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热退火对等离子体增强化学气相沉积SiCOH薄膜结构与性能的影响

谭再上 吴小蒙 范仲勇 丁士进

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热退火对等离子体增强化学气相沉积SiCOH薄膜结构与性能的影响

谭再上, 吴小蒙, 范仲勇, 丁士进

Effect of thermal annealing on the structure and properties of plasma enhanced chemical vapor deposited SiCOH film

Tan Zai-Shang, Wu Xiao-Meng, Fan Zhong-Yong, Ding Shi-Jin
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  • 热退火是多孔低介电常数薄膜制备过程中的重要一环, 对薄膜结构及性能具有重要影响. 本文以四乙氧基硅烷和双戊烯为前驱体, 采用等离子体增强化学气相沉积方法制备了SiCOH薄膜, 对其进行了氮气氛围下的热退火处理, 分析了热退火对薄膜结构与性能的影响, 探究了退火过程中薄膜结构变化的可能的反应机理. 傅里叶变换红外光谱和固体核磁共振谱结果表明, 沉积薄膜是一种有机无机杂化薄膜. 退火过程中, 薄膜中的-CH2, -CH3等有机组分被分解除去, 形成了以稳定的Si-O-Si等无机组分为骨架的多孔结构, 并通过氮气吸附/脱附等温线测试得到了验证. 在此期间, 薄膜骨架微结构亦发生一系列调整, C=C, Si-C含量增加, Si、O、C等元素间发生进一步键合. C=C 含量的提高, 使得薄膜的消光系数和漏电流密度增大. 实验证明, 退火后薄膜具有低折射率、低介电常数特性, 是一类具有优异的介电性能和力学性能的材料, 作为芯片后端互连层间介质具有极大的应用潜力.
    The development of high-performance integrated circuit chips and the shrinkage of feature sizes according to Moore’s law bring forward continuously the requirements for low dielectric constant (low-k) materials with various excellent properties in the back-end-of-the-line (BEOL) interconnect. Porous SiCOH films prepared by plasma enhanced chemical vapor deposition (PECVD) through a porogen approach are widely applied to industry and extensively studied. Thermal annealing is an important process for fabricating the porous low-k films, which has a great influence on film structure as well as properties. SiCOH films are deposited by PECVD using tetraethoxysilane and limonene as precursors, and annealed at 450 ℃ for 1.5 h under nitrogen atmosphere. The evolutions of film structure and properties during thermal annealing are revealed, and the reaction mechanism for structure change is also proposed. Fourier transform inferred spectroscopy and solid state nuclear magnetic resonance results show that the as-deposited film is an organic-inorganic hybrid film composed of various kinds of Si-O-Si, -CHx, Si-O-CH2CH3, etc. The organic component is removed almost completely during thermal annealing, making a porous film with a Si-O-Si inorganic skeleton. The skeleton is also rearranged at the same time. Deconvolution of the Si-O-Si absorption band of the FTIR spectrum reveals that the cage-like Si-O-Si occupies the major part for both as-deposited and annealed films, while the amount of silicon suboxide Si-O-Si decreases and that of network Si-O-Si increases during thermal annealing, making the film more robust. More C=C and Si-C are formed through chemical reactions between Si-H, -CHx and Si-O-CH2-CH3, and crosslinking is further enhanced. Nitrogen adsorption/desorption isothermal measurement reveals that a large number of micropores with diameter less than 2-3 nm are created during thermal annealing, which is consistent with the removal of organic groups and the existence of cage-like Si-O-Si. As a result, both the refractive index and dielectric constant decrease significantly from 1.476 (λ =630 nm) and 3.45 to 1.365 and 2.60, respectively. Because of the increase of C=C after annealing, extinction coefficient and leakage current density increase. Although there is a shrinkage of 14.7% in film thickness and a reduction of mechanical properties after annealing, the Young’s modulus is still larger than 4 GPa. Considering all kinds of properties, the obtained film appears to be a competitive candidate as inter layer dielectrics in the BEOL interconnect of integrated circuits.
    • 基金项目: 国家科技重大专项(批准号: 2011ZX02703-004)资助的课题.
    • Funds: Project supported by the National Science and Technology Major Project of the Ministry of Science and Technology of China (Grant No. 2011ZX02703-004).
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    Doniat F, Anderson C, Dussarrat C, Mcandrew J, Opila R, Wright B, Yang D 2012 Microelectron. Eng. 92 34

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    Ye C, Ning Z Y 2010 Chin. Phys. B 19 553

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    Castex A, Jousseaume V, Deval J, Bruat J, Favennec L, Passemard G 2008 J. Vac. Sci. Technol. 26 1343

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    Castex A, Favennec L, Jousseaume V, Bruat J, Deval J, Remiat B, Passemard G, Pons M 2005 Microelectron. Eng. 82 416

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    Gourhant O, Gerbaud G, Zenasni A, Favennec L, Gonon P, Jousseaume V 2010 J. Appl. Phys. 108 124105

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    Gates S M, Neumayer D A, Sherwood M H, Grill A, Wang X, Sankarapandian M 2007 J. Appl. Phys. 101 94103

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    Jousseaume V, Favennec L, Zenasni A, Gourhant O 2007 Surf. Coat. Technol. 201 9248

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    Jousseaume V, Zenasni A, Favennec L, Gerbaud G, Bardet M, Simon J P, Humbert A 2007 J. Electrochem. Soc. 154 G103

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    Zenasni A, Jousseaume V, Holliger P, Favennec L, Gourhant O, Maury P, Gerbaud G 2007 J. Appl. Phys. 102 94107

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    Grill A, Neumayer D A 2003 J. Appl. Phys. 94 6697

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    Du J, Ye C, Yu X Z, Zhang H Y, Ning Z Y 2009 Acta Phys. Sin. 1 575 (in Chinese) [杜杰, 叶超, 俞笑竹, 张海燕, 宁兆元 2009 物理学报 1 575]

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    Yan J M, Zhang Q Y 1979 Adsorption and Condensation: Surface and Pores of Solids (Beijing: Liberation Press) pp111-116 (in Chinese) [严继民, 张启元 1979 吸附与凝聚: 固体的表面与孔(北京: 解放出版社)第111-116页

    [21]

    Gates S M, Dubois G, Ryan E T, Grill A, Liu M, Gidley D 2009 J. Electrochem. Soc. 156 G156

    [22]

    Jiang T, Zhu B, Ding S J, Fan Z Y, Zhang D W 2014 J. Mater. Chem. C 2 6502

    [23]

    Xu H Y, Wang X B, Wu Z Y 2006 Chem. Res. Chin. Univ. 1 104 (in Chinese) [徐洪耀, 王献彪, 吴振玉 2006 高等学校化学学报 1 104]

    [24]

    Marsik P, Verdonck P, de Roest D, Baklanov M R 2010 Thin Solid Films 518 4266

    [25]

    Baklanov M R, Zhao L, Besien E V, Pantouvaki M 2011 Microelectron. Eng. 88 990

    [26]

    Dubois G, Volksen W, Magbitang T, Miller R D, Gage D M, Dauskardt R H 2007 Adv. Mater. 19 3989

  • [1]

    Baklanov M R, Ho P S, Zschech E 2012 Advanced Interconnects for ULSI Technology (Wiley) pp x-xxi

    [2]

    Davis J A, Meindl J D (translated by Luo Z Y, Ye Z C, L Y Q, Yu W J) 2010 Interconnect Technology and Design for Gigascale Integration (Beijing: China Machine Press) pp1-3 (in Chinese) [戴维斯 J A, 梅因道 J D著(骆祖茔, 叶佐昌, 吕勇强, 喻文健 译) 2010 吉规模集成电路互连工艺及设计(北京: 机械工业出版社) 第1-3页

    [3]

    Volksen W, Miller R D, Dubois G 2010 Chem. Rev. 110 56

    [4]

    Favennec L, Jousseaume V, Rouessac V, Fusalba F, Durand J, Passemard G 2004 Mat. Sci. Semicon. Proc. 7 277

    [5]

    Grill A, Patel V 2001 Appl. Phys. Lett. 79 803

    [6]

    Favennec L, Jousseaume V, Gerbaud G, Zenasni A, Passemard G 2007 J. Appl. Phys. 102 64107

    [7]

    Grill A, Patel V 2008 J. Appl. Phys. 104 24113

    [8]

    Doniat F, Anderson C, Dussarrat C, Mcandrew J, Opila R, Wright B, Yang D 2012 Microelectron. Eng. 92 34

    [9]

    Park J, Choi J K, An C J, Jin M L, Kang S, Yun J, Kong B, Jung H 2013 J. Mater. Chem. C 1 3414

    [10]

    Ye C, Ning Z Y 2010 Chin. Phys. B 19 553

    [11]

    Castex A, Jousseaume V, Deval J, Bruat J, Favennec L, Passemard G 2008 J. Vac. Sci. Technol. 26 1343

    [12]

    Castex A, Favennec L, Jousseaume V, Bruat J, Deval J, Remiat B, Passemard G, Pons M 2005 Microelectron. Eng. 82 416

    [13]

    Gourhant O, Gerbaud G, Zenasni A, Favennec L, Gonon P, Jousseaume V 2010 J. Appl. Phys. 108 124105

    [14]

    Gates S M, Neumayer D A, Sherwood M H, Grill A, Wang X, Sankarapandian M 2007 J. Appl. Phys. 101 94103

    [15]

    Jousseaume V, Favennec L, Zenasni A, Gourhant O 2007 Surf. Coat. Technol. 201 9248

    [16]

    Jousseaume V, Zenasni A, Favennec L, Gerbaud G, Bardet M, Simon J P, Humbert A 2007 J. Electrochem. Soc. 154 G103

    [17]

    Zenasni A, Jousseaume V, Holliger P, Favennec L, Gourhant O, Maury P, Gerbaud G 2007 J. Appl. Phys. 102 94107

    [18]

    Grill A, Neumayer D A 2003 J. Appl. Phys. 94 6697

    [19]

    Du J, Ye C, Yu X Z, Zhang H Y, Ning Z Y 2009 Acta Phys. Sin. 1 575 (in Chinese) [杜杰, 叶超, 俞笑竹, 张海燕, 宁兆元 2009 物理学报 1 575]

    [20]

    Yan J M, Zhang Q Y 1979 Adsorption and Condensation: Surface and Pores of Solids (Beijing: Liberation Press) pp111-116 (in Chinese) [严继民, 张启元 1979 吸附与凝聚: 固体的表面与孔(北京: 解放出版社)第111-116页

    [21]

    Gates S M, Dubois G, Ryan E T, Grill A, Liu M, Gidley D 2009 J. Electrochem. Soc. 156 G156

    [22]

    Jiang T, Zhu B, Ding S J, Fan Z Y, Zhang D W 2014 J. Mater. Chem. C 2 6502

    [23]

    Xu H Y, Wang X B, Wu Z Y 2006 Chem. Res. Chin. Univ. 1 104 (in Chinese) [徐洪耀, 王献彪, 吴振玉 2006 高等学校化学学报 1 104]

    [24]

    Marsik P, Verdonck P, de Roest D, Baklanov M R 2010 Thin Solid Films 518 4266

    [25]

    Baklanov M R, Zhao L, Besien E V, Pantouvaki M 2011 Microelectron. Eng. 88 990

    [26]

    Dubois G, Volksen W, Magbitang T, Miller R D, Gage D M, Dauskardt R H 2007 Adv. Mater. 19 3989

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  • 收稿日期:  2014-12-12
  • 修回日期:  2015-01-04
  • 刊出日期:  2015-05-05

热退火对等离子体增强化学气相沉积SiCOH薄膜结构与性能的影响

  • 1. 复旦大学材料科学系, 上海 200433;
  • 2. 复旦大学微电子学院, 专用集成电路与系统国家重点实验室, 上海 200433
    基金项目: 国家科技重大专项(批准号: 2011ZX02703-004)资助的课题.

摘要: 热退火是多孔低介电常数薄膜制备过程中的重要一环, 对薄膜结构及性能具有重要影响. 本文以四乙氧基硅烷和双戊烯为前驱体, 采用等离子体增强化学气相沉积方法制备了SiCOH薄膜, 对其进行了氮气氛围下的热退火处理, 分析了热退火对薄膜结构与性能的影响, 探究了退火过程中薄膜结构变化的可能的反应机理. 傅里叶变换红外光谱和固体核磁共振谱结果表明, 沉积薄膜是一种有机无机杂化薄膜. 退火过程中, 薄膜中的-CH2, -CH3等有机组分被分解除去, 形成了以稳定的Si-O-Si等无机组分为骨架的多孔结构, 并通过氮气吸附/脱附等温线测试得到了验证. 在此期间, 薄膜骨架微结构亦发生一系列调整, C=C, Si-C含量增加, Si、O、C等元素间发生进一步键合. C=C 含量的提高, 使得薄膜的消光系数和漏电流密度增大. 实验证明, 退火后薄膜具有低折射率、低介电常数特性, 是一类具有优异的介电性能和力学性能的材料, 作为芯片后端互连层间介质具有极大的应用潜力.

English Abstract

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