nm的(AlCrTaTiZrMo)N高熵合金氮化物薄膜在600 ℃下退火7 h后,其非晶包裹纳米晶的结构能有效阻挡Cu的扩散,表现出了优异的热稳定性与扩散阻挡性。     

Cu互连中Ta-Si-N/Zr阻挡层热稳定性的研究

用射频反应磁控溅射的方法在Si(100)衬底和Cu膜间制备Ta-Si-N(10 nm)/Zr(20 nm)双层结构的扩散阻挡层.Cu/Ta-Si-N/Zr/Si样品在高纯氮气的保护下从600至800℃退火1 h.通过四探针电阻测试仪(FPP)、SEM、XRD和AES研究Cu/Ta-Si-N/Zr/Si系统在退火过程中的热稳定性.结果表明:沉积到Zr膜上的Ta-Si-N表面平坦,为典型的非晶态结构;Cu/Ta-Si-N/Zr/Si样品650℃以上退火后Zr原子扩散到Si中形成的ZrSi2能有效地降低Ta-Si-N与Si之间的接触电阻;Ta-Si-N/Zr阻挡层750℃退火后仍能有效地阻止Cu的扩散.     

Al_(0.3)CrFe_(1.5)MnNi_(0.5)高熵合金氮化物薄膜的微观结构及摩擦磨损性能研究

采用反应磁控溅射法制备了Al0.3CrFe1.5MnNi0.5高熵合金氮化物薄膜,分析了不同氮气含量反应下薄膜的微观结构,并考察了薄膜的摩擦磨损性能。结果表明:溅射时氮含量(RN)为0%时,薄膜为体心立方结构,RN为10%时,氮化物镀层主相为面心立方CrN,且存在其他原子置换CrN的晶格中部分Cr原子而形成固溶体。RN达到15%时,薄膜形成非晶结构,随着RN的增大,薄膜非晶化趋势明显。RN为20%~30%时,氮气的固溶度逐渐达到饱和。高熵合金氮化物薄膜的摩擦系数较合金薄膜有明显提高,在磨耗过程中,能够有效阻止裂纹,抗摩擦磨损性能较合金薄膜均有不同程度的提高。     

W-Ti-N薄膜的制备及其热稳定性

以W-10%Ti二元合金靶材为原材料,采用直流磁控溅射法在Si基体上制备了W-Ti-N三元薄膜,研究了N_2分压和溅射功率对薄膜相结构和N含量的影响;在W-Ti-N/Si结构的基础上制备了Cu/W-Ti-N/Si多层结构,并对其在不同的温度下进行真空热处理。结果表明:通过调整N_2分压和溅射功率,即N_2/Ar比为1∶3且功率为70 W时可以获得非晶态W-Ti-N薄膜。薄膜在700℃以下热处理时具有非常好的热稳定性,方块电阻小于0.6Ω/□,略高于退火前的0.285Ω/□。但退火温度超过700℃后,稳定性迅速下降,在800℃退火后方块电阻达到170Ω/□。Cu布线用W-Ti-N非静态薄膜扩散阻挡层退火过程中的失效机理主要为元素间的界面扩散及反应。     

高熵合金AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7扩散阻挡层的制备与性能研究

目的 验证15 nm厚度AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7的势垒层热稳定性和扩散阻挡性能。方法 采用直流磁控溅射技术在n型Si(111)基片上真空溅射沉积15 nm的AlCrTaTiZrRu(3 nm)/(AlCrTaTiZrRu)N0.7 (12 nm)双层阻挡层，随后在双层AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7薄膜的顶部沉积50 nm厚的Cu膜，最终制得Cu/AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7/Si复合薄膜试样。将样品在真空退火炉中分别进行600~900 ℃高温退火30 min，以模拟最恶劣的应用环境。用场发射扫描电镜(FE-SEM)、X射线衍射仪(XRD)、能谱分析仪(EDS)、四探针电阻测试仪(FPP)以及原子力显微镜(AFM)对试样的表面形貌、物相组成、化学成分、方块电阻和粗糙度进行表征分析。结果 沉积态AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7薄膜呈现非晶结构，与Cu膜和Si衬底的结合良好。在800 ℃退火后，Cu/AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7/Si薄膜系统结构完整，膜层结构界面之间未出现分层现象，表面Cu颗粒团聚现象加剧，Si衬底和Cu膜表面未发现Cu-Si化合物生成，薄膜方阻保持在较低的0.070 ?/sq;900 ℃退火后，薄膜系统未出现层间分离和空洞现象，Cu膜表面形成孤立的大颗粒Cu-Si化合物，薄膜电阻率大幅上升。结论AlCrTaTiZrRu/(AlCrTaTiZrRu)N0.7双层结构在800 ℃退火后仍能有效抑制Cu与Si相互扩散，其非晶结构增强了Cu/HEA/HEAN0.7/Si体系的热稳定性和扩散阻挡性。     

NiCrAlY/Al-Al2O3/Ti2AlNb高温抗氧化和力学性能研究

采用电弧离子镀技水在NiCrAlY涂层与O相Ti₂AlNb合金之间沉积不同Al:Al₂O₃比例的Al-Al₂O₃薄膜作为扩散阻挡层.研究了900℃下恒温氧化500 h后NiCrAlY/Al-Al₂O₃/Ti₂AlNb体系中Al-Al₂O₃层阻挡合金元素互扩散的行为,以及对涂层氧化动力学曲线的影响.结果表明,没有添加扩散阻挡层的NiCrAlY/Ti₂AlNb体系,涂层和基体之间的元素互扩散十分严重,涂层丧失抗氧化能力;而添加扩散阻挡层的材料体系,涂层和基体之间的元素互扩散受到抑制,涂层的长期抗高温氧化性能得到提高.对于3Al-Al₂O₃,1Al-Al₂O₃和0Al-Al₂O₃ 3种扩散阻挡层,综合比较材料体系的抗氧化性能、阻挡层阻挡涂层和基体元素互扩散能力、以及涂层和基体之间结合力,当1Al-Al₂O₃薄膜作为扩散阻挡层时,材料性能最优异.同时,本文利用扩散阻挡系数简洁定量地表示出不同Al:Al₂O₃比例阻挡层的阻挡扩散能力.     

Cr掺杂对Cu/Si(100)薄膜体系的微观结构及电阻率的影响

利用简易合金靶在Si(100)衬底磁控溅射制备Cu、Cu-1.19%Cr和Cu-2.18%Cr薄膜,研究Cr对Cu薄膜在300～500 ℃真空退火前后的结构和电阻率的影响.X射线衍射分析表明Cu及Cu(Cr)薄膜均呈现Cu(111) 和Cu(200)衍射峰,并且Cu(Cr)薄膜一直保持较强的(111)织构.原子力显微分析表明Cu薄膜在500 ℃退火时,薄膜与硅基底发生明显的互扩散,薄膜表面的致密度及平整度下降;而Cu(Cr)薄膜在退火时保持较高的致密度,Cr显著提高Cu/Si薄膜体系的热稳定性.Cu(Cr)薄膜的电阻率随温度升高先减小而后增加,在400 ℃及500 ℃退火30 min后分别达到最小值2.76 Μω.cm和2.97 μΩ.cm,与纯Cu膜相近(2.55 μΩ.cm).Cu(Cr)薄膜退火电阻率的大幅度减小与薄膜晶粒尺寸的增加以及Cr的扩散有关.适量的Cr掺杂和合理的退火工艺使得Cu(Cr)合金薄膜在高温互连材料方面具有很大的应用前景.     

Cu和Ni原子在高熵合金CuCoCrFeNi中的扩散行为

研究了CuCoCrFeNi高熵合金在镀镍和镀铜并经不同温度退火不同时间后扩散层的显微组织、成分以及扩散层厚度。结果表明,Cu原子在CuCoCrFeNi高熵合金中不易发生晶格扩散,但经高温或长时间热处理后,Cu原子可在晶界处发生扩散。Ni原子与高熵合金中的组元发生了明显的互扩散;Cu和Ni原子在高熵合金中的扩散是空位机制,只有"适配空位"才能为原子在高熵合金中提供迁移的位置。显微硬度测试结果表明,Cu/高熵合金界面处显微硬度较低,而Ni/高熵合金界面处显微硬度逐渐提高。     

Temperature dependence of copper diffusion in different thickness amorphous tungsten/tungsten nitride layer

The amorphous W/WN films with various thickness (10, 30 and 40 nm) and excellent thermal stability were successfully prepared on SiO₂/Si substrate with evaporation and reactive evaporation method. The W/WN bilayer has technological importance because of its low resistivity, high melting point, and good diffusion barrier properties between Cu and Si. The thermal stability was evaluated by X-ray diffractometer (XRD) and Scanning Electron Microscope (SEM). In annealing process, the amorphous W/WN barrier crystallized and this phenomenon is supposed to be the start of Cu atoms diffusion through W/WN barrier into Si. With occurrence of the high-resistive Cu₃Si phase, the W/WN loses its function as a diffusion barrier. The primary mode of Cu diffusion is the diffusion through grain boundaries that form during heat treatments. The amorphous structure with optimum thickness is the key factor to achieve a superior diffusion barrier characteristic. The results show that the failure temperature increased by increasing the W/WN film thickness from 10 to 30 nm but it did not change by increasing the W/WN film thickness from 30 to 40 nm. It is found that the 10 and 40 nm W/WN films are good diffusion barriers at least up to 800°C while the 30 nm W/WN film shows superior properties as a diffusion barrier, but loses its function as a diffusion barrier at about 900°C (that is 100°C higher than for 10 and 40 nm W/WN films).     

Effects of Co content on the Cu diffusion barrier property of electroless NiCoP film

The characteristics of electroless NiCoP films were investigated as a function of Co content. Sheet resistance of a multi-stacked film of SiO₂/Ta/Cu/NiP dramatically increased after annealing at 500 °C, but as more Co was co-plated in NiCoP film, the change in sheet resistance of the stacked film of SiO₂/Ta/Cu/NiCoP at 500 °C became smaller. A CoP/Cu film showed no change in resistance value after annealing, which indicates the CoP film is the most effective Cu diffusion barrier. X-ray diffraction analysis showed that an as-plated NiP film of amorphous structure is easily crystallized by thermal annealing over 300 °C, while CoP showed an insignificant change in crystal structure by thermal annealing up to 500 °C. This result reveals that the CoP film is capable of preventing the diffusion of Cu at 500 °C due to the thermal stability of CoP film.     

The Characterization of Sputtered Zr-Ge-N Thin Films as Diffusion Barriers Between Copper and Silicon

The main purpose of the present micro-structural analysis by transmission electron microscopy(TEM)and X-ray diffraction(XRD)was to investigate whether amorphous Zr-Ge-N films are a potential candidate as a diffusion barrier for Cu wiring used in Si devices.The Zr-Ge-N films were prepared by a radio frequency(RF)reactive magnetron sputter-deposition technique using N2 and Ar mixed gas,and the film structure was found to be sensitive to the gas flow ratio of N2 vs.Ar during sputtering.Polycrystalline Zr-Ge-N films were obtained when the N2/(Ar+N2)ratio was smaller than 0.2 and amorphous-like Zr-Ge-N films were obtained when the ratio was larger than 0.3.Diffusion barrier test was performed by annealing the Cu/Zr-Ge-N/Si film stack under Ar atmosphere.The deposited Zr-Ge-N(C)films remained amorphous even after high temperature annealing.The Cu diffusion profile in the film was assessed by the Auger electron spectroscopy(AES).The results indicate that Cu diffusion was minimal in amorphous Zr-Ge-N(C)films even at high annealing temperatures of 800℃.     

氮含量对Mo-Ta-W-N多主元合金氮化物薄膜的影响

目的 探究氮含量对MoTaW多主元合金薄膜的微观组织和力学性能的影响,并提高Mo-Ta-W多主元合金薄膜的力学性能。方法 采用反应多靶磁控溅射技术在单晶硅片上制备出了具有不同氮含量的Mo-Ta-W-N多主元合金氮化物薄膜,通过X射线光电子能谱仪、掠入射角X射线衍射、场发射扫描电子显微镜、原子力显微镜对薄膜的成分、组织结构、表面及截面微观形貌、厚度和粗糙度进行了表征分析,并采用纳米压痕仪对薄膜的硬度和弹性模量进行了测试。结果 Mo-Ta-W-N多主元合金氮化物薄膜中的氮含量随着溅射过程中氮气流量的增加而增加,当氮气流量达到50%时,薄膜中的氮含量升至49%,而钽含量则随之降低至12%。形成氮化物后,Mo-Ta-W多主元薄膜由BCC结构转变成了单相FCC固溶体结构,表面由层片状结构转变为花椰菜状团簇结构,随着氮含量的增加,表面的粗糙度先降低后升高,厚度则不断降低。与Mo-Ta-W多主元合金薄膜相比,Mo-Ta-W多主元合金氮化物薄膜的力学性能有所提高,但随着氮含量的增加而下降,当氮气流量为10%时,Mo-Ta-W-N多主元合金氮化物薄膜的硬度和弹性模量分别为34.3 GPa和327.5 GPa。结论 氮化物的形成对Mo-Ta-W多主元合金薄膜的相结构、表面形貌等有影响,可有效提高薄膜的力学性能。     

Effect of Annealing Ambience on the Chemical Stability of Zr-Si-N Diffusion Barrier

Cu has been drawn much attention as a newinterconnect material in ULSI due to its low resistivity,high resistance to electromigration and stress migration[1].However,Cu can easily diffuse into Si wafer evenat temperature below200°C,which degrades thereliability of the devices.It is well recognized that adiffusion barrier between Cu and Si is necessary toprevent the diffusion.Diffusion barriers are usuallychosen among refractory metals and their nitrides suchas Ta,TiN,TaN,and ZrN[2,5].R…     

Improved Diffusion-Resistant Ability of Multicomponent Nitrides: From Unitary TiN to Senary High-Entropy (TiTaCrZrAlRu)N

Multicomponent high-entropy nitrides have been attempted as robust diffusion barrier materials to inhibit the severe interdiffusion of Cu and Si; however, the improvement in their diffusion resistance relative to the abilities of few-component nitrides has actually not been verified. Thus, in this study, nitride barriers with different numbers of components (metallic elements), from unitary TiN to senary high-entropy (TiTaCrZrAlRu)N (with the same face-centered cubic structure and a thickness of 5 nm), were prepared. The failure of these nitride barriers in resisting the interdiffusion of Cu and Si was examined, and the activation energy of Cu diffusion through the nitrides was determined. With more components incorporated, the failure temperature of the nitrides was found to markedly increase from 550°C to 900°C, and the activation energy of Cu diffusion was effectively raised from 107 kJ/mol to 161 kJ/mol. Severe lattice distortions and random cohesions are suggested as the dominant factors for the improved diffusion-resistant ability of the multicomponent high-entropy nitrides.     

AlCoCrCu0.5 NiFe高熵合金氧化物薄膜光学特性的研究

目的制备AlCoCrCu_(0.5)NiFe高熵合金氧化物薄膜,并对其光学性能进行表征。方法使用磁控溅射设备在单晶硅片和玻璃上制备AlCoCrCu_(0.5)NiFe高熵合金氧化物薄膜,并对膜进行退火处理。使用椭圆偏振光谱仪对薄膜的光学特性进行分析。结果随着氧含量的增加,折射系数减小。当光波长为633 nm时,折射系数为1.69~2.40。当氧分压为10%,折射率色散曲线在475 nm和600 nm处出现拐点,在600 nm之后折射率随着波长的增大而逐渐减小。当氧分压为30%时,折射率曲线在500 nm和600 nm处出现拐点,在600 nm后折射率趋于稳定。当氧分压为50%时,折射率曲线在525 nm处出现拐点,之后折射率随波长的增大而逐渐增大。在450~550 nm波段内,AlCoCrCu_(0.5)NiFe氧化物薄膜的吸收系数随氧分压的增加而增加。在550~850 nm波段内,薄膜的吸收系数随工作气压的变化趋势不明显。随着氧分压的增加膜的颜色逐渐变深。经过退火处理后,膜的颜色进一步加深。在相同工艺参数的情况下,氧的分压增加,膜厚减小。结论适当减小氧分压,能获得具有高折射率的AlCoCrCu_(0.5)NiFe氧化物薄膜。不同的分压下,AlCoCrCu_(0.5)FeNi氧化物薄膜的吸收系数随波长的增加均存在一个拐点,并且随氧分压的增加,拐点的波长减小。氧含量增加导致氧化物薄膜厚度减小,颜色加深。