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Chng 2: Cc phng php ch to ZnO cu trc nano

n ngy nay, rt nhiu phng php tng hp ZnO cu trc nano c s dng ph bin nh phng php nh tng ha, tng hp pha dung dch (Solutionphase synthesis ), CVD, lng ng xung laser ( pulsed-laser deposition ), phng php EBL (electron-beam lithography) kt hp vi CVD hay phng php dung dch, phn x[12]. Mi phng php u c u im v nhc im ring, quan trng hn l ty vo mc ch s dng khc nhau, ngi ta s chn phng php ch to ph hp nht. Nh cp trong phn gii thiu, trong phm vi lun vn, tc gi s tng hp si nano ZnO theo 2 phng php: phng php dung dch hoc phng php vn chuyn pha hi v 2 phng php ny ph hp vi iu kin thc t ca Phng th nghim tc gi ang thc hin ti.

2.1 Phng php dung dch Cu trc si nano ca nhiu loi vt liu c tng hp t phng php dung dch do phng php ny c th tng hp c vi s lng ln. Bn cnh , si nano tng hp t phng php dung dch c u im l thit b thc nghim n gin, c thc hin trong mi trng khng kh v nhit thp (t 50oC 150oC). Trong iu kin c bit, si nano ZnO thu c khi ch to t phng php ny s c nh hng thng v u trn b mt ( thy tinh, thch anh hay Si) [11]. Vi phng php ny, hu ht tin cht thng l cc mui km (km nitrat hay km axetat, km sunfat) c ha tan trong dung mi c th l nc hay dung mi hu c (hnh 2.1). Trong mi trng nc, Zn2+ c th tn ti di dng nhng nhm hydroxyl nh ZnOH+(aq), Zn(OH)2(aq), Zn(OH)2(s), Zn(OH)3-(aq), Zn(OH)42-(aq) . Nhng mm ZnO s c hnh thnh bi qu trnh kh cc nhm hydroxyl ny theo phng trnh: Zn(OH)2 (aq) ZnO (s) + H2O (aq)

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Hnh 2.1: M hnh s to si nano ZnO bng phng php dung dch

S pht trin cu trc 1D ca ZnO trong dung dch ph thuc vo nhiu yu t nh nhit , thi gian phn ng, pH ca dung dch. Trong dung dch, bn cnh dung mi v tin cht, s c mt ca cc amin (hexamethylenetetramine - HMTA, ethylenediamine, triathanolamine) vi nng thch hp gip s n nh pH ca dung dch. Mi trng pH thch hp s l nhn t quyt nh cho phn ng to si nano ZnO. Thng thng, vi nhit cho phn ng thy phn v ngng t ca cc mui km t 50oC 200oC th pH ca dung dch vo khong 5 12 s thun li cho ZnO pht trin cu trc si [10]. Nhm nghin cu ca Oleg Lupan, Lee Chow, Guangyu Chai thuc i hc K thut Moldova v i hc Florida to ZnO cu trc nano tetrapods trn thy tinh t dung dch ca km sunphat v ammoniac 98oC trong 15 pht. Kt qu cho thy ZnO pht trin dng nano tetrapods, mi nhnh ca mt nano tetrapod (hnh 2.2) l mt thanh ZnO cu trc lc gic c ng knh khong 0,5 m v chiu di khong 6 8 m [15].

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Hnh 2.2: nh SEM v ph XRD ca ZnO nano tetrapods [15]

Ring nhm tc gi Xiulan Hu, Yoshitake Masuda, Tatsuki Ohji, Kazumi Kato ca Vin Khoa hc v k thut tin tin quc gia Nht Bn tng hp ZnO cu trc si nano bng phng php dung dch nhit thp 85oC t tin cht km axetat, amin HMTA trong dung mi nc. ng knh si nano vo khong 80 nm 100 nm. Si nano c cu trc lc gic, nh hng thng ng t b mt (hnh 2.3) [27].

Hnh 2.3: nh SEM ZnO nanowires to bng phng php dung dch [27]

Nhm tc gi khc cng tng hp thnh cng ZnO cu trc ng nano (hnh 2.4) bng phng php dung dch l nhm ca Yi Xi, Jinhui Song,Sheng XuTheo kt qu ca nhm nghin cu ny, trn thch anh c ph lp mng mng GaN, ng nano ZnO pht trin theo hng trc giao vi , c cu trc lc gic, chiu di ng nano

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tng theo thi gian phn ng tuy nhin ng knh v dy thnh ng nano thay i khng ng k [30].

Hnh 2.4: nh SEM ca ng nano ZnO to 50oC, vi thi gian phn ng khc nhau [26]

Qua nhng v d trn, ta thy rng vi phng php dung dch, cu trc 1D ca ZnO tng hp c tng i a dng. Thm vo l nhng u im ca phng php ny nh thit b n gin, d thao tc(nh cp pha trn) m phng php ny l mt trong nhng la chn u tin ca cc nh nghin cu khi tng hp vt liu cu trc 1D.

2.2 Phng php lng ng vn chuyn pha hi (vapor transport deposition) Mt c ch thng thy trong qu trnh pht trin cu trc nano ca vt liu l c ch hi-lng-rn (vapor-liquid-solid, vit tt VLS) hay c ch hi-rn (vapor-solid, vit tt l VS) (ta s tm hiu k hn trong phn sau). Cc c ch ny c hnh thnh trong phng php lng ng vn chuyn pha hi (hay phng php CVD vi tin cht l pha rn), l 2 trong nhng phng php dng tng hp vt liu cu trc nano.

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Theo nguyn tc, phng php CVD v phng php lng ng vn chuyn pha hi c c ch tng t nhau, ch khc nhau v ngun vt liu ban u cn lng ng. hiu r hn v lng ng vn chuyn pha hi, ta s tm hiu tht tng qut phng php CVD. Trn c s ca phng php CVD, tc gi s trnh by r hn v phng php vn chuyn pha hi v c ch VLS to cu trc 1D ca vt liu ZnO.

2.2.1 Tng quan phng php CVD [35] Bn cnh phng php dung dch, mt trong nhng phng php tng hp vt liu rn c tinh khit cao l phng php lng ng hi ha hc (Chemical Vapour Deposition vit tt l CVD). Phng php CVD tng hp vt liu rn bng cch cho cc cht ha hc ban u (precursor) phn ng vi nhau v lng ng trn c nng nhit hnh thnh mng vt liu rn trn . S hnh thnh vt liu ca phng php CVD bao gm cc qu trnh: vn chuyn precursor vo bung phn ng, cc precursor phn ng vi nhau v lng ng vt liu ln nn (di iu kin nhit , p sut thch hp), cc sn phm ph sau phn ng s c gii hp v c a ra ngoi bung phn ng. Phng php ny c th hin thng qua s bn di (hnh 2.5):

Hnh 2.5: S ca qu trnh CVD

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Ta c th tm tt cc qu trnh trong phng php CVD nh sau: Vn chuyn cc precursor vo bung phn ng: Qu trnh ny nhm cung cp lin tc v ng nht lng precursor lng ng trn . Precusor s c dng nhit lm ha hi, sau hi precusor c a vo bung phn ng bng dng kh mang. C th ch mt loi precursor, cng c th hai hay nhiu loi precursor, ty vo vt liu ta cn lng ng. Do s chnh lch nng kh trong bung phn ng nn s hnh thnh dng khuch tn t dng chy vt liu xung nn gy ra hin tng lng ng vt liu trn . Ba i lng cn c quan tm y l lp bin vn tc, lp bin nng , lp bin nhit (hnh 2.6). Lp bin vn tc sinh ra do nht ca dng kh v s ma st ga dng kh vi thnh bung. Lp bin nng c to ra do s chnh lch nng cc cht phn ng trong bung v cc cht ny phn ng vi nhau v hp ph ln b mt . Lp bin nhit cng tng t nh lp bin vn tc, c to ra do s chnh lch nhit gia thnh bung v tm bung phn ng. Ba lp bin ny cho ta thy c s phn b ca dng kh, ca nng cc cht phn ng cng nh l s phn b nhit trong bung phn ng.

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Hnh 2.6: S thay i cc lp bin (a) vn tc, (b) nhit , (c) nng trong bung phn ng

Quan st trn hnh 2.6 ta thy, lp bin ca ba i lng vn tc, nng , nhit a s l trng nhau trong cc trng hp. Tuy nhin, mt vn cn lu l cng vo su trong bung, lp bin cng dy, s chnh lch nng cng gim, lm cho mng lng ng khng c ng u. Do , khi tin hnh thc nghim, ngi ta thng t nn nghing, song song vi b mt lp bin nhm gip qu trnh lng ng din ra ng u, gip dy mng ng u hn. Cc precursor phn ng vi nhau v lng ng to mng: hi cc loi precusor sau khi c dng kh mang a vo bung s phn ng vi nhau, cc phn ng ny c th xy ra pha kh ri mi lng ng xung

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hay cc cht khi khuch tn xung b mt mi phn ng vi nhau hoc xy ra ng thi hai qu trnh trn. Sau khi cc phn ng xy ra, nhng phn t vt liu mi hnh thnh ny s c hp ph ln b mt , khuch tn trn b mt v pht trin thnh mng. Cc phn ng c th xy ra trong mi trng khng kh hay di iu kin chn khng cao. Ty theo p sut hot ng m ngi ta phn loi phng php CVD thnh AP CVD ( CVD p sut khng kh ), LP CVD ( CVD p sut thp ),Hay da v ngun nng lng cung cp cc phn ng xy ra m ngi ta cn c th phn loi phng php CVD thnh nhit CVD (nng lng nhit cung cp cho cc phn ng xy ra) hay PE CVD (to ra mi trng plasma cung cp nng lng cho cc phn ng trong qu trnh to mng). Qu trnh gii hp cc sn phm ph: cc sn phm ph sau phn ng c gii hp ra khi b mt v c a ra khi bung phn ng theo dng kh mang.

Phng php CVD c th c xem l mt trong nhng phng php to mng c tinh khit cao. Bn cnh , phng php ny cn c mt s u im nh: tc lng dng nhanh, c th lng ng mng trn nhng cu trc hnh dng phc tp, cho php thay i hp cht phn ng ngay c trong qu trnh lng ngTuy nhin ta vn phi k n nhng hn ch khi lng ng mng bng phng php CVD. Hn ch u tin l phng php ny kh thc hin vi mt s loi km bn vi nhit v a s cc h CVD ch hot ng trn 600oC. Hn ch tip theo cng l vn cn quan tm khi thc hin phng php ny, l cc sn phm ph sau phn ng c th c hi. V vy, h thng x l cht thi ca h CVD cn c thit k an ton bo v cho mi trng.

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2.2.2 Phng php lng ng vn chuyn pha hi Lng ng vn chuyn pha hi (vapor transport deposition) l phng php lng ng hi ha hc vi nng lng cung cp cho cc phn ng ha hc gia cc precursor xy ra l nng lng nhit. C ch vn chuyn v lng ng ca phng php ny ging phng php CVD, ch khc nhau v ngun precursor ban u ca 2 phng php. Vi phng php CVD nh tm hiu phn trn, precusor c a vo bung phn ng pha hi. Cn vi phng php lng ng vn chuyn pha hi th ngun precursor c th dng bt, c t sn trong bung phn ng. Ngun precursor cng c lm nng chy xy ra qu trnh bay hi, sau c dng kh mang thi n nn, ti nn ( c nng nhit) s xy ra qu trnh lng ng (hnh 2.7). Ty thuc vo yu cu ca mi loi vt liu cn lng ng khc nhau m h nhit c thit k iu chnh c nhit , p sut hot ng khc nhau. Tuy vy chng vn phi c cu thnh bi nhng b phn tha nhng yu cu chung nh: h o c v truyn kh vo bung phn ng, h cung cp nhit cho qu trnh phn ng v lng ng din ra, h x l sn phm ph sau phn ng [35].

Hnh 2.7: S h lng ng vn chuyn pha hi

Vi ZnO cu trc nano tng hp theo phng php ny, thng thng l hi km v oxi s di chuyn v phn ng vi nhau to cu trc ZnO trn c nng nhit. c c hi km v oxi, ngi ta c th phn hy trc tip bt ZnO. Tuy

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nhin hn ch ca phng php ny l nhit phn hy ZnO tng i cao (1400oC) [2]. Mt cch khc c th tng hp ZnO cu trc nano l nung nng bt Zn di dng kh oxi chy qua 2 vt liu ny phn ng vi nhau. Phng php ny ch thc hin khong 500oC 700oC, tuy nhin cn phi kim sot k p sut hi km v p sut oxi to c cu trc nano ZnO. Nhiu nghin cu cho thy thay i t l p sut ny s c th tng hp c rt nhiu dng th hnh ca ZnO cu trc nano [33]. Khi tng hp vt liu nano ZnO bng phng php ny, nhiu tc gi rt ra c kt lun rng ZnO pht trin theo 2 c ch: c ch VS (khng c xc tc) v c ch VLS (c xc tc). Cc trng thi hnh hc c th quan st c vi ZnO pht trin theo 2 c ch ny rt a dng nh cu trc si nano ZnO, thanh nano ZnO, ng nano ZnO hay hn hp ca cc trng thi hnh hc ny [23]. V d, theo nhm tc gi X.Y Kong v X.Z Wang, tng hp ZnO cu trc nano vi hnh dng l xo th bt ZnO s c phn hy thnh Zn2+ v O2- nhit 1350oC, sau di tc dng ca dng kh Ar, hi Zn2+ v O2- s phn ng vi nhau v lng ng trn Al 300oC 400oC hnh thnh cu trc nano ZnO (hnh 2.8). y l tiu biu cho c ch VS, v trng thi tinh th ca vt liu ZnO c hnh thnh trc tip t hi Zn2+ v O2- [28]

Hnh 2.8: Cu trc l xo ca ZnO tng hp theo c ch VS ca tc gi X.Y Kong, X. Z. L.Wang

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2.2.3 To ZnO cu trc nano bng phng php lng ng vn chuyn pha hi theo c ch VLS i vi c ch VS, nhiu dng hnh hc ca cu trc nano c to ra. Tuy nhin theo c ch ny th ngi ta kh kim sot c hnh thi hc, s nh hng ca cu trc nano ZnO. Ring i vi phng php lng ng vn chuyn hi theo c ch VLS th cu trc 1D ca ZnO c kim sot tt hn nh s dng xc tc l nhng ht kim loi kch thc nano nh Au, Cu, Sn [33] C ch VLS c pht hin vo nm 1964 pht trin cu trc si nano trn Si vi s c mt ca ht nano Au (hnh 2.9).

Hnh 2.9: Cu trc si nano pht trin theo c ch VLS

C ch VLS c bn gm 3 bc: Hnh thnh hp cht gia ht xc tc kch thc nano vi vt liu cn to cu trc 1D: vt liu cn to pha hi s khuch tn v ha tan vo ht xc tc kim loi ang pha lng (do qu trnh nng nhit). Pha lng ca ht xc tc s nhanh chng t n trng thi qu bo ha v vt liu s kt tinh mt ngoi ca ht xc tc. Vt liu kt tinh mt ngoi ht xc tc s tip tc pht trin thnh cu trc 1D theo s nh hnh 2.10 bn di.

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Hnh 2.10: S 3 bc pht trin ca cu trc si theo c ch VLS

Theo s ca c ch VLS, ta thy rng ng knh si nano ph thuc vo ng knh ca ht kim loi xc tc. Xc tc ng vai tr quan trng trong s pht trin cu trc 1D. Cht xc tc phi c chn sao cho vt liu to cu trc si nano (nanowires) tan trong pha lng ca cht xc tc nhng cht xc tc khng c hnh thnh hp cht rn bn hn cu trc si nano ta cn to. To ZnO cu trc nano theo c ch VLS tng hp ZnO cu trc 1D theo c ch VLS, thng c ph cc ht nano vng. Ngun precusor (thng l bt ZnO hay bt Zn) c t ti tm bung phn ng, khong cch gia v ngun c th thay i c c th kim sot s pht trin ca si nano ZnO. Ngun precursor c nng nhit lm ha hi bt ZnO. Hi ZnO c dng kh mang (cc loi kh tr) thi n b mt . Ti y s pht trin cu trc 1D ca ZnO theo c ch VLS. Nu ngun vt liu l bt Zn th ngi ta s cho dng kh oxi thi hi Zn n lng ng to si ZnO (hnh 2.11) [33].

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Hnh 2.11: S pht trin si nano ZnO theo c ch VLS t bt Zn di dng kh O2 v ht xc tc Au Nhm tc gi Z.Fan, D.Wang, P.Chang [33] tng hp thnh cng si ZnO cu trc nano trn Si ph ht nano Au t bt Zn, dng kh oxi. nh SEM thu c cho thy ng knh si nano vo khong 30 nm, tng ng ng knh ht xc tc Au. nh SEM phng to gc bn phi pha trn cho thy r si nano ZnO pht trin theo c ch VLS t ht Au xc tc (hnh 2.12).

Hnh 2.12: nh SEM ca si nano ZnO pht trin theo c ch VLS trong th nghim ca nhm tc gi Z.Fan, D.Wang, P.Chang, W.Tseng- Appl. Phys. Lett. 85, 5923 (2004).

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2.2.4

Cc yu t nh hng n qu trnh hnh thnh ZnO theo c ch VLS:

2.2.4.1 Nhit Vi phng php lng ng vn chuyn pha hi, yu t nhit nh hng nhiu n qu trnh hnh thnh cu trc vt liu ZnO. C th l nhit ngun vt liu s nh hng n p sut ring phn ca chnh vt liu ngun pha hi nn cng s nh hng n qu trnh to mm ban u. Nhit s nh hng n qu trnh lng ng ca vt liu. Do nhit ni chung s nh hng n kch thc v cu trc vt liu cn lng ng. Thng thng nu vt liu ngun l bt ZnO s cn nhit cao bay hi nhng nu bay hi qu nhanh vi s lng ln s dn n s lng ng khng ng nht. Theo Chen v cc ng nghip, to si nano ZnO th nhit ti u cho ngun vt liu ZnO bay hi l khong 1100oC, nhit khong 550oC [35]. V th cn c s iu chnh ph hp cho nhit ngun vt liu v nhit nn.

2.2.4.2 Tc dng kh mang Bn cnh nhit , tc dng kh mang cng nh hng n qu trnh lng ng. Tc dng kh ny nhanh s dn n suy gim lng hi vt liu n , do lm gim s qu bo ha ca Zn pha hi. iu ny dn n s khc bit trong c ch hnh thnh cu trc nano ZnO nn c th to ra nhng dng hnh hc khc nhau. Theo nghin cu ca Z.Chen [33], vi cng iu kin nhit , khi dng kh nit khong 70 sccm, cu trc ZnO nano tetrapods c to thnh. Nhng tng tc thi kh ln 90100 sccm th s thu c cc si nano ZnO.

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(a)

(b)

Hnh 2.13: nh SEM ca ZnO c hnh thnh di dng kh thi khc nhau: (a) ZnO nano tetrapods, (b) si nano ZnO

2.2.4.3 p sut ring phn Khi vt cht pha hi t n trng thi bo ha, chng s lng ng ln b mt to cu trc nano. p sut ring phn cng nh hng n qu trnh qu bo ha ca hi ZnO hay Zn. Vi iu kin to thnh ZnO theo c ch VLS p sut kh quyn, bn cnh p sut ring phn ca pha hi Zn cn phi tnh n p sut ring phn ca oxi v n nh hng n mt ZnO to thnh. M.Yen cho rng, ng vi mt gi tr p sut nht nh ca oxi th s lng cc thanh nano ZnO to thnh l ln nht. Di gi tr ny, p sut khng ln duy tr cc mm Zn hnh thnh v lng ng. Cn trn gi tr ny, p sut cao duy tr s c mt ca mm ZnO trn tuy nhin li lm gim ng lng ca cc ion, lm gim mt thanh nano ZnO [35].

2.2.4.4 Vt liu c th ng dng si nano ZnO vo cc thit b quang in t trong thc t, ta cn kim sot c cu trc cng nh s nh hng ca chng. Vt liu ng vai tr kh quan trng trong vic nh hng cc si nano ZnO. Khi chn vt liu , ta phi quan tm n s hp mng gia ZnO v . Mt vi loi thng c s dng

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nh thch anh, GaN, Si hay SiC, hoc c ph lp mng mng ZnOBng 4 bn di cho ta tham kho cc thng s v hng s mng v hp mng gia ZnO (0001) v mt s loi .

Bng 2.1: Cc thng s v mt s loi [33] Vt liu Cu trc tinh th Hng s mng (nm) Mt hp mng H s lch mng ZnO Wurtzite a=0,325 c=0,521 (0001) 0 GaN Wurtzite a=0,319 c=0,519 (0001) 1,9% Thch anh Hexagonal a=0,475 c=1,299 (11-20) 0,08% SiC Wurtzite a=0,309 c=1,512 (0001) 5,5% (100) 18,6% Si Kim cng a=b=c=0,543

Ta thy trong cc loi vt liu c lit k bng trn, thch anh l vt liu c u tin s dng tng hp si ZnO do c s lch mng so vi ZnO thp nht. Tuy nhin, GaN cng l mt la chn v c cu trc tinh th v hng s mng tng i ph hp vi ZnO. Tc gi Fan s dng hai loi l thch anh v GaN (0001) tng hp si ZnO cu trc nano bng phng php lng ng vn chuyn pha hi. Kt qu cho thy si nano pht trin trn GaN c nh hng thng v u hn so vi si nano ZnO pht trin trn thch anh. Mt u im na khi s dng GaN l ngi ta c th to ra chuyn tip n-ZnO/p-GaN, y l cu trc si nano ZnO c rt nhiu ng dng trong thit b pht x in t [33].

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Hnh 2.14: nh SEM ca mng cc si nano ZnO trn (a) thch anh v (b) GaN mt (0001)

Nh vy, mi phng php ch to u c u, nhc im ring. Ty vo mc ch ng dng m ta la chn phng php tng hp c th to c ZnO cu trc nano khc nhau. Vn quan trng l lm th no iu chnh c cc thng s trong qu trnh thc nghim cu trc thu c tt nht. Vn ny s c thy c th hn trong qu trnh thc nghim.

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