Cryogenic etching of porous material

Zhang Quan-Zhi; Zhang Lei-Yu; Ma Fang-Fang; Wang You-Nian

doi:10.7498/aps.70.20202245

Abstract

With the shrinkage of chip feature sizes, porous materials are widely used in microelectronics. However, they are facing severe challenges in plasma etching, as the reactive radicals can diffuse into the interior of material and damage the material, which is called plasma induced damage. In this paper, we review two kinds of etching processes based on low chuck temperature, i.e. cryogenic etching. By lowering the chuck temperature, either the etching by-products or the precursor gas can condense in the porous material, and thus preventing the radicals from diffusing and protect the material from being damaged by plasma. The technology of cryogenic filling inside the porous material is simple but effective, which allows it to have a good application prospect.

Keywords:

Authors and contacts

School of Physics, Dalian University of Technology, Dalian 116024, China

Corresponding author: Wang You-Nian, ynwang@dlut.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 11675036, 11935005) and the Scientific Research Foundation from Dalian University of Technology, China (Grant No. DUT19RC(3)045)

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References

[1]	Sicard E, Boyer A 2019 EMC Compo Haining, China, October 21–23, 2019 ffhal-02403882
[2]	Iwai H 2007 Second International Conference on Industrial and Information Systems, Sri Lanka, August 8−11, 2007 p571
[3]	王婷婷, 叶超, 宁兆元, 程珊华 2005 54 892 Google Scholar Wang T T, Ye C, Ning Z Y, Cheng S H 2005 Acta Phys. Sin. 54 892 Google Scholar
[4]	Zhang L, Marneffe J F, Heyne M, Naumov S, Sun Y T, et al. 2015 ECS J. Solid State Sci. Technol. 4 N3098 Google Scholar
[5]	Baklanov M, Marneffe J F, Shamiryan D, Urbanowicz A, Shi H, Rakhimova T, Huang H, Ho P 2013 J. Appl. Phys. 113 041101 Google Scholar
[6]	Lionti K, Volksen W, Magbitang T, Darnon M, Dubois G 2015 ECS J. Solid State Sci. Technol. 4 N3071 Google Scholar
[7]	Frot T, Volksen W, Purushothaman S, Bruce R, Dubois G 2011 Adv. Mater. 23 2828 Google Scholar
[8]	Frot T, Volksen W, Purushothaman S, Bruce R L, Magbitang T, Miller D C, Deline V R, Dubois G 2012 Adv. Funct. Mater. 22 3043 Google Scholar
[9]	Tachi S, Tsujimoto K, Okudaira S 1988 Appl. Phys. Lett. 52 616 Google Scholar
[10]	Tachi S, Tsujimoto K, Arai S, Kure T 1991 J. Vac. Sci. Technol., A 9 796 Google Scholar
[11]	Tsujimoto K, Okudaira S, Tachi S 1991 Jpn. J. Appl. Phys. 30 3319 Google Scholar
[12]	Zhang L, Ljazouli R, Lefaucheux P, Tillocher T, Dussart R, Mankelevich Y A, de Marneffe J F, de Gendt S, Baklanov M R 2013 ECS Solid State Lett. 2 N5 Google Scholar
[13]	Zhang L, Ljazouli R, Lefaucheux P, Tillocher T, Dussart R, Mankelevich Y A, de Marneffe J F, de Gendt S, Baklanov M R 2013 ECS J. Solid State Sci. Technol. 2 N131 Google Scholar
[14]	Zhang L, de Marneffe J F, Leroy F, Lefaucheux P, Tillocher T, Dussart R, Maekawa K, Yatsuda K, Dussarrat C, Goodyear A, Cooke M, De Gendt S, Baklanov M R 2016 J. Phys. D: Appl. Phys. 49 175203 Google Scholar
[15]	Dussart R, Tillocher T, Lefaucheux P, Boufnichel M 2014 J. Phys. D: Appl. Phys. 47 123001 Google Scholar
[16]	Chanson R, Zhang L, Naumov S, Mankelevich Yu A, Tillocher T, Lefaucheux P, Dussart R, De Gendt S, De Marneffe J F 2018 Sci. Rep. 8 1886 Google Scholar
[17]	Chanson R, Tahara S, Vanstreels K, de Marneffe J F 2018 Plasma Research Express 1 015006 Google Scholar
[18]	Chanson R, Dussart R, Tillocher T, Lefaucheux P, Dussarrat C, De Marneffe J F 2019 Front. Chem. Sci. Eng. 13 511 Google Scholar
[19]	Rezvanov A, Miakonkikh A, Vishnevskiy A, Rudenko K, Baklanov M 2017 J. Vac. Sci. Technol. B 35 021204 Google Scholar
[20]	Kushner M 2009 J. Phys. D: Appl. Phys. 42 194013 Google Scholar
[21]	Sankaran A, Kushner M J 2004 Vac. Sci. Technol., A 22 1242
[22]	胡艳婷, 张钰如, 宋远红, 王友年 2018 67 225203 Google Scholar Hu Y T, Zhang Y R, Song Y H, Wang Y N 2018 Acta Phys. Sin. 67 225203 Google Scholar
[23]	蒋相占, 刘永新, 毕振华, 陆文琪, 王友年 2012 61 015204 Google Scholar Jiang X Z, Liu Y X, Bi Z H, Lu W Q, Wang Y N 2012 Acta Phys. Sin. 61 015204 Google Scholar
[24]	Zhang Q Z, Tink S, De Marneffe J F, Zhang L P, Bogaerts A 2017 Appl. Phys. Lett. 111 173104 Google Scholar
[25]	Zhang Q Z, Jiang W, Hou L J, Wang Y N 2011 J. Appl. Phys. 109 013308 Google Scholar

Cited By

图 1 (a)等离子体损伤示意图; (b)无等离子体损伤和(c)等离子体损伤后的low-k多孔材料化学结构^[6]

Figure 1. (a) Schematic of plasma induced damage; chemical structure of low-k porous materials (b) before plasma damage and (c) same structure after plasma damage^[6].

DownLoad: Full-Size Img PowerPoint

图 2 多孔材料无损伤刻蚀技术: P4, 极低温刻蚀, 低温刻蚀(利用刻蚀前驱气体凝结作用)^[14]

Figure 2. Damage free etching of porous low-k material: Post porosity plasma protection (P4), cryogenic etch and low temperature etch using precursor condensation^[14].

DownLoad: Full-Size Img PowerPoint

图 3 OSG-2.0材料刻蚀前后的FTIR谱线　(a)无偏压刻蚀; (b)有偏压刻蚀^[13]

Figure 3. FTIR spectra of OSG-2.0 material (before and after plasma etching): (a) Without bias; (b) with bias^[13].

DownLoad: Full-Size Img PowerPoint

图 4 OSG-2.0材料在不同基片温度下的刻蚀率^[13]

Figure 4. Etching rate of OSG-2.0 material at different chuck temperature^[13].

DownLoad: Full-Size Img PowerPoint

图 5 等离子体刻蚀后OSG-2.0材料的介电常数k值　(a)纯SF₆等离子体刻蚀; (b) SiF₄/O₂/SF₆等离子体^[13]

Figure 5. k value of OSG-2.0 material (before and after plasma etching): (a) Pure SF₆ plasma etching; (b) SiF₄/O₂/SF₆ plasma etching^[13].

DownLoad: Full-Size Img PowerPoint

图 6 不同基片温度下, 多孔材料在CF₃Br等离子体中的刻蚀率和材料折射率^[19]

Figure 6. Etching rate and refractive rate of porous material after CF₃Br plasma etching at various chuck temperature^[19].

DownLoad: Full-Size Img PowerPoint

图 7 在不同温度下, CF₃Br等离子体刻蚀多孔材料的FTIR谱线　(a)加热处理前; (b)加热处理后^[19]

Figure 7. FTIR spectra of porous material after CF₃Br plasma etching: (a) Before annealing; (b)after annealing^[19].

DownLoad: Full-Size Img PowerPoint

图 8 不同基片温度下, 多孔材料在CF₄等离子体中的刻蚀率和材料折射率^[19]

Figure 8. Etching rate and refractive rate of porous material after CF₄ plasma etching at various chuck temperature^[19].

DownLoad: Full-Size Img PowerPoint

图 9 多孔材料内部分别充入SF₆和C₄H₈气体后, 在不同温度下的折射率(反应气体的凝结比例, 1 Torr = 1.33322×10² Pa)^[14]

Figure 9. Change of refractive index as a function of temperature, showing the condensation of pure SF₆ or C₄H₈ into a porous low-k SBA-2.2^[14].

DownLoad: Full-Size Img PowerPoint

图 10 C₄F₈/SF₆等离子体刻蚀多孔材料　(a)折射率; (b)刻蚀率; (c)介电常数k^[14]

Figure 10. Plasma etch results with mixture of C₄F₈/SF₆ at different chuck temperature: (a) Refractive index; (b) etching rate; (c) k value^[14].

DownLoad: Full-Size Img PowerPoint

图 11 多孔材料内部分别充入HBPO, SF₆和C₄F₈气体后, 在不同温度下的折射率(反应气体的凝结比例)^[16]

Figure 11. Refractive index of porous material at various chuck temperature in HBPO, SF₆ and C₄F₈ gas^[16].

DownLoad: Full-Size Img PowerPoint

图 12 不同温度下, HBPO等离子体刻蚀多孔材料后的介电常数^[16]

Figure 12. k value of porous material after HBPO plasma etching at various chuck temperature^[16].

DownLoad: Full-Size Img PowerPoint

图 13 多种工艺气体在不同温度下, 对多孔材料刻蚀过程中的刻蚀率和介电常数k值^[18]

Figure 13. Etching rate and k value of porous material for different gas discharge as a function of chuck temperature^[18].

DownLoad: Full-Size Img PowerPoint

图 14 计算得到的不同温度下的刻蚀轮廓　(a) –50 ℃; (b) –95 ℃; (c) –104 ℃; (d) –110 ℃; (e) –115 ℃; (f) –120 ℃^[24]

Figure 14. Etching profiles at various chuck temperature: (a) –50 ℃; (b) –95 ℃; (c) –104 ℃; (d) –110 ℃; (e) –115 ℃; (f) –120 ℃^[24].

DownLoad: Full-Size Img PowerPoint

图 15 不同基片温度(–50, –104, –120 ℃)下3个时刻(t₁, t₂, t₃)的刻蚀轮廓^[24]

Figure 15. Evolution of etching profiles at various chuck temperature (–50, –104, –120 ℃)^[24].

DownLoad: Full-Size Img PowerPoint

图 16 SF₆/C₄F₈等离子体刻蚀多孔材料的截面结构　(a) –50 ℃刻蚀后结构; (b) –50 ℃刻蚀后浸到dHF酸溶液30 s; (c) –110 ℃刻蚀后结构; (d) –110 ℃刻蚀后浸到dHF酸溶液30 s^[24]

Figure 16. Cross-sectional images of narrow spacing trench profiles: (a) –50 ℃, after plasma etching; (b) –50 ℃, after plasma etching and 0.5% dHF dip 30 s; (c) –110 ℃, after plasma etching; (d) –110 ℃, after plasma etching and 0.5% dHF dip 30 s ^[24].

DownLoad: Full-Size Img PowerPoint

图 17 低温刻蚀–50 ℃时, (a) F密度分布, (b) C₂F₄自由基分布, (c)离子能量分布; 低温刻蚀–120 ℃时, (d) F密度分布, (e) C₂F₄自由基分布, (f)离子能量分布^[24]

Figure 17. Calculated (a) and (d) F atom density (in cm^–3), (b) and (e) C₂F₄ molecule density (in cm^–3), and (c) and (f) normalized ion energy and angular distributions, at –50 ℃ (a)–(c) and –120 ℃ (d)–(f)^[24]

DownLoad: Full-Size Img PowerPoint

表 1 等离子体材料损伤检测手段^[6]

Table 1. Characterization methods of plasma induced damage^[6].

	优点	缺点
傅里叶变换红外光谱	通过吸收峰变化, 可表征材料化学结构变化	对操作环境较敏感, 要避免材料二次污染的影响
光谱椭偏仪测量	通过反射率变化, 可间接推测介电常数等变化	需要额外数据处理
dHF酸浸泡法	操作简单, 易观测损伤	使用化学试剂, 腐蚀损伤材料

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[1]	Sicard E, Boyer A 2019 EMC Compo Haining, China, October 21–23, 2019 ffhal-02403882
[2]	Iwai H 2007 Second International Conference on Industrial and Information Systems, Sri Lanka, August 8−11, 2007 p571
[3]	王婷婷, 叶超, 宁兆元, 程珊华 2005 54 892 Google Scholar Wang T T, Ye C, Ning Z Y, Cheng S H 2005 Acta Phys. Sin. 54 892 Google Scholar
[4]	Zhang L, Marneffe J F, Heyne M, Naumov S, Sun Y T, et al. 2015 ECS J. Solid State Sci. Technol. 4 N3098 Google Scholar
[5]	Baklanov M, Marneffe J F, Shamiryan D, Urbanowicz A, Shi H, Rakhimova T, Huang H, Ho P 2013 J. Appl. Phys. 113 041101 Google Scholar
[6]	Lionti K, Volksen W, Magbitang T, Darnon M, Dubois G 2015 ECS J. Solid State Sci. Technol. 4 N3071 Google Scholar
[7]	Frot T, Volksen W, Purushothaman S, Bruce R, Dubois G 2011 Adv. Mater. 23 2828 Google Scholar
[8]	Frot T, Volksen W, Purushothaman S, Bruce R L, Magbitang T, Miller D C, Deline V R, Dubois G 2012 Adv. Funct. Mater. 22 3043 Google Scholar
[9]	Tachi S, Tsujimoto K, Okudaira S 1988 Appl. Phys. Lett. 52 616 Google Scholar
[10]	Tachi S, Tsujimoto K, Arai S, Kure T 1991 J. Vac. Sci. Technol., A 9 796 Google Scholar
[11]	Tsujimoto K, Okudaira S, Tachi S 1991 Jpn. J. Appl. Phys. 30 3319 Google Scholar
[12]	Zhang L, Ljazouli R, Lefaucheux P, Tillocher T, Dussart R, Mankelevich Y A, de Marneffe J F, de Gendt S, Baklanov M R 2013 ECS Solid State Lett. 2 N5 Google Scholar
[13]	Zhang L, Ljazouli R, Lefaucheux P, Tillocher T, Dussart R, Mankelevich Y A, de Marneffe J F, de Gendt S, Baklanov M R 2013 ECS J. Solid State Sci. Technol. 2 N131 Google Scholar
[14]	Zhang L, de Marneffe J F, Leroy F, Lefaucheux P, Tillocher T, Dussart R, Maekawa K, Yatsuda K, Dussarrat C, Goodyear A, Cooke M, De Gendt S, Baklanov M R 2016 J. Phys. D: Appl. Phys. 49 175203 Google Scholar
[15]	Dussart R, Tillocher T, Lefaucheux P, Boufnichel M 2014 J. Phys. D: Appl. Phys. 47 123001 Google Scholar
[16]	Chanson R, Zhang L, Naumov S, Mankelevich Yu A, Tillocher T, Lefaucheux P, Dussart R, De Gendt S, De Marneffe J F 2018 Sci. Rep. 8 1886 Google Scholar
[17]	Chanson R, Tahara S, Vanstreels K, de Marneffe J F 2018 Plasma Research Express 1 015006 Google Scholar
[18]	Chanson R, Dussart R, Tillocher T, Lefaucheux P, Dussarrat C, De Marneffe J F 2019 Front. Chem. Sci. Eng. 13 511 Google Scholar
[19]	Rezvanov A, Miakonkikh A, Vishnevskiy A, Rudenko K, Baklanov M 2017 J. Vac. Sci. Technol. B 35 021204 Google Scholar
[20]	Kushner M 2009 J. Phys. D: Appl. Phys. 42 194013 Google Scholar
[21]	Sankaran A, Kushner M J 2004 Vac. Sci. Technol., A 22 1242
[22]	胡艳婷, 张钰如, 宋远红, 王友年 2018 67 225203 Google Scholar Hu Y T, Zhang Y R, Song Y H, Wang Y N 2018 Acta Phys. Sin. 67 225203 Google Scholar
[23]	蒋相占, 刘永新, 毕振华, 陆文琪, 王友年 2012 61 015204 Google Scholar Jiang X Z, Liu Y X, Bi Z H, Lu W Q, Wang Y N 2012 Acta Phys. Sin. 61 015204 Google Scholar
[24]	Zhang Q Z, Tink S, De Marneffe J F, Zhang L P, Bogaerts A 2017 Appl. Phys. Lett. 111 173104 Google Scholar
[25]	Zhang Q Z, Jiang W, Hou L J, Wang Y N 2011 J. Appl. Phys. 109 013308 Google Scholar

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