CN104022075B - 一种可控自形成Cu3Ge/TiN双层扩散阻挡层制备方法 - Google Patents
一种可控自形成Cu3Ge/TiN双层扩散阻挡层制备方法 Download PDFInfo
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Abstract
本发明公开了一种在超深亚微米集成电路铜互连技术中应用的可控自形成Cu3Ge/TiN双层阻挡层制备方法。本发明先采用气相物理共溅射技术制备Cu(Ge,Ti)合金层,随后通过控温氮气(N2)氛退火等步骤,利用Cu(Ge,Ti)合金层中各元素在高温退火过程中能自发选择性反应特性,在Si/Cu(Ge,Ti)/Cu界面可控自形成Cu3Ge/TiN双层阻挡层,其在高温(750℃)条件下仍能有效阻挡Cu与Si基体的相互扩散。采用Cu(Ge,Ti)合金可控自形成Cu3Ge/TiN双层阻挡层能有效降低互连膜系电阻率,降低互连电路的阻容耦合(RC)延迟效应,提高半导体器件的运行速度和稳定性。
Description
技术领域
本发明属于半导体集成电路制造工艺技术领域,涉及一种适用于超深亚微米Cu互连用的可控自形成Cu3Ge/TiN双层扩散阻挡层制备方法。
背景技术
铜(Cu)具有低阻、高抗电迁移性能,已取代铝(Al)成为当今高性能超大规模硅(Si)集成电路主流互连材料,见文献[Delsol R, Jacquemin J P, Gregoire M, GiraultV, Federspiel X, Bouyssou R X, Vannier P, Normandon P. Microelectron Eng,2006; 83: 2377]。但Cu与Si低温下(<300℃)直接反应形成高阻Cu3Si化合物相,且Cu易扩散至Si基体内形成深能级杂质,弱化器件性能,见文献 [B. Liu, Z.X. Song, Y.H. Li,K.W. Xu, Appl. Phys. Lett. 93/17 (3008)]。因此,如何选择适当的具有低电阻率和良好阻隔性能的材料来抑止Cu与Si基体或Si基介质间的相互扩散仍然是工业界和学术界的研究热点问题。
国际半导体发展规划预言,2016年14 nm节点技术要求其互连结构中阻挡层厚度缩减至2 nm,见文献[The international Technology Roadmap for Semiconductors(ITRS), 2003]。传统阻挡层材料如Ta/TaN在此尺度下的稳定性面临巨大挑战。诸多文献研究表明采用Cu基合金(CuM (M=Ti、Mg、Ti、Al、 Ti、 Ru、WN、等))直接沉积在Si或SiO2基体上,通过后续退火处理驱使合金元素扩散至Cu(M)/Si界面并反应形成数纳米厚钝化层,如TiSiyOx,TiOx,TiOx,MgO和AlyOx等的自形成阻挡层技术可能是解决此技术瓶颈的一种有效途径,见文献[Kohama K, Ito K, Tsukimoto S, Mori K, Maekawa K, Murakami M. J.Electron. Mater., 2008, 37: 1148]和[Iijima J, Haneda M , Koike J. Proc IEEEIITC 2006, 155]。然而,在升温初期,尚未达到合金元素扩散所需的热动力学条件(通常大于400℃)时,合金中的Cu原子与Si或SiO2基介质间已发生互扩散反应(<300℃),最终引发器件性能恶化,见文献[Liu A Y, Cohen M L. Phys. Rev. B, 1990, 41(15): 10727]和[Aboelfotoh M O, Svensson B G. Phys. Rev. B, 1991, 44(23): 12742]。
近年来,铜锗化合物作为一种潜在的低温Cu金属化材料而备受人们关注。研究表明,Cu 在低温度下(<150℃)和Ge原子反应形成低阻ε-Cu3Ge (~5.5 μΩ cm)且成分可调范围宽(Ge含量在25-40 %);再者,Cu3Ge具有高的抗氧化和阻挡Cu的扩散性能并可作浅结器件欧姆接触首选材料,见文献[Liu C Y, Wang S J. J. Electron. Mater., 2003; 32:L1]和[Tsukimoto S, Morita T, Moriyama M, Ito K , Murakami M. J. Electron.Mater., 2005; 34: 592]。然而,仍存在两个关键性的问题制约其在Cu金属化制程中的应用:其一,Borek等人 [Borek M A, Oktyabrsky S, Aboelfotoh M O, Narayan J. Appl.Phys. Lett., 1996; 69(23): 3560] 的研究表明, Cu3Ge/Si在温度高于400℃时两者发生互扩散,Si原子扩散至Cu3Ge体内并导致电阻率显著升高;其二,Gaudet等人 [Gaudet S,Detavernier C, Kellock A J, Desjardins P, Lavoie C. J. Vac. Sci. Technol.,2006, A 24: 474] 研究表明Cu3Ge膜体表面形貌在高于350 ℃退火条件下已经开始明显粗化,这显然远不能满足Cu互连工艺的要求。
发明内容
本发明的目的在于针对上述Cu互连技术中自形成阻挡层材料性能研究面临的不足,提供一种可控自形成Cu3Ge/TiN双层扩散阻挡层制备方法,该方法不仅简便易行,而且通过该方法获取的Cu3Ge/TiN双层自形成扩散阻挡层电阻率低、抗氧化性强,且能够进一步有效阻挡Cu的扩散,是当今先进纳器件互连提供了一种新的技术途径。
为达到上述目的,本发明基本思想是:采用气相物理共溅射技术在Cu膜中同时掺入Ge和Ti合金元素,所制备Cu(Ge,Ti)/Si样品在N2气氛下经不同温度退火,利用Cu(Ge,Ti)合金层中各元素在N2气氛退火过程中能自发选择性在Si/Cu(Ge,Ti)/Cu界面反应自形成Cu3Ge/TiN双层阻挡层,有效阻挡Cu与Si基体的相互扩散。选择Ti为掺杂元素主要基于以下几点理由:首先,400℃下Cu和Ge与 Ti都不互溶,Ti元素掺杂不会阻碍Cu与Ge的反应;其次,较高温度下Ti易从Cu基合金沉淀析出,并能与N进一步反应能形成数纳米厚的TiN稳定的化合物层,Cu3Ge/TiN双层阻挡层相结合进一步提高多层膜系热稳定性。
本发明提供的技术方案是:提供一种可控自形成Cu3Ge/TiN双层扩散阻挡层制备方法,先通过在常温下利用气相物理沉积技术获取Cu(Ge,Ti)合金,随后在N2气氛下对其控温退火处理自反应合成阻挡层,其特征在于包含以下步骤:
a、清洗衬底材料:
将衬底材料Si(111)基体依次放入丙酮、无水乙醇中分别进行30分钟超声波清洗,干燥后放入真空室内,抽真空度至4.5×10-4 Pa;
b、沉积前对衬底的处理:
保持真空室真空为4.5×10-4 Pa条件下,采用偏压反溅射清洗10分钟、预溅射清洗5分钟,去除Si衬底和靶材表面杂质;反溅射功率为100-200 W;预溅射功率为100-200 W;反溅射偏压和预溅射偏压分别为-500 V、-150 V;反溅射和预溅射气体均为Ar;工作真空度为1.0-3.0 Pa;
c、沉积Cu(Ge,Ti)合金层:
采用气相物理共溅射技术,在步骤b得到的Si(111)基体上使用磁控Cu靶、磁控Ge靶和直流Ti靶共溅射沉积Cu(Ge,Ti)合金层,沉积时间30-40秒;磁控Cu靶溅射功率为120-150 W;磁控Ge靶的溅射功率为100-120 W;直流Ti靶溅射功率为80-100 W;偏压为-100到-300 V之间;工作气氛Ar,Ar流量为180 标准立方厘米/分钟(sccm);工作真空度为0.40-0.50 Pa;沉积完成后关闭磁控Cu靶、磁控Ge靶和直流Ti靶,关闭气体Ar,恢复反应室真空为4.5×10-4 Pa,冷却后出炉样品即为Cu(Ge,Ti)合金层;
所述磁控Cu靶、磁控Ge靶和直流Ti靶纯度均为99.99%。
所述可控自形成阻挡层用Cu(Ge,Ti)合金采用磁控Cu靶、磁控Ge靶和直流Ti靶共溅射的方法,磁控Cu靶、磁控Ge靶与真空腔中心轴线方向呈45夹角,直流Ti靶与真空腔中心轴线方向一致。
所述可控自形成阻挡层用Cu(Ge,Ti)合金沉积过程中通过调节各磁控靶材的功率来控制合金中各组元的成分,磁控Cu靶溅射功率为150 W,磁控Ge靶溅射功率为120 W,直流Ti靶溅射功率为80 W。
上述步骤c中的冷却是在反应室基底真空度为4.5×10-4下自然冷却。
d、控温N2气氛退火反应自形成Cu3Ge/TiN双层阻挡层:
采用真空退火炉退火处理,本底真空为4.5×10-3 Pa,随后退火炉腔内通入N2气,Ar流量为260 标准立方厘米/分钟(sccm),设置在300 ℃和400 ℃段各保温10分钟,升温速率为5 ℃/秒。退火处理后随炉冷却,即能获得自形成Cu3Ge/TiN双层扩散阻挡层。
本发明与现有技术相比具有以下有益效果:
1、 本发明在单晶Si基体上沉积Cu(Ge,Ti)合薄膜,利用Cu(Ge,Ti)合金层中各元素在高温退火过程中能自发选择性在Si/Cu(Ge,Ti)/Cu界面反应自形成Cu3Ge/TiN双层阻挡层,其在750 ℃条件下仍能有效阻挡Cu与Si基体的相互扩散;
2、 本发明使用的Si/Cu(Ge,Ti)/Cu结构,无需传统工艺中沉积扩散阻挡层和电镀Cu籽晶层等步骤,Cu(Ge,Ti)合金层表面可直接电镀Cu且仅需通过控温N2气氛退火处理,可反应自形成Cu3Ge/TiN双层阻挡层,简化了Cu金属化制程的工艺步骤;
3、本发明采用Cu(Ge,Ti)合金可控自形成Cu3Ge/TiN双层阻挡层能有效降低互连膜系电阻率,降低互连电路的阻容耦合(RC)延迟效应,提高半导体器件的运行速度和稳定性。
4、本发明采用的是气相物理共溅射技术,具有技术成熟,成本低,工艺稳定性强,污染物少的特点,并可与现有的微电子制备工艺相兼容。
附图说明
图1为Cu(Ge,Ti) (20 nm)/Si样品在400 ℃退火态的截面高分辨透射明场像(HRTEM)。
图2为Cu (100nm)/Cu(Ge,Ti)(20 nm)/Si样品方块电阻率随退火温度变化曲线。
具体实施方式
下面结合附图及实施例对本发明进行详细的说明,但不意味着对本发明保护内容的任何限定。
本发明提供一种可控自形成Cu3Ge/TiN双层扩散阻挡层制备方法,先通过在常温下利用气相物理沉积技术获取Cu(Ge,Ti)合金,随后对其控温退火处理自反应合成阻挡层。所用磁控Cu靶、磁控Ge靶和直流Ti靶的纯度均为99.99%;所用磁控Cu靶、磁控Ge靶与真空腔中心轴线方向呈45夹角偏头,直流Ti靶与真空腔中线轴线方向一致,三靶共溅射沉积获得样品;制备的Cu(Ge,Ti)合金层厚度为20 nm。采用真空退火炉退火处理,本底真空为4.5×10-3 Pa,随后退火炉通入N2气,N2流量为260 sccm,设置在300 ℃和400 ℃段各保温10分钟,升温速率为5 ℃/秒。退火处理后随炉冷却,即能获得自形成Cu3Ge/TiN双层扩散阻挡层。
实施例1
本实施例制备可控自形成Cu3Ge/TiN双层扩散阻挡层包含以下步骤:
a、清洗衬底材料:
将衬底材料Si(111)基体依次放入丙酮、无水乙醇中分别进行30分钟超声波清洗,干燥后放入真空室内,然后抽真空度至4.5×10-4 Pa;
b、沉积前对衬底的处理:
在步骤a的真空条件下,用偏压反溅射清洗10分钟、预溅射清洗5分钟,去除Si衬底和靶材表面杂质;反溅射功率为150 W;预溅射功率为150 W;反溅射偏压和预溅射偏压分别为-500 V、-150 V;反溅射和预溅射气体均为Ar;工作真空度为2.0 Pa;
c、沉积Cu(Ge,Ti)合金层:
采用气相物理共溅射技术,在步骤b得到的Si(111)基体上使用磁控Cu靶、磁控Ge靶和直流Ti靶共溅射沉积Cu(Ge,Ti)合金层,沉积时间30秒;磁控Cu靶溅射功率为150 W;磁控Ge靶溅射功率为120 W;直流Ti靶的溅射功率为80 W;偏压为-150 V;工作气氛Ar,Ar流量为180 sccm;工作真空度为0.49 Pa;沉积完成后关闭磁控Cu靶、磁控Ge靶和直流Ti靶,关闭气体Ar,恢复反应室真空度为4.5×10-4 Pa,冷却后出炉样品即为Cu(Ge,Ti)合金层。
d、控温退火反应自形成Cu3Ge/TiN双层阻挡层:
采用真空退火炉退火处理,本底真空为4.5×10-3 Pa,随后退火炉通入Ar,Ar流量为200 sccm,设置在300 ℃和400 ℃段各保温10分钟,升温速率为5 ℃/秒。退火处理后随炉冷却,即能获得自形成Cu3Ge/TiN双层扩散阻挡层。
对上述实施例1所述的Cu/Cu(Ge,Ti)/Si样品采用四探针测试仪对其表面进行测试,先后在样品表面测试了5个点,取其平均值计算电阻率为7.9 μΩ.cm,相比常规阻挡层电阻率而言大幅降低。图1示出Cu(Ge,Ti)/Si 样品在400 ℃保温退火1小时后的截面高分辨透射电镜明场像(HRTEM),可见在Cu/Si界面处自发形成了Cu3Ge/TiN双层扩散阻挡层,其中 TiN层约4 nm,图中各层界面清晰,未发现有Cu-Si化合物出现,表明Cu3Ge/TiN双层扩散阻挡层有效阻挡了Cu/Si间互扩散。图2所示为Cu/Cu(Ge,Ti)/Si分别在沉积态和不同退火温度退火后电阻率的变化。从图2结果可知750℃高温退火后多层膜系的电阻率并未出现显著变化,亦表明自形成Cu3Ge/TiN双层扩散阻挡层在750℃情况下未发生失效,具有高的热稳定性能。
实施例2
因Cu(Ge,Ti)合金成分的变化直接关联自形成Cu3Ge/TiN双层扩散阻挡层的成分、厚度和微观结构等。通过调控Cu(Ge,Ti)合金成分可实现多种自形成Cu3Ge/TiN双层扩散阻挡层。本实施例Cu(Ge,Ti)合金层所用镀膜设备和其他工作条件均与实施例1基本相同,并保持所述合金层沉积厚度20 nm不变,通过改变磁控磁控Cu靶、磁控Ge靶和直流Ti靶的溅射功率可调控Cu(Ge,Ti)合金层中Cu、Ge、Ti的原子百分比,如选定直流靶Ti功率分别为50 W、80 W、120 W、150 W、进而调控Ti原子的百分含量在3.5、7.8、11.5、15.8 (at.%),进而实现自形成Cu3Ge/TiN双层扩散阻挡层中TiN层的厚度、电阻率和耐高温性等性能进行调控,以满足产品用途的使用需求。
实施例3
由于在沉积Cu(Ge,Ti)合金层过程中,溅射偏压对涂层成分、均匀度及结构影响较大。本实例沉积Cu(Ge,Ti)合金层操作步骤及条件、参数与实例1基本相同。只是在沉积Cu(Ge,Ti)合金层层时通过分别改变沉积偏压,如选定沉积偏压为-50 V、-100 V、-150 V、-200 V,可对Cu(Ge,Ti)合金层的成分,均匀度和厚度进行调控,进而实现自形成Cu3Ge/TiN双层扩散阻挡层中Cu3Ge/TiN各层的厚度、电阻率和耐高温性等性能进行调控,以满足不同互连工艺用途的使用需求。
Claims (5)
1.一种可控自形成Cu3Ge/TiN双层扩散阻挡层,先通过在常温下利用气相物理共溅射沉积技术获取Cu(Ge,Ti)合金,随后对其在N2气氛下控温退火处理自反应合成Cu3Ge/TiN双层扩散阻挡层,其特征在于包含以下步骤:
a、清洗衬底材料:
将衬底材料Si(111)基体依次放入丙酮、无水乙醇中分别进行30分钟超声波清洗,干燥后放入真空室内,抽真空度至4.5×10-4 Pa;
b、沉积前对衬底的处理:
保持真空室真空为4.5×10-4 Pa条件下,采用偏压反溅射清洗10分钟、预溅射清洗5分钟,去除Si衬底和靶材表面杂质;反溅射功率为100-200 W;预溅射功率为100-200 W;反溅射偏压和预溅射偏压分别为-500 V、-150 V;反溅射和预溅射气体均为Ar;工作真空度为1.0-3.0 Pa;
c、沉积Cu(Ge,Ti)合金层:
采用气相物理共溅射沉积技术,在步骤b得到的Si(111)基体上使用磁控Cu靶、磁控Ge靶和直流Ti靶共溅射沉积Cu(Ge,Ti)合金层,沉积时间30-40秒;磁控Cu靶溅射功率为120-150 W;磁控Ge靶的溅射功率为100-120 W;直流Ti靶溅射功率为80-100 W;偏压为-100到-300 V之间;工作气氛Ar,Ar流量为180 标准立方厘米/分钟(sccm);工作真空度为0.40-0.50 Pa;沉积完成后关闭磁控Cu靶、磁控Ge靶和直流Ti靶,关闭气体Ar,恢复反应室真空为4.5×10-4 Pa,冷却后出炉样品即为Cu(Ge,Ti)合金层;
d、控温N2气氛退火反应自形成Cu3Ge/TiN双层阻挡层:
采用真空退火炉退火处理,本底真空为4.5×10-3 Pa,随后退火炉腔内通入N2气,N2气流量为260 标准立方厘米/分钟(sccm),设置在300 ℃和400 ℃段各保温10分钟,升温速率为5 ℃/秒;退火处理后随炉冷却,即能获得自形成Cu3Ge/TiN双层扩散阻挡层。
2.根据权利要求1所述自形成Cu3Ge/TiN双层扩散阻挡层用Cu(Ge,Ti)合金制备工艺,其特征在于:所述磁控Cu靶、磁控Ge靶和直流Ti靶纯度均为99.99%。
3.根据权利要求1所述自形成Cu3Ge/TiN双层扩散阻挡层用Cu(Ge,Ti)合金制备工艺,其特征在于:采用磁控Cu靶、磁控Ge靶和直流Ti靶共溅射沉积的方法,磁控Cu靶、磁控Ge靶与真空腔中心轴线方向呈45˚夹角,直流Ti靶与真空腔中心轴线方向一致。
4.根据权利要求1所述自形成Cu3Ge/TiN双层扩散阻挡层用Cu(Ge,Ti)合金制备工艺,其特征在于:沉积过程中通过调节各磁控靶及直流靶的功率来控制Cu(Ge,Ti)合金中各组元的成分,磁控Cu靶溅射功率为150 W,磁控Ge靶溅射功率为120 W,直流Ti靶溅射功率为80W。
5.根据权利要求1所述自形成Cu3Ge/TiN双层扩散阻挡层的制备工艺,其中Cu3Ge/TiN双层扩散阻挡层是通过对Cu (Ge,Ti)合金控温退火工艺处理获得,其特征在于:步骤d中真空退火炉本底真空为4.5×10-3 Pa,随后退火炉通入N2气, N2流量为260 标准立方厘米/分钟(sccm), 设置在300 ℃和400 ℃段各保温10分钟,升温速率为5 ℃/秒,退火处理后随炉自然冷却,即能获得自形成Cu3Ge/TiN双层扩散阻挡层。
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