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Please Note: The author retains the copyright while the New Jersey Institute of Technology reserves the right to distribute this thesis or dissertation Printing note: If you do not wish to print this page, then select “Pages from: first page # to: last page #” on the print dialog screen The Van Houten library has removed some of the personal information and all signatures from the approval page and biographical sketches of theses and dissertations in order to protect the identity of NJIT graduates and faculty. ABSTRACT UNDERSTANDING THE ORIGINS OF METASTABILITY IN THIN FILM GROWTH; TANTALUM AND THE EARLY GROUP VB-VIB METALS by Neme Okechukwu Nnolim ntl ( tl tht hhl przd fr t ppltn n vrt f ndtr, nldn th rltrn ndtr, hr t lrl d n thn fl dftn n rdr t hv vr ltrn, nt nd trtrl pblt n ldtt dv. frntl fr ttbl ph, nldn th llnn 0ph, drn th prprtn f thn fl b tndrd fl dptn thd h pttrn nd ltrdptn. In rdr t n nht nt ttbl ph frtn, th n trnfrtn hn tdd fr nd th nhbrn bd ntrd b (b trntn tl n Grp nd 6 f th rd bl, rltn n th prdtn f hpthtl bd ntrd ttrnl (bt nd f ntrd b (f ph fr ll th tdd tl t rt rtr thn .6 nd l t E rptvl. nt ntnl hr ( n th nrzd Antd ln Wv (AW frl nd th t Ordr rtnl Apprxtn (OA fr th ltn f th ltznn trnprt tn hv bn d t llt th tprtr dpndnt rtvt fr th tdd tl nd rvl tht btrtndd fl trn nt b tlf ffnt t th frtn f 0. r rf lltn f th n ltrn vlt n th prpd 42n trtr f t tht th hh vl f rtvt frntl rd fr 13 -Ta are not an intrinsic property. UNDERSTANDING THE ORIGINS OF METASTABILITY IN THIN FILM GROWTH; TANTALUM AND THE EARLY GROUP VB-VIB METALS by Neme Okechukwu Nnolim A Dissertation Submitted to the Faculty of New Jersey Institute of Technology and Rutgers, The State University of New Jersey-Newark in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Applied Physics Federated Physics Department August 2003 Cprht © 200 b Oh nl A IGS ESEE APPROVAL PAGE UNDERSTANDING THE ORIGINS OF METASTABILITY IN THIN FILM GROWTH; TANTALUM AND THE EARLY GROUP VB-VIB METALS Neme Okechukwu Nnolim r. rvr A. n, rttn Ar t At rfr f h, I r.Knnth rr, Ctt Mbr t At rfr f h, I r. Sr] Svrv, Ctt Mbr t Atnt rfr f h, I r. Mhl C. Y. n, Ctt Mbr t Atnt rfr f Chl Ennrn, I r. Ax, Ctt Mbr t At rfr f Cvl Ennrn, I IOGAICA SKEC Athr: Oh nl r: tr f hlph t: At 200 Undrrdt nd Grdt Edtn: • tr f hlph n Mtrl Sn nd Ennrn, r Inttt f hnl, r, , 200 • Mtr f Sn n hl Chtr, Mhtt Inttt f hnl, Cbrd, MA, 6 • hlr f Sn n Chl Ennrn, Unvrt f htr, htr, Y, 2 Mjr: Mtrl Sn nd Ennrn rnttn nd bltn: 0. nlrn, rvr A. n nd Ax, "hr f th trtrl ph f Grp — 6 tl nd thr trnprt prprt", rnl f Appld h, l , br 8, p 44 — 460, Aprl 200. 0. nl, rvr A. n nd Ax, "A td f th trtrl ph f th Grp — 6 lnt nd thr hnl prprt", Mtn f th Mtrl rh St, tn, MA, br 2002. 0. nl, rvr A. n nd Ax, "trntn f ttbl trtrl ph n ln — 6 tl b ttl nr pttn", Mtn f th Arn hl St, Indnpl, I, Mrh 2002. v I would like to express my deepest gratitude and appreciation to my dear wife Charlotte Messina-Nnolim and my dear family including my mother Dorothy Adaku Nnolim, my father Benedict Nwankwo Nnolim, my brothers Chukwuma Nnolim and Uche Nnolim, my sister Chiemedinam Nnolim, my Aunt Guy Ilobi, my cousin Chudi Ejekam, my sister-in-law Pamela Messina and my uncle Geoffrey Nnolim for their constant encouragement, support and advice. I could not have done this without them. On Kj, jl p n n I: nh n n Kj b (Whn n fnd nlf tp tll nd ht tr thrn d, ft nt n ptn IGO OE V ACKNOWLEDGMENT I would like to express my sincere appreciation and gratitude to my research supervisor, Dr. Trevor Tyson, who in instances too numerous to count gave me invaluable advice, support and scientific insight and who cheerfully provided resources whenever they were needed. Special thanks are due to Dr. Michael C. Y. Huang, Dr. Sergej Savrasov, Dr. Lisa Axe, and Dr. Kenneth Farmer for being active members of my committee, and to David Perel of the NJIT Computing Services Division for his assistance over the years. vi TABLE OF CONTENTS Chapter Page IOUCIO I.I vr nd Orrn f ntl 2 .2 Extrtn f ntl 6 I. Iprtnt ntl Sr 8 I.4 Crl Mnftr f ntl I . Mhnl nd hrdn rprt f ntl I6 .6 Chl rprt f ntl .6.I ntl Oxd 8 I.6.2 ntlt I.6. ntl ld .6.4 ntl Crbd I.6. ntl trd 20 I.6.6 ntl Slt 20 .6. Anltl Chtr f ntl 20 . U f ntl 2 I.. Crrn rttn 2 ..2 Cptr 22 .. Mdl U f ntl 24 ..4 ntlbd All nd Sprll 28 .. Othr U f ntl 2 TABLE OF CONTENTS (Continued) Chapter Page 2 YSICS A AICAIOS O I IM ECOOGY 2 2.I hn l hnl 2 2.2 Strtrl rprt f hn l 4 2. Eltrl rprt f hn l 2..I hn l tr 2..2 hn l Cptr 2.. hn l Sprndtr 42 2..4 hn l Sndtr 4 2.4 Mnt rprt f hn l 0 2.4.I vrl f Mnt n Unxl hn l 6 2.4.2 Appltn f Mnt Sthn 60 2.4. Strtr pndn f hn l Mnt rprt 6 2. ntl hn l 68 2.. Eltrl Cndtn n ntl hn l 2..2 Sprndtvt n ntl hn l 2.. Strtrl rprt f hn ntl l 2...I h f ntl 6 2...2 h h f ntl 8 I IM GOW A MEASAE ASE OMAIO 88 . ltn hr 88 .2 Mn ld ltn hr viii TABLE OF CONTENTS (Continued) Chapter Page . hrdn l Grth Mdl 0 .4 Knt Mdln f l Grth r I06 . Mttbl h n hn l .. Mttbl h f ntn ..2 Mttbl h f nd 6 .. Mttbl h f ntl 8 .6 hn l ptn Mthd 8 .6. Eltrpltn .6.2 Eltrl ltn I20 .6. Evprtn I2 .6.4 Spttr ptn I2 .6.4. C Gl hr Spttrn 2 .6.4.2 d rn ( Spttrn I2 4 ESIY UCIOA EOY 6 4. h Intrtn Mnd rbl 6 4.2 h hnbrKhn hr 8 4. h KhnSh Etn 40 4.4 tntl Enr rltn n 0 4.4.I h dtntl Mthd I0 4.4.2 h ht ndn Mthd 4.4. h Mffnn tntl Mthd 6 ix TABLE OF CONTENTS (Continued) Chapter Page h Orthnlzd ln Wv (OW Mthd I5 5 h Antd ln Wv (AW Mthd I5 h nrzd Antd ln Wv (AW Mthd 1 7 h AW+l Mthd 17 5 r Mnztn n th AW rl 1 Mnztn f At r 171 1 h rbl Mtr Mthd 171 pd tn n 173 7 r Clltn Mthd 173 Spn-Orbt Cpln n th AW rl 175 5 MEASAE ASES O GOU 5 — ASIIO MEAS 13 51 Strn Anl 1 5 Elt rprt nd th Etn f Stt 193 51 Cb Str 19 5 trnl Str 53 h Eptxl n th 3 5 Mttbl h f th Grp 5 — Mtl 51 Iplnttn tl 5 Clltd Mttbl h nd Enr ffrn 1 53 h - Enr ffrn nd th trnl Shr Cntnt 1 55 Eltrn Strtr pndn f Elt rprt 1 TABLE OF CONTENTS (Continued) Chapter Page 5 nt f Stt 51 h OS 5 t h OS 9 57 d -bnd lln nd th — h Enr ffrn 3 5 Crrltn btn th n nd rr rnfrtn 35 ASO OEIES A MEASAE ASES 1 1 Eltrl tvt 1I Eltrn-hnn Sttrn 7 1 Eltrn-Eltrn nd Othr r f Sttrn 51 hr f th Eltrl tvt 5 I n hr f tvt 5 t Ordr rtnl Apprxtn (OA t th tvt 73 3 l rn 3 rr pndn f rnprt rprt 91 5 Clltd tvt nd Ipltn fr 3- rtn 95 7 OIGI O EA AAUM ESISIIY 35 7I Strtr f 3- 35 71I -1 3- trtr 35 71 2/n 13- trtr 3 7 r Mnztn f /n Strtr f 13- 37 73 Eltrn Strtr f /n Strtr f 3- 311 xi TABLE OF CONTENTS (Continued) Chapter Page 7 Eltrl tvt f 13- 31 71 Ettn f 1- prtr tvt 35 7 Iprtn f Grn ndr nd Iprt Sttrn 3 AEI AAUM I IM EAAIO EAIS 39 EEECES 33 ii LIST OF TABLES Table Page 11 ntl pt Wrldd 5 I Cptn f Iprtnt ntl-ntnn Mnrl 13 ntl Cntnt f th Mt Iprtnt Sl Grd 9 1 Mhnl rprt f Sft Annld ntl 1 15 Crtllrph hrdn nd Eltrn rprt f ntl 17 1 pl rprt f Cptr Grd ntl dr 3 1 S rprtn tl f ntl hn l Obtnd b C Spttrn 31 Intrf Wdth a , trl Crrltn nth nd Avr rr Wdth /I fr Svrl St III 51 Clltd t Elbr tt rtr nd tl Enr r Unt Cll f Mttbl nd Stbl h f Stdd Cb Mtl nd h Enr ffrn ΔEbt-b I 5 Clltd tt Cntnt fr nd h f Mtl n Grp -I f th rd bl nd h Enr ffrn 19 53 Clltd h Shr Cntnt nd l Mdl fr th nd t h f th tdd Mtl 1 5 Clltd tl nt f Stt nd tl d nt f Stt t th r Enr (εF nd Nd (EF ), fr t nd h f th Stdd Mtl 7 55 tl d nt f Stt t th r Enr Nd (EF ), nd Str pd Cpnnt f Nd (EF ) fr nd t h f th Stdd Mtl 5 tl nd rtnl d Opn fr b nd M nd h 3 1 Clltd nd t l rn l ha) fr Stdd Grp 5 nd Grp Mtl 9 Sr f tvt Clltn Mthd 95 x LIST OF TABLES (Continued) Table Page 71 At tn n th -1 Strtr f 13- 3 7 At rtr Adptd fr 13-U /n Strtr nd fnd n th 3- /n Strtr 37 73 At Str p nd thr rt nd xt-rt hbr trbtn n th /n nd -1 Strtr 31 7 r lt nd l rn l Clltd fr /n nd Strtr f 3 75 Exprntll trnd 3- Grn Sz 37 xv LIST OF FIGURES Figure Page I1 Wrldd rrv f tntl r n 1 Mjr tntl prn rt I3 Ct- ht f hp tp tntl ptr dn 1 rnd n hpnt nd nftrn pt f tntl ptr 15 t lltd fr n vv rrn xprnt hn thr dffrnt tr f t rtn t plnt d fr vr tll lnt nd ll 1 rpn t plnt n btn rt t ftr prd f nd n bn frtn rnd plnt n rt fr bn rr ftr th prd f t 7 17 Mrt hr f tntl ppltn fr 1935-1993 31 1 Inr n IC trntr ntrtn dnt vr thr dd 33 Sht dr f nnn ltrn rp (SEM t 35 3 r n fr th fbrtn f rtr nd ptr fr dffrnt tntl thn fl n th btrt I Mr dv prn f "rd" nd "rt" dl nd flp-flp 5 A thn fl trntr 9 t thn th pld fld 59 7 Cnfrtn fr hh pd AM l n n "rd" nd "rt" d I 9 Mntztn ndtn fr bbbl dn frtn 1 S trl d fr bbbl dn 3 Dv LIST OF FIGURES (Continued) Figure Page 1I tl nr pr nt ll fr vrl tl lltd fntn f th Wnr-Stz rd 1 Ar-t-r v plnt fr pttrn 7 13 hn dpndn f 7 fr thn fl 75 I (1 nd (I1I v f nt ll f dtrtd b prltt trtr prpd fr 3- I5 (1 nd (1I1 v f nt ll f /n trtr prpd fr 3- 1 (1 nd (1I1 v f th prpd trtr f 3- 17 (1 nd (II1 v f bd ntrd ttrnl (bt trtr f 3- hxnl trtr f 3- nd A15 trtr f 3- 31 prtr dpndn f th ltr frtn