I HC QUC GIA H NI TRNG I HC CNG NGH

Nguyn Duy Khanh

NGHIN CU CH TO V C TRNG TNH CHT MNG MNG NANOCOMPOSITE TRN C S NG CARBON NANO NG DNG TRONG CH TO OLED

KHA LUN TT NGHIP I HC H CHNH QUY Ngnh: Vt l k thut

H NI - 2011

I HC QUC GIA H NI TRNG I HC CNG NGH

Nguyn Duy Khanh

NGHIN CU CH TO V C TRNG TNH CHT MNG MNG NANOCOMPOSITE TRN C S NG CARBON NANO NG DNG TRONG CH TO OLED

KHA LUN TT NGHIP I HC H CHNH QUY Ngnh: Vt l k thut Cn b hng dn: TS. Nguyn Phng Hoi Nam

H NI 2011

LI CM N

Li u tin cho php em gi li cm n chn thnh nht n Ts. Nguyn Phng Hoi Nam. Thy khng ch truyn t kin thc m cn tn tnh ch bo em t nhng cng vic n gin nht trong nhng ngy u bt tay vo lm kha lun cho n khi hon thnh. Em xin gi li cm n chn thnh n cc anh, ch nghin cu vin ti cc phng th nghim-Khoa Vt l k thut & Cng ngh nano, Trng i hc Cng ngh. Cc anh, ch tn tnh ch bo v hng dn em t cch s dng my mc cng nh cch lm vic ca mt ngi nghin cu khoa hc. Em cng xin gi li cm n s gip n t Phng chp nh FESEM-Vin Khoa hc v Cng ngh VN, Kha Ha-Trng i hc Khoa hc T nhin, hai n v gip em trong vic chp hnh v phn tch kt qu. V cui cng, em xin gi li cm n chn thnh v su sc nht n cc thy c trong Khoa Vt l k thut & Cng ngh nano ni ring, cc thy c ging dy ti Trng i hc Cng ngh ni chung du dt, nng bc em trong sut 4 nm hc va qua. qu l nhng tnh cm qu bu v nhng k nim mi mi i theo em n sut cuc i. Bn kha lun c hon thnh vi s ti tr kinh ph ca ti NCKH cp HQG H Ni, m s CN.10.08.

H Ni, thng 5-2011 Sinh vin Nguyn Duy Khanh

TM TT NI DUNG

ng nano cacbon (CNTs) ngoi nhng tnh cht c hc u vit cn th hin kh nng dn in vt tri. Mc d mi c pht hin cch y khng lu nhng CNTs c mt trong rt nhiu nhng nghin cu chuyn su v c nhng ng dng thc t quan trng. PEDOT-PSS, mt dn sut ca PEDOT, l mt polymer dn s dng nhiu trong cng ngh ch to OLED bi kh nng dn in cng nh cho nh sng truyn qua. T hp vt liu composite gia CNTs v PEDOT-PSS c d on s l mt vt liu composite mi thch hp ch to ra cc loi mng mng c c tnh dn v nh sng d dng truyn qua. Vt liu t hp nanocomposite ca PEDOT-PSS v CNTs vi cc t l thnh phn khi lng khc nhau c nghin cu ch to. Mng mng trong sut v c c tnh dn c s dng lm lp truyn l trng trong cng ngh ch to OLED. T hp CNTs/PEDOT:PSS theo khi lng c dn tt nht v truyn qua cao, c s dng ch to linh kin OLED cu trc a lp. Cc kt qu nghin cu cho thy OLED s dng mng t hp nanocomposite ca PEDOT-PSS v CNTs c s ci thin r rt v cng , hiu sut cng nh n nh v tui th ca linh kin.

Li cam oan

Kha lun ny c thc hin vi s nghim tc, t m v c gng ca tc gi. Tc gi cam oan khng sao chp bt c mt ti liu hay cng trnh nghin cu ca ngi khc m khng trch dn. Tt c cc ti liu tham kho c trnh dn c th v r rng trong bn kha lun.

MC LC

Nguyn Duy Khanh.....................................................................................................1 .............................................................................................................................. 2 ...................................................................................................................... 2 Polythiophene.............................................................................................2 Hnh 1. Cu trc phn t ca mt vi polymer dn thng dng.............................2

DANH MC CC T VIT TT

Ch vit tt CNTs EL ETL FESEM

Ting Anh Carbon Nano Tubes Emission Layer Electron Transport Layer Field Emission Scanning Electron Microscopy Fourier Transform Infrared spectroscopy Highest Occupied Molecular Orbital Hole Transport Layer Indium Tin Oxide Lowest Unoccupied Molecular Orbital poly[2-methoxy-5-(2ethylhexyloxy)-1,4phenylenevinylene Multiple Wall Carbon Nano Tubes Poly(3,4ethylenedioxythiophene) poly(styrenesulfonate) poly(N-vinylkarbazone)

Ting Vit ng nano cacbon Lp pht Lp truyn dn in t Knh hin vi in t qut pht x trng Ph hng ngoi bin i Fourier Vng qu o phn t c in y cao nht Lp truyn dn l trng Oxit ca Indium v thic Vng qu o phn t c in y thp nht

FTIR HOMO HTL ITO LUMO MEH-PPV

MWCNTs PEDOT:PSS

ng Nano Cacbon a tng

PVK

SWCNTs TL

Single Wall Carbon Nano Tubes Transport Layer

ng nano cacbon n tng Lp truyn

M U

it pht sng hu c (OLED) ang l ti hp dn nghin cu cho nhng ng dng m n mang li. So vi it pht sng thng thng (LED), OLED c nhng u th vt tri nh bn, nh, hiu sut pht sng cao, mn hnh bng OLED cho gc nhn rng, sc nt, c th un cong, tiu th in nng tChnh v nhng u im vt tri so vi LED thng thng nn hin nay, rt nhiu hng cng ngh quan tm nghin cu v ch to. Cu trc ca mt OLED c bn (single device) gm 3 phn chnh: in cc ant, in cc catt v lp pht quang hu c kp gia hai in cc. Thng thng in cc ant c s dng l mng ITO trong sut c kh nng cho nh sng truyn qua. Lp pht quang hu c l cc polymer dn nh PPV; PPP; MEHPPV hay cc phn t hu c nh nh Alq 3; TPD, lp ny chnh l ni xy ra s ti hp ca in t v l trng v pht ra nh sng. in cc catt c ph trn lp pht quang, lp in cc ny thng c lm bng kim loi chng hn nh Al. Vi cu trc OLED n lp nh vy, cng v hiu sut pht sng cng nh n nh ca linh kin l khng cao. Chnh v vy cc linh kin OLED c cu trc a lp c quan tm nghin cu v ch to nhm khc phc cc nhc im ca OLED cu trc n lp. Vic nghin cu ch to v s dng cc vt liu c kh nng truyn dn in t v l trng tt lm cc lp truyn (TL) gia in cc v lp pht quang trong ch to linh kin a lp nhm ci thin s tip xc ti b mt phn chia pha v tng cng s dch chuyn ca cc dng ht ti l hng nghin cu v ang c quan tm hin nay, mang li nhiu trin vng ng dng thc t cho OLED . K t khi pht hin nm 1991 n nay, ng nanocacbon lun l ti nng thu ht cc nghin cu v ng dng thc tin bi nhng c tnh u vit ca n. Cc c tnh l: bn c hc cao, dn in dn nhit tt...Trong nghin cu ny, chng ta s li dng tnh dn in siu vit ca n to lp mng m cho OLED. Trong khi , PEDOT:PSS l mt dn sut ca PEDOT s dng nhiu trong ch to cc linh kin in t bn dn. Nu nh c th t hp c hai vt liu ny thnh mt vt liu composite s cho dn in rt tt, kh nng truyn quang cao c th dng lm lp truyn dn ht ti cho OLED v v th tng kh nng lm vic cng nh ci thin hiu sut ca OLED. Trn c s , ni dung nghin cu ca ti c xc nh l: Nghin cu ch to v c trng tnh cht mng mng nanocomposite trn c s ng nano cacbon ng dng trong ch to OLED.

CHNG 1. TNG QUAN V IT PHT QUANG HU C (OLED) 1.1. Vt liu polymer dn 1.1.1. Gii thiu chung v polymer dn Polymer dn l cc polymer c h thng ni i lin hp trong cu trc phn t, y l cht bn dn hu c. u im ca polymer dn l d gia cng, ch yu bng cch ha tan trong dung mi.

PPV

PPP

Polythiophene

Hnh 1. Cu trc phn t ca mt vi polymer dn thng dng. Cc ht ti trong cht bn dn hu c l in t v l trng trong lin kt . S truyn ht ti trong cht bn dn hu c ph thuc vo cc qu o lin kt v s chng chp ca cc hm sng c hc lng t. Kh nng truyn ht ti ph thuc vo kh nng cc ht ti vt qua t mt phn t ny ti mt phn t khc. Cc polymer truyn thng nh polyethylene, cc in t ha tr c lin kt trong cc lin kt ha tr lai ha sp3. Chng hn nh cc in t lin kt sigma c linh ng thp v khng gp phn vo qu trnh dn in. Tuy nhin, i vi cc polymer dn th iu ny li hon ton khc. Cc polymer dn c cc tm cacbon lai ha lin k nhau sp2, mi in t ha tr trn mi tm c tr trong qu o p z, lin kt ny trc giao (vung gc) vi 3 lin kt sigma khc. Cc in t trong cc qu o dch chuyn ny c linh ng cao khi vt liu c pha tp bi qu trnh oxi ha.

V vy cc qu o lin hp p hnh thnh mt cu trc vng in t mt chiu v cc in t bn trong vng ny tr ln linh ng khi cu trc vng khng in y mt phn. Cu trc vng ca polymer dn c th d dng tnh ton bng mt m hnh lin kt cht. V mt l thuyt, cc vt liu ging nhau c th c pha tp bng qu trnh kh nh thm vo cc in t ti mt vng khng y khc. Trong thc t, tt c cc vt liu dn hu c c pha tp tr thnh vt liu bn dn loi p. Phn ng oxi ha kh pha tp ca cc vt liu dn hu c ging nh qu trnh pha tp trong cht bn dn silic m mt phn nh nguyn t silic c thay th bng cc vt liu t in t (Bo) hay nhiu in t (P) to thnh cht bn dn loi n hay loi p. S khc nhau ng k nht gia polymer dn v cc cht bn dn v c l linh ng in t ca polymer dn thp hn nhiu so vi cc cht bn dn v c. S khc nhau ny ngy nay c ci thin nh vic pht minh ra cc polymer mi v s pht trin ca cc k thut mi trong qu trnh tng hp polymer. linh ng ca cc ht ti thp lin quan n s mt trt t ca cu trc. Thc t, i vi cc cht bn dn v nh hnh v c, dn in nh l mt hm ca rng vng linh ng (mobility gaps)[7] vi phonon linh ng v polaron xuyn hm gia cc trng thi xc nh. Cc polymer dn khng pha tp, trng thi ban u c th l cht bn dn hay cch in. Chng hn nh rng vng cm nng lng ln hn 2 eV l qu ln i vi chuyn ng nhit. V vy, cc polymer dn khng pha tp nh polythiophenes, polyacetylenes ch c dn thp khong 10 -10 n 10-8 S/cm. Tuy nhin, ch cn pha tp rt t (<1%) dn in tng ln khong vi bc ln n gi tr 0,1 S/cm. Nu pha tp thm na, gi tr dn in s bo ha vi gi tr t 0,1-10kS/cm ty thuc vi cc polymer khc nhau. Gi tr ln nht hin nay c cng b l 80kS/cm i vi polyacetylene. Mc d c nghin cu su, mi quan h gia hnh thi hc, cu trc chui, v dn cho n nay vn cn kh phc tp. Nhn chung ngi ta gi nh rng polymer dn tt l polymer c gc tinh th ln v chui sp xp thng hng. Tuy nhin iu ny khng ng i vi PEDOT v polyaniline bi chng l cht v nh hnh [14].

1.1.2. Cu trc vng nng lng ca cht bn dn hu c

Hnh 2. S cu trc vng nng lng trong cht bn dn hu c. Trong cht bn dn hu c, tn ti hai vng gi l vng qu o phn t c in y cao nht (Highest Highest Occupied Molecular Orbital-HOMO) v vng qu o phn t c in y thp nht (Lowest Unoccupied Molecular Orbital-LUMO). Hai vng HOMO v LUMO ny tng ng ging nh hai vng ha tr v vng dn trong cht bn dn v c. trng thi c bn vng HOMO c cc in t c in y trong khi vng LUMO khng c in t. Khi c tc nhn kch thch chng hn nh nh sng hay nhit , cc in t vng HOMO nhn nng lng v trng thi kch thch, nu chng nhn nng lng ln chng c th nhy ln vng LUMO, qu trnh ny cng ging nh qu trnh in t t vng ha tr nhy ln vng dn khi in t c kch thch trong cht bn dn v c. nhit cao, cc in t c th nhy ln t vng HOMO ln vng LUMO nh nng lng chuyn ng nhit ca cc in t. Trong trng hp kch thch bng nh sng, cc in t s hp th photon thu nhn nng lng v nhy ln vng LUMO. Lu rng photon nh sng kch thch phi c nng lng ln hn hiu nng lng gia hai vng HOMO v LUMO th in t mi thu nhn nng lng nhy ln vng LUMO. Tm li, khi in t c kch thch n s t vng HOMO nhy ln vng LUMO nn tn ti s xen ph (chng chp) gia cc m my in t gia hai vng ny v do cht bn dn hu c c th dn in.

1.1.3. PEDOT v dn sut

Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) hay PEDOT-PSS l mt dn sut ca Poly(3,4-ethylenedioxythiophene) (PEDOT), n l mt polymer dn c s dng nhiu trong cng nghip in t v bn dn. u im ca PEDOT-PSS l n c truyn quang tt trong trng thi dn in, n nh cao, rng vng cm va phi. Hnh 2 trnh by cng thc phn t ca PEDOT v PEDOT-PSS.

(a)

(b)

Hnh 2. Cng thc phn t ca PEDOT (a) v PEDOT-PSS (b). PEDOT l mt polymer dn to thnh t cc monomer 3,4ethylenedioxylthiophene (EDOT). PEDOT-PSS c s dng lm polymer dn in v truyn quang vi c tnh mm do cho rt nhiu ng dng. Do c dn cao, n c th s dng lm catot trong t in. PEDOT-PSS c th to ra mt mng mng dn bng cch phn tn u n trn mt thy tinh bng phng php quay ph. c bit, cc loi mc s dng PEDOT-PSS c s dng trong cc qu trnh in n v quay ph. Cc ht PEDOT-PSS c th c to ra bng cch lm lnh kh tc l phn tn li trong nc hay cc dung mi khc, chng hn nh ethanol lm tng tc sy kh trong qu trnh in. Mt ng dng khc na l PEDOT-PSS c dng khc phc s thoi ha, bin cht vt liu do nh sng t ngoi, nhit v m cao gy ra.

1.2. ng nano cacbon (CNTs)

C th ni, CNTs l vt liu ang c quan tm nhiu trong khoa hc v cng ngh hin nay bi cc tnh cht u vit. K t khi c pht hin ra vo nm 1991 n nay, ch trong thi gian ngn CNTs c mt trong rt nhiu nhng ng dng khoa hc & cng ngh ni bt. ng nano cacbon (CNTs) l ng c cu trc hnh tr cu to bi cc nguyn t cacbon, cu trc thnh cc vng su cnh. CNTs c th c hnh thnh vi t l chiu di v ng knh ln ti 132.000.000:1.[17]. CNTs c cc tnh cht ni bt hn rt nhiu vt liu khc nn n c ng dng rng ri trong cc lnh vc nh cng ngh nano, in t, quang hc v cc lnh vc khc ca khoa hc vt liu. 1.2.1. Phn loi CNTs c chia thnh 2 loi chnh: ng nano cacbon n tng (SWCNTs) v ng nano cacbon a tng (MWCNTs), ngoi ra cn mt s dng khc nh Torus ( hoa), Nanobud (nm hoa). 1.2.1.1. ng nano cacbon n tng (SWCNTs) Tt c cc SWCNTs u c ng knh gn bng 1 nm, vi chiu di ng c th gp hng triu ln ng knh. Cu trc ca mt SWCNTs c th tng tng nh mt cun giy trn hnh tr. Cc cun ny c biu din bi mt cp ch s (n,m). Cc s nguyn n v m ch ra s vector n v dc theo hai hng trong mng tinh th t ong ca graphene. Nu nh m = 0, ng nano cacbon l zigzag. Nu n = m, ng nano cacbon gi l armchair. Cc trng hp khc chng c gi l chiral. ng knh ca ng nano cacbon c th c tnh t cc ch s (n,m) ca chng:

Vi a = 0.246 nm.

Hnh 3. S sp xp theo h thng ca ng nano cacbon c cp ch s (n,m) c th c biu din qua vector (Ch) trong tm graphene v hn m t tm ny cun ln nh th no to thnh ng nano cacbon. T biu din trc ng, a1, a2 l cc vector n v ca graphene trong khng gian thc.

Armchair

Zigzag Hnh 4. Cc cu trc ca CNTs.

Chiral

SWCNTs th hin cc tnh cht in khc bit so vi ng nano cacbon a tng. C th, rng vng cm c th thay i t 0 eV n 2 eV v dn in c th l kim loi hay bn dn trong khi MWCNTs c rng vng cm bng khng tc dn in nh kim loi. SWCNTs c s dng thu nh cc linh kin in t, chng c th lm dy in cho dn in rt tt. Mt trong nhng ng dng hu ch ca SWCNTs l c s dng trong transistors hiu ng trng (FET). Sn phm s dng trng thi logic ni phn t u tin l dng FET da trn SWCNTs thnh cng trong bo co gn y[2]. to ra mt trng thi logic chng ta phi c c p-FET v n-FET.

1.2.1.2. ng nano cacbon a tng (MWCNTs)

ng nano cacbon a tng bao gm nhiu lp graphite cun li to thnh cc ng hnh tr ng tm. C 2 m hnh c th dng m t cc cu trc ca MWCNTs. Theo m hnh ca Russian Doll, cc tm graphite c sp xp trong cc hnh tr ng tm, mt ng nano cacbon vi ng knh nh hn nm trong cc ng nano cacbon vi ng knh ln hn. Theo m hnh ca Parchment, mt tm graphite c cun vo ging nh mt cun giy hay mt cun bo. Khong cch gia cc lp trong cc ng nano cacbon a tng gn bng vi khong cch gia cc lp graphene khong 3,4 . Trong cc ng nano cacbon a tng, ng nano cacbon hai tng c quan tm bi hnh thi hc v cc tnh cht rt ging vi ng nano cacbon n tng nhng in tr v tnh cht ha hc ca chng c ci thin ng k. y l tm quan trng c bit khi chng ta chc nng ha n (ngha l ghp cc nhm chc ha hc ln b mt ca ng) thm cc tnh cht mi cho ng nano cacbon. i vi trng hp SWCNT, chc nng ha cng ha tr s lm gy mt s lin kt i C=C, li cc l trng trong cu trc ca ng nano cacbon v thay i c hai tnh cht in v c ca chng. Trong trng hp ng nano cacbon 2 tng, ch mt tng ngoi c bin tnh. 1.2.2. Cc tnh cht 1.2.2.1. bn c ng nano cacbon l loi vt liu bn nht, cng nht c bit n hin nay. bn ny l kt qu ca lin kt ha tr sp 2 c hnh thnh gia cc nguyn t cacbon. Vo nm 2000, ng nano cacbon a tng c kim tra v c c kt qu bn ko l 63 GPa. iu ny c hnh dung bng mt si dy cp c tit din 1mm 2 c th chu c lc cng 6422 kg. Khi lng ring ca ng nano cacbon rt thp vi khong 1,3 -1,4 g/cm3, l vt liu c sc bn ring ln nht hin nay vi gi tr ln ti 48.000 kN.m/kg so vi bn ca thp cacbon cht lng cao l 154 kN.m/kg.

Bng 1. So snh cc tnh cht c hc ca CNTs vi cc cu trc khc nhau. [3],[8], [13],[15]

Vt liu SWCNT Armchair SWCNT Zigzag SWCNT Chiral SWCNT MWCNT Inoc Kevlar (o chng n)

Sut Young (TPa) 1-5 0,94 0,94 0,92 0,2-0,8-0,95 0,186-0,214 0,06-0,18

bn ko 13-53 126,2 94,5

gin n im gy (%) 16 23,1 15,6-17,5

11-63-150 0,38-1,55 3,6-3,8 15-50 2

1.2.2.2. cng ng nano cacbon n tng c th chu ng c p lc ln ti 24GPa m khng b bin dng. p lc ln nht o c l 55 GPa, tuy nhin, cc ng nano siu cng ny s b gy ti mt p lc cao hn. 1.2.2.3. Tnh dn in Do cu trc i xng ca graphene, cu trc ca ng nano cacbon nh hng mnh n cc tnh cht in ca n. Ch s (m,n) ca CNTs cho bit n l kim loi, kim hay bn dn cng nh rng vng cm ca chng. Vi mt ng c ch s (n,m), nu n = m th ng l kim loi; nu |n m| =3k (k l s nguyn) th ng l kim loi; nu |m-n| = 3k +1, ng l bn dn; cc trng hp cn li l cht bn dn vi rng vng cm va phi. Bng sau y ghi li tnh cht dn in ca CNTs:

Bng 2. Cu trc ca CNTs vi ch s (m,n). Cu trc ca CNTs Ch s a (m,n) c tnh dn in

Armchair Zigzag Zigzag Chiral Chiral

(n,n) (n,0) v n/3 nguyn (n,0) v n/3 khng nguyn |n-m| = 3k |n-m| = 3k +1

Kim loi Kim loi Bn dn Kim loi Bn dn

Tuy nhin, cc iu kin trn cng c ngoi l, bi cu trc cong nh hng ti cc ng nano cacbon c ng knh nh c th nh hng mnh n cc tnh cht in. V vy, SWCNT vi a (5,0) theo iu kin trn l bn dn nhng thc cht n li l kim loi, iu ny c xc nh trong thc nghim. Theo l thuyt, cc ng nano kim loi c th ti mt dng vi mt dng in ln ti 4.10 9 A/cm2, ln hn 1000 ln so vi cc kim loi dn thng thng nh ng. MWCNTs vi cc lp v c mi lin h bn trong tr thnh siu dn ti nhit chuyn tip tng i cao vi Tc = 12K, ngc li, gi tr Tc ny l thp i vi ng nano cacbon n tng hay ng nano cacbon a tng khng c cc lp v lin kt vi nhau. 1.2.2.4. Tnh dn nhit Tt c cc ng nano cacbon u dn nhit tt dc theo cc ng, Cc kt qu o c ch ra rng, mt ng SWCNT ti nhit phng dn nhit dc theo trc ca n ln ti 3500 W.m-1.K-1 so vi ng c coi l kim loi dn nhit tt cng ch t c 385 W.m-1.K-1. n nh nhit ca ng nano cacbon c xc nh ln ti 2800 oC trong chn khng v 750oC trong khng kh.

1.2.2.5. Tnh cht quang Cc tnh cht quang ca CNTs lin quan n s hp th, s pht quang v ph tn x Raman ca n. Cc tnh cht ny cho php xc nh c im cht lng ng nano cacbon nhanh chng v chnh xc. 1.2.2.5.1. Hp th quang

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Hp th quang trong CNTs khc vi hp th quang trong vt liu khi 3D thng thng bi s hin din ca cc nh nhn (ng nano cacbon c cu trc 1D) thay v mt ngng hp th bi s tng hp th (trong trng thi rn c cu trc 3D). Hp th trong ng nano bt u t s chuyn tip in t t v 2 n c2 hay t v1 n c1. S chuyn tip ny l tng i nhanh v c th s dng nhn ra cc loi ng nano. Ch rng, sc ca nh cng gim th nng lng cng tng v nhiu ng nano c cc mc nng lng tng t E 22, E11 v v th c s chng chp ng k trong ph hp th.

Hnh 5. Cu trc nng lng hp th quang ca CNTs.

Hp th quang thng c s dng xc nh cht lng ca bt ng nano cacbon.

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Hnh 6. Ph hp th quang t s phn tn ca ng nano cacbon n tng. 1.2.2.5.2. S pht quang Hin tng pht sng quang ha (PL) l mt trong nhng cng c quan trng xc nh c im ca ng nano cacbon. C ch ca hin tng pht sng quang ha thng c m t nh sau: mt in t trong ng nano cacbon hp th nh sng kch thch t chuyn tip S22 to ra mt cp in t-l trng (exciton). C in t v l trng nhanh chng nhy t trng thi c2 n c1 v t v2 n v1. Sau chng ti hp thng qua mt qu trnh chuyn i nh sng pht x t c1 n c2. 1.2.2.5.3. Tn x Raman Ph tn x Raman c phn gii v nhy tt. Tn x Raman trong SWCNTs l cng hng, tc l ch nhng ng c d c mt rng vng cm bng vi nng lng kch thch laser.

Hnh 7. Ph Raman ca SWCNTs. Cng ging nh ph PL, nng lng ca nh sng kch thch c th c qut v vy m to ra c ph Raman. Ph ny cng cha cc c im ni bt nhn ra ch s (n,m). Tri ngc vi ph PL, ph Raman pht hin ra khng ch cht bn dn m cn nhn ra cc ng kim loi. 1.2.2.6. Khuyt tt, sai hng (Defects) trong CNTs Cng ging nh cc vt liu khc, lun tn ti cc li trong tinh th hc nh hng n tnh cht ca vt liu. Cc defect ny c th c tm thy trong qu trnh

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hnh thnh khong trng nguyn t. Mt dng li khc ca ng nano cacbon cc li Stone Wales defect, y l mt dng li do hnh thnh vng 5 cnh hay 7 cnh bi s sp xp li ca cc lin kt. Do cu trc rt nh ca CNTs, bn ko ca ng ph thuc vo cc on yu nht ca n ni m ch lin kt yu nht tr thnh sc bn dai ca c chui.

Hnh 8. Cc defect trong CNTs. Cc li tinh th hc cng nh hng n cc tnh cht in ca ng. Ni chung, cc ch c li th dn gim. Mt li trong kiu ng armchair c th gy ra vng bao quanh tr thnh bn dn, v khong trng ca cc n nguyn t gy ra cc tnh cht t. Ngoi ra, cc li v tinh th hc cng nh hng ln n cc tnh cht nhit ca ng, chng hn nh cc li dn n tn x phonon. 1.3. Vt liu t hp nanocomposite PEDOT-PSS:CNTs PEDOT-PSS l mt polymer dn, CNTs l mt trong nhng cht dn in tt nht hin nay. Kt hp hai cht ny to thnh vt liu composite ca PEDOT-PSS v CNTs s to ra mt cht dn tt c ng dng nhiu trong vic ch to ra cc loi mng va c kh nng dn in tt va c kh nng cho nh sng i qua. Vic to mng composite PEDOT-PSS:CNTs vi t l pha tp CNTs 0,01% v khi lng tuy c gim kh nng truyn nh sng i i cht nhng lm in tr b mt mng gim i t 3-6 ln so vi mng ch c PEDOT:PSS[6]. Bng vic s dng cht lin kt trung gian l PIL (poly(ionic liquid)) lin kt gia PEDOT-PSS v CNTs, kh nng dn in ca mng c ci thin ng k, l vi t l pha tp CNTs vo hn hp PIL-PEDOT-PSS l 0,2% v khi lng in tr b mt mng gim xung ti 70 ln so vi mng ch c PIL-PEDOT-PSS[10]. 1.4. Cu to v nguyn tc hot ng ca OLED

13

1.4.1. Gii thiu chung v OLED OLED (Organic light emitting diode) l it pht sng hu c m nh sng pht ra t lp mng hu c khi t mt in p thch hp vo hai cc ca n. Lp bn dn hu c ny c kp gia hai in cc, mt trong hai in cc l trong sut nh sng c th truyn qua. OLED ang rt c quan tm nghin cu v nhng u im ca n. Th nht, mng mng hu c nh hn so vi mng mng v c. Th hai, mng mng hu c c th c ph vi mt din tch ln trn b mt , do c th sn xut nhng mn hnh hin th ln. Th ba, mng mng hu c c tnh do dai v mt c hc, do c th un cong, gp li m khng nh hng ti thit b, thm ch nu c ri xung t hay b vt nng ri vo th cng kh c th lm hng mn hnh[10]. Nm 1999, chic mn hnh hu c u tin c thng mi ha bi Pioneer v hin nay mn hnh OLED c sn sut ph bin bi nhiu tp on cng ngh ln nh Sony, Samsung, Nokia 1.4.2. OLED cu trc n lp OLED vi cu trc n gin nht gm 3 lp: lp in cc anot trong sut, tip theo l lp pht sng hu c v mt lp trn cng l lp in cc catot. in cc anot dng truyn dn l trng v ITO thng c s dng lm lp ny. Lp pht quang kp gia hai in cc l mt polymer hay cht hu c dn in nh Alq 3, PPV, PPP, MEH-PPV, lp ny s pht ra nh sng. Lp in cc catot trn cng dng truyn in t, thng thng Al c s dng lm catot. Hnh 9 trnh by m hnh ca mt OLED n lp.

Hnh 9. Cu trc ca OLED n lp.

14

Ti lp pht quang, vt liu s dng l cht bn dn ha c, lp ny c hai vng l HOMO v LUMO. Hai vng ny ging nh vng ha tr v vng dn tng ng trong cht bn dn v c. Hnh 10 trnh by gin vng nng lng ca mt OLED.

Hnh 10. S nguyn l hot ng ca OLED. Khi t mt in p phn cc thun vo hai cc ca OLED, s c dng in chy qua n. Cc l trng di chuyn t in cc anot vo vng HOMO ca lp pht quang ng thi cc in t cng di chuyn t in cc catot vo vng LUMO ca lp pht quang. Do , ti lp pht quang s xy ra s ti hp gia in t v l trng, s ti hp ny to ra exciton v pht ra nh sng. nh sng s i t lp pht quang qua in cc trong sut anot v truyn ra ngoi. Bc sng ca nh sng pht ra s ph thuc vo rng vng cm gia vng HOMO v LUMO ca vt liu lm lp pht quang. 1.4.3. OLED cu trc a lp OLED vi cu trc nh hnh trn c hiu sut pht sng thng khng cao v kh khng ch c s khuych tn v dch chuyn ca cc cc dng ht ti sao cho in t v l trng gp nhau v hnh thnh cc cp exciton ch yu ti lp pht quang. ci thin cc tnh cht cng nh hiu sut ca linh kin, OLED vi cu trc a lp c ch to. Vai tr ca cc lp truyn dn in t (Electron Transport Layer-ETL) v lp truyn dn l trng (Hole Transport Layer-HTL) l ci thin qu trnh tim cc ht ti in cc, iu chnh qu trnh dch chuyn ca chng t tng cng s to thnh cc cp exciton ti lp pht quang . Lp truyn dn in t c chn vo gia in cc catot v lp pht quang, lp truyn dn l trng s c chn vo gia lp pht quang v in cc anot. Hnh 11 trnh by cu trc ca mt OLED a lp.

15

Hnh 11. Cu trc ca OLED a lp. Nguyn l lm vic ca OLED a lp v c bn cng ging nh OLED vi n lp. Tuy nhin, do c thm lp truyn in t v lp truyn l trng, cc dng ht ti s i nh sau: Khi p mt in th phn cc thun thch hp vo OLED, l trng s t anot c truyn vo lp pht quang thng qua lp truyn l trng ng thi in t s i t catot vo lp pht quang thng qua lp truyn in t. Nh vy, khi s dng vt liu thch hp c th iu chnh c vn tc dch chuyn ca cc dng ht ti sao cho in t v l trng gp nhau ti lp polyme pht quang. 1.4.4. Hiu sut ca OLED p ng c cc yu cu thc t s dng, mt OLED cn tha mn 3 yu cu sau: in p t vo thp, pht sng tt v thi gian sng di. Theo[11], yu cu in th t vo thp ph thuc vo in tr ca lp pht v ro th ti lp tip xc ca hai in cc. Nu ro th thp, in p t vo s thp cn in tr ca lp pht ph thuc vo bn cht ca vt liu. Yu cu pht sng cao ph thuc vo s ti hp ca in t v l trng phi xy ra trong lp pht v iu ny ph thuc vo nhiu yu t. Thc t, t l ti hp xy ra trong lp pht cao th in t v l trng phi c cng linh ng. Nu nh s ti hp xy ra gn lp tip xc gia lp pht quang v in cc th thng xy ra hin tng dp tt exciton do gim qu trnh ti hp. Hn na nu nh ht ti phn in cc ny linh ng hn ht ti lp in cc kia, cc ht ti s i qua lp pht quang v khng c s ti hp ht ti. V mt l tng, cc ht ti nn ti hp phn gia ca lp pht quang c hiu sut pht sng cao nht. Trn thc t, khng th c cc ht ti c linh ng nh nhau nhng c th s dng mt vi gii php nhm giam cm cc ht ti bn trong lp pht sng v xa hai in cc c s ti hp cao nht. nh sng pht ra t lp pht quang s i qua lp anot trong sut, nh sng pht ra khng ch ph thuc vo kh nng cho nh sng truyn qua ca anot m cn ph

16

thuc vo hng s in mi ca lp pht. Trn thc t, ch mt phn nh nh sng c pht ra t diot do s phn x v hp th xy ra ti lp tip xc ca in cc v lp pht sng. S photon c pht ra t diot c gi l hiu sut lng t ni, gi tr ny ph thuc vo ch s khc x n ca vt liu. So vi diot v c, gi tr n ny nhn chung l nh hn v v vy nh sng mt mt s t hn. Thi gian sng ca diot c nh ngha l khong thi gian t khi n hot ng n khi n b hng. 1.4.4.1. Ci thin in p m ca OLED Vi cu trc ca OLED n lp nh ch ra n c hai nhc im: Th nht, ro th cao ti lp tip xc. Kim loi vi cng thot thp nh Ca (2,87 eV), Mg(3,66 eV) l ph hp c ro th thp ti in cc catot. Tuy nhin cc kim loi ny d dng b oxy ha v cn phi c bo v trnh tip xc vi khng kh. i vi anot, ITO l vt liu thng c s dng vi cng thot khong 4,5 eV. Nhc im th hai l lp pht quang va l ni truyn ht ti va l ni ti hp ht ti pht sng. Vi hai nhim v nh vy, hiu sut OLED s gim i. Nh vy cn phi phn tch hai nhim v ra bng cch thm vo OLED cc lp truyn in t v lp truyn l trng nh cp trn. C rt nhiu vt liu c th lm lp ETL v HTL. S la chn ny ph thuc vo cng thot ca in cc ( E) v vt liu lm lp pht ( S). Lp truyn (TL) nn c cng thot nm gia E v S. iu ny s lm gim ro th cao m cc ht ti phi vt qua n c lp pht v do in p t vo OLED s gim. Ni cch khc, s ht ti tim vo s tng v hiu sut ca OLED v th s tng theo. Mt khc, la chn lp truyn ph hp cng c th mang li s bao vy hay giam gi cc ht ti trong lp pht gp phn lm tng xc xut ti hp.

1.4.4.2. Ci thin cng pht quang sng ca OLED c th c ci thin thng qua vic giam gi cc ht ti bn trong lp pht quang v ci thin nh sng pht ra qua anot. cc ht ti c giam cm trong lp pht, c rt nhiu cch, chng hn nh dng mt ni pin hay mt ni ro Schottky hoc s dng vng offset (band offsets)Tuy nhin, c mt cch n gin hn nhiu l s dng vt liu lm ETL, HTL ph hp. Chng hn, giam gi l trng trong lp pht, lp ETL nn c vng ha tr thp hn vng ha tr ca lp pht trong gin nng lng. Nh vy, cc l trng c tim t anot phi vt qua mt ro th ln ti ch tip xc gia lp EL v ETL c th n catot v nu nh ro th

17

c chn cao l trng s b giam gi trong lp pht v khng th nhy qua c. Ngoi ra, giam gi ht ti s phn phi li in trng bn trong OLED, iu ny gip cn bng in t v l trng tt hn v do tng kh nng ti hp trong lp pht. Cc oxit kim loi nh Vanadium oxide (VOx), molybddnum oxide (MoOx), ruthenium oxide (RuOx) v Al pha tp km oxit (AZO) c dng lp HTL c u im gi c cng nh sng pht ra bi cc vt liu ny c truyn qua cao. thu c nh sng pht ra c hiu sut cao, nn s dng in cc anot trong sut. ITO l vt liu c tin dng nht bi cc c tnh truyn quang cao (c th t n 90%). Tuy nhin, kinh nghim ch ra rng, anot dng ITO thng khng lin kt c hc tt do n khng n nh, iu ny dn n tui th ca thit b gim i. Tin oxide (TO) v AZO vi mng trong sut cao v in tr thp c th dng thay th ITO trong OLED s dng lp pht l PPV s ci thin c n nh [12]. 1.4.4.3. Ci thin tui th ca OLED Kinh nghim thc t ch ra rng lp tip xc kim loi/hu c (polymer) c nh hng ln n s suy yu c hc. Trc tin, cht lng c hc lp tip xc gia cc lp khc nhau ca OLED c th tc ng n dn in v nhit ca n. Mt lp tip xc c hc km s lm in tr tip xc v hiu ng nhit Joule c th ph hy vt liu. Ni cch khc, nu nh mng khng ng nht, s thay i dng qua thit b cng c th gy ra s tng nhit ng k v s on mch c th xy ra. Cht lng ca b mt mng ph thuc vo k thut v cc thng s ph mng. Chng hn, ph indium ln poly(3-octyl thiophene) s to thnh cc t m indium v b mt khng ng nht; OLED s dng cc lp ny s b on mch sau mt thi gian hot ng. Ngc li khi s dng nhm lm catot, thit b s n nh hn v c tui th lu hn. Tng t, in cc mng hn s dn n s ph hy iot nhanh hn do s vt qu dng nhit. i vi in cc anot, knh hin vi lc nguyn t (AFM) ch ra rng hnh thi b mt ca mng ITO ph thuc nhiu vo nhit ca (substrate). Tnh ng nht ca mng vi b mt phng v gim th rp s tng ln khi gi n nhit tng i cao (> 473K hay 200 oC) trong sut qu trnh quay ph[9]. B mt ca tt c cc mng trong OLED nn c lm phng nhng thc t rt kh lm c iu ny v vy thay v c gng c c b mt mng phng c th s dng mt lp m (buffer layer) chn gia lp mng hu c v in cc. Cc lp ny nn c lm tht mng (khong 10nm) cho php cc ht ti chui ngm qua n m khng thay i cc tnh cht in ca OLED. Lu rng, cc lp m khng ng vai tr ca lp IL hay TL m c bn n dng cho mc ch c hc l to

18

mng c phng hn. Mt khc, bn phn anot, cc lp m cng phi c truyn qua cao nh sng c th i qua d dng. Cui cng, mng nn l ng nht c b mt phng v khng c cc li c hc. Nguyn nhn th hai gy ph hy OLED nhanh l do s phn tn ca cc nguyn t kim loi t in cc vo lp pht. Qu trnh phn tn c th xy ra ti c hai in cc. Cc nguyn t kim loi phn tn vo bn trong lp hu c c th gy ra tng tc gia chng cht hu c to ra cc hp cht mi v lm thay i cc tnh cht quang ca lp pht. ngn cn hay hn ch s phn tn, c th s dng lp tip xc gia cc in cc v lp pht quang bng cch chn thm cc lp m. Cc lp m ny thng l lp oxit rt mng ging nh mt ro cn ngn cn s phn tn . Tuy nhin, cc lp m ny c th lm tng in p t vo thit b do dy ca mng phi c cc tiu ha to ra mt lp ro cn tr phn tn m khng nh hng n tch cht in ca OLED. Chng hn, gia Alq 3v Al s dng lp m l mng Al 2O3 dy c 2 nm cn tr phn tn ca nguyn t nhm vo Alq3.

CHNG 2. CC PHNG PHP NGHIN CU V THC NGHIM

2.1. Nghin cu bin tnh ng nano cacbon a tng (MWCNTs) bng hn hp axit HNO3 v H2SO4 2.1.1. Quy trnh lm sch v bin tnh MWCNTs MWCNTs ban u dng th, cn phi lm sch v bin tnh n. Mc ch x l CNTs trong axit l loi b cc tp cht nh cc nguyn t nit, oxy, st c ln trong CNTs. Quy trnh bin tnh MWCNTs c thc hin theo[10]. C th nh sau: Cn 120 mg MWCNTs cho vo hn hp axit gm 60 ml HNO 3 : 20 ml H2SO4 (t l 3:1),

19

khuy u trong 3h ti 800C. Tip theo ngui hn hp n nhit phng v tin hnh lc, ra nhiu ln bng nc ct loi b hon ton lng axit d. MWCNTs sch c sy kh trong chn khng 80 0C trong 24h. Lng MWCNTs sch thu c l 87 mg MWCNTs, hiu sut t 72,5%. Hnh 12 ch ra cu trc ca CNTs trc v sau khi x l bng axit. Qu trnh x l CNTs bng axit cng l qu trnh bin tnh n v CNTs trong hn hp axit ti nhit cao s phn ng vi axit to ra nhm chc (-COOH). Sau y l phng trnh phn ng: MWCNTs + HNO3 + H2SO4(xt)
H+

MWCNTs-COO + NO2 + H2O (2.1)

MWCNTs-COOH

Hnh 12. Cu trc ca CNTs sau khi bin tnh bi hn hp axit.

2.1.2. Phn tch cu trc MWCNTs bng ph hng ngoi FTIR Trong ph hng ngoi, cc bc x hng ngoi s i qua mu, mt s s bc x khc li b mu hp th. Phn tch ph s cho bit s hp th v truyn qua ca cc bc sng hng ngoi i vi cc phn t, nhm chc khc nhau t xc nh c thnh phn cu trc ca vt liu. Hnh 13 trnh by s nguyn l lm vic ca thit b ghi ph FTIR.

20

Hnh 13. S nguyn l lm vic ca my o FTIR.

1. Ngun sng: Nng lng hng ngoi c pht ra t mt ngun sng, Chm sng ny s mt khe h, n c nhim v iu chnh nh sng hng ngoi i n mu. 2. My o giao thoa: Chm tia hng ngoi qua khe hp n my o giao thoa ni to thnh ph m ha. 3. Mu: Chm tia i vo ngn cha mu, ti y chm tia hng ngoi c truyn qua hay phn x trn b mt mu. Ti y, cc tn s xc nh (bc sng) ca nh sng hng ngoi s l c trng duy nht ca mu c hp th. 4. Detector: Detector s xc nh cc tn hiu giao thoa xc nh. 5. My tnh: Tn hiu o c s c s ha v gi n my tnh thc hin cc bin i ton hc Fourier, sau ph hng ngoi bin i Fourier s c hin th trn mn hnh my tnh cho ngi s dng. Cc mu CNTs bin tnh v cha bin tnh c phn tch cu trc bng ph hng ngoi FTIR thc hin ti Kha Ha, Trng HKHTN vi nhn hiu my GXPerkinElmer (USA). 2.2. Nghin cu ch to v xc nh cc c tnh ca mng nanocomposite PEDOT-PSS:MWCNTs 2.2.1. Ch to mng mng nanocomposite PEDOT-PSS:MWCNTs bng phng php quay ph (spin coating) 2.2.1.1. Hn hp dung dch PEDOT-PSS:MWCNTs Cng trnh ca nhm tc gi J.H. Moon [9] thc hin nm 2005 a ra khong kho st ca hm lng CNT v phn trm khi lng trong PEDOT-PSS l [0-0,03] v a ra mt kt qu truyn dn in quang ti u ti 0,01% vi in tr ca mng tng ln t 3-6 ln ty thuc vo loi CNTs. Nhm ca tc gi Tran Thanh Tung, Tae

21

Young Kim thc hin nm 2010 lm mng dn composite PEDOT-PSS-CNTs s dng thm cht lin kt trung gian l PIL a ra khong kho st l [0-0,4] v cho ra mt t l ti u ti 0,2 % hm lng CNTs c trong PEDOT:PSS-PIL, vi t l ny tr ca mng gim ti 70 ln[4]. Trong ti ny, s dng dung dch PEDOT-PSS trong dung mi nc cha 5% isopropanol. T l kho st thnh phn khi lng ca MWCNTs so vi 100 phn khi lng dung dch PEDOT-PSS c trnh by trong bng 3. Bng 3. Thnh phn t hp nanocomposite PEDOT-PSS:MWCNTs. TT 0 1 2 3 4 5 6 CNTs (mg) 0,00 0,25 0,50 0,75 1,00 1,25 1,50 PEDOT-PSS (mg) 100 100 100 100 100 100 100

Qu trnh phn tn MWCNTs trong dung dch PEDOT-PSS c thc hin bng khuy c hc trong 48h sau rung siu m trong 6h ti nhit phng. Kt qu l CNTs c phn tn u trong dung dch PEDOT-PSS. 2.2.1.2. Quy trnh lm sch thy tinh Cc mu thy tinh ct theo hnh vung vi t l 1x1 cm, sau tin hnh lm sch tun t theo cc bc sau: Rung siu m trong dung dch cn:axeton (t l 1:1) trong 20 pht; tip rung siu m trong cn 20 pht; cui cng rung siu m trong nc ct vi thi gian 10 pht. thy tinh sau khi lm sch c sy kh v a vo s dng. Hnh 14 trnh by quy trnh lm sch .
Rung siu m (RSA) trong cn:axeton(t l 1:1) trong 20 pht

RSA trong cn 20 pht

RSA trong nc ct 10 22 pht

Sy kh ti 80 0C trong 20 pht

thy tinh sch

Hnh 14. Quy trnh lm sch thy tinh. 2.2.1.3. Ch to mng mng bng phng php quay ph (spincoating) Ky thut tao mang bng phng phap quay phu ly tm da trn nguyn l di tc dng ca lc ly tm, dung dch cht to mng c dn u trm mt phng to thnh mng.

Hnh 15. S qu trnh quay ph.

Qu trnh quay ph c chia lm 4 giai on: a l giai on nh dung dch ln thy tinh v dn u ra ton mng, b l giai on gia tc quay, c l giai on quay vi tc n nh, c l giai on ngng quay v bay hi (lm kh). Chiu dy ca mng s ph thuc vo rt nhiu yu t chng hn nh nht, khi lng ring v nng ca dung dchHnh 16 trnh by s ph thuc ca dy mng vo tc v thi gian quay ph. Hu ht cc vt liu th dy mng t l nghch vi tc v thi gian quay ph.

23

(a)

(b)

Hnh 16. a - S ph thuc ca dy mng vo tc v thi gian quay ph. b- Thit b spin-coating Laurell WS-400B-6NPP. Cc mu mng mng c ch to ch : Vn tc quay 1500 vng/pht, thi gian gia tc 3 giy, quay n nh trong 60 giy. Sau khi quay ph, mng c sy kh trong chn khng vi thi gian 2h nhit 800C. 2.2.2. Kho st cc c tnh ca mng t hp nanocomposite PSS:MWCNTs PEDOT-

2.2.2.1. Kho st dn ca mng bng phng php o in tr bn mi d Phng php 4 mi d c s dng o tr b mt ca mng hoc in tr khi ca cc tm wafer. S nguyn l ca phng php ny c trnh by trn hnh 17.

24

(a)

(b)

Hnh 17. S o in tr bng phng php 4 mi d(a) v thit b o JANDEL(b.) Hai mi d bn ngoi dng cp mt dng n nh mt chiu, hai mi d bn trong dng o in th trn b mt mng mng. in tr sut s c xc nh bng cc biu thc sau: = 2V/I (Ohm-cm) nu t>>s v = (t/ln2)V/I (Ohm-cm) nu t<<s (2.3) (2.2)

Trong t l dy ca mng mng, s l khong cch ca cc mi d. T 2.3, in tr ca mng mng s c xc nh nh sau: R = /t = (/ln2)V/I = 4,53 V/I (Ohms/sq) vi s>>t. (2.4)

Cc mu mng t hp nanocomposite PEDOT-PSS:MWCNTs c xc nh in tr b mt ca mng ti nhit phng trn thit b JANDEL (Anh), kt qu trnh by trong bng 4.

Bng 4. dn ca mng nanocomposite PEDOT-PSS:MWCNTs. TT 1 2 3 4 PEDOT-PSS PEDOT-PSS:CNTs = 100 : 0,25 (p.t.l) PEDOT-PSS:CNTs = 100 : 0,5 (p.t.l) PEDOT-PSS:CNTs = 100 : 0,75 (p.t.l) Vt liu in tr (/) 73.3 60 36 52,3

25

5 6 7

PEDOT-PSS:CNTs = 100 : 1

(p.t.l)

63,8 74 78

PEDOT-PSS:CNTs = 100 : 1,25 (p.t.l) PEDOT-PSS:CNTs = 100 : 1,5 (p.t.l)

Ghi ch: p.t.l Phn trng lng 2.2.2.2. o ph truyn qua ca mng mng bng phng php o ph hp th UV-Vis My quang ph UV-Vis c th o c ph hp th, ph truyn qua, ph phn x ca mt cht no . S cu to ca my trnh by trn hnh 18.
L
1

Io

IS

Knh lc sc Io L
1

Detector IG

Hnh 18. S cu to ca my quang ph UV-Vis. nh sng sau khi i qua knh lc sc s tr thnh ngun sng n sc c tch lm hai tia 1 v 2 c cng I 0 nh nhau nh gng bn m L 1, tia 1 truyn thng ti vt nn, tia 2 sau khi phn x trn gng L2 s a ti mu cn xc nh hp th. Sau khi so snh cng nh sng sau khi truyn qua mu I S v cng nh sng nn IG ta s xc nh c hp th ca mu: IS = IO IG (2.5)

Ngoi vic xc nh c ph hp th, ph phn x ca cc cht, my quang ph UV-Vis cn o c ph truyn qua trong di bc sng t ngoi, nhn thy v gn hng ngoi. Cng nh sng i qua mt mu (I) so snh vi cng nh sng trc khi n i qua mu (I0), t t l I/I0 c gi l h s truyn qua c th hin

26

di dng phn trm truyn qua (%T). H s hp th A c xc nh qua h s truyn qua theo cng thc: A = -log (%T/100%) (2.6)

Cc mu nghin cu c o ph truyn qua trn my JASCO V-570, Phng th nghim Vt liu v linh kin lai cu trc nano-Trng H Cng ngh. 2.2.2.3. Nghin cu cu trc hnh thi b mt ca mu bng nh FESEM Cc mu mng c tin hnh chp nh FESEM trn thit b kinh hin vi in t qut pht x trng phn giai cao HITACHI S-4800, Vin Khoa hc & Cng ngh VN. Nguyn l hot ng ca thit b trnh by trn hnh 19.

Hnh 19. Nguyn l hot ng ca FESEM. V c bn, nguyn l hot ng ca FESEM cng gn ging nh SEM. S khc nhau ch trong my SEM cc in t c bn ra t sng bn in t cn trong my FESEM cc in t c bn ra t mt ngun catot pht x trng. Trong chn khng, cc in t c bn ra mt ngun pht x trng c gia tc trong mt gradient trng. Chm in t i qua thu knh in t sau bn vo b mt ca mu. Qu trnh bn in t ny s sinh ra cc loi in t khc nhau c bn ra t mu. Mt detecter s thu li cc in t c bn ra t mu v hnh nh ca b mt mu c hnh thnh bng cch so snh cng ca cc in t sau khi bn ra khi mu vi cng ca cc in t ban u khi cha ti mu. Detecter s chuyn tn hiu ti ng tia catot x l tn hiu s. Sau tn hiu s s c a v my tnh tnh ton v gii m ra hnh nh, cui cng hnh nh s c hin th trn mn hnh my tnh.

27

Hnh 20. Hnh nh ca chic my Hitachi FE-SEM model S-4800. FESEM cho hnh nh sc nt, t b bin dng hnh nh tnh in vi phn gii xung ti 1 nm thm ch l 0,5 nm, phn gii ny gp t 3-6 ln so vi nh SEM, hnh nh c cht lng cao, in th t vo thp (in th gia tc trong khong 0,5 n 30 kV), phng i hnh nh siu cao. Lu rng i vi vt liu khng dn in cn ph mt lp dn ln n trc khi chp. 2.3. Nghin cu ch to linh kin OLED 2.3.1. Quy trnh to hnh in cc ITO bng phng php n mn ha hc t. Ban u ITO bao ph ton b thy tinh, to ra nhiu linh kin trn mt ITO cn tin hnh n mn ITO to ra cc mng in cc ITO trn thy tinh.

ITO

thy tinh

Hnh 21. Mng ITO sau khi c n mn Qu trnh gm 3 bc: Bc 1: To mt n bo v lp mng ITO cn gi li.

28

Bc 2: n mn ITO bng hn hp dung dch HCl:H 2O:HNO3 vi t l 8:4:2 trong thi gian 5 pht. Bc 3: Lm sch mng in cc ITO nh sau: Rung siu m trong acetone, tip theo rung siu m trong cn (C2H5OH) v sau cng l rung siu m trong nc ct. Mi qu trnh trn c thc hin ring bit trong thi gian 10 pht. 2.3.2. Qu trnh ch to OLED 2.3.2.1. OLED n lp cu trc ITO/MEH-PPV/Al

Al MEH-PPV:PVK ITO thy tinh

Hnh 22. OLED cu trc n lp ITO/MEH-PPV:PVK/Al Lp pht quang MEH-PPV:PVK c ph trn ITO vi cc thng s cng ngh c trnh by trong bng 5. Sau khi to mng cc mu c sy chn khng (khong 10-3 torr) ti 80oC trong thi gian 90 pht.

Bng 5. Cc thng s cng ngh ch to mng MEH-PPV:PVK. Bc Vn tc (v /ph) 1 2 800 2500 Thi gian gia tc (s) 5 5 Thi gian quay (s) 20 30

2.3.2.2. OLED cu trc a lp ITO/PEDOT-PSS/MEH-PPV :PVK/Al

29

Al MEH-PPV:PVK PEDOT:PSS

ITO thy tinh

Hnh 23. OLED a lp cu trc ITO/PEDOT:PSS/MEH-PPV:PVK/Al

Bng 5 trnh by cc thng s cng ngh ch to cc mng mng ca OLED a lp. Qu trnh x l mng tng t nh ch to OLED n lp.

Bng 5. Cc thng s cng ngh ch to mng PEDOT-PSS v MEH-PPV:PVK Lp Bc Vn tc (v/ph) Thi gian gia tc (s) 1 800 5 PEDOT-PSS Thi gian quay (s) 20

3500

30

30

1 2

800 2500

5 5

20 30

2.3.2.3. OLED cu trc a lp ITO/ PEDOT-PSS:MWCNTs/MEH-PPV:PVK/Al

Hnh 24 trnh by cu trc ca OLED a lp s dng mng nanocomposite PEDOT-PSS:MWCNTs. Cc thng s cng ngh ch to cc mng mng ca OLED c trnh by trong bng 6. Bng 6. Cc thng s cng ngh ch to mng PEDOT-PSS:CNTs v MEHPPV:PVK Lp Bc Vn tc (v/ph) Thi gian gia tc (s) 5 5 Thi gian quay (s) 20 30

MEHPPV:PVK 1 2 PEDOTPSS:CNTs

Al MEH-PPV:PVK PEDOT:PSS/CNTs

ITO thy tinh

Hnh 24. OLED cu trc ITO/PEDOT-PSS:CNTs/MEH-PPV:PVK/Al

800 4000

31

1 2

800 2500

5 5

20 30

2.3.3. Ch to in cc Al bng phng php bc bay nhit chn khng Sau khi ch to xong cc lp ca OLED, giai on cui cng l tin hnh ch to in cc nhm (Al). C nhiu cch to thnh mng mng kim loi nh bc bay nhit, bc bay chm tia in t, bc bay laze, Epitaxy chm phn t y chng ti s dng phng php bc bay nhit chn khng. Bc bay nhit chn khng l cng ngh lng ng pha hi vt l m cc phn t ha hi (phn t, nguyn t) c ha hi trong chn khng cao.Vt liu cn bc bay c t trong thuyn in tr trong chung c chn khng cao (10-3-10-8 Torr). Vt liu c t nng nh s t nng ca thuyn in tr khi c dng in chy qua v ta nhit theo nh lut Jun-Lenxo. Khi vt liu c t nng n nhit bay hi, cc phn t s bc bay ln v to thnh lp mng mng kim loi. Nhit bc bay ca vt liu ph thuc rt mnh vo p sut, p sut trong chung cng nh th nhit bc bay cng gim. Bc bay trong chn khng thp i hi nhit ngun bc bay cao hn, iu ny dn n cc phn ng ha hc gia ngun bc bay v vt liu cn bc bay. khc phc hin tng ny trong nhiu trng hp ngi ta s dng chn ng vt liu. Cc loi chn c ch to t vt liu c nhit nng chy rt cao nh Al 2O3, oxit bery, thory...[1]. Hnh 24 trnh by mt vi hnh dng thuyn in tr thng dng.

MEHPPV:PVK

32

Hnh 25. Cc loi thuyn in tr bng kim loi: dy in tr (a-d), l in tr (e-g). y bc bay nhm s dng dy in tr l W c hnh dng nh hnh d trong hnh 24.

CHNG 3. KT QU V THO LUN

3.1. Nghin cu bin tnh MWCNTs bng hn hp axit 3.1.1. nh hng ca MWCNTs n nht v th tch ca hn hp dung dch PEDOT-PSS:MWCNTs Khi thc hin phn tn CNTs vo PEDOT-PSS, nhn thy rng CNTs nh hng mnh ti nht ca hn hp dung dch. Hnh 26 cho thy s thay i th tch ca

33

hn hp dung dch khi so snh th tch 2 l, mt l cha 5ml PEDOT-PSS v mt l cha 5ml PEDOT-PSS v 75 mg CNTs.

Hnh26. (a) Dung dch PEDOT-PSS (phi) v hn hp dung dch PEDOTPSS:CNTs(tri). (b) hn hp dung dch PEDOT-PSS:CNTs. Khi c mt CNTs th th tch ca hn hp dung dch gim mnh v nht tng ng k. iu ny c nh hng n cht lng ca mng trong qu trnh quay ph. Hin tng ny c th c gii thch l do CNTs c cu trc ng rng, khi phn tn vo dung dch PEDOT-PSS n c th ht cht lng vo trong v lm cho th tch ca hn hp dung dch gim i. Hn na, y s dng CNTs a tng, lng PEDOT:PSS khng ch b ht vo trong lng ng m cn b ht vo cc thnh tng ca ng lm cho th tch ca l ng hn hp gim i mnh.

3.1.2. Kh nng phn tn ca MWCNTs bin tnh trong PEDOT-PSS Quan st CNTs sau khi bin tnh v phn tn vo PEDOT-PSS cng nhn thy hn hp dung dch c s ng u v n nh tt hn nhiu so vi CNTs th. Sau mt thi gian kh lu hn hp dung dch ca CNTs bin tnh khng c hin tng sa lng, trong khi hn hp dung dch ca CNTs th c lng CNTs lng ng xung di y l kh r. iu ny c th gii thch l do sau khi bin tnh bng hn hp axit, CNTs c cc nhm chc (-COOH) hnh thnh trn ng, cc nhm chc ny c tnh phn

34

cc , d dng lin kt vi phn t (OH-) ca nc d dng phn tn vo mi trng nc. 3.2. Nghin cu cu trc MWCNTs bng ph hng ngoi FTIR Ph hng ngoi ca CNTs trc v sau khi x l bng axit trnh by trn hnh 27.

Hnh 27. Ph FTIR ca CNTs trc v sau khi bin tnh. T hnh 27 nhn thy c hi ph hp th c cc nh chung l: nh 1627 cm -1, y chnh l nh nhn dng CNTs v n th hin lin kt vng cacbon (-C=C-), lin kt chnh trong cu trc ca CNTs; nh 3435 cm -1, y l nh th hin s c mt ca nhm (-OH) do s tn ti ca nc gy ra; nh 2923 cm -1, nh ny l s gp mt ca lin kt (-C-H) i xng; nh 1380 cm-1, nh ny l nh ca lin kt (-C-O-); nh 1109 cm-1, nh ny c trng cho lin kt (C-N),[16],[5],[18] tt c cc lin kt ny c hnh thnh trong qu trnh tng hp CNTs. Gia CNTs cha bin tnh v CNTs bin tnh c duy nht mt nh khc bit l nh 1253 cm -1, y chnh l nh lin kt (-C=O) th hin s tn ti ca nhm chc (-COOH)[16] hnh thnh do phn ng oxi ha bi hn hp axit mnh. Mt iu d nhn thy na l ph ca CNTs bin tnh, cc nh hp th c cng mnh v r rng hn nhiu so vi CNTs th. iu cho thy CNTs sau khi x l axit c tinh khit tt.

35

3.3. Nghin cu cu trc hnh thi hc b mt ca mng mng nanocomposite PEDOT-PSS:MWCNTs tin hnh chp nh FESEM ca cc mu mng vt liu, kt qu c trnh by trn hnh 28.

(a)

(b)

Hnh 28. nh FESEM ca mng PEDOT-PSS (a) v PEDOT-PSS:CNTs (b). T hnh 28 nhn thy rng b mt ca mng PEDOT-PSS thun c nhp nh kh r. B mt ca mng PEDOT-PSS:CNTs vi t l khi lng PEDOTPSS:CNTs=100/0,5 c nhp nh (roughness) t hn th hin hnh 28b, qua chng t CNTs c phn tn kh ng u trong t hp vt liu. Quan st trn hnh 28b cho thy cc ng nano cacbon CNTs s dng c ng knh khong 1030nm, v c di khong 300-500nm. 3.4. Kho st tnh cht in-quang ca t hp vt liu nanocomposite PEDOTPSS:MWCNTs in tr b mt v h s truyn qua ca cc mng mng nanocomposite ti bc sng 600 nm c kho st, kt qu trnh by trn hnh 29.

36

Hnh 29. in tr b mt v h s truyn qua ca cc mng mng nanocomposite T hnh 29 thy rng in tr b mt ca mng gim dn khi thnh phn khi lng CNTs tng t 0 n 0,5 phn so vi 100 phn khi lng dung dch PEDOTPSS. Khi hm lng CNTs vt qu 0,5 th in tr b mt mng tng ln, thm ch ti gi tr 1,5 in tr ca mng cn cao hn c in tr ca mng PEDOT-PSS thun. iu ny c th c gii thch nh sau: CNTs l mt cht dn in rt tt, khi pha vi mt hm lng nh va phi vo PEDOT-PSS th in tr ca t hp nanocomposite PEDOT-PSS:CNTs s gim v t gi tr cc tiu ti hm lng ti u CNTs. Khi hm lng CNTs vt qu gi tr ti u, cu trc ca mng s xut hin cc khuyt tt v iu lm tng in tr ca mng. Mt khc cc ht ti chuyn ng dc theo ng CNTs nhng khi s lng ng CNTs qu nhiu c th lm cho qu trnh dn in b ngn cn do qu nhiu ng CNTs nm ngn ngang s ngn cn s chuyn ng ca cc ht ti in v iu ny lm in tr b mt mng tng theo. H s truyn qua ca mng PEDOT-PSS:CNTs ti bc sng 600 nm gim khi tng phn trm khi lng ca CNTs vo trong t hp PEDOT-PSS:CNTs. iu ny l do cng nhiu ng CNTs trong t hp nanocomposite PEDOT-PSS:CNTs th cng cn tr nh sng truyn qua mng. ng CNTs c cu trc hnh tr, khi nh sng chiu vo s phn x theo nhiu hng khc nhau lm suy yu kh nng truyn qua. Mt khc nhng vng bc sng nht nh, CNTs c th hp th mt phn nh sng ti. Tm li, nh sng b phn x theo cc hng khc nhau, s hp th quang l nguyn nhn dn n h s truyn qua gim khi nng CNTs trong mng nanocomposite PEDOT-PSS:CNTs tng.

37

Cng t hnh 29 thy rng in tr ca mng t gi tr c 36 /sq i vi mu vt liu PEDOT-PSS:CNTs-100:0,5 (theo khi lng), nh vy gi tr in tr gim khong 2 ln so vi mng PEDOT-PSS thun. Mt khc h s truyn qua ca mng bc sng 600 nm l khong 71%, gi tr ny c th chp nhn c khi s dng mng mng ny lm lp tip xc in cc trong cng ngh ch to OLED. Hnh 30 th hin ph truyn qua ca cc mng t hp nanocomposite PEDOTPSS:CNTs vi di bc sng t gn t ngoi n gn hng ngoi.

Hnh 30. Ph truyn qua ca cc mng t hp nanocomposite PEDOT-PSS:CNTs. T hnh 30 thy rng CNTs c s hp th nh sng vng t ngoi vi nh hp th bc sng 350 nm. y l iu khc bit ca CNTs so vi PEDOT-PSS th hin r qua s khc bit ca cc ng b,c,d so vi a. Ph truyn qua ca mng PEDOTPSS thun khng xut hin nh hp th nh sng vng t ngoi, h s truyn qua ca mng gim dn v pha bc sng di. Ph truyn qua ca cc mng t hp nanocomposite PEDOT-PSS:CNTs c h s truyn qua tng dn v vng nh sng kh kin v hng ngoi. 3.5. c trng I-V ca cc linh kin OLED ch to Hnh 31 cho thy c trng I-V ca OLED cu trc n lp. Ngng lm vic ca OLED khong 3V v cng dng l khong 0,01mA. Nh vy ngng lm vic l kh cao trong khi dng thu c l nh. iu ny cho thy in tr ti lp tip xc gia ITO v lp pht hoc in tr tip xc gia lp pht v nhm l tng i ln.

38

0.015

ITO/PVK+MEH-PPV/Al

0.010

Curent (mA)

0.005

0.000 0 1 2 3 4 5

Voltage (V)

Hnh 31. c trng I-V ca OLED cu trc ITO/ PVK:MEH-PPV/Al. ci thin tnh cht ca OLED, tin hnh ch to OLED cu trc a lp. Hnh 32 trnh by c trng I-V ca OLED a lp s dng PEDOT-PSS v t hp nanocomposite PEDOT-PSS:CNTs=100:0,5 (theo khi lng).

0.5

a-ITO/PEDOT-PSS+CNTs/PVK+MEH-PPV/Al b-TO/PEDOT-PSS/PVK+MEH-PPV/Al

0.4

Curent (mA)

0.3

0.2

b
0.1

0.0 0 1 2

Voltage (V)

Hnh 32. c trng I-V ca OLED cu trc a lp. T hnh 32 thy OLED cu trc a lp c n nh tt, in ngng lm vic t vo thp v cng dng cao hn hn so vi cu trc OLED n lp. i vi OLED cu trc ITO/PEDOT-PSS/PVK:MEH-PPV/Al, ngng lm vic khong 1,5V v cng dng l 0,15mA. iu ny chng t khi thm lp truyn l trng bn

39

PEDOT-PSS lm gim in tr tip xc gia anot ITO v lp pht quang ng thi gim ro th do l trng d dng i t in cc ITO vo lp pht dn n ngng lm vic t vo thp hn v cng dng thu c cao hn. i vi OLED cu trc ITO/PEDOT-PSS:CNTs/PVK:MEH-PPV/Al vi lp truyn l trng l t hp nanocomposite PEDOT-PSS:CNTs th ngng lm vic ch khong 0,8V v cng dng l 0,4mA. Nh vy mng mng nanocomposite PEDOT-PSS:CNTs ci thin tt tnh cht ca linh kin. Khi s dng mng t hp nanocomposite PEDOT-PSS:CNTs lm lp HTL trong OLED khng nhng gim in tr tip xc m cn gim ro th gia in cc ITO v lp pht quang iu ny lm cho l trng d dng i t in cc ITO vo lp pht quang v do lm cho ngng lm vic ca OLED thp v cng dng cao.

40

KT LUN

tin hnh x l axit ng nano cacbon a tng MWCNTs. Sau khi bin tnh, MWCNTs c tinh khit cao v kh nng phn tn trong dung dch PEDOT:PSS tt. ch to thnh cng mng mng nanocomposite trn c s PEDOT-PSS v CNTs. Cc tnh cht in-quang ca mng c kho st. Mng vt liu PEDOTPSS:CNTs=100:0,5 (theo khi lng) l mng mng trong sut c dn tt, c th in tr mng khong 36 /sq v h s truyn qua bc sng 600 nm c 71%. Kho st ph truyn qua ca mng nanocomposite PEDOT-PSS:CNTs thy rng CNTs c s hp th nh sng vng t ngoi vi nh hp th bc sng 350 nm. Mng vt liu PEDOT-PSS:CNTs=100:0,5 (theo khi lng) c s dng lm lp tip xc in cc trong ch to OLED. Cc linh kin OLED cu trc n lp v a lp c ch to v kho st c trng tnh cht. OLED cu trc a lp s dng mng t hp nanocomposite c in p m thp, khong 0,8V v cng dng l 0,4mA.

41

TI LIU THAM KHO

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[15] Tatiana Makarova, Fernando Palacio, Carbon-Based Magnetism: An Overview of the Magnetism of Metal Free Carbon-based Compounds and Materials, Elsevier, 2006. [16] Tung Tran Thanh , Tae Young Kim, Kwang S.Suh, Nanocomposite of singlewalled carbon nanotubes and poly(3,4-ethylenedioxythiophene) for transparent and conductive film, ELSEVIER, 2010. [17] Yu Min-Feng, Lourie Oleg, Dyer, "Strength and Breaking Mechanism of Multiwalled Carbon Nanotubes Under Tensile Load", Science, 2000. [18] Zuzana MITROOVA, TOMASOVICOVA, Preparation and characterization of CNTs functionalized by magnetite nanoparticles, NANOCON, 2010.