低介电常数材料与铜导线之界面研究

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Thermal reactions of sputtered Cu films on thethermally grown silicon dioxide (SiO2) and spin-on

hydrogen silsesquioxane (HSQ) layers are investigated byexaminng the sheet resistance, surface microstructure,phase formation and compositional depth profiles of

Cu/thermal SiO2 and Cu/HSQ structures on Si wafers afterannealing in vacuum at 400~700 ¢J. It is found that thesheet resistance values of both samples decreased afterannealing at 400 ¢J. The decrease of sheet resistance wasin conjunction with growth of Cu grains and annihilation ofmicrocracks of the as-deposited Cu films. Cu2O was firstfound in the Cu/HSQ/ samples after annealing at 600¢J. After annealing at 700 ¢J, the whole copper layer ofCu/HSQ/ sample reacted with oxygen to form severalcopper oxides. On the contrary, only a minor part of copperin Cu/thermal SiO2/ structure was transformed to Cu2Oafter annealing at 700 ¢J. The reaction and/or diffusioncharacteristics of the two structures upon vacuum annealingare discussed.

Keywords: low k materials, HSQ, copper¤G¡B½t¥Ñ»P¥Øªº¥Nª÷ÄݾT¾É½uªº¾É¹q§÷½è¡C¥t¤@¤è-±¡A¦b§C¹q®e¤¶¹q§÷®Æ³¡¤À¡A»Ý-n§C¤¶¹q±`¼Æ§÷®Æ¨ú¥N¤¶¹q±`¼Æ¬ù¬°4.0ªº¶Ç²Î¤G®ñ¤Æª¿¡A§@¬°¥Î©óª÷Äݾɽu¶¡ªº¤¶¹q§÷½è¼h(Intermetal dielectric)¡C ¥»¹êÅç¨Ï¥Î§t²Bª¿»ÄÆ¡Q]HydrogenÃþSilsesquioxane,²ºÙ,HSQ¡^§C¤¶¹q±`¼Æ§÷®Æ¡A§t²Bª¿»ÄÆQÃþ¬°¦h¤Õ½è§÷®Æ¡i3¡j¡A¥B¬°¥Ø«e¨Ï¥Î³Ì¤j¶qªº±Û¶î¦¡¶î§G§C¤¶¹q±`¼Æ§÷®Æ¡i4¡j¡C¦]¬°¤Õ»Ø¤@¯ë¬°-ì¤lÂX´²ªº³q¹D¡A¥B»É«Ü®e©ö¦b¤G®ñ¤Æª¿©Îª¿¤§¶¡ÂX´²¡i5¡j¡A¦]¦¹¥»¹êÅç¬ã¨s»É¦b¦h¤Õ»Ø§÷½èHSQ§C¤¶¹q±`¼Æ§÷®Æªº¤¶-±©Ê½è¡C¤T¡B¹êÅç¤èªk ¨Ï¥În-type(100)ª¿´¹¤ù¡A¸g¹L¤T´â¤A²m¡B¤þଡB²§¤þ¾J²M¬~«á¦A§Q¥Î5wt%²B¬t»Ä¥h°£-ì©l®ñ¤Æ¼h¡C±Nª¿´¹¤ù¸m©óºÞ«¬Äl¤º¦¨ªø¤G®ñ¤Æª¿¡A®ñ¤Æ±ø¥ó¬°1050¢J¡A®ñ®ðª^¬°126sccm¡A¤G®ñ¤Æª¿ªº«p«×¬°4500Å¡C¥t¥~¥H±Û¶î¦¡¶î§G§t²Bª¿»ÄÆQÃþ§÷®Æ©ó¤w²M¬~ªºª¿´¡¹A¤ù±¤ÛW¶î±ø¥ó¬°step1=1500r.p.m/10sec.¡Fstep2=2400r.p.m/15sec¡A¤§«á±N¶î§G«áªºª¿´¹¤ù¸m©ó200¢J¼ö¹ÔªO¤W¯M¯N2¤ÀÄÁ¡A¨Ã¦P®É§j©Ø´á®ð¡CµM«á¸m©400ó¢JºÞ«¬Äl(100sccm´á®ð)©T¤Æ¤@¤p®É¡A§t²Bª¿»ÄÆQÁ¡½¤«p«×¬°6000 Å¡C»ÉÁ¡½¤§Q¥Îª½¬yÂqÁá¾÷Áá»s¡A«p«×¬°1800 Å ¡C±N¸Õ¤ù¸m©ó¥Û-^¦à¤W(¥Û-^¦à¤º©ñ¸mÜgºä¡A©M´Ý¾l®ñ¤ÏÀ³)¯uªÅÄlºÞ¤º°h¤õ¡AÄlºÞ¯uªÅ«×¬°2×10-5torr¡A°h¤õ·Å«×¬°400¢J~700¢J¡A°h¤õ®É¶¡¬°¤@¤p®É¡C ¤ù¹qªý¨Ï¥Î¥|ÂI±´°w»ö¾¹¡Aµ²ºc¤ÀªR«h¬O¨Ï¥Î§C±°¨¤X¥ú¶®g»ö¡Aªí-±Åã·LÆ[¹î¬O¨Ï¥Î³õµo®g¦¡ªºSEM¡AÁa²`¤ÀªR¨Ï¥Î¼Ú³Ç¹q¤l¯àÃлö»P¤G¦¸Â÷¤l½èÃлö¡C ÀHµÛ¥b¾ÉÅé»sµ{§Þ³Nªº¤£Â_ºt¶i¡AIC½u¸ô³]-pªº½ÆÂø¤Æ¡A¥Ø«e¥b¾ÉÅé¼tªº¹h·¥¼e«×»sµ{§Þ³N¬°¥|¡Bµ²ªG»P°Q½×0.18£gm¡A¹w-p¤½¤¸2003¦~·|¶i¤J0.13£gm¹h·¥¼e4.1 ¤ù¹qªý«×ªº»sµ{§Þ³N¡i1¡j¡CÀHµÛ¤¸¥ó¤Ø¤o©M½u¼eªºÁY¤p ªìÁὤ©M°h¤õ«á¸Õ¤ùªº¤ù¹qªý-ÈÅã¥Ü©ó¤Æ¡A¾É½u¶¡ªº¤¶¹q¼h·|²£¦¨¤j¼Æ-Ȫº±H¥Í¹q®e¡A¨ÃFig.1¡A¥Ñ¹Ï¤¤¥i¥H¬Ý¥X»É/¤G®ñ¤Æª¿/ª¿»P»É/§t²Bª¿©M¾É½uªº¹qªý§Î¦¨¹q¤l°T¸¹¦bª÷Äݳs½u¶¡¶Ç°eªº»ÄÆQ/ª¿¨â²Õ¸Õ¤ùªìÁὤªº¤ù¹qªý-ȤÀ§O¬°202m®É¶¡©µ¿ð(RC time delay,¬°¹qªý»P¹q®eªº-¼¿n)¡A¨Ï£[/¡¼¤Î218 m£[/¡¼¡AÀHµÛ°h¤õ·Å«×¤W¤É¨ì400¢J¡A±o¤¸¥óªº³t«×¨ü--¨î¡C ³q±`¬°¤F-n-°§C®É¶¡©µ¿ð¡A¦³¨âºØ¤èªk¡C²Ä¤@¨â²Õ¸Õ¤ùªº¤ù¹qªý-È-°§C¡A¨ä¤¤»É/§t²Bª¿»ÄÆQ/ª¿³o²Õ¸Õ¤ù-°¨ì³Ì§C-È¡A¦Ó»É/¤G®ñ¤Æª¿/ª¿³o²Õ¸Õ¤ù700¢J¡A¤ù¹qªý-ȨS¦³ÅãµÛªº¤U-°¡A»É/§t²Bª¿»ÄÆQ/ª¿¸Õ¤ùÀHµÛ°h¤õ·Å«×¤W¤É¨ì700¢J¤ù¹qªý-ȤW¤É¨ì·¥¤j-È(¦¹®É¥|ÂI±´°w»ö¤w¸g¶W¹L°»´ú--«×)¡C4.2 µ²ºc¤ÀªR

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Fig.3»PFig.4ªºSEM·Ó¤ùÅã¥Ü¡A»É/¤G®ñ¤Æª¿/ª¿»P»É/§t²Bª¿»ÄÆQ/ª¿ªºªìÁὤ¦b¸Õ¤ùªí-±¬Ò¥X²{·L¤pªºµõ²ª¡A¦¹·L¤pµõ²ª¥X²{ªº-ì¦]¥i¯à¦³¤G¡A-º¥ý¥i¯à¬OÂqÁá³t²v¤Ó§Ö(~15Å/sec)³y¦¨»É°ï¿n¤Ó§Ö¡A¬Y¨Ç¦a¤è°ï¿n¤£¦n¡A§Î¦¨¤F·L¤pµõ²ª¡F¥t¤@-Ó-ì¦]¥i¯à¬O¦]¬°»É-ì¤l»P¤G®ñ¤Æª¿©Î§t²Bª¿»ÄÆQªºª¿-®ñ-ì¤l¤§¶¡ªº-ì¤l¥b®|¤£¦P¡A¦b¨H¿nÁ¡½¤®É²£¥Í¤FÀ³¤O¡A¦¹À³¤O³y¦¨¤F·L¤pµõ²ªªº²£¥Í¡C¥ÑFig.3»PFig.4ªº(a)¹Ï¥i¥Hµo²{·L¤pµõ²ªªº¼Æ¶q¦b»É/¤G®ñ¤Æª¿/ª¿¥X²{ªº¸û¦h¡A³o¥i¯à¬O¦]¬°§t²Bª¿»ÄÆQ¬O¦h¤Õ©Ê§÷½è¡A¦]¦¹¦b¨H¿n®É³æ¦ì-±¿n¤º»É-ì¤l»Pª¿-®ñ-ì¤l±µÄ²ªº¼Æ¶q¸û¤Ö¡A©Ò¥H-ì¤l¥b®|¤£¦P©Ò³y¦¨ªºÀ³¤O¸û¤p¡A¦]¦Ó²£¥Í¸û¤Öªº·L¤pµõ²ª¡C ÀHµÛ°h¤õ·Å«×ªº¤É°ª¡A¨â²Õ¸Õ¤ùªº´¹²É¤]ÀH¤§¦¨ªø¡C¦P®É·L¤pµõ²ª¤]¦³»E¶°¦¨ªøªº²{¶H¡A»É/¤G®ñ¤Æª¿/ª¿¸Õ¤ù´X¥G¦b600¢J(Fig.3(d))µõ²ª®ø¥¢¤£¨£¡A¦Ó»É/§t²Bª¿»ÄÆQ/ª¿¦b500¢J(Fig.4(c))´X¥G®ø¥¢¤£¨£¡C¥ÑFig.4(d)¥iµo²{»É/§t²Bª¿»ÄÆQÃþ/ª¿¸Õ¤ù¸g¹L600¢J°h¤õ¡A¸Õ¤ùªí-±¦ü¥G¦³·sªº¬Û¥Í¦¨¡A¹ï·Ó§C²¤¨¤X¥ú¶®g¤ÀªR¹Ï(Fig.2)¥i¬Ý¥X³o¨Ç·s¥Í¦¨ªº¤p´¹²É¥i¯à¬°®ñ¤Æ»É¬Û¡A¸g¹L700¢J°h¤õ³o¨Ç·s¬Û´¹²É¦¨ªø¡A¦Ó¥B¸Õ¤ùªí-±«D±`ªº²ÊÁW¡C³o¨Ç®ñ¤Æª«¦¨ªø³y¦¨Fig.2(b)ªº¸Õ¤ù¸g¹L700¢J°h¤õ«á§Î¦¨¤j¶qªº®ñ¤Æª«Â¶®g®p¡A¦P®É¥Ñ©ó³o¨Ç®ñ¤Æª«Â¶®g®p¡A³£¬O¤@¨Ç°ª¹qªý¬Û¡A¨Ï±o»É/§t²Bª¿»ÄÆQÃþ/ª¿¸Õ¤ù¸g¹L700¢J°h¤õ¡A¤ù¹qªý-È«æÁؤW¤É¡A³y¦¨¥|ÂI±´°w»ö¶W¹L°»´ú--«×¡C°Ñ¦Ò¤åÄm1.1997 The National Technology loadmap forSemiconductors, Semiconductor IndustryAssociation,Sam Jose,1997.

2.A. Alptekin, G. Czeremuszkin, L. Martinu, M.Meunier, E. Sacher, and M. Direnzo, Mat. Res.Soc. Symp.Proc.Vol.443, 79, (1997).3.M.Grant Albercht, Craig Blanchette, J.Electrochem.Soc.145.,4019(1998).

4.4Áa²`¦¨¥÷¤ÀªR4. Laura Peters, Semiconductor

INTERNATIONAL,June.108(2000).4.4.1 ¼Ú³Ç¹q¤lÁa²`¤ÀªR

¥»¹êÅç-º¥ý§Q¥Î¼Ú³Ç¹q¤l¯àÃлö°µÁa²`¤À5. Y. Shacham-Diamond and

A.Dedhia,J.Electrochem.Soc.140, 2427(1993).ªR¡A±o¨ìªºµ²ªGÅã¥Ü©óFig.5¡CFig.5¬°»É/¤G®ñ¤Æª¿/ª¿ªºªìÁὤ(Fig.5(a))»P700¢J°h¤õ(Fig.5(b))ªº¼Ú250Cu/thermal SiO2 /).Cu/HSQ/qs200/smhom(ecn150atsiserteehS100500As-dep.200400600800Anneal Temperature (¢J)Fig.1 Dependence of sheet resistance of

Cu/thermal SiO2/ andCu/HSQ/ samples on the annealingtemperature in vacuum.

(a)Cu/thermal SiO2 /Cu)11Cu2 O1()002())0))12.01U0322(((.A700 ¢J(ytisnetn)0I0)20(22(600 ¢J(b)Cu/HSQ/Cu)1Cu1Cu2O1(CuO4O3)))0))0))010002011110221)1((432)(2((((2.¢2U700 J(.A()y11ti1(snet)n0)00I22))(012(11600 ¢J11((20406080Two theta (degrees)Fig.2 GIA-XRD spectra of (a) Cu/thermal

SiO2/ , and (b) Cu/HSQ/samples after annealing at 600 ¢J and700 ¢J.

(a)(b)(c)(d)(e) 500nmFig.3 Scanning electron micrographs onthe surfaces of Cu/thermal SiOsamples (a) as-deposited, and after2/annealing at (b) 400 ¢J, (c) 500 ¢J,(d) 600 ¢J, (e) 700 ¢J.

(a)(b)1.2Atomicconcentration(c)(c)Cu/HSQ/ (as-dep.)Cu0.8OSi0.4(d)0.01.2(d)Cu/HSQ/ (700¢J)(e)Atomicconcentration0.8O 500nmFig.4 Scanning electron micrographs on the

surface of Cu/HSQ/ samples (a) as-deposited, and after annealing at (b)400¢J,(c)500 ¢J,(d)600 ¢J,(e)700 ¢J.

1.2(a) Cu/thermal SiO2 / (as-dep.)Cu0.4CuSi0.0010002000Sputtering time (SEC.)

Atomicconcentration0.8OFig.5 AES compositional depth profiles of (a)Cu/thermal SiO2/ samples , as deposited (b)Cu/thermal SiO2/ samples after annealing at700 ¢J(c) Cu/HSQ/ samples , as deposited(d) Cu/HSQ/ samples after annealing at 700¢J

(b)Cu/thermal SiO2/J700 ¢(b)Cu/HSQ/SiSiOJ700 ¢1E+71E+60.4Si1E+5Secondaryioncounts1E+4O0.01.2(b)Cu/thermal SiO2/ (700¢J)1E+31E+2CuCuCuAtomicconcentration1E+10.8O1E+004008001200040080012001600Sputtering time (sec.)0.4SiSputtering time (sec.)0.0Fig.6 SIMS depth profiles of (a) Cu/thermal

SiO2/sample after annealing at 700¢J(b)Cu/HSQ/ sample after annealing at 700¢J.

010002000Sputtering time (SEC.)