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I HC QUC GIA H NI TRNG I HC KHOA HC T NHIN

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Hong Th Thu Hng

KHO ST NH HNG CA MT S IU KIN CH TO LN PH PHT QUANG CA ZnS : Mn CH TO BNG PHNG PHP THU NHIT

Chuyn ngnh: Quang hc M s: 60.44.11


LUN VN THC S KHOA HC

NGI HNG DN KHOA HC: PGS.TS. PHM VN BN

H Ni - 2011

TM TT NI DUNG LUN VN Cc hp cht bn dn A2 B6 l i tng nghin cu ca rt nhiu cng trnh khoa hc do chng c rng vng cm ln, chuyn mc thng Hp cht bn dn vng cm rng ZnS (Eg 3,67 eV 300 K) c bit n nh mt loi vt liu in-hunh quang truyn thng. ZnS c rng vng cm rng do c th to ra nhng by bt in t kh su trong vng cm, to iu kin thun li cho vic a cc tm tp (cc cht kch hot) vo to nn trong vng cm nhng mc nng lng xc nh. Cc cht kch hot thng s dng l cc nguyn t kim loi chuyn tip c lp v in t 3d cha lp y nh Mn, Fe, Ni, Co, Cu. Ngoi ra th ZnS cn l cht t kch hot ngha l t trong khi cht c sn cc ion Zn2+ v S2- cn d hoc nt khuyt ca chng to thnh cc tm bt in t hoc bt l trng. Khi pha tp Mn vo ZnS th tr thnh bn dn bn t. Trong bn dn ny do xy ra tng tc trao i s-d gia cc in t dn v cc in t 3d ca cc ion t Mn2+ nn chng th hin nhng tnh cht quang v t ht sc th v nh: s xut hin m pht quang da cam- vng c trng cho cc ion Mn2+, s gim rng vng cm khi tng nng Mn trong mt khong nng Mn xc nh. Vi mc ch ch to bt nano ZnS:Mn c cu trc v tnh cht quang n nh trong khong nng Mn kh ln v kho st mt s c trng quan trng ph pht quang ca chng, chng ti tin hnh: Kho st nh hng ca mt s iu kin ch to lnph pht quang ca ZnS:Mn ch to bng phng php thu nhit. Phng php thu nhit c la chn bi phng php ny n gin, d ch to, n nhtng i tt. Lun vn gm ba chng: Chng 1: Tng quan c ch bc x v hp th trong vt liu nano Chng 2: Mt s phng php ch to ZnS:Mn v thit b thc nghim Chng 3: Kt qu thc nghim v bin lun

Trong chng 1 nu cc c ch hp th v bc x trong vt liu nano. Cc c ch hp th trong tinh th - Hp th ring - Hp th exciton - Hp th ni trong mt tm - Hp th cp D-A C ch bc x - Ti hp bc x vng- vng - Ti hp bc x vng tp cht - Ti hp ono-axepto - Ti hp bc x ni trong mt tm Mt s phng php ch to ZnS, ZnS:Mn - Phng php phn x catt - Phng php sol gel - Phng php gm - Phng php ng kt ta - Phng php thy nhit Phng php thy nhit l phng php trong ngnh ha vt liu dng thu cc vt liu v c c cu trc nano tinh th. Tng hp thy nhit l qu trnh tng hp c nc tham gia vi vai tr ca cht xc tc, xy ra nhit cao (ln hn 1000C) v p sut ln (ln hn vi atm). Trong phng php ny ngi ta s dng kh nng ha tan trong nc ca hu ht cc cht v c nhit cao, p sut ln v s tinh th ha ca cht lng vt liu ha tan. Da vo cc kt qu thc nghim, ta thy khong nhit c dng trong qu trnh thy nhit t 1000C n 18000C, p sut khong 15 atm n 104 atm. Cc th nghim dng phng php thy nhit c gi n nh, trnh rung ng

nhit v p sut khng i.Nhit , p sut nc v thi gian phn ng l ba thng s chnh trong phng php thy nhit. Nhit ng vai tr quan trng cho s hnh thnh sn phm cng nh n nh nhit ng hc ca cc pha sn phm. p sut cn thit cho s ha tan, khong qu bo ha to ra s tinh th ha cng nh gp phn to ra s n nh nhit ng hc ca pha sn phm. Thi gian cng l mt thng s quan trng bi v cc pha n nh din ra trong thi gian ngn, cn cc pha cn bng nhit ng hc li c xu hng hnh thnh sau mt khong thi gian di. Khi ch to mu bng phng php thy nhit th p sut hi bo ha trong bnh thy nhit l thng s v cng quan trng, n nh hng trc tip n s to thnh kt ta ca phn ng ha hc, p sut li hi bo ha li ch ph thuc vo nhit . Khi bnh thy nhit c a vo nung nhit cao, nc s bay hi. Do bnh kn nn hi nc s t trng thi bo ha. p sut trong bnh thy nhit l do hi nc bo ha gy nn. Khi thay i nhit thy nhit th p sut trong bnh cng thay i theo do p sut hi bo ha ca nc ph thuc vo nhit . Ni dung kt qu v bin lun: Hnh 3.2 l gin nhiu x tia X (XRD) ca cc mu bt nano ZnS, ZnS:Mn(CMn = 5mol%) thy nhit 220oC vi cc thi gian khc nhau. Ph ny gm cc vch nhiu x tng ng vi cc mt phn x chnh (111), (200), (220), (311) v (400), trong vch (111) c cng ln nht.T gin nhiu x tia X,cho thy ZnS:Mn c cu trc lp phng tm khi (cubic)thuc nhm khng gian vi kch thc ht tng nh theo thi gian thu nhit (bng 3.4). S tng nh hng s mng l do bn knh ca ion Mn2+(0.89A0) ln hn khng nhiu so vi bn knh ca ion Zn2+(0.88A0). Nhn chung, khi a Mn vo ZnS vi thi gian thu nhit thay i, v tr cc vch nhiu x hu nh khng i nhng ln cng gia cc vch v hng s mng b thay i. S thay i ny ph thuc vo thi gian thu nhit .

Trong ph EDS ca bt nano ZnS thu nhit 2200C, 15h khng lc ra bng dung mi CS2 ch yu xut hin cc vch c trng cho cc nguyn t Zn, S vi cc thnh phn phn trm tng ng v s lng nguyn t c t l l 53.33% : 46.67%. Trong qu trnh lc ra, chng ti c s dng dung mi CS2 ra bt nano ZnS sau khi thy nhit, kt qu l dung mi CS2 kh c cc nguyn t S bm trn b mt cc ht nano lm cho t l Zn: S gn nh nhau t 53.33% : 46.67% tr thnh 50.46% : 49.54% (bng 3.5). iu ny chng t nh c ra bng dung mi CS2 m lng lu hunh trong hn hp b gim i. Trong ph EDS ca bt nano ZnS:Mn (CMn = 5 mol% v 9 mol%) thu nhit 2200C trong 15 h c ra bng dung mi CS2 ch yu xut hin cc vch c trng cho cc nguyn t Zn, S, Mn vi cc thnh phn phn trm tng ng v s lng nguyn t dn ra bng 3.5. S c mt ca Mn trong ph EDS ca ZnS:Mn l mt c s quan trng chng t cc ion Mn2+ thay th cc ion Zn2+. Kh nng ny thay th cao v bn knh ion Mn2+ (0.89 Ao) rt gn vi bn knh ca ion Zn2+(0.88 Ao). Tng t nh bt nano ZnS, cc bt nano ZnS:Mn sau khi lc ra bng dung mi CS2 th t l gia cc thnh phn S:Zn:Mn c thay i. + Lng nguyn t lu hunh S gim. + Lngnguyn t Mn thay i khng nhiu trc v sau khi ra bng dung mi CS2. T nh TEM cho thy bt nano ZnS:Mn c dng ta cu, phn b kh u vi kch thc tng dntheo thi gian thu nhitl: 28.5nm (5h), 32.4nm(10h), 34,6nm (15h), 114nm(30h). Ngoi ra, khi cng tng thi gian thu nhit th ranh gii bin gia cc ht nano cng tr nn r rng hn v tch nhau r rt. Ph pht quang ca bt nano ZnS v ZnS :Mn 300K c thy nhit 2200C trong 5 h vi cc nng Mn khc nhau. Trong ph pht quang ca ZnS xut hin mt m xanh lam khong 450nm. Khi pha tp Mn vo ZnS vi nng CMn= 5mol% trong ph pht quang ca ZnS :Mn ngoi m xanh lam cn xut hin mt m da cam vng c cng v rng ln khong 586nm. Khi

tng nng Mn t 0.5mol% n 9mol%, cng m xanh lam c cng gim dn, m da cam - vng c cng tng dn nhng v tr ca n hu nh khng thay i. m ny c trng cho s chuyn di bc x cu cc in t trong lp v cha lp y ca ion Mn2+ trong trng tinh th ZnS [4T1(4G)
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A1(6S)]

Ph pht quang ca bt nano ZnS v ZnS :Mn 300K c thy nhit. Khi thu nhit 1200C trong 15h trong ph pht quang ca bt nano ZnS:Mn(CMn= 5mol%) ch yu xut hin m da cam - vng c cng nh khong 586nm, 2200C trong 15 h vi cc nhit thy nhit khc nhau. Khi tng nhit thu nhit t 1200C n 1600C cng ca ph tng chm, t 1600C n 2000C cng ca ph tng nhanh hn, sau t 2000C n 2200C tng chm li. S tng cng ca m theo nhit thu nhit l bng chng cho thy m da cam vng 586nm c trng cho ion Mn2+ v khi tng nhit th s ion Mn2+ thay th ion Zn2+ trong tinh th ZnS tng. Ph pht quang ca bt nano ZnS v ZnS :Mn (CMn = 5mol%) 300K c thy nhit 2200C vi cc thi gian thy nhit khc nhau.Trong ph pht quang ca ZnS : Mn (CMn= 5mol%) thu nhit trong 3h xut hin mt m da cam vng c cng nh khong 586nm. m ny ho vi m xanh lam thnh mt m rng (hnh 3.10a). Khi tng thi gian thu nhit t 5h n 30h th cng ca m u tng v t cc i nhit 15h, sau cng b gim. Nhng v tr ca n hu n iu ny chng t m 586nm cng c trng cho cc ion Mn2+. Khi tng thi gian thu nhit th s ion Mn2+ thay th ion Zn2+ trong mng tinh th ca ZnS tng v th cng ca m da cam - vng tng ln. Khi thi gian thu nhit ln, mc d s ion Mn2+ thay th ion Zn2+ tng ln nhng khi xy ra tng tc gia cc ion Mn2+ vi cc ion mng tinh th v cc ion vi nhau v th cng pht quang ca m gim i. Ph kch thch pht quang ca bt nano ZnS:Mn (CMn = 5mol%) thy nhit 2200C vi nhng thi gian thu nhit khc nhau. Hnh 3.14 l ph kch thch pht quang m da cam vng ca bt nano ca ZnS v ZnS:Mn (CMn = 5mol%) thy

nhit 2200C vi nhng thi gian thu nhit khc nhau 300K. Khi kch thch bng bc x ca n Xe- Ne, trong ph kch thch pht quang ca ZnS:Mn, xut hin mt m rng c cng nh 335nm, c trng cho hp th vng vng ca ZnS, ngoi ra cn xut hin mt s m c cng nh cc bc sng:342nm, 390nm, 429nm, 465nm, 490nm, 498nm. Khi thi gian thu nhit t 3h n 30h th v tr ca m c trng cho hp th vng vng b dch chuyn v bc song di khong 342nm, v tr ca cc m c trng cho s hp th ca ion Mn2+ hu nh khng i nhng cng ca chng tng ln v t cc i 15h sau gim dn.Trong m 465nm c cng ln nht. Cc m ny c trng cho s dch chuyn ca cc in t mc c bn 6A (6S) n cc mc nng lng kch thch tng ng 4E(4S), 4T2(4D), 4A1 (4G), 4E1 (4G), 4T2(4G), 4T1(4G)ca cc ion Mn 2+. V tr ca cc m ny dch chuyn v pha nng lng thp. iu c bit trong ph kch thch pht quang ca ZnS:Mn, m hp th vng xanh lam( bc sng t 470nm n 525nm) c tch thnh hai m vi cc i 490nm v 498nm, m theo cc ti liu tham kho th hai m ny thng ho vi nhau thnh mt m rng. Dng ln lt cc bc x ng vi cc bc sng 342nm, 421nm, 459nm, 494nm, 521nm v 528nm ca n Xe kch thch ZnS:Mn (CMn= 5%) chng ti thu c ph pht quang hnh 3.15v 3.16.T ph ny cho thy: v tr m 586nm c trng cho cc ion Mn2+ trong ZnS khng ph thuc vo bc sng bc x kch thch nhng cng ca m li ph thuc vo bc x kch thch. Theo chng ti, kch thch bng bc sng 342nm l kch thch gin tip cc ion Mn2+ v nng lng ng vi bc sng ny rt gn rng vng cm ZnS, cn kch thch bng cc bc x ca bc sng 421nm n 528nm l kch thch trc tip v nng lng ca cc photon nh hn nng lng ca rng vng cm. Hnh 3.18 v hnh 3.19 l ph hp th ca ZnS (2200C, 15h) v ZnS:Mn( CMn= 5mol%, 2200C) vi cc thi gian khc nhau. Trong ph hp th ca ZnS xut hin mt m hp th gn b vng cm c bc sng khong 332 nm. m ny c trng cho hp th vng vng ca ZnS.

Khi pha tp Mn vo ZnS vi nng CMn = 5 mol%, trong ph hp th ca n, m hp th ca ZnS b dch v pha bc sng di khong 466 nm v 490nm, c trng cho s dch chuyn hp th ca cc in t - electron trong ion Mn2+. Khi tng thi gian thu nhit th cc m c trng cho hp th vng vng cng b dch v bc sng di 340nm thoi gian 30h v c cng gim dn nhng cc m c trng cho hp th ion Mn2+ li c cng tng dn nhng v tr ca n hu nh khng thay i. 4Bn cht m pht quang trong bt nano ZnS:Mn * T ph pht quang ca bt nano ZnS:Mn ta thy: + Theo nng Mn : dng ph ca m da cam- vng i xng hn vi v tr ca m khng thay i bc sng 586 nm khi thay i nng Mn. iu ny chng t rng m 586 nm phi c trng cho bc x ca cc tm kch hot Mn2+ trong mng tinh th ca ZnS + Theo nhit v thi gian thu nhit: Khi nhit v thi gian vt liu tng, cng ca m da cam-vng tng dn cn m xanh lam gim dn. iu ny chng t rng khi tng nhit v thi gian tng, kh nng thay th cc ion Zn2+ bi cc ion Mn2+ l nhiu hn * T ph hp th ca bt nano ZnS:Mn cng cho thy nng lng vng cm tng nh khi thi gian thu nhit tng ln. iu chng t cc ion Mn2+ khuch tn vo mng tinh th ca ZnS, thay th cc ion Zn2+ v cc nt khuyt ca chng. * T ph kch thch hunh quang ta thy: Khi pha Mn2+ (CMn= 5 mol%) vo cht nn ZnS th m 334 c trng cho hp th gn b vng ca ZnS b dch v pha sng di v xut hin thm nh 490nm v 498nm c trng cho hp th ca cc electron t trng thi c bn
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A1(6S) n cc trng thi kch thch 4 A1 ( 4 G ); 4 E ( 4 G ) ca in Mn2+. * Da vo nhng c im trn v so snh vi cc ti liu tham kho,

chng ti xem rng c ch pht quang ca bt nano ZnS:Mn nh sau:

m ny da cam- vng c trng cho s chuyn di bc x cu cc in t trong lp v cha lp y ca ion Mn2+ trong trng tinh th ZnS[4T1(4G)
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A1(6S)].

S cc mc nng lng v cc dch chuyn bc x c th trong bt nano ZnS:Mn c cho hnh 3.21.
EC

4 A1, 4E 4 T 4 2 T1

Eg
A

450 nm

586 nm
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A1

EV

Hnh3.21:S cc mc nng lng v s dch chuyn bc x tng ng vi cc m pht quang ca bt nano ZnS:Mn

KT LUN Thc hin ti lun vn thc s: Kho st nh hng ca mt s iu kin ch to lnph pht quang ca ZnS:Mn ch to bng phng php thu nhit, chng ti thu c mt s kt qu chnh sau : 1. Thu thp ti liu v cu trc tinh th, tnh cht quang: ph hp th, ph pht quang, ph kch thch pht quang... v quy trnh ch to ca vt liu ZnS:Mn bng mt s phng php khc nhau, c bit l phng php thy nhit.

2. nghin cu xy dng quy trnh ch to bt nano ZnS:Mn bng phng php thy nhit i t tin cht Zn(CH3COO)2.2H2O, Na2S2O3.5H2O, Mn. (CH3COO)2.4H2O. 3. Kho st mt s tnh cht cu trc ca bt nano ZnS:Mn thng qua ph Xray, nh TEM, t cho thy tinh th ZnS:Mn c cu trc cubic thuc nhm khng gian l . vi hng s mng v kch thc ht thay

i theo cc iu kin ch to theo thi gian thy nhit. 4. Kho st nh hng ca dung mi CS2 th hin ln thnh phn phn trm nguyn t Zn,S, Mn trong ph tn sc nng lng (EDS): ra bng dung mi CS2 lm gim cc nguyn t S cn d bm trn b mt cc ht nano ZnS, ZnS:Mn. 5. Kho st s nh hng ca nng Mn, nhit thy nhit, thi gian thy nhit ln ph pht quang, ph kch thch pht quang ca bt nanoZnS:Mn theo thi gian thy nhit. 6. Lm sng t thm mt vi c ch ti hp bc x, hp th trong cc bt nano ZnS v ZnS:Mn a. C ch ti hp bc x + Trong ZnS, m xanh lam 450 nm gm mt s m c trng cho cc c ch ti hp bc x khc nhau lin quan n cc nt khuyt ca Zn, S v cc nguyn t Zn, S nm l lng gia cc nt mng + Trong ZnS:Mn, m da cam-vng 586 nm c trng cho s chuyn di bc x ca cc in t trong lp v 3d5 cha lp y ca cc ion Mn2+[ 4T1(4G) 6

A1(6S)] trong trng tinh th ca ZnS. b. C ch hp th Cc m hp th trong ph kch thch pht quang khong 336 nm n 348

nm c trng cho s chuyn di hp th gn b vng 342nm, cn xut hin cc m c cng yu hn 421, 459, 494, 521 v 528nm c trng cho s chuyn di hp th ca cc in t t trng thi c bn 6A1(6S) n cc trng thi in t

kch thch tng ng 4E(4S), 4T2(4D), 4A1 (4G), 4E1 (4G), 4T2(4G), 4T1(4G) ca cc ion Mn2+ trong trng tinh th ca ZnS.