I.

Phng php bc bay nhit Bc bay nhit (ting Anh: Thermal evaporation) hoc bay bc nhit trong chn khng l k thut to mng mng bng cch bay hi cc vt liu cn to trong mi trng chn khng cao v ngng t trn (c t nng hoc khng t nng). K thut ny i khi cn c gi l bay hi trong chn khng nhng t dng hn.

S nguyn l h bay bc nhit 1.Nguyn l ca h bc bay nhit B phn chnh ca cc thit b bay bc nhit l mt bung chn khng c ht chn khng cao (c 10-5 - 10-6 Torr) nh cc bm chn khng (bm khuch tn hoc bm phn t...). Ngi ta dng mt thuyn in tr (thng lm bng cc vt liu chu nhit v t tng tc vi vt liu, v d nh vnphram, tantan, bch kim...) t nng chy cc vt liu ngun, v sau tip tc t sao cho vt liu bay hi.

Vt liu bay hi s ngng ng ln cc c gn vo gi pha trn. i khi cn c t nng (ty theo mc ch to mng tinh th hayv nh hnh...) iu khin cc qu trnh lng ng ca vt liu trn mng. Chiu dy ca mng thng c xc nh trc tip trong qu trnh ch to bng bin t thch anh. Khi mng bay hi s bm ln bin t t cnh , bin thin tn s dao ng ca bin t s t l vi chiu dy ca mng bm vo bin t.

nh chp thit b bay bc nhit ca Angstrom Engineering 2.u im, nhc im v nhng ci tin gn y Phng php bay bc nhit c u im l n gin, v d to mng hp cht v khi lm bay hi vt liu th ton th hp cht hoc hp kim s b bay hi do mng to ra c hp thc kh gn vi thnh phn ca vt liu ngun (c bit l cc hp kim).

Nhc im quan trng l khng th to cc mng qu mng, kh nng

khng ch chiu dy ca phng php ny rt km do tc bay bc kh iu khin. ng thi, vic ch to cc mng a lp l rt kh khn vi phng php ny.

Gn y ngi ta ci tin phng php ny nh s dng chm in t

bay bc, ci tin tng bao quanh ngun t (phng php tng nng)... Tuy nhin t l s dng phng php bay bc nhit trong k thut mng mng ang ngy cng t. II. Knh him vi in t qut (SEM) Knh hin vi in t qut (ting Anh: Scanning Electron Microscope, thng vit tt l SEM), l mt loi knh hin vi in t c th to ra nh vi phn gii cao ca b mt mu vt bng cch s dng mt chm in t (chm cc electron) hp qut trn b mt mu. Vic to nh ca mu vt c thc hin thng qua vic ghi nhn v phn tch cc bc x pht ra t tng tc ca chm in t vi b mt mu vt. 1. Lc s v knh him vi in t qut Knh hin vi in t qut ln u tin c pht trin bi Zworykin vo nm 1942 l mt thit b gm mt sng phng in t theo chiu t di ln, ba thu knh tnh in v h thng cc cun qut in t t gia thu knh th hai v th ba, v ghi nhn chm in t th cp bng mt ng nhn quang in.Nm 1948, C. W. Oatley i hc Cambridge (Vng quc Anh) pht trin knh hin vi in t qut trn m hnh ny v cng b trong lun n tin s ca D. McMullan vi chm in t hp c phn gii n 500 Angstrom. Trn thc t, knh hin vi in t qut thng phm u tin c sn xut vo nm 1965 bi Cambridge Scientific Instruments Mark I.

S knh him vi in t qut 2. Nguyn tc hot ng v s to nh trong sem Vic pht cc chm in t trong SEM cng ging nh vic to ra chm in t trong knh hin vi in t truyn qua, tc l in t c pht ra t sng phng in t (c th l pht x nhit, hay pht x trng...), sau c tng tc. Tuy nhin, th tng tc ca SEM thng ch t 10 kV n 50 kV v s hn ch ca thu knh t, vic hi t cc chm in t c bc sng qu nh vo mt im kch thc nh s rt kh khn. in t c pht ra, tng tc v hi t thnh mt chm in t hp (c vi trm Angstrong n vi nanomet) nh h thng thu knh t, sau qut trn b mt mu nh cc cun qut tnh in. phn gii ca SEM c xc nh t kch thc chm in t hi t, m kch thc ca chm in t ny b hn ch bi quang sai, chnh v th m SEM khng th t c phn gii tt nh TEM. Ngoi ra, phn gii ca SEM cn ph thuc vo tng tc gia vt liu ti b mt mu vt v in t. Khi in t tng tc vi b mt mu vt, s c cc bc x pht ra, s to nh trong SEM v cc php phn tch c thc hin thng qua vic phn tch cc bc x ny. Cc bc x ch yu gm: in t th cp (Secondary electrons): y l ch ghi nh thng dng nht ca knh hin vi in t qut, chm in t th cp c nng lng thp (thng nh hn 50 eV) c ghi nhn bng ng nhn quang nhp nhy. V chng c nng lng thp nn ch yu l cc in t pht ra t b mt mu vi su ch vi nanomet, do vy chng to ra nh hai chiu ca b mt mu. in t tn x ngc (Backscattered electrons): in t tn x ngc l chm in t ban u khi tng tc vi b mt mu b bt ngc tr li, do

chng thng c nng lng cao. S tn x ny ph thuc rt nhiu vo vo thnh phn ha hc b mt mu, do nh in t tn x ngc rt hu ch cho phn tch v tng phn thnh phn ha hc. Ngoi ra, in t tn x ngc c th dng ghi nhn nh nhiu x in t tn x ngc, gip cho vic phn tch cu trc tinh th (ch phn cc in t). Ngoi ra, in t tn x ngc ph thuc vo cc lin kt in ti b mt mu nn c th em li thng tin v cc men st in. 3. Mt s php phn tch trong sem Hunh quang catt (Cathodoluminesence): L cc nh sng pht ra do tng tc ca chm in t vi b mt mu. Php phn tch ny rt ph bin v rt hu ch cho vic phn tch cc tnh cht quang, in ca vt liu.

Thit b knh hin vi in t qut Jeol 5410 LV ti Trung tm Khoa hc Vt liu, i hc Quc gia H Ni Phn tch ph tia X (X-ray microanalysis): Tng tc gia in t vi vt cht c th sn sinh ph tia X c trng, rt hu ch cho phn tch thnh phn ha hc ca vt liu. Cc php phn tch c th l ph tn sc nng lng tia X (Energy Dispersive X-ray Spectroscopy - EDXS) hay ph tn sc bc sng tia X (Wavelength Dispersive X-ray Spectroscopy - WDXS)... Mt s knh hin vi in t qut hot ng chn khng siu cao c th phn tch ph in t Auger, rt hu ch cho cc phn tch tinh t b mt. SEMPA (Knh hin vi in t qut c phn tch phn cc ting Anh: Scanning Electron Microscopy with Polarisation Analysis) l mt ch ghi nh ca SEM m , cc in t th cp pht ra t mu s c ghi nhn nh mt detector c bit c th tch cc in t phn cc spin t mu, do cho php chp li nh cu trc t ca mu.

4. u im ca knh him vi in t qut Mc d khng th c phn gii tt nh knh hin vi in t truyn qua nhng knh hin vi in t qut li c im mnh l phn tch m khng cn ph hy mu vt v c th hot ng chn khng thp. Mt im mnh khc ca SEM l cc thao tc iu khin n gin hn rt nhiu so vi TEM khin cho n rt d s dng. Mt iu khc l gi thnh ca SEM thp hn rt nhiu so vi TEM, v th SEM ph bin hn rt nhiu so vi TEM. III. CH TO MNG NITRIC COBAN BNG K THUT BC BAY BNG XUNG LASER PHN NG (PLD) Nitric kim loi t tr nn quan trng do chng c tim nng ng dng ln trong cng ngh. Trong bi bo ny, mng mng Nitric Coban c ch to bng phng php bc bay bng xung laser phn ng ( mi trng nit ) trn Silic ti nhit phng. c tnh ca mng sau khi ch to c xc nh ti ch bng phng php Auger, ph quang in t tia X v ph tn hao nng lng in t. Lin kt ha hc ca CoNx c lin quan mt thit n tnh hp phc v n c th c iu khin bng p sut nn N . Chng ti cho rng phng php bc bay ny l mt phng tin c ch cho s tinh chnh nhng tnh cht ca Nitric Coban. 1. Gii thiu K t khi thit b lu tr d liu t u tin c ch to, mng mng vt liu t ngy cng c quan tm. S thu nh kch thc ca men t lu tr nhng yu t thng tin nh l yu t then cht lm tng kh nng lu tr ca cc thit b lu tr t. V vy, s iu khin thch hp nhng tnh cht ha hc v vt l ca mng mng t c th cho php tng kh nng lu tr ca nhng thit b lu tr hin nay. Nitric kim loi t ang nhn c nhng s ch c bit trong lnh vc nghin cu ny. Nitric t tnh c xp vo loi vt liu mi cho nam chm cht lng cao bi v tnh d hng n trc ca chng mnh v t ha bo ha cao. Nhiu loi mng mng c sn xut bng phng php phn x phn ng. Tuy nhin, cc vt liu st t cao rt kh sn xut bng cng ngh

ny khi s dng ngun kiu magnetron. S dng vt liu st t lm bia phn x dn n s xut hin mt t thng ngu nhin pha trc b mt bia magnetron [2], dn n cht lng km, mng khng ng nht. V vy, cn phi pht trin mt k thut bc bay mng mng t thay th. Mt cng ngh ch to mng mng vt liu t y ha hn xut hin l k thut bc bay bng xung laser ( PLD ). PLD c s dng bc bay nhiu vt liu khc nhau nh kim loi, cht in mi, cht in st v cht bn dn. Khng ging nh k thut phn x , PLD khng ph thuc vo t trng bc bay mng mng, v th thun li cho qu trnh to mng [4]. Trong thi gian gn y, ngi ta thy PLD l phng php a thch trong vic sn xut mng t ng nht hoc mng d cu trc. Ngy nay, cng ngh lin kt vi PLD c pht trin cho PLD tr thnh phng php ng tin cy v c th d on c. Mc d nhiu cng trnh nhm n vic ph bin kin thc v PLD, nhng trong thc t s chuyn giao cng ngh PLD cho cng nghip cn chm . Mc ch ca bi bo ny l chng t rng PLD l mt k thut ng tin cy cho vic bc bay mng t nitric. hon thnh mc tiu ny, mng mng Nitric Cobal cn c chun b bng cch n mn mt bia Co c tinh khit cao vi s c mt ca phn t Nit. 2. Thc nghim Tt c mng c bc bay ti nhit phng trong h thng n mn laser, Riber LDM - 32, vi quang ph in t Auger ( AES ), ph tn hao nng lng in t (EELS ) v cc thit b quang in t tia x ( XPS ). Qu trnh bc bay c hon thnh bng cch lm mn bia Cobal 99.9% trong mt nn phn t nit c tinh khit cao. p sut ca Nit, PN vo khong (1 Torr = 1,33 . 102 Pa ) 1.10-9 P/N 1,2.10-1. Cc lp c lng t trn mt phin Silic pha tp n (111), ngha l khng c qu trnh lm sch no. Qu trnh n mn bia c hon thnh bng mt laser excimer KrF ( c bc sng bng 248 nm ) hi t trn mt bia lch 500

C vi php tuyn b mt. Nng lng laser, thi gian lng ng v tc lp li ca xung n nh 400 mJ, 10 pht v 10 Hz, cn tng cng khong 6000 xung laser cho mi mng. Trn c s xem xt s mt mt ti mt ca s laser, mt nng lng ti b mt bia c c lng l 2 Jcm-1 .Ph AES v EELS c thu dng mt chm tia in t vi nng lng ti tng ng l 3 KeV v 1 KeV. Php o XPS thu c bng cch s dng ng Mg K ca mt ngun tia X vi nng lng l 1253.6 eV eV. Thang o nng lng c hiu chnh theo cc quy chiu Co2p3/2 v Ag3d5/2 tng ng nng lng 932.67 eV v 368.26 eV. 3. Kt qu v tho lun Vic phn tch XRD khng cho thy bt c peak ph ng ch no, ngoi tr nhng peak lin quan ti . Ngoi l duy nht l i vi mng c x l ti PN = 0 m Torr, mt nh hin r ti 2 = 51,80. nh ny c quy cho mt (111) ca khi Coban mng lp phng. dy ca mng c gi bnh qun khong 90nm ( 10 nm), cha mt tn hiu tt nu phn cn li ca mng kt tinh. Do chng ti kt lun rng mng mng Cobal c x l nhit phng trong mi trng nit c cu trc v nh hnh. B mt ca mng rt mn, gn gii hn phn gii ca SEM, nh biu din trong hnh 1 i vi mt loi mng thng thng.

Mt vng ra l tng i thp trong k thut bc bay ny, ngoi tr mng c hnh thnh PN = 0 m Torr, c xut hin cc ht dng tan chy ln trn b mt mng. nh AFM , hnh 2, cho thy mng c cu trc ht. Cc mng c gh gh vo khong 10% dy mng ( gi tr RMS, khong 10 nm ). Php phn tch XPS v AES c thc hin trn nhng mng c n mn cho thy hp cht Nitric Coban khng c tp cht trong gii hn pht hin ca nhng k thut ny ( gn 1% nguyn t ). Hnh 1 cho thy ph XPS in hnh ca mng mng Nitric Coban, ch thy s pht x quang in t t Co v N. Nng tng i ca Co v N c tnh t din tch bn di nh Co2p3/2 v N1s theo phng php tr nn Touggard. Thng s nhy c tnh ton bng k thut tng t nh c m t trong bo co trc [7]. Nng nguyn t ca Co v N c v nh mt hm theo p sut nit c minh ha trong hnh 2. Biu ny cho thy s tng n iu ca

nng N nhng mng vi p sut nit. S kt hp nit vo Co b n mn ch yu l tuyn tnh trong phm vi 25-120 m Torr ca p sut N. Trng thi tuyn tnh ca ng cong N cho php tinh chnh hp phc Cobal nitric bng cch iu khin p sut kh nit. Tnh hp phc ca mng c sn xut bng PLD c thit lp ph thuc vo p sut kh ton phn. Hp phc Co2N, CoN v Co2N3 c hnh thnh tng ng vi cc p sut PN bng 40, 90 v 120 m Torr. S kim tra v tr peak ca cc vch Co2p3/2 v N1s c th cho thy bt c s thay i trng thi ha hc m Co v N phi chu trong qu trnh n mn. V th cng cc i ca cc vch Co v N nh mt hm theo nng nit tng i, x=[N] / [Co] trong cc mng cho thy s dch chuyn dn ca cc nh Co2p3/2 v N1s ( hnh 3). S dch chuyn tng i ny khng phi l h qu ca vic pht sinh nhng thnh phn l cm ng in bi v s khc bit v mc nng lng ca Co v N khng cho thy mt gi tr hng s nh hm theo x. Do , nhng dch chuyn peak c lin quan n s thay i trng thi ha hc.

S thay i v tr ca cc peak l kt qu ca s chuyn giao in tch gia cc nguyn t Co v N. Nguyn t Co c c c tnh ion khi x tng, dch chuyn chm nng lng lin kt ca cc in t Co2p3/2 t trng thi trung ha 777.8 eV, ti trng thi c c tnh ion no ti 778.3 eV . Trong trng hp ca cc nguyn t nit, iu ny c hp nht vo trong mng vi c trng ion cao hn, quan st s thay i nng lng lin kt ca cc in t N1s t 398.5 n 396.8 eV trong ton b ch x c phn tch. S dch chuyn nng lng lin kt ca cc in t N1s c lin quan n vic thm in t ca N nguyn t s tiu hao ca cc nguyn t Co. Xu hng ny xut hin khi c thm nhiu nguyn t Nit c hp nht vo trong mng. C th, nng lng lin kt o c i vi cc hp phc ca Co2N, CoN v Co2N3 l 778.0, 778.2 v 778.4 eV i vi cc in t Co2p3/2 v 398.0, 397.4 v 396.8 eV i vi cc in t N1s ( Hnh 4).

EELS c th cung cp nhiu thng tin chnh xc v s thay i trng thi in t trong cht rn. Mt s thay i trong cu trc in t dn n s thay i mnh trong trong ph EELS. C nhiu bi bo tp trung vo ph tn hao ca kim loi chuyn tip [9] , vi Co gia chng. Mc d nn tng

l thuyt ca lnh vc ny c tho lun rng ri trn nhng bi bo khc [10-15], gii thch ph mt mt vn cn cha sng t i vi Co. Hnh 5 cho thy ph EELS ca mt s mng c ch to nhng gi tr sau: PN = 0, 40, 90, 100, 120 m Torr. Ph mt mt ca Co kim loi cho thy 1 peak chnh 25-27 eV c Barbier v cc cng s xp vo loi tn s plasmon ( v ), mc d c gi tr nh hn nhiu so vi gi tr mong i t l thuyt in mi. Peak cng nh ti 8 - 9 eV c xp vo loi peak kiu trng thi th tch. Plasmon b mt c tin on s xut hin ti 18-19 eV th li khng quan st c trong ph. Cn ch rng quy tc ch ng cho cc b mt nguyn t phng. Trong trng hp ny, mng mng c dng cc ht c dng phn b cu kch tht bin i. y c th l mt l do l gii cho s bin mt ca Plasmon b mt. Trong trng hp ca mng CoNx , cu trc tn hao nng lng trong phm vi 5 - 30 eV thay i mnh, v mi hp phc Coban nitric a vo cu trc tn hao ring ca n. Khi nng nit tng trong nitric, peak dch chuyn n nng lng thp hn. Vic ny cho bit s gim trong mt in t ca pha nitric.

4. Kt lun

Tm li, mng mng nitric coban c pht trin bng cch n mn bia Co trong mi trng nit ti p sut nn khc nhau. S khc nhau 0.5 eV v 1.5 eV trong nng lng lin kt tng ng ca cc electron Co2p3/2 v N1s, l bng chng cho thy s phn ng gia N v Co c thc hin hiu qu. Tnh hp phc c th c iu chnh bng cch thay i p sut kh nit. Vic ch to cc hp phc khc nhau l kh thi. Ti p sut cao hn, tnh hp phc dng nh khng thay i. PLD c th l phng thc rt c gi tr bc bay nitric ca vt liu st t, l mt phng tin iu chnh tnh cht ca vt liu c sn xut.