AlCrTaTiNi/(AlCrTaTiNi)N ÖÞ

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1 Ü 49 Ü 12 Vol.49 No Ý 12 Ü ACTA METALLURGICA SINICA Dec pp AlCrTaTiNi/(AlCrTaTiNi)N ÖÞ ÏÒÜ (ÒÉ È Á¾ÈÙ Ì Ü«ÑÙ ÞÌ, ) «Æ Ô, º Ç (AlCrTaTiNi)N  AlCrTaTiNi/(AlCrTaTiNi)N Ä, Ú XRD, EDS  SEM Í Ç Æ² ¾Æ ÒÆ Ô³ Û., Cu/(AlCrTaTiNi)N/Si 500 Ì Ç Þƹ, 700 Ì Cu Ò Æ. AlCrTaTiNi Cu  (AlCrTaTiNi)N Ô. AlCrTa- TiNi/(AlCrTaTiNi)N 800 Ì Û Þ Ô Ä Û, 900 ÅºÇ ÛÖÔ Cu Si ¾, ÐÄÔµÃ, ±Ä Ç. Ó ËÆ, Ä, ³ ØÑ TN ÐÚ A Æ Ñ (2013) FABRICATION AND THERMAL STABILITY OF AlCrTaTiNi/(AlCrTaTiNi)N BILAYER DIFFUSION BARRIER ZHANG Lidong, WANG Fei, CHEN Shunli, WANG Yuan Key Laboratory for Radiation Physics and Technology of Education Ministry of China, Institute of Nuclear Science and Technology, Sichuan University, Chengdu Correspondent: CHEN Shunli, associate professor, Tel: (028) , chenshunli@scu.edu.cn Supported by National Natural Science Foundation of China (Nos and ), Program for New Century Excellent Talents in University (No.NCET ), Scientific and Technical Supporting Programs of Science and Technology Department of Sichuan Province (No.07FG ) Manuscript received , in revised form ABSTRACT The (AlCrTaTiNi)N and AlCrTaTiNi/(AlCrTaTiNi)N thin films were deposited on Si substrates as copper interconnects diffusion barriers by magnetron sputtering methods. The phase structure, phase composition and thermal stability at high temperature were investigated by XRD, EDS and SEM in this work, respectively. The results indicate that the gap could be observed between Cu and (AlCrTaTiNi)N layers when the samples were annealed at 500 for 30 min, and the Cu film fall off at 700 under visual conditions. The bonding properties of Cu and (AlCrTaTiNi)N layers can be improved by inserting a AlCrTaTiNi layer. The XRD patterns, SEM cross sectional micrographs and sheet resistance data show that the AlCrTaTiNi/(AlCrTaTiNi)N bilayers is stable up to 800. KEY WORDS high entropy alloy, bilayer diffusion barrier, thermal stability Û Ð ÑÊ, Ð Ã * Þ É Õ Â , µ ݵ¹ NCET , ÓÊÅ Ú Û Õ 07FG Ä º : , ³ º : È :, Ø, 1985 ÞÁ, Ñ Á DOI: /SP.J ³, Ãϲ«ß, Å Ê Ü Õ ««. ÈĐÄ Ã«Ü, Á ² Ù Å ÜÕ Đ, ß Û Ù Å Õ Å ÃËÅ. ß, ÌÇ (high entropy alloys, HEAs)»ÆÈÜÄÕÀÇ Ü, ¾ ß Å [1,2] [3] ¼ Ë [4,5] Ó¼ [6] Ø, Í Ñ ÕÛ. ÑÐ Cu à Š½»Æ ÕÕÛ Á [1]. Î [7 12],

2 1612 Ç Ü 49 HEAs Ó (HEANs) Ë Õ Å ß¼ Õ. ¾ Tsai Ø [8] λ, AlMoNbSi- TaTiVZr ÌÇ ÓÜß Ûŵ Cu à Si Õ. Chang à Chen [7]» ÈËÅÅ 50 nm Õ AlCrTaTiZr ÓÉ Cu à Å, È Å 900,»ÆÈÄÀÕ Ã Å Ü. ÈÁ Å Õ, Chang Ø Í ÜÈËÅ 10 nm Õ (AlCrTaTiZr)N [9], 5 nm Õ (AlCrTaTiZrRu)N 0.5 [10] Ó 4 nm Õ (AlCrRuTaTiZr)N x [11] Å., Đ Cu Õ µ, «ÐÊÅ È [12,13], ý TiZr)N/ (AlCrTaTiZr)N 0.7 Å, Å ½Õ N Å, Đ Ç ÜÕÖÕ. (AlCrTaTiZr)N 0.7 Í Õ Ê ßÈ µõ Å, ÍÑ Ã µïâ. ÓÎ, ¾Å ²¹ Ù ÜÕ Ê, ÜÛ Ù µ Å Ö ÌÇ ÕÛ À½Õ Ù. Ñ ÑÕ, ÕÛ Õ Ta/TaN Å, ½ Ta ² ¹ Ù TaN ÜÕ Ê, Å µđ Õ Ç Ü [15 22]., Õß, ÀÅ Ù º Å µõ Å [12,17]. ÓÎ, ÌÇ Å ÕÀÇ Ü, ¾É Û Å Õ» È È [14]. Î, Chang à Chen [12] ÜÈ (AlCrTa- AlCrTa- TiNi/Ó (AlCrTaTiNi)N Õ Å. ² Õ ß ºÛ ÕÕ Ó É Cu ÕÍ Ã Å, ¾ Đ, Ü. 1 Å ºÛ QX 500 2/D ÅÍ Ó, N Si(100) л ËÅ 20 nm Õ AlCrTaTiNi/(AlCrTaTiNi)N ÌÇ Ó, Ó (AlCrTaTiNi)N ÌÇ Ó. Å ÌÅ 99.95% Ta à Ti Å ÌÅ % Al à Cr Å, ÓÌÅ 99.95%Õ Ni. ± À ʵÍ, 15 min. Ú Pa. Ó ÏÀ¾ : Si Û ÕÍ (AlCrTaTiNi)N Ó, ½ Ar N 2 ÏÅ 1 1, Ê¾É Ê Á 0.6 Pa, 80 W. Í (AlCrTaTiNi)N AlCrTaTiNi Ó, Ê Ar ¾É Ê 0.6 Pa, Á².» (AlCrTaTiNi)N ÓÊݺ۾ Đ. Å Ê» Í, ºÛ³Ï ËÅÅ 100 nm Õ Cu(Cu Å, 99.95%), ½ Ar ¾É Ê 0.6 Pa, 100 W.» ÍÛ, 500, 600, 700, 800 à min, ½ Ú Pa, Ê ÅÜ Pa. ÛÔß (FPP) ½ ½Å Ó Å. Û D/Max 3A X ½ (XRD) Ó Ð½ (CuK α, 40 kv, 40 ma). ºÛ X Pert Pro MPD ½ ± (CuK α, 30 kv, 40 ma, ÅÅ 2 ). Û (FESEM, S 4800) Ó ÕÜ ± (EDS) ½ ÓÕ Ã. 2 ÅÔÐ Ù 2.1 ÎÛ 1 EDS ݽÑÕ AlCrTaTiNi à (Al- CrTaTiNi)N ÓÕ. ½»Æ, Ó½» Õ 5% 35%Õ Ú, ÌÇ [1]. (AlCrTaTiNi)N ½ N Õ Å 50%, Õ ÃÅ 50%. 2.2 (AlCrTaTiNi)N ß Ý «1 Cu/(AlCrTaTiNi)N/Si ÍÕ SEM. Ý«, ß Cu à (AlCrTa- TiNi)N ², Æ» ¹ min Í, Õ ³ Æ»» («1b). Û ÅÕÄ, ºÎß Å («1c), 700 Ê, Ö Cu Ó. ÎÊ (AlCrTaTiNi)N Đ Si ÚÕ ¹, Ð (AlCrTaTiNi)N à Cu Õ Ç Ü, Ü Ó Ã Cu Õ µ Ý [13,23], Cu Õ µ , Õ µ Ù, ¾ TaN , TiN , AlN [24]. µ à µ Í Â»Ð ÕÁ, Ë Ê Ó ½ [25 27], ÍÑ (AlCrTa- TiNi)N à Cu Í Ù, Í Cu Ó. 2.3 AlCrTaTiNi/(AlCrTaTiNi)N Đ ß Ý «2 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ßÓ² Å ÍÕ XRD., Û 1 EDS ¾Ò AlCrTaTiNi Ä (AlCrTaTiNi)N ÔÖ Table 1 Compositions of AlCrTaTiNi and (AlCrTaTiNi)N thin films by EDS (atomic fraction, %) Film Al Cr Ta Ti Ni N AlCrTaTiNi (AlCrTaTiNi)N

3 Ü 12 : AlCrTaTiNi/(AlCrTaTiNi)N à ӹ Ѳ Đ 1613 Intensity, a.u. (012) 3 (111) Cu Si Cu (300) Cu Si 3 (200) Cu Cu 4 Si Annealing at 900 o C Annealing at 800 o C Annealing at 700 o C As-deposited , deg 2 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÞÒ± ÌÔ XRD Fig.2 XRD patterns of the Cu/AlCrTaTiNi/ (AlCrTa- TiNi)N/Si samples with as deposited and different temperature annealed Square resistance, Temperature, o C 1 Cu/(AlCrTaTiNi)N/Si ÞÒ ÌÔÆ SEM Fig.1 SEM images of the cross section of Cu/(AlCr- TaTiNi)N/Si sample (HEANs indicates (AlCrTa- TiNi)N, dotted lines present the interface of different layer) (a) as deposited (b) annealing at 500 for 30 min (c) annealing at 600 for 30 min ÅÕ Ä, (111) Cu ¹, ÊÆß Õ (200) Cu Æ». ßÎ, (111) Cu ß ÀÕ¼ ÜÁ [28 30]. 900 Í, (111) Cu à (200) Cu È, Æ»È ÅÕ Cu Si. Ð ÎÊ Cu Đ Si Â, Â È Ü, Å È. «3 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÅÛ Å Õ ½. 700 Í µõ ÅÆ», Ý Cu ÀÃ,, À, Ý Õ Åà Đ, ÓÎ µõ Å Ù [31]. Å 3 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÐÄÚ Ô Fig.3 Square resistance vs temperature of the Cu/AlCr- TaTiNi/(AlCrTaTiNi)N/Si before and after annealing 900 Ê, µõ ÅÕ Ä, Ç«2 Õ XRD, ±ÎÊ ÓÚ Â È ÅßÕ Cu Si. «4 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÍÕ SEM. 800 Å Í, µ Á, (AlCrTaTiNi)N Đ AlCrTaTiNi Õ ÑÎ, Ü Ý N Ù Å Õ.»,» Õ Ç Ü À. Ó Cu à ÌÇ AlCrTaTiNi Õ µ [14] ², Cu , Al , Cr , Ni , Ti , Ta ÌÇ Õ µ ÏÜÙ [32] : α = Σα i i% (1) Ͻ, α ÌÇ Õ µ, α i Ç Õ

4 1614 Ç Ü 49 µ, i% Ç Õ, i Ç. Ç 1 ½Õ Å Ù AlCrTaTiNi Õ µ Å , Đ Cu Õ µ ². ĐË ÕÕ Å (¾ TaN, TaN/Ta à Ru Ta N Ø), Õ AlCrTaTiNi/(AlCr- TaTiNi)N»ÆȼÀÕ, Đ ÌÇ Å»ÆÈ ÀÕÍ. Ó µ 900 Í Cu ÓĐÅ ß ¼ Õ (¾«4d ½È À½ Ý ), Æß Å Æ», Cu Ó Å. «5 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÍÕ SEM. ß Cu Ó ÃÄ, Ú ¹Õ ¼ («5a), 700 Í», ß ÕË,» ÕÅ, Cu À Õ («5b). Û ÅÕ ³ Ä, Ý ÕÁ à ÁÕÉÛ, ºÎ» («5c). ÅÄ 900 Ê, Cu ºÎ Ñ ¼ ²ÃÄ, ³ Æ» ÆÕ ½À («5d). ½À Õ EDS ± («5e)»½À ½ ß Cu à Si. Ç 900 ÍÕ XRD, Â È ÅßÕ Cu Si. Ð Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si 900 Ê È. «6 AlCrTaTiNi/(AlCrTaTiNi)N/Si ² Å XRD. «½»Æ, ß Æ» È bcc(200), 800 ÍÆ»È (330) Õ,. 900 Í Æ»È Õ (222) à (310), Ê (200) ¹, (330) ßÝ ß, AlCrTaTiNi/(AlCrTaTiNi)N Ë, Å Õ Cu Đ ØÕ Ð [33], Ì Õ Cu à Si ɽ Å Å Â. Ó Î, Ì Ç Å ÕË Å È Õ Ó. À, AlCrTaTiNi/(AlCrTaTiNi)N Å»ÆÈ ÀÕ Å Ü. Õ ß Øº Õ Ó [1,7 12].,» ², ÍÇ ß Õ ÇÌ, Ì Õ ÙÈ µ Õ ÝÜ, ± µ¼ß, ÁÈ Cu/ AlCrTa- TiNi/(AlCrTaTiNi)N/Si µ Õ. Ï, ÕË Õ ¹ Â È Õ Ø Å. Ý, à ² Õ Å, È ÕÆ», ÙÈ ØÅ. ÝÎ, Õ AlCrTaTiNi/(AlCrTaTiNi)N Å µß ÉÀÕÕÛ. 4 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÞÒ ÌÔÆ SEM Fig.4 SEM images of the cross section of the Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si sample before and after annealing (HEAs indicates AlCrTaTiNi, the dotted line position is interface of different layer, the ellipse dotted line position indicates the interface of Cu layer and the HEAs/HEANs layer is disappearing) (a) as deposited (b) annealing at 700 (c) annealing at 800 (d) annealing at 900

5 Ü 12 : AlCrTaTiNi/(AlCrTaTiNi)N à ӹ Ѳ Đ 1615 (e) Intensity, a.u. Cu Intensity, a.u. O Energy, kev 5 Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si ÆÌÔ SEM ÒÆ EDS Fig.5 SEM images of surface of the Cu/AlCrTaTiNi/(AlCrTaTiNi)N/Si sample before and after annealing and Si EDS result of the selected range denoted by frame in Fig.5d (Inset in Fig.5d shows the enlarged view of the rectangle) (a) as deposited (b) annealing at 700 (c) annealing at 800 (d) annealing at 900 (e) EDS result of the selected range in Fig.5d bcc(200) bcc(310) bcc(222) Annealing at 900 o C bcc(330) Annealing at 800 o C As-deposited , deg 6 AlCrTaTiNi/(AlCrTaTiNi)N/Si ± Ô XRD Fig.6 Glancing angle XRD patterns of the AlCrTa- TiNi/(AlCrTaTiNi)N/Si samples in the as deposited state and after heat treatment at various annealing temperatures 3 ÔÙ (1) (AlCrTaTiNi)N ß Õ, Ý µ Đ Cu, Đ Cu ÕÍ. 700 Ê Cu Ó. (2) AlCrTaTiNi Cu à (AlCrTaTiNi)N Õ Í. (3) AlCrTaTiNi/(AlCrTaTiNi)N Å ß Õ. 800 ¹ÜÅ ÉÀÕ Å ÉÛ, 900 ÊÅ È. È Õ Ó Al- CrTaTiNi/(AlCrTaTiNi)N µë Õ. Õ [1] Chen Y Y, Duval T, Hung U, Yeh J W, Shih H C. Corros Sci, 2005; 47: 2257 [2] Zhu J M, Fu H M, Zhang H F, Wang A M, Li H, Hu Z Q. Mater Sci Eng, 2010; A527: 6975

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