Ly Viet Anh Tap chf KHOA HOC & CONG NGHE
NGHIEN c t r u , PHAT TRIEN PHU"OfNG PHAP MA TIEN TIEN THAN THIEN VOfI MOI TRir6NG TREN VAT LIEU K H 6 N G D A N DIEN
LS Vift Anh Trudng Dai hoc Ky thugt Cong nghiep ~ DH Thdi Nguyen TOM TAT
Trong bai vi^t nay chiing toi tap tmng vao mot each tiip can hoan toan mdi de ma kim loai ISn tren bg mat vgt li?u khong din dlSn. Phuang phap ma tren vgt lieu each di?n cua chiing toi gidi thlSu sau day chi yeu cau nhiing chat nen trong dung djch hoa hpc dang long, vdi dieu kien khong khi hd va nhiet do moi trudng binh thudng. L6p ma Niken (Ni) sB dugc ma len be m5t bl mat tam nhua KMPR, vdi hifiu qua kinh te cao v& vo ciing than thiSn vdi moi trudng. Qua trinh hoat hoa be mSt dugc thuc hien bSng viec cay ghep true tiep cac nhom phiic hpp Palladi - Amin - Silicontrong moi trudng dung dich nude ma khong c3n tac dung ciia A-xit Cromic. C4c liSn ket cong hda trj vk dSc tinh CO ly ciia ldp ma Ni trSn nin KMPR dugc trien khai kiem nghiem b3ng c^c ky thu§t SEM, EDX, XPS... Dp bam dinh ciia Idp ma trSn chat nen dugc kiem tra theo tieu chuin ASTMD ciia My
Til- khoa: Ma tren nin nhita. Mg vgt lieu cdch diin; Lien kit cpng hda trj; Chi tao MEMS, Xiic tdc Palladi; A-xit Cromic
GIOI THIEU
Hien nay, nhua la chat lieu nen dugc sir dung pho bien trong che tao cac he thdng vi ca dien tii' (Microelectromechanical systems-MEMS) [1]. Vat lieu nhya thdng thudng sir dung trong ITnh vyc MEMS nhu: PMMA, HSQ, SU-8 va KMPR [2], trong dd KMPR la vgt lieu nhua pho bien nhat cho san xuat vi mgch dien tit cung nhu lam chat nen cho cac dien cue [1,4], cac he thflng Chip da Idp [5],...Vat lieu nhua KMPR cd nhirng dgc diemndi bat nhu: bam dinh manh tren cac logi vat lieu khac nhau [6], kha nang hogt dgng tdt trong mdi trudng dung dich nude ngng (Tetramethylammonium hydroxide), de dang tgo mang mdng bam dinh tren cac loai bl mgt [3,7]. Tuy nhien, viec ma tren nen nhua ndi chung la mdt qua trinh rat phirc tgp, chii yeu dua tren cac phuang phap truyin thflng nhu phii PVD va CVD hoac ma hoa hpc khflng dien (Chemical electroless plating) [7]. Den nay, mdi chi co rat it cac cdng bd khoa hpc ve phii PVD trSn vat lieu KMPR [1,7]. Trong qua trinh phu PVD ddi hdi phai tgo ra mpt Idp hgt nho li ti (Crom hoac Titan) nham tang cudng dp bam dinh giu'a chit nin vdi kim loai can mg. Phuang phap phii nay ludn lufln ddi hdi sii' dung chat ' Tel 0978626955. Email- Vietanhly4@gmadc,
hda hoc Crom, dac biet la Cr^"" trong A-xit cromic -chat da bi cam su dyng d nhiSu nude tiSn tien vi co kha nang gay ra hien tuong quai thai d tre so sinh neu ngudi me bi nhiem Crom trong qua trinh mang thai [8]. Hon niJa, phii PVD ciing ySu cau cac thiSt bi san xuat phuc tap Do vay, viec nghiSn cuu mflt phuang phap ma don gian va hieu qua han dflng thdi than thien vdi moi trudng ludn la mpt bai toan vd ciing cap thiet.
Trong bai bao nay, chung tdi dS xuat mpt qua trinh mg hda hpc hoan toan thyc hien trong mdi trudng dung djch Idng, su dung Ni de tao Idp ma mong trSn tam nhya KMPR.Phuang phap mdi nay dya tren co sd lien kSt cOng hoa trj giQ'a Idp be mat KMPR vdi chat xiic tac Pd, ndcho phepgiam thieu ham lupng cac chat xiic tac bang kim logi quy nhu Pd, Au, Ag,...qua dd ha gia thanh qua trinh ma. Viec cay ghep lien ket cOng hoa tri ciia phiic hgp Palladi (Pd) - Silicon giu'a chat nin KMPR va Idp ma cung dupcnghien ciiu va chii'ng minh.
Qua dd cho phep dieu khien sd lugng cac Cation Pd^* va tao ra su gan ket rat tdt giiia KMPRvaNi.
PHU'ONG P H A P N G H I E N CUU Chudn bl chat nen
Chat nen KMPR dupe trang tren chi tiSt dgng dia lam bang Siliconcd dudng kinh 200mm 43
Ly Vi?t Anh Tap chi KHOA HQC & CONG NGHb 1 /o^ioj: m -tn tuong ty nhu trong thdng cao khoa hpc [1,7]
vasau dddugc lam sgch bang be siSu am. Dfl day ciia Idp mang mdng KMPR khoang 10 pm.Tilp theo, dia Silicon trang nhya KMPR dugc cit thanh nhiing tim hlnh chu- nhgt cd kich thu'dc 3cm x 5 cm, tir day gpi la tam KMPR. Cac tim KMPR dugc rua sach trong nude cit, cdn Propanol va lam khd bang may say thdi khlNi-to.
Tien xii- ly bi mat bdng hon hgp dung dich A-xit+d-xi gid
Nhung tim KMPR nggp trong dung dich A- xit + 6-xi gia bao gdm: HCI ndng dp 37%;
HjOinflng dp 50% va nude cat vdi ti le the tich 1:1:5 trong vong 20 phiit. DiSu chinh dp pH trong dung dich la sip xi 1,0. Qua trinh lam sach dugc thuc hien d 60''C, rdi nia sgch bing nude cat sau dd say khfl bang ddng khi Ni-ta.
Cay ghep nhdm phdv hgp Pd - Amin - Silicon
Cho 88,7 mg PdClj vao dung dich 100 mL HCI 0,1 M (Sigma Aldrich) dl tao ra dung dich PdCb 5mMol. Dung dich nay dugc gia nhiet ISn eS^C cho tdi khi PdCb tan hoan toan va chuyin hda thanh H2PdCl4. Hda tan 1,12 mL N[3 (trimethoxysilyl) propyl]
ethylenediamine (Sigma Aldrich, 97%, khdi lugng rieng la 1,028 g/mL) vao 49 mL nude cit dl dugc mflt lugng dung djch khoang 50 mL. Toan bg dung djch nay dugc rdt ttr tii vao lOOmL dung djch H2PdCl4. Tiep tyc them vao 25 mL NH4OH dl trung hoa hdn hgp dung dich va tao ra phiic hgp Pd - Amin -- Silicon ([(OH)3Si-(CH2)3-NH(CH2)2- NH2]PdX2) vdi X la CI" hoac OH^Sau khi nhiing trong dung djch phuc hcrp 30 phiit, tam KMPR dugc riia sach trong nude cat roi say d ISO^C cung trong khoang 30 phiit bang lokhi tro (Ni-ta).
Mg Ni len tam KMPR
Qua trinh ma Ni ISn KMPR dugc thuc hien trong be sieu am (Cole Parmer, model 08895- 91) trong 7 phiit d nhiet dp 65''C- dugc thuc hien tgi Trung tam nghien cdu MiQro -
C2MI/ Teledyne Dalsa - Canada. Hon hgp dung djch ma bao gdm: Nickel sulfat 0,1M;
A-xit Nitric 0,2M, Dimethylamine borane (DMAB) 0,05M dugc sd dyng de duy tri dung dich d dg pH 9. Saukhi mg Ni, tam KMPR dugc rua sach bang nude cit trong b^
siSu am va say khd bing ddng khi Ni-to Sir dung ky thugt quang pho hong ngogi FTIR xdc dinh cdc hgp chat hda hgc tren ldp mg
Quang phfl hdng ngoai ciia tim KMPR dugc
^ i lgi bang thiet bi quang pho ke Bruker Vertex 70 nhim xac dmh xac dinh cac hgp chit hoa hpc tren Idp ma.Thi n^iem dugc thuc hien tai dugc thuc hien tai Tmng tam nghien Cliu MiQro - C2M1/ Teledyne Dalsa - Canada.
Sir dung ky thugt PhS huynh quang tia X (XPS) xdc dinh xdc dinh nang lurgng lien kit giira cdc nguyen tir tren ldp mg XPS dugc thyc hien vdi nguon quang pho tia X don sic (K Alpha, Thermo Scientific), thiit bj tia chilu cd ngufln nang lupng 1486,6 eV.
Dilu chinh ngudn dien d miic dp trung binh nhim tranh cac tac dung xau vS hinh anh trong qua trinh XPS.Thi nghiem nay ciing dugc thuc hien tgi dugc thuc hien tgi Trung tam nghiSn cdu MiQro - C2MI/ Teledyne Dalsa - Canada.
Phdn tich mat cdt ngang va vd cau triic te v{
l&p mg bdng hien vi dien td- quet SEM Hinh anh mat cat ngang ciia tam Ni-KMPR-Si dupcghi Igi bdi kinh hiSn vi dien tii quel HitachiSU3500dl0kV.
Kiim tra dd bam dinh l&p mg theo tiiu chudn ASTM
Dp bam dinh giifa ldp ma Ni va nen KMPR dugc danh gia theo tieu chuan bam dinh ASTM, Thi nghiSm dugc thuc hien ba lan dS kiSm chung.
KET QUA vA B A N LUAN
Mg Ni len tam KMPR thong qua cay ghep phirc hgp phuc hgp Pd
Hau het cac logi A-xit dugc su dung trong qua trinh liim sach Ankal va hiru ca tren be
Ly Viet Anh Tap chi KHOA HOC & CONG NGHE 176(16): 43-48 mat chat nSn khdng nhiing loai bd cac hii'u ca
ma cdn lam tan ca cac kim logi tren bl mat chat nen, ngoai ra chiing cdn gay anh hudng rat tieu cyc den mdi trudng. Trong nghiSn cuu nay viec sii dung hdn hgp bao gflm HCI, H2O3 va H2O (dugc gpi la dung dich SC2) da chiing minh dupe nhiing hieu qua rat ti'ch cyc trong qua trinh Hidro hda bS mat chit nin.
(a) KMPR nguyen ban
Hat nfiln Phenyl
3600 3000 2400 1800 1200 600 So song (cm"'}
(b)
3 '
^
'f>
w
KMPR sau khi xii ly
- Hat nhan
" 0 . 0 2 ' " " "
1 Nhdm -CH;; -CH,
• Nhom OH ,
A P\
f\ A
U^UJ
ll
• fill
1 •f '
•,1
W V
w -^
3600 3000 2400 1800 1200 600 So sdng (cm'^)
Hinh 1. Hlnh dnh phdn llch FTIR cua bi mat KMPR nguyen bdn (a); vd be mdt KMPR dd duac
xirly(b)
Quan sat tren Hinh 1 nhgn thay d sfl sdng 1000 - 1275 (cm""') cd su xuat hien ciia cac Phenyl; hgt nhan Phenyl xuat hien d sd sdng 1500 (cm"'); nhom-CHj va-CH2 xuat hien d so sdng giiJa 2850-^3000 (cm"'); va dang chii -y nhat la trong khoang so sdng 3000-3500
(cm ) xuat hien d5c trung ciia cac nhdm Hidroxit (-0H)
Cac thflng ke XPS tren KMPR da dugc xu ly bdi H2O2 dugc the hien trSn Hinh 2 cho thay ti IS nguyen tii 0/C ciia KMPR tang tii 0,31%
len 0,34%, dieu nay ly giai cho viec hinh thanh cic nhdm Oxigen tren be mat KMPR.
Dieu nay la rat quan trpng cho viec kham pha tfnh chat hda hpc ciia cac nhdm Oxigen trSn tam KMPR thdng qua khao sat XPS miic dfl quang phd ciia hat nhan Cacbon.
(a)r
KMPR nguyen b i n 0 1sC I S
1250 1000 750 500 250 0 NSng li/gng Men ket (eV)
1250 1000 750 500 250
Nang li/ging lien ket (eV) I Hlnh 2. Hlnh dnh phdn tich XPS ciia bi mat KMPR nguyin bdn (a); vd bi mgi KMPR dd duac
xuly(b)
Phfl huynh quang tia X (XPS) tren Hinh 3 da cung cap them cho chung ta 3 dac trung ciia tam: vj tri khi nang luong liSn ket 284,8 eV hien thi lien kit C=C; vi tri 286,4 eV hien thj lien kSt C=0 va C-OH va tgi vj tri cd nang lugng lien kSt 289,2 eV hiSn thi lien kit 0-C=0.
Vdi be mat KMPR nguyen ban ti le nguyen tii C-C;C=0/C-0H va 0 = C - 0 lin lupt la
45
Ly Viet Anh Tap chf KHOA HOC & CONG NGHE 176(16): 43-48 51,4%; 41,4% va 7,2%. Sau khi tam K M P R
dugc lam sgch bang SC2 ti le nay dugc thay dfli lin lugt la 4 7 , 7 % ; 4 3 , 3 % va 7,0%. Rd rang la trong khi ti IS cCia nhom Cacboxyl hau nhu khflng cd su thay ddi ( a 7 % ) thi viec Iam sach dan den su thay ddi tuong ddi dang ke ciia cac nhdm C - C va C - O H (Hinh 3).
(a). KMPR nguven Dan ^ Q -[^
r I
5k C=O.C-OH
292 290 288 286 284 282 Nang \ugng lien ket (eV)
292 290 288 286 284 282 NSng li/ong lien k^t (eV) Hinh 3. Do phdn gidi quang phd Cacbon cua bi mdt KMPR nguyen bdn (a) vd bi mat KMPR da
dugc xu ly (b)
Budc tiSp theo cac nhom Amin ciia 3 - aminopropyltriethoxysilane (APTES), se tiln tdi lien ket vdi cac Cation kim loai quy Pd^""
tao ra lien ket phiic hgp cue ky ben chat Pd - Amin - Slllicon nhu mfl ta tren Hinh 4.
Giai doan cudi ciing ciia qua trinh la su lien kit gi&a cac phan tii Ni len nhdm phiic hgp Silicon - Amin - Pd. Ban chat ciia qua trinh nay la qua trinh mg Ni len bS mat tim nhya thflng qua xiic tac Pd nhu la nipt qua trinh 6 - 46
xi hda khii, nd giflng n h u la ma Ni ISn vgt cin mg la Pd. Trong giai doan nay cac Cation Pd^"^ giam hoa trj trd thanh cac kim logi Pd trong dung dich ma, chiing trd thanh cac h?i nhan xiic tac cho cac Cation Ni"*. Cac phan tii Ni bam d i u len bS mat chat n i n KMPR tao thanh t i m K M P R ma Ni-B nhu tren hinh S, Qua trinh ma Ni len tam KMPR da dugc xir ly be mat bang cac hop chat hiru c a va Pd dugc diSn ra trong 7 phiit va nhiet dp 65''C.
CH,—»1 HO
U-CH,—OH- -HO-^i—ICH,!;,—NH—iCHib-;*H,
»,l.„.
1 • „c,o„, x / X
Hinh 4. Lien kit cgng hoa tri cuaphuc hgp Silicon — Amin — Pd Irin ldm nhua KMPR
Hinh 5. (a) •inh Jnip lam KMPR iigincn ban (bSl^
trdi) Vfl tdm KMPR dugc ma Ni sau khi da ^wp^l xd ly be mai bdng phuc hgp Pd Poliamin Si (ben'->
phdi). (h) Hlnh dnh SEM cua be mat tdm mong ' Ni-B, (c) Hinh dnh SEM mat cat ngang lap mg'
Ni-B vd nin KMPR Kiem tra do hdm dinh ctia l&p mg Ni tren be mat tam KMPR
D o bam di'nh ciia ldp ma Ni ISn t i m KMPR cd t h i ndi la ySu tfl quan trpng n h i t d l co th^
Ly Viet Anh Tap chi KHOA HQC & CONG NGHE 176(16): 43- ket luan phuang phap ma mdi ciia chiing tfli
CO the dugc chap nhan hay khflng. Dp bam dinh ciia ldp ma dugc kiem tra bang tam bang dinh mang tiSu chuan thir nghiSm (ASTMD3359-09) Thi nghiem vl do bam dinh Idp ma dugc thyc hien bdi bang dinh mang tieu chuan thii nghiem (ASTMD3359-09) ciia Hoa Ky dugc thyc hipn d ca Trung tam nghiSn cuu MiQro - C2M1/ Teledyne Dalsa - Canada va Trudng Dai hgc KTCN - Dai hgc Thai Nguyen. Theo tieu chuan nay, do bam dinh ciia Idp mg coi nhu dam bao khi nd dat dugc muc 5B, khi cd 0% dien tich Idp ma bj giat len bdi tam bang dinh. Hinh 6 the hien qua trinh thii nghiem do bam dinh ciia Idp ma vdi bang dinh kiem tra theo tieu chuin ASTMD3359-09. Mpt tim ludi 4 ddng x 4 ddng dugc cat len tren tam KMPR da dugc ma Ni, mfli dong cat each nhau I mm nhu tren hinh 6a Dan tam bang dinh kiem tra nay len tam KMPR da cao xudc nhu tren hinh 6b, hinh 6c thS hien sau khi bdc tam bang dinh ra khdng cd bat cii' d vuong nao bj hoc ra khdi tam. Ro rang theo thii' nghiSm tren hinh 6 Idp ma Ni da thda man dfl bam dinh theo yeu cau len tren tam KMPR.
^
Hinh 6. Kiim tra dg bdm dinh ciia Ni tren Idin KMPR; (a) ludi cdt 4x4: (b) ddn bang dinh kiim Ira tren luai cat; (c) gd- tdm bdng dinh vd ddnh gid
do bdm dinh
Tuy nhien vdi cac nen nhya co dfl dflng nhat khflng cao, Idp mg bam dinh kem hon nhieu, day la thach thdc khdng nhd ddi vdi de tai.
Tren Hinh 7 la Logo Trudng Dai hpc Ky thugt cdng nghiep bing chat lieu nhua dugc mg Ni. Co thi nhan thiy vdi cac vat lieu nhua khac nhau viec ma Ni bj ban che kha nhieu, do quy trinh ma tren mdi chi thti nghiem trSn vat lieu nhua KMPR tieu chuan.
Hinh 7. Logo TNUTbang nhua duac ma Ni KET LUAN
Trong bao cao nay chiing tdi da nghiSn ciiu, thiit kl va chiing minh duoc tinh diing dan ciia mdt phuang phap ma tien tien than thien vdi mfli trudng va cd nhiing hieu qua nhat djnh vl kinh tl va chat lugng. Phuong phap mdi thay thS viec su dyng dung djch Cromic bing dung djch chiia cac phtic chat hftu co Pd-Amin-Silane qua dd giam dugc dpc td.
Qua trinh mg Ni len chit nSn KMPR diln ra trong 7 phut d nhiet dd 65'*C. Sau ma tam KMPR dugc kilm tra theo tieu chuan ASTMD3359-09, da hoan toan chirng minh dugc chit lupng rat tdt ve dp bam dinh ciia Idp ma.
LCJI C A M ON
Tac gia xin gui Idi cam on chan thanh den nhung giup dd quy bau ciia trudng Dai hpc KTCN - Dai hpc Thai Nguyen vl co sd hg tang va tai chinh cho bai bao nay.
TAI LIEU THAM KHAO 1. B. Zhang, "Chapter 2 - Electroless Plating Baths of Metals, Binary Alloys, and Multicomponent Alloys," in Amorphous and Nano Alloys Electroless Depositions, B. Zhang, Ed, ed Oxford: Elsevier, 2016, pp. 51-106.
2. K. De Bruyn, M. Van Stappen, H. De Deurwaerder, L. Rouxhet, and J. P. Cells, "Study
47
Ly Viet Anh Tgp chf KHOA HOC & CONG NGHE , ,^{iu). -,., -^6 of pretreatment methods for vacuum metallization „. S. Faraji and F. N. Anl, "The development of plastics," Surface and Coalings Technology, supercapacitor from activated carbon bjfi, vol. 163-164, pp. 710-715,2003. electroless plating—A review," Renewable and 3. A. Yli-Pentti, "4.11 - Elecfroplatlng and
Electroless Plating," in Comprehensive Materials Processing, S. H. F. B. J. V. T. Yilbas, Ed., ed
Sustainable Energy Reviews, vol. 42, pp. 823-834, 2015.
bxfo^rd: Etsevier'20i47pp.'277-306.''''"'"'' " " " " ?. L.-p. Wu, J.-j Zhao, Y.-p. Xie, and Z.-d. Vang, 4. M. Proust, F. Judong, J. M. Gllet, L. Liauzu, "Progress of electroplating and electroless plating and R. Madar, "CVD and PVD copper integration on magnesium alloy," Transactions of Nonferrous for dual damascene metallization in a 0.18 jim Metals Society of China, vol. 20, Supplement 2,' process," Microelectronic Engineering, vol. 55, pp. s630-s637,2010.
pp. 269-275,2001. g ^_ union, "European parliament and tht 5. J. A. T. Nomian, M. Perez, S. E. Schulz, and T.
Waechtler, "New precursors for CVD copper metallization," Microelectronic Engineering, vol.
coHMC//," Official Joumal ofthe European Union, vol. 2005/90/EC (EC) No 907/2006 pp. (OJ L 168, 85, pp. 2159-2163, 2008. 21.6.2006, p. 5). 2006.
S U M M A R Y
R E S E A R C H , D E V E L O P M E N T AN E N V I R O N M E N T - F R I E N D L Y COATING M E T H O D ON INSULATING S U B S T R A T E S
Ly Viet Anh' University ofTechnology - TNU In this paper, we demonstrate here that electroless deposition can be considered as an altemate efficient approach to metallize the surface of insulating substrates. Our electroless nickel plating requires only immersing the substrates into aqueous solutions in open air at low temperatures. Thin films of nickel alloy have been deposited electrolessly on KMPR surface, through a cost-effective and environmental chromium-iree process, mediated through direct grafting of Palladium - Amine - SiJiicon complexes in aqueous medium, without Acid Cromic. Covalent grafting and characterization ofthe deposited have been carried out by means of SEM, EDX, XPS techniques, The nickel film's adhesion was tested In accordance with ASTMD standard of US.
Keywords: Metallization of polymers; Electroless deposition; Covalent grafting; MEMS fabrication; Acid Cromic
Ngdy nhgn bdi: 01/11/2017; Ngdypltdn biin: 24/11/2017; Ngdy duyet ddng: 05/01/2018 Tel 0978 626955: Email: Vietanh.ly4@gmail c.
