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DCH TING ANH CHUYN NGHNH K THUT CHNH XC NHT V NHANH NHT: http://mientayvn.com/dich_tieng_anh_chuyen_nghanh.html XEM TI LIU VI NH DNG P V Y HNH NH THEO LINK SAU: https://docs.google.com/file/d/0Bw5sTGnTS7NhVW14MG1NbWJTVFNiRmpPWXNHdjdYdw/edit Tn tp tin trong google document: N_Nhiet_sac.doc BN CH C PHP XEM TI LIU. MUN TI TI LIU, BN PHI GI TI LIU CA BN CHO CHNG TI QUA A CH GMAIL:quangphituyen@gmail.com. MI MB TI LIU BN GI CHO CHNG TI NG

VI MT NGY S DNG TON B NGUN TI NGUYN CA CHNG TI. V D: BN GI CHO CHNG TI 5 MB TI LIU, BN S C S DNG TON B NGUN TI NGUYN CA CHNG TI TRONG 5 NGY. THI GIAN TR LI MAIL: NGAY TC KHC TRONG MAIL, BN PHI GHI R TN CC TI LIU BN CN TI V M T Y V CC TI LIU M BN GI CHO CHNG TI. CC TI LIU SAU Y C YU THCH: Lun vn tt nghip i hc, cao hc, lun n tin s. Ti liu dch t cc ti liu nc ngoi, ghi r ngun ca ti liu gc Ti liu ging dy cho sinh vin, trnh tc gi phi t thc s tr ln .v.v Cc seminar, tiu lun ca sinh vin, hc vin, nghin cu sinh CH : HY GI TI LIU CNG M T V TI LIU QUA GMAIL: quangphituyen@gmail.com CC THC MC V CC VN KHC XIN GI QUA MAIL: thanhlam1910_2006@yahoo.com NU BN GI TH KHNG THEO NG HNG DN BN TRN, TN TRUY CP V MT KHU CA BN C TH B KHA. PHN CH TRONG TI LIU NY Trng i hc Khoa Hc T Nhin Tp H Ch Minh Khoa Vt l B mn Vt l ng dng PHNG PHP THC NGHIM CHUYN NGNH

ti: NHIT SC (Thermochromism) GV: TS. L Trn HVCH: Phm Minh Thng

Tp. H Ch Minh 4/11/2011 LI CO BCH

Ngy nay, khi khoa hc cng pht trin, th con ngi li cng khm ph thm c rt nhiu iu th v v thin nhin v v chnh bn thn mnh. V cng lc cng c thm nhiu b n ca thin nhin (trong c c con ngi) c h m. Nhng ng dng t nhng iu diu k y em li khng bit bao nhiu l php mu i vi nn vn minh hin i ngy nay. Trong bi cnh y, php mu Nhit sc c con ngi pht hin; v nhng ng dng ca n vn khng ngng c tm thy v a vo thc tin cho n ngy sau Trong bi vit ny, Ti ch trnh xin by 1 phn rt nh nht v rt c bn ca php mu y Tuy ngun t liu v vn cng hi nhiu, nhng v s hn ch v kin thc chuyn nghnh, vn t ting anh v vn phong cng cha trau chut; nn trong qu trnh bin tp li kh trnh nhng sai st. Nn y, hi vng cc Cao nhn gn xa ch bo bi vit ny c hay hn v hon thin hn 4/11/2011 Ngi vit

NI DUNG BI VIT

Li co bch I. Khi nim v phn loi nhit sc II. C ch nhit sc III. Kho st s lc mng VO2

IV. Phng php tng hp mng oxit nhit sc V. Phn tch kt qu to mng VO2 VI. ng Dng

I. KHI NIM V NHIT SC: Vt liu Chromeogenic l nhng vt liu c kh nng thay i nhng thuc tnh quang ca n (tc thay i mu ca chng) khi c kch thch ngoi tc ng vo . Tng ng vi mi loi kch thch th n s nhng tn gi khc nhau tng ng. Nh l Vt liu thay i mu do kch thch ca nh sng = > gi l vt liu quang sc (Photochromic) Vt liu thay i mu do s thay i nhit = > gi l vt liu nhit sc (Thermochromic) Vt liu thay i mu do p in trng vo = > gi l vt liu in sc (Electrochromic) . Nh vy, vt liu nhit sc l nhng vt liu c th thay i mu khi nhit thay i (tc l khi c nhit tc ng ln vt liu, s lm chng thay i truyn qua , phn x hay hp th) Tuy nhin, khi h nhit xung, th tnh cht quang in ca chng li c thit lp (ngha l qu trnh thay i nhit quang ny mang tnh cht thun nghch). Mi vt liu c nhit chuyn pha TC xc nh; n y ta s c c 1 iu th v. l Nu Tvt liu < TC <=> vt liu trong sut i vi c nh sng trong vng hng ngoi v kh kin Nu Tvt liu > TC <=> vt liu trong sut trong vng kh kin, nhng phn x hu ht bc x hng ngoi Vt liu nhit sc thay i mu khi nhit ca n t n nhit chuyn tip TC (c trng cho tng vt liu nhit sc). V c th ni rng tnh cht quang ca vt liu nhit sc ph thuc vo s thay i ca nhit . Khi xt v s thay i v nhit , th c 2 loi vt liu nhit sc Vt liu nhit sc lin tc: (tc mu thay i trong 1 khong nhit lin tc) hin tng ny

thng lin quan n s thay i ha hc xy ra trong h Vt liu nhit sc khng lin tc (tc mu thay i t ngt ti nhit c trng). Hin tng ny thng l do 2 nguyn nhn sau Hoc l do s chuyn tip pha Hoc l do phn ng ng phn ha hc Khi xt thnh phn to ln vt liu nhit sc, th c my loi sau: Oxit kim loi chuyn tip nhit sc Tinh th lng (liquid crystal) Conjugated oligomer Cht nhum leuco (leuco dyes)

II. C CH NHIT SC I VI MNG MNG NHIT SC TRNG THI RN: 1. C ch Chuyn tip bn dn kim loi: Mi vt liu (kim loi bn dn cht cch in) u c gin vng nng lng tng ng Khng phi mi chuyn tip bn dn - kim loi u l kt qu tng tc gia cc in t vi nhau. Bn cht ca qu trnh chuyn tip ny khng th gii thch hon ton bng l thuyt in t khng tng tc; bi v mi s thay i trong cu trc tinh th u c th hnh thnh 1 vng cm (band gap). D lc u l cht bn dn; nhng khi nhit ca vt liu chuyn tip vt qua nhit chuyn tip th truyn qua gim mnh v h s phn x tng nhanh (th hin tinh cht ca kim loi) . Vo nm 1967-1968, Adler v Brooks pht hin ra oxit kim loi chuyn tip c th l nhng cht cch in, bn dn V h cng khm ph ra rng: chng ta c th dng l thuyt vng nng lng gii thch hu ht nhng s chuyn tip y ca vt liu y. H nhn ra rng: 1 s bin dng ca mng tinh th ti nhit chuyn tip c th gy ra1 khe nng lng ( energy gap) gia trng thi in t trng v trng thi in t b chim. Khi nhit tng ln th rng vng cm gia vng dn v vng ha tr gim 1 cch tuyn tnh( v c 1 vi in t b kch thch nhit s nhy t vng ha tr sang vng dn). T dn n s bin mt ca sai hng kia, v vng cm b bin mt(tc l vng ha tr nm chng 1 phn ln vng dn). Khi vt liu th hin tnh kim loi (do m bn dn lc u, gi c th phn x c) = > y l ni dung khi qut ca c ch chuyn tip bn dn - kim loi 2. M t s lc c ch ca hin tng nhit sc (i vi mng oxit kim loi chuyn tip): Tht ra, c ch chuyn tip bn dn kim loi cng chnh l ni dung chnh ca c ch trong hin tng nhit sc ri y vy!!! Lc u vt liu nhit sc c tnh bn dn Sau khi c kch thich nhit vo vt liu, cc in t vng ha tr nhn c nng lng nhit

kch thch s dao ng. Nhit kch thch cng tng th dao ng in t cng mnh; v khi nng lng th in t s bc ra khi vng ha tr v nhy ln vng dn. V c th, cng lc cng nhiu in t bc sang vng dn (tng ng vi vng cm dn dn s b thu hp li). n 1 lc no , c th l khi nhit vt liu nhit scln hn nhit ti hn TC ca vt liu th c kh nhiu in t nhy sang vng dn n ni vng cm bin mt (tc l khi vng ha tr s overlap vng dn). Khi vt liu chuyn thnh vt liu mang tnh kim loi.

= > Do , nh sng truyn n vt liu th s khng c truyn qua na m s phn nhiu s b phn x li (do c tnh kim loi) ;tng ng vi mi bc sng truyn qua s c 1 mu ( chinh l l do ti sao vt liu nhit sc chuyn mu khi vt qu nhit ti hn) Tng t, khi vt liu nhit sc c lm lnh i, th s lng in t t vng h tr nhy ln vng dn gim dn (v n 1 lc no vng cm xut hin), ri cui cng tr v vi trng thi bn dn ban u (tc nh sng truyn n vt liu khng cn b phn x na). = > l m t s lc c ch ca hin tng nhit sc. Nh Bn thy: hin tng nhit sc mng oxit kim loi chuyn tip c tnh thun nghch. Tuy nhin, hin tng nng ln hay lnh i ca vt liu li khng hon ton ging nhau ( nguyn nhn l do s tr nhit ca vt liu. V nh chng ta thy, i vi mng oxit v c th khng phi no mng no cng c th c hin tng nhit sc; m ch nhng mng oxit ca kim loi chuyn tip th mi c hin tng ny. l nhng mng nh mng oxit ca vanadium (VO2, V2O3,V2O5,V6O13 ) , mng Titan oixt theo cng thc TinO2n+1 (nh Ti2O3, Ti3O5, ) v nhng mng oxit c pha tp cht ca chng 3. Phn ni thm (c ch nhit sc i vi thnh phn hu c) C th y ta s kho st c ch nhit sc ca thuc nhum Leuco (c dng lm mc in, hoc lm mng ph) Thnh phn chnh ca loi nhit sc ny gm c 3 thnh phn Dung mi (solvent) Thuc nhum mu (colorant) Axit hu c (organic axit) V n c c ch nh sau: Khi nhit tc ng vo vt liu nh hn nhit nng chy ca dung mi,; dung mi v thuc hum mu tng tc vi nhau = > Do tng tc in t, m mu trong vng kh kin xut hin Khi nhit tc ng vo vt liu cao hn nhit nng chy ca dung mi; dung mi v thuc nhum khng tng tc c vi nhau = > o c tng tc in t, cho nn o c mu xut hin Phn ng ny c th b gin on bi cc nh hng bn ngoi nh: Tip xc nh sng cc tm

 C s din din ca dung mi phn cc Nhit qu cao Lc ct qu mnh (excessive shear) III. KHO ST S LC MNG VO2: 1. Khi nim v oxit kim loi nhit sc chuyn tip (Thermochromic transition metal oxides): K t khi khm ph ra s chuyn tip pha xy ra nhit ti hn TC, th nhng oxit kim loi chuyn tip tr thnh nhng vt liu nhit sc trng thi rn c nghin cu nhiu nht (trong TC l nhit m ta quan st thy nhng tnh cht quang v in ca vt liu b thay i t ngt). V oxit kim loi tr thnh i tng l tng cho vic kho st trng thi kim loi v trng thi kim ca vt liu. Nm 1968, khi nghin cu nhng vt liu ny, Adler pht hin 1 kh khn trong vic nui n tinh th sch v hp thc; t ng nhn thy rng: nhng php o in thng thng t c khng ph hp vi nhng thuc tnh ni ti ca vt liu ( l do nng sai hng v tp cht qu ln). Khi , ngi ta phn nhng oxit kim loi chuyn tip kt tinh sch v hp thc thnh kim loi hoc bn dn hoc cht cch in (m chng c th chuyn tip bn dn thnh kim lai). Theo , nhng kim loi c c trng bi in tr sut nh (t 10-2 n 10-3cm) ti nhit phng; v khi nhit tng ln th in tr sut cng tng ln 1 cch tuyn tnh. Trong khi , bn dn v cht cch in c in tr sut ln hn nhiu (t 103 n 1017cm) ti nhit phng; s tng theo hm m khi nhit tng. 1 vi oxit vanadium th hin nhng tnh cht nhit sc. Nhng vt liu ny c ng dng trong nhiu lnh vc cng ngh ( nh chuyn mch quang in ). Nghin cu nhng tnh cht ca vabadium oxit ngi ta tp trung xoay quanh s chuyn tip pha gia kim loi v cht cch in ( s chuyn tip pha y nh l 1 hm ca nhit ). Nhng vt liu nhit sc ny th hin nhng tnh cht bt thng v in cu to v tnh t ca vt liu. 2. Kho st v mng VO2 Vanadium (IV) oxit l vt liu nhit sc trng thi rn c nghin cu nhiu nht (v n c nhiu trin vng trong ng dng). 1 tinh th n VO2 nguyn cht c nhit chuyn tip bn dn kim loi 341K (hay 68oC). V khi nhit thay i qua TC, th s c 1s thay i cu trc 1 cch tng ng Khi T > TC (tc nhit cao ) VO2 c cu trc mng dng t gic (hnh 6) Khi T < TC (tc nhit thp) VO2 c cu trc mng dng n t (hnh 7) Bn cht ca s chuyn tip bn dn kim loi trong VO2 c kho st thng qua vic nghin cu bng tnh ton, thc nghim v l thuyt (t 1950s). Nhng c ch ch yu ca s chuyn tip ny n gi vn l 1 iu huyn b; v 3 pha ca VO2 tuy th hin nhng cu trc mng khc nhau , nhng chng li c nhng tnh cht in tng t nhau (nh l chuyn tip bn dn-in t th tng t nng lng kch hot v dn in). hiu r s chuyn tip ny, nm 1971, Goodenough a ra 1 s l gii hu ch bng vic da vo

nhng qu o phn t v gin vng nng lng Goodenough cho rng s chuyn tip kim loi bn dn l kt qu chuyn tip cua phn sc in (antiferroelectric) trong vanadium (IV) oxit); trong s ghp cp ca V4+- V4+ trong pha t din tr thnh cc k bn vng; ch n khi lm lnh th c s sp xp trong cu trc vng nng lng (dn n thnh pha n t). Sau ng ta thy xut hin 2 nhit chuyn tip khc nhau, TC l kt qu ca s bin dng phn sc in v T`C l kt qu t s bin dng ca tinh th. Goodenough kt lun rng: thnh phn phn sc in ca pha n t nhit thp ( trong VO2) l lc dn ng ca bin dng. Ngoi ra, nhit chuyn tip TC khng b chi phi bi kch thch nhit ca iin t , m l do entropy ca mode dao ng mng. Ngi ta cng nhn thy rng: s bin mt ca band gap l do phonon quang hc; t dn n thay i cu trc pha. Do s sp xp nguyn t ca mng rutile nhit cao c xem nh l nguyn nhn xut hin pha kim loi ca VO2. Khi vt qua nhit chuyn tip, dn in tng 1 cch ng k. Dn n tng h s phn x vng hng ngoi, v khng c thay i g vng kh kin. = > y nhit ti hn TC cng rt l ngha; bi Di nhit TC ny = > vt liu tr nn trong sut i vi vng hng ngoi v kh kin ca ph in t Trn nhit TC ny = > ngi ta thy tnh cht hon ton khc; vt liu tr thnh c tnh kim loi v vn trong sut i vi vng kh kin, nhng li phn x vng hng ngoi. = > iu ny c ng dng trong vic ch to ca s thng minh. Tnh cht quang v in ca mng VO2 hu nh ph thuc vo s hp thc v vi cu trc ca mng, cng nh ph thuc vo bc ng sut d (residual stress) do k thut lng ng gy ra. Hin tng ph thuc ny l tnh tinh th ca mng. dy ca mng nh hng hnh thi ca mng .Bi s gia tng mp m ca mng tng do dy mng tng th dn n nhit chuyn tip tng. Ngoi ra, dy ca mng cng nh hng n h s truyn qua (khi mng cng dy, h s truyn qua cng gim) V d: khi mng mng hn 100nm, truyn qua ca pha kim loi ln hn truyn qua ca bn dn ( vng hng ngoi); trong khi , nu mng dy hn 100nm, truyn qua ca pha bn dn tri hn pha kim loi. Tuy mng mng Vanadium (IV) oxit c nghin u mt cch rng ri (v nhit ti hn ca n rt gn vi nhit phng). Tuy nhin, iu ny cng cha c tt, v nhit ny vn qu cao nhit 68oC s dng hiu qu vi nhit mi trng xung quanh . gii quyt vn ny, ngi ta s dng pha tp (doping) vo trong mng gim nhit chuyn tip ca VO2 xung. Nhng tp chat c th lm tng hoc lm gim nhit ti hn TC (ty thuc vo 1 vi yu t) 3. Hiu ng ca pha tp: Thng thng, cc mng oxit nhit sc kim loi chun tip c nhit ti hn qu cao p dng

thc tin nhit thng. Cho nn ngi ta pha tp vo lm tng hoc gim nhit ti hn: Nu pha tp nhng nguyn t c kch thc ln hn ion vanadium lm gim nhit chuyn tip TC Nu pha tp nhng nguyn t c kch thc nh hn ion vanadium lm tng nhit chuyn tip TC Tuy nhin; s thay i nhit chuyn tip ch xy ra r rang khi m nng tp cht c pha vo trong cu trc tinh th ln. Ngoi ra, cc yu t (nh in tch ca ht ti v mt ht ti in) ca tp cht cng c th lm nh hng n nhit chuyn tip. V d: Pha tp vi nhng ion kim loai ha tr cao nhiu (nh tungsten (VI) v niobium (V) th c th lm gim nhit chuyn tip xp x gn bng nhit phng (25o C); trong khi pha tp nhng ion ha tr thp (nh aluminium (III) hoc chromium (III)) th li lm tng nhit chuyn tip Ngi ta thy rng: tungsten (IV) l cht pha tp hu ch v gip gim nhit chuyn tip ca VO2 (c th l 25oC per atom.%). Vic gim nhit ny l do s thay th mi ion vanadium (IV) bng 1 ion tungsten (VI) bng c ch chuyn in tch. Ta c th gii thch : l do s chn in t b sung vo vng d ca vanadium, ho c l do ion tungsten c kch thc ln hn kch thc ca vanadium. Tng t, ta cng c rt nhiu cht pha tp hu ch khc nh: Fluorine c th gim nhit chuyn tip xung 20oC (trong nguyn t Fluorine thay th nhng nguyn t Oxy trong qu trnh pha tp vi 1.2atom%fluorine) Vng c th c dung pha tp v lm gim nhit chuyn tip S pha tp ng thi tungsten v fluorine vo trong mng VO2 (bng phng php PVD) c th lm tng truyn qua trong vng kh kin nhiu hn so vi ch pha tp 1 mnh tungsten . Tuy nhin, vic pha tp ny ch lm gim nhit chun tip khong 27oC. V. NHNG PHNG PHP TO MNG Hin nay, c nhiu phng php khc nhau trong vic lng ng mng mng nhit sc c s dng vo thc tin (c bit l i vi mng mng VO2). 5.1. Lng ng hi vt l (PVD): y, ta c th s dng cc phng php phn x nh sau: phn x DC phn x RF phn x Magnetron phn x phn ng phn x chm ion

Phng php phn x c 1 vi u im sau: D dng ch to cc mng a lp nh to ra nhiu bia ring bit. ng thi, y l phng php r tin, v d thc hin nn d dng trin khai quy m cng nghip.

 bm dnh ca mng trn rt cao do cc nguyn t n lng ng trn mng c ng nng kh cao. Mng to ra c mp m b mt thp v c hp thc gn vi ca bia, c dy chnh xc hn D thc hin doping bng cch thay th target trong bung chn khng Ngoi ra, n cng c 1 vi nhc im sau bm dnh ca mng tng i thp Chi ph thit b cn cao Ch to mng chm 5.2. Lng ng bng xung laser: y cng l 1 dng khc ca phng php lng ng hi vt l; v n c s nh sau:

Phng php ny cng c nhng u im nh sau: Gi c hp thc ca bia trong nhng mng c lng ng V ngun laser c t bn ngoi bung phn ng, nn d iu chnh thit b Tc hnh thnh nhng lp epytaxy v hp mng cao xy ra nhit thp y l 1 phng php lng ng sch, a nng v hiu qu v gi c Tuy nhin n cng c nhc im nh: Kch thc mu gii hn = > kh khn trong vic kim sot v dy v ng u ca mng to thnh; cng nh kim sot s bn ph ca tp cht ln mng (nn gy ra nhng sai hng trn b mt do shock nhit) = > phng php khc phc: S dng thit b lc ht c hc (mechanical particle filter) S dng bia mt cao (high density target) v c b mt nhn (hoc mi nhn bia trc khi lng ng) S dng c ch mt nng lng thp hn ho c ch lng ng chm hn 5.3. Tng hp Sol-gel Sn xut mng mng thng qua phng php sol-gel c ng dng rng ri trong vic lng ng mng nhit sc VO2 . Con ng tng hp ny cung cp mt phng php va tng i r, va ph hp cho vic lng ng 1 khu vc b mt ln (lm gim nh s pha tp cht kim loi vo va nhit ca qu trinh tng hp tng i thp) Tuy nhin mng c to bng phng php ny c m c (density) thp hn so vi nhng mng c lng ng bng cc phng php PVD khc; v vy n d b h gy Tin cht (precursor) thng c dng nht ch to mng VO2 (bng phng php ny) l vanadyl tri(iso-propoxide) v vanayyl tri(tert-amyloxide) 5.4. Lng ng hi ha hc (CVD):

Phng php lng ng hi ha hc l 1 phng php lng ng hi c s dng rng ri trong cng nghip. u im ca phng php ny l: C kh nng to vt li c tinh khit v m c cao Mng ng u c to c bm dnh tuyt vi C ch lng ng mng c th c iu chnh Hot ng ti nhit thp C th c sn xut li Phng php CVD thng c dng sn xut ra mng VO2 l phng php lng ng hi ha hc hu c kim loi (Organometallic Chemical Vapour Deposition) Phng php CVD ny c 2 loi Phng php lng ng hi ha hc p sut kh quyn Phng php lng ng hi ha hc c thm bnh sol kh V. PHN TCH KT QU TO MNG VO2 : y, chng ta s phn tch kt qu to mng VO2 bng phng php PLD v Phn x Magnetron. Tnh cht ca mng lng ng s c xc nh bng nhng k thut khc nhau: Dng nhiu x tia X (XRD) = > xc nh cu trc mng to thnh Dng knh hin vi lc nguyn t (AFM) = > xc nh b mt mng Dng ph UV-VIS = > xc nh tnh cht quang ca mng 1. Mng VO2 c to theo phng php lng ng bng xung laser (PLD) a) Cu trc mng: y, bng phng php nhiu x tia X ta s kho st s nh hng ca nhit n kt tinh ca mng VO2 (c to bng phng php PLD) Trc ht, ta c ph XRD ca mng VO2 c lng ng ti nhng nhit khc nhau T hnh trn ta thy, mng VO2 c to thnh ch c pha bn dn ca cu trc n t VO2 (ngoi ra khng cn pha no khc na. V tt c mng c lng ng trong nhit t 350 450oC u c kt tinh; trong cc mt mng nhiu x m ta chp tng ng vi cc gc 2theta trong bng sau Thng thng, s m rng ca nh ph v cng ph ph thuc vo kch thc ht v mc kt tinh cua mng. V vy, t nh nhiu x ta c vi kt lun sau: Tt c cc mng u c peak u tin ti gc 27,87 (ng vi mt nhiu x (011) ) => chng t lc ny xut hin VO2 Mng lng ng ti nhit 350oC c 2 nh ti gc 27..87o v 57.91o(ng vi mt(011) v mt(022) . V v khng cn thy nh ph no na, cho nn mng VO2 lng ng 350oC c tnh nh

hng cao vi mt tinh th (011). Chng ta quan st thy mt (011) xut hin kt cu m rng ( broad structure) = > iu ny chng t s xut hin cu trc v nh Mng lng ng (vi nhit ti 400oC va450oC ) c dng ph XRD tng t nhau. Ngoi ra chng cn xut hin them 2 nh phoo63 mi ti gc 2theta =39.75 v64.90 (tng ng vi mt (002) v (013)) = > S xut hin ny ch ra s suy gim ca s nh hng ht VO2 ( deterioration of Vo2 grains orientation). Hn na, ph XRD ca mng ti 450oC cn c them vi nh ph khng xc nh = > iu ny chng t s xut hin pha th 2 ca oxit ny. Ngi ta thng dng cng thc Debye Schere tnh kch thc trung bnh < > ca ht: Trong FWHM l rng nh ph l gc nhiu x Bragg = > p dng cng thc trn kho st kch thc ht cho nh ph (011) theo3 nhit ca = > ta thy, khi nhit cng tng th kch thc ht to thnh cng tng theo = > Vy kt tinh ph thuc vo nhit b) B mt mng to thnh Ta kho st mp m ca mng bng knh hin vi lc nguyn t (AFM) ti 3 nhit nh trn, th ta thu c nh: Ri dng phn mm Nanoscope tm gi tr mp m b mt Rn th ta c c bng gia tr sau Kt qu ny cho ta thy Ra ti nhit 3500C v 4000C khng ging nhau v v n tng t ngt ti450oC c) Tnh cht nhit sc ca mng c to thnh: y chng ta s dng ph UV VIS kho st s thay i tnh cht nhit sc ca mng lng ng ti nhng nhit khc nhau (trong quang ph k UV-VIS l 1 thit b c dng o cng nh sang truyn qua mu). th ta s c hnh nh sau: T hnh v ta thy,: i vi VO2 ( c 3 trng hp nhit ) th vng hng ngoi(IR) c 1s tng phn r nt gia truyn qua ca pha bn dn nhit thp (25OC) va2d9o65 truyn qua ca pha kim loi nhit cao (100OC). V ta thy tng phn y gim khi nhit ca tng. 2. Mng VO2 c to theo phng php phn x magenetron Tng t, ta cng lm nhng bc phn nh trn , th ta s c nhng kt qu sau: a) Cu trc mng: y ta cng s vn dng nhiu x tia X xc nh nh hng ca nhit l ln s kt tinh ca mng mng VO2. V ta cng c ph nhiu x tia X nh sau

V vi gc nhiu x theta tng ng: Ri p dng cng thc Debye- Schere kho st kch thc ht cho nh ph (011) theo 3 nhit ca th ta c gin sau = > v ta thy kt tinh ca mng cng ph thuc vo nhit . b) B mt ca mng to thnh: Ta kho st mp m ca mng bng knh hin vi lc nguyn t (AFM) ti 3 nhit nh trn, th ta thu c nh: Ri dng phn mm Nanoscope tm gi tr mp m b mt Rn th ta c c bng gia tr sau Kt qu ny cho ta thy Ra ti nhit 4500C v 5000C khng ging nhau v v n tng t ngt ti 550oC . c) Tnh cht nhit sc ca mng c to thnh: y chng ta s dng ph UV VIS kho st s thay i tnh cht nhit sc ca mng lng ng ti nhng nhit khc nhau (trong quang ph k UV-VIS l 1 thit b c dng o cng nh sang truyn qua mu). th ta s c hnh nh sau: T hnh v ta thy,: i vi VO2 ( c 3 trng hp nhit ) th vng hng ngoi(IR) c 1s tng phn r nt gia truyn qua ca pha bn dn nhit thp (25OC) v truyn qua ca pha kim loi nhit cao (100OC). V ta thy tng phn y tng khi nhit ca tng. 3. nh gi chung i vi kt qu mng to c t 2 phng php y, ta c 1 vi nhn xt nh sau: Nhit ca u nh hng n kt qu lng ng mng (ca c hai phng php). Tuy nhin, v mt cu trc tinh th, mng c to bng phng php PLD th hin 1 s thay i quyt lit hn; trong khi , s thay i camng c to bi phng php ICMS th t ra bnh thng hn.(kt qu XRD ca c 2 phng php cho ta thy r c iu ny) mp m ca mng c to thnh (t c 2 phng php) u tng khi nhit tng = > Dn n vic tng kch thc ht c to thnh Mng c tng hp bng phng php PLD c truyn qua gim khi nhit tng; trong khi mng c lng ng bng phng php ICMS th bin thin (fluctuation) khi nhit tng. Ngoi ra ngi ta cn c th xac nh c dy ca mng VO2 bng phng php tn x ngc Rutherford v tnh cht in ca mng bng phng php bn mi d (four point Probe) (nhng y khng trnh by). Nn ta c them 2 nhn xt na m y ta xem nh l chp nhn dy ca mng c to thnh (t c 2 phng php) hu nh khng i khi nhit tng (bi

 dy ca mng trong mi phng php tng ln khng nhiu). V nu xt kch thc nanomt, th phng php PLD to mng dy hn v t cn nhit cao nh ca ICMS Kt qu ca PLD Kt qu ca ICMS Khi tng nhit , mng c lng ng bng phng php ICMS c dn in tt hn mng c to bng phng php PLD VI. NG DNG: Vt liu nhit sc c th c dng ph ln lp ca s thng minh Trong mng VO2 c trin vng nhiu nht (v n c nhit ti hn TC =68oC rt gn nhit phng)

Vic s dng tp cht lm gim nhit chuyn tip ca vt liu nhit sc ang c nghin cu 1 cch rng ri. Trong tungsten (VI) l c trin vng nhiu nht (v l do ta k trn). Tuy nhin, v mt thng mi, th c 1 hn ch khi pha tp tungsten vo mng mng VO2. l sau khi lng ng trn thy tinh th mng pha tp s c 1 mu nu khng c hp dn cho lm. V vy, ngi ta ngh n vic pha tp cc ht nano vng vo. Bi v n khng ch gip gim nhit chuyn tip ca mng VO2, m cn s cn to cho mng 1 mu xanh dng hay xanh l cy (ty thuc vo nng ht nano vng pha tp vo) Tuy nhin, nhng kt qu ny ch c th ng dng trong nhng ni c kh hu nng m; ch n khng ph hp cho nhng ni c kh hu lnh hn (bi i vi nhng ni c kh hu lnh th nhit chuyn tip ca cc lp mng c l cng qu cao, v cng khng thi gian dng trong sut nhng thng h) Ngoi ra mng mng VO2 cn c dng trong cc thit b B chuyn mch in ton Gng quang hc Thit b lu tr d liu Cm bin nhit quang (optical temperature sensor) ....

Mng oxit Vanadium (IV) pha tp ht nano vng v mng V2O5 cn c th c dng dng lm b chuyn i quang hc

V cn nhiu ng dng khc na Mt s hnh nh ng dng ca cc vt liu nhit sc khc ng dng ca mng nhit sc tinh th lng

ng dng ca mng nhit sc thuc nhum leuco (leuco dyes)

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CC PHNG PHP CH TO MNG NHY KH - CC PHNG PHP CH TO MNG HA HC HV: Trn Th Thanh Thy CHK18 CC LOI MNG HA Mng nhy kh/lng: Al2O3,Ta2O5, Si3N4-> mng nhy pH ZnO:Ga, SnO2:Sb -> nhy hi cn.. Mng chng n mn: Tb-Fe-Co hay Tb/Fe-Co Al-SiO2, Al2O3:Mg Mng ngn khuch tn: Ta-Si-N, ZnO, Ni (Al/Si trong bn dn loi n) ZnAl3 (Al/Au) TiN, TiO2 dng tinh th hay v nh hnh (PbTiO3/Si) Phn x TVA (thermionic vacuum arc) PE-ALD, PLD (pulse laser deposotion) Phn x ALD(atomic layer deposition),PE-ALD, CCVD (combustion CVD) Solgel Phn x CVD,MOCVD (metalorganic CVD), PECVD,LPE LPCVD,EPD, spray pyrolysis LP CHNG OXI HA HOC N MN LP NGN KHUCH TN CM BIN KH/LNG PHNG PHP SOLGEL Sol (solution), Gel(gelation) y l phng php ha hc t tng hp cc phn t huyn ph dng keo rn (precursor:SnCl4.5H2O, SbCl3.2H2O) trong cht lng sau d to thnh nguyn liu lng pha ca b khung cht rn,c cha y dung mi cho n khi xy ra qu trnh chuyn tip Sol-gel. Cc alkoxide M(RO) l la chn ban u to ra dung dch solgel vi cc xc tc thch hp. C CH TO DUNG DCH SOLGEL T ALKOXIDE M(OR)+H2O -> M(OH) + R(OH) (thy phn) M(OH)+M(OH)-> MOM + H20 (ngng t) M(OH)+M(OR)-> MOM +ROH (ngng t) V D: to mng SiO2 Thy phn: (C2H5O)3-Si-OC2H5 + H2O -> (C2H5O)3-Si-OH + C2H5OH Ngng t: (C2H5O)3-Si-OH + OH-Si- (OC2H5)3 -> (C2H5O)3-Si-O-Si-(OC2H5)3 alkoxide sol CC K THUT TO MNG T DUNG DCH SOLGEL K thut ph nhng (dip coating) K thut ph quay (spin coating) K thut ph dng chy (flow coating)

K thut phun (spray coating).. Capillary coating DIP COATING Ph nhng vt liu c mt cong nh mt knh, thu knh. C th ph nhng vt liu c dy t 20nm n 50micromet bng cch chn nht ca cht lng sao cho ph hp. High precision micro Stepp driven stepper motor Barrier motor 0.01 to 400 mm/min Speed of linear movement 0 to 600 mm Linear range of movement of dipper unit Drive Belt system: 100x100x10 mm (100 % immersion) Maximum size of substrate Servo controlled DC motor Dipper motor Adjustable from 1 to 9999 seconds Delay times Unlimited Deposition cycles 145 mm Arm stroke 0.1 mm/min (ly lm n v) Speed adjustment 0.1 to 85 mm/min Deposition speed Deposition system: CC THNG S K THUT CA MY : dy lp cht lng : nht cht lng :vn tc rt :khi lng ring cht lng : gia tc trng trng FLOW COATING - dy ca mng ph thuc: nghing ca , nht cht lng,tc bay hi dung dch -S dng i vi khng bng phng v ph trn din tch ln - C th thc hin quay mu sau khi ph tng dng u ca dy mng mng. K THUT PH QUAY MU Phng php ny s dng lc quay li tm ph mng, mng c ng u cao nh lc li tm cn bng vi lc o nht ca dung dch Cc bc tin hnh: DY LP PH KHNG PH THUC LNG DUNG DCH CHO LN :khi lng ring ban u ca cht lng : khi lng ring : vn tc gc ca : nht ca cht lng : tc bay hi ca cht lng Capillary coating - Tit kim vt liu

- Ph c nhiu lp - iu chnh dy mng bng cch iu chnh tc slot-tube X L NHIT CHO MNG -Trong qu trnh to mng khu x l nhit rt quan trng v n nh hng trc tip n vi cu trc ca mng. Giai on ny c tc dng lm bay hi ht dung mi cn li trong mng, vt cht kt ni vi nhau chc ch hn hnh thnh nn bin ht lm nh hng n vi cu trc ca mng. i vi mng nhy kh cu trc xp ca mng rt c quan tm -Sau khi x l nhit ta c th tin hnh ph in cc d dng cho vic phn tch mu. K THUT PH C IN +Kh duy tr tinh khit +Gm nhiu bc tin hnh phc tp (hiu sut thp), tn thi gian. +Ch c duy nht c nhit cao Sol-gel +Kh ph mng c nhiu thnh phn. +Bung chn khng phi c p sut cao. + phi tng thch. +Kh to b mt phng Physical Vapor Deposition (PVD) +i hi nhit v p sut thp + chu nhit cao +kh ph mng c nhiu thnh phn Chemical Vapor Deposition (CVD) NHC IM PHNG PHP PHNG PHP CCVD ( Combustion Chemical Vapor Deposition) HNH NH THC T Left: One of nGimat's small pilot facilities for production of nanopowders Right: nanopowderproducing CCVC flame. U IM C kh nng sn xut vt liu a thnh phn mt cch n gin v nhanh chng nh iu chnh dung dch ha hc-> m rng phm vi ng dng iu chnh c kch thc, hnh dng v hnh thi hc ca cc ht nano. My hot ng mi trng khng kh bnh thng NHC IM Tin cht phi ha tan c v d bt la Dng c t tin K THUT PLD (pulse laser deposition) Phng php PLD c ch trong vi nm va qua v phng php ny ph c thnh cng nhng hp cht phc tp. K thut PLD ln u tin s dng ph mng siu dn YBa2Cu3O7. K t nhiu vt liu kh ph bng nhng phng php bnh thng , c bit l nhng hp cht gm nhiu loi oxit khc nhau c ph thnh cng bi phng php ny. Phng php ny dng ph nhng mng nhy PH nh Al2O3, Ta2O5, cc loi mng chng oxi ha hoc n mn 1 nm 6 thng 3 nm bn 1 1 1

Thi gian hng ng(pht) 56-58 53-55 54-56 Cng (mV/pH) 2-12 2-12 2-12 Khong o (pH) Ta2O5 Si3N4 Al2O3 Mng Sensor pH pH pH Loi Sensor LCH S PHT TRIN CA PLD 1916 Albert Einstein gi nh qu trnh pht x kch thch. 1960 Theodore H. Maiman xy dng my maser (microwave amplification by stimulated emission radiation)-my khuch i vi sng bng bc x cm ng s dng thanh ruby nh l mi trng tc dng laser. 1962 Breech v Cross s dng laser ruby lm bay hi v kch thch nguyn t t b mt cht rn 1965 Smith v Turner s dng laser ruby ph mng . Dnh du s khi u ca k thut PLD u thp nin 80- nh du s to ra thit b ph mng bng laser v k thut epitaxy . Mt vi nhm nghin cu t c nhng kt qu ng ch trong vic sn xut ra nhng mng mng bng cch s dng k thut ny 1987 PLD thnh cng trong vic ch to nhng mng mng siu dn nhit Cui thp nin 80 PLD l mt k thut kh ni ting trong vic ch to mng mng v c ch n rt nhiu. 1990s s pht trin nhanh chng ca laser ko theo s pht trin ca k thut PLD. 2000s- Drs. Koinuma and Kawasaki nghin cu ci tin h thng PLD to ra nhng mu c cht lng cao v gim thi gian ph mng Nguyn tc hot ng Adhesion, capacitors, catalytic applications, corrosion resistance, gas diffusion barriers, electronics, engines, ferroelectric materials, flat panel displays, fuel cells, interface layers, optics, piezoelectrics, resistors, RF and millimeter wave components solar cells, superconductors, thermal barrier, thermal control, and wear resistance Some Applications Al, Brass, Ag, Cu, Pt, Ni, Stainless and C-Steel, Al2O3, Fiber Tows, Glass, Graphite, LaAlO3, MgO, NafionTM, NiCr, Optical fibers, OPP, PET, Polycarbonate, Silica, Si, Si-Ti/Pt wafers, SiC, Si3N4, Superalloys, TeflonTM, Ti, TiAl alloy, YSZ, powders Substrates Used Over 10 polymers (polyimides, NafionTM, epoxies), numerous composites of metals, ceramics and polymers Al2O3, Al2O3MgO, 3Al2O32SiO2, BaCeO3, BaCO3, BaTiO3, BST, doped-CeO2, Cr2O3, CuxO, [La.95Ca.05]CrO3, Fe2O3, In2O3, ITO, LaAlO3, LaPO4, LSC, LSM, MgO, Mn2O3, MoO3, Nb2O5, NiO, NSM, PbSO4, PbTiO3, PdO, PLZT, PMN, PMT, PNZT, PZT, RbOx, RhOx, RuO2, SiO2, Spinels (e.g. NiAl2O4, NiCr2O4), Silica Glasses, SnO2, SrLaAlO4, SrRuO3, SrTiO3, Ta2O5, TiO2, V2O5, WO3, YBa2Cu3Ox, YbBa2Cu3Ox, YIG, YSZ,

YSZAl2O3, YSZ-Ni, ZrO2, ZnO (+ dopants in many cases) Ag, Au, Cu, Ir, Ni, Rh, Pt, Ru, Zn Others Ceramics Metals VT LIU PH PLD-3000 Bia Thit b gi