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[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf

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[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf
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[CN12]EDY Riyanto, 黄高山*, 赵宇婷, 张菁, 石建军, 梅永丰, 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性[J], 材料科学与工程学报, 36(05), 705-712+719(2018)..pdf

材 料 科 学 与 工 程 学 报 Journa lo f Ma t e r i a l sSc i enc e & Eng i ne e r i ng 第36卷 第5期 Vo l. 36 No. 5 总第175期 Oc t. 2018 Ar t i c l eID: 1673-2812( 2018) 05-0705-09 umi num-Dope dZ i ncOx i d eTh i nF i lmsSyn t he s i z e dbyAt omi cLay e r Al Depo s i t i onf o rPho t o c a t a l s i s y , EDY Ri t o1 2,HUANG Gao s han2,ZHAO Yu t i ng2,ZHANGJ i ng3,SHIJ i an un3, yan j f eng2 MEIYong ( 1. o r Mod i f i c a t i ono fCh emi c a lF i b e r sandPo l r Ma t e r i a l s,Co l l e eo f Ma t e r i a l s r a t o r S t a t eKe yme g yf yLabo S c i enc eandEng i n e e r i ng,DonghuaUn i v e r s i t i201620,Ch i na;2. Depa r tmen to f Ma t e r i a l sS c i enc e,Fudan y,Shangha Un i v e r s i t i200433,Ch i na;3. Co l l e eo fS c i enc e,DonghuaUn i v e r s i t i201620,Ch i na) y,Shangha g y,Shangha 【 Ab s t r a c t】 Z h i nf i lms we r ef abr i c a t edby i ncox i de ( ZnO)anda l umi num-doped ZnO (AZO)t l e t hanea sas a c r i f i c i a lt emp l a t e.ZnOandAZO we r ef i r s t l a t omi cl aye rdepos i t i onus i ngpo r ouspo yur y r oust emp l a t ef o l l owed by a c a l c i na t i on a t500℃ i n depos i t edon t ot hesur f a c eo fpo l e t hane po yur oxygena tmosphe r e.Thr e e-d r ouss t ruc t ur e sa sar ep l i c ao ft hes a c r i f i c i a l imens i ona l l emi conduc t o rpo ys r ouss t ruc t ur e swe r ebr okeni n t osma l l l ve r i z i ng,t hepo r oust emp l a t ewe r et husa ch i eved.Af t e rpu po t oc a t a l t s.Wi t hi nc r e a s i ngAldop i ng,t heop t i c a lbandgaps i e c e s,wh i chwe r et henemp l oyeda spho p ys t oc a t a l t i cpe r f o rmanc ei nc r e a s eco r r e spond i ng l andt hepho y. y 【 r d s】 a Ke t omi cl aye rdepos i t i on;Al-dopedZnO;pho t oc a t a l i s ys ywo CLCnumb e r: TB3 4 Do c ume n tc o d e:A / DOI: 1 0. 1 4 1 3 6 c nk i. i s s n1 6 7 3-2 8 1 2. 2 0 1 8. 0 5. 0 0 4 j. 原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性 EDY R i a n t o12,黄高山2,赵宇婷2,张 y , 菁3,石建军3,梅永丰2 ( 1.东华大学材料科学与工程学院,纤维材料改性国家重点实验室,上海 201620;2.复旦大学材料科学系, 上海 200433;3.东华大学理学院,上海 201620) 【摘 要 】 采用原子层沉积技术和多孔聚氨酯牺牲模板制备了氧化锌 ( ZnO)和铝掺杂氧化锌 ( AZO) 纳米薄膜并研究了其光催化性能 。 首先利用原子层沉积技术 ,将 ZnO 和 AZO 沉积到多孔聚氨酯模板上 , 然后在 500℃ 高温煅烧处理去掉牺牲模板 ,得到复制了多孔模板的氧化物纳米薄膜三维多孔结构 。 将该三 维多孔结构压碎 ,得到片状纳米薄膜 。 实验结果表明 ,随着铝掺杂含量的提高 ,材料的带隙和光催化性能 也相应提升 。 【关键词 】 原子层沉积 ;铝掺杂氧化锌 ;光催化 [ 1 I n t r odu c t i on Semi conduc t o r pho t oc a t a l i s ha s r e c e i ved ys i n t ens i ve a t t en t i on i n env i r onmen t a l pur i f i c a t i on owi ngt oi t ss imp l i c i t l dr e a c t i oncond i t i ons,and y,mi ] l ow ene r t i on1-2 .Tr ans i t i on me t a lox i de gyconsump s emi conduc t o r ssuch a s TiO2 ,and ZnO have be en ex t ens i ve l t ud i edf o rapp l i c a t i onsi n pho t oc a t a l t i c ys y c a landb i o l og i c a l a c t i v i t i t h i umi onba t t e r y,l y,chemi [ ] s enso r s, and e l e c t r on i c dev i c e s2-12 . ZnO ha s Re c e i v e dda t e: 2017-03-20;Mod i f i e dda t e: 2017-04-19 Founda t i oni t em:Na t i ona l Na t ur a lSc i enc e Founda t i on o f Ch i na ( 51322201,51475093);Sc i enc e and Te chno l ogy Commi s s i on o f Shangha i Mun i c i l i t 14JC1400200) pa y( B i o r a EDY R i a n t o,ma l e,I ndon e s i a,c a nd i d a t eo fPhD.E-ma i l:e dy r_ 01@y aho o. c o. i d. y g ph y: Co r r e s o nd i n u t h o r: HUANG Ga o s h a n,p r o f e s s o r.E-ma i l:g s hu a ng@f ud a n. e du. c n. p ga 材料科学与工程学报 · 706 · a t t r a c t ed cons i de r ab l ea t t en t i on be c aus eo fi t sl ow 2018 年 10 月 .TiO2i sknownt obe Alsour c eo ft he pr e cur so ri st r ime t hy la l umi num ( TMA).Fo ra l ldop i ngandnodop i ngdepos i t i ons, t he mos ta c t i vepho t oc a t a l tf o ro rgan i cox i da t i on. ys Somec e r t a i ns t ud i e s,howeve r,haver epo r t edt ha t t heALDr e a c t o rt empe r a t ur e wa ss e ta t150℃ ,and t he t empe r a t ur e so ft he TMA, DEZ, and H2O ZnO exh i b i t s a be t t e ra c t i v i t n pho t oc a t a l t i c yi y e cur so rbo t t l e swe r es e ta t60℃ ,45℃ ,and50℃ , pr [ 1,13-15] cos tandnon-t ox i cna t ur e [ 16-18] .Theh i gh r e spe c t i ve l h i ckne s so ft he ox i de f i lm wa s y.The t t oc a t a l t i ce f f i c i enc f ZnO i sa t t r i bu t edt oi t s pho y yo h i rab i l i t o gene r a t e H2O2 , mo r ea c t i ve s i t e s ghe yt con t r o l l edbyt henumbe ro fALDcyc l e s.I no rde rt o f abr i c a t eAZOt h i nf i lm,as i ng l el aye ro fAl2O3 wa s r f o rmanc ea scompa r ed wi t h TiO2 pe [ , ] and h i r sur f a c e r e a c t i v i t han TiO2 17 19 . ghe y t Howeve r,i twa sc l a imedt ha tZnOa sapho t oc a t a l t ys ha ss eve r a ld r awba cksi nc l ud i ngl ow s t ab i l i t o yduet [ 1] t oco r r os i on ,t he h i e comb i na t i on r a t eo f pho gh r i ns e r t edbe twe ent heZnOcyc l e s.Two AZOs amp l e s we r ef abr i c a t ed.Thes t ruc t ur eo fAZO1i s5l oopso f /Al2O3( 1cyc l e),wh i l et hes t ruc t ur e ZnO ( 40c l e s) yc t ogene r a t ed e l e c t r on-ho l e pa i r s, and a l ow pho /Al2O3 o f AZO2 i s 10 l oops o f ZnO ( 20 c l e s) yc (1cyc l e ). To a ch i eve c a t a l t ma t e r i a l s, t he ys i e l di nt he pho t oc a t a l t i cr e a c t i ons i n t um y y quan depos i t edsponge s we r ec a l c i neda t500℃ i n oxygen aqueous so l u t i ons wh i ch have be en obs t ruc t i ng a tmosphe r e. Th i spr oc c e s s wa s ab l et of o rm t he [ 16] t oc a t a l t i cma t e r i a l s . comme r c i a l i z a t i ono ft hepho y Cons equen t l r owi ng i n t e r e s ti s exh i b i t i ng i n y,a g t hr e e-d imens i ona l l r ous s t ruc t ur e s compos ed o f y po impr ov i ng t he pho t oc a t a l t i ca c t i v i t f ZnO.The y yo l e t hanet emp l a t ewa sc a rbon i z edandr e a c t swi t h po yur impr ovemen ti de a si nc l ude mo r l og i c a lchangei n pho nano-s c a l e,compos i t e ss t ruc t ur eop t imi z a t i on,de f e c t oxygent of o rmsCO2 .Even t ua l l a r to f yal geamoun t h i nf i lms ( f l ake s) c an be f o rmed by manua l i n t r oduc t i on, and dop i ng wi t h t r ans i t i on me t a l [ 16, 20-21] .Amongt ox i de s hem,Al-doped ZnO (AZO) l ve r i z a t i on o f t he t hr e e-d imens i ona l l r ous pu y po r t z s t ruc t ur e s.Th i nf i lms we r ea l sodepos i t edonqua ha sr e c e i ved cons i de r ab l ea t t en t i on be c aus eo fi t s subs t r a t e sf o rcompa r i son. ope r t i e s and l ow i c a l and chemi c a l pr un i que phys 2. 2 Cha r a c t e r i z a t i on [ 16, 22-24] cos t s . I nt h i ss t udy, Aldoped ZnO t h i nf i lms we r e epa r a t i onandt he i r exp l o r edi nt e rmso f ma t e r i a l spr t oc a t a l t i cpe r f o rmanc e.I nt heexp l o r a t i on,t he pho ys s es t ruc t ur e, ene r t ruc t ur e, e l e c t r on pha gy band s conduc t i ve pa t h and a c c e l e r a t i on o f e l e c t r on movemen t sc aus ed by t he dop i ng we r et aken i n t o cons i de r a t i ons. 2 Expe r imen t a lme t hod s 2. 1 Syn t he s i so fox i det h i nf i lms I nt h i s wo rk,ZnO and AZO f i lms we r ef i r s t l y epa r ed by a t omi cl aye r ed depos i t i on (ALD)on pr r ouspo l e t hanes a c r i f i c i a lt emp l a t e( 67×20× po yur many sma l lt h i n f i lms o r f l ake s due t o t he Thet h i nf i lms mo r l og i e s we r e imaged by pho s c ann i ng e l e c t r on mi c r os copy (SEM, Phenom t oc a t a l twe r e wo r l d).Thec r t a ls t ruc t ur e so fpho ys ys t e s t ed by X-r ay d i f f r a c t i on (XRD ) on a D8 spe c t r ome t e ro fAdvanc eBruke rAXS GMBH,us i ng Cu Kαr ad i a t i on wi t hi r r ad i a t i onscond i t i ono f40kV and40mA.X-r aypho t oe l e c t r onspe c t r os copy ( XPS) expe r imen t s we r ec a r r i ed ou t on a RBD upg r aded PHI-5000C ESCA s t em ( Pe rk i n Elme r)wi t h Mg ys Kαr ad i a t i onandt he X-r ayanode wa sruna t150W. Op t i c a l pr ope r t i e so f ZnO and AZO t h i nf i lms on s r t zg l a s s subs t r a t e we r e eva l ua t ed by UV-Vi qua ( Sh spe c t r opho t ome t e r imadzu UV-2550 spe c t r ome t e r). nt heALD,d i e t hy lz i nc ( DEZ)wa sus eda s 3mm ).I t hepr e cur so ro fZnand mi xed wi t h wa t e r (H2O)a s 2. 3 Pho t o c a t a l t i cme a s u r emen t y t her e a c t an t s.Bo t h DEZ and H2O we r eexpos edt o we r e me a sur ed by pho t odeg r ada t i ono f MO so l u t i on t heALDr e a c t o rv i acompu t e r-con t r o l l edva l ve s wi t h l s eandpurget imeo f50msand30s,r e spe c t i ve l pu y. s spe c t r opho t ome t e r. The ZnO-ba s ed us i ng UV-Vi 3 I nt he c a s eo f AZO, Al2O3 a s a doped-l aye r wa s depos i t ed wi t h i nt hes amepu l s eandpurget ime.The Pho t oc a t a l t i c pe r f o rmanc eo f ZnO and AZO y t h i nf i lmswi t ht hewe i to f0. 0125g we r ep l a c edi n gh 50mL MO so l u t i on wi t h ani n i t i a lconc en t r a t i on o f 10mg/L,wh i ch wa s kep ti nt he da rkf o r30mi nt o 第 36 卷第 5 期 t o,等 .原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性 EDY Ri yan · 707 · a ch i eve t he adso r t i on equ i l i br i um, and t hen p i l l umi na t edunde rt he UVl i ti r r ad i a t i ono f200-W gh xenonl amp (Lanpu,Ch i na) wi t ht he d i s t anc eo f 50cmf r omt he MO so l u t i on.Thedeg r ada t i ono ft he MO wa s me a sur ed eve r n. The abso r t i on y 20mi p i n t ens i t tt he wave l eng t ho f464nmi sf oundt obe ya t he max imum abso r t i on pe ak o f MO, and t he p i n t ens i t s ex t r a c t ed t o c a l cu l a t e t he MO y wa deg r ada t i on. s u l t sandd i s c u s s i on 3 Re F i e1showst hef abr i c a t i ons chema t i co fZnO gur and AZO t h i nf i lms syn t he s i z ed by ALD.I nt he l e t hanet emp l a t e oc e s s,t he o r i i na lpo r ous po yur pr g ( F i 1( a))wa sdepos i t edby ZnO o r AZO wi t h~ g. 200 ALD cyc l e s (F i t a i n pur e g.1 (b)). To ob t oc a t a l t,t hedepos i t edsponge wa sc a l c i nedi n pho ys oxygena tmosphe r ea t500℃.Oxygenr e a c t s wi t ha c a rbon i z ab l eo rgan i c ma t e r i a lt of o rm CO2 andf l ow ou to ft he c a l c i na t i on chambe r, wh i ch even t ua l l y imens i ona l l r ous c aus e st hef o rma t i on o ft hr e e-d y po s t ruc t ur e scons i s t i ngo ft h i nf i lms ( F i 1( c)).The s e g. l ve r i z ed manua l l of o rm s t ruc t ur e s we r et hen pu yt / r t h i nf i lms (F i 1( d)).I nt he f o l l owi ng powde g. t oc a t a l t i c app l i c a t i ons, t he t h i n f i lms we r e pho y emp l oyeda spho t oc a t a l t. ys F i 2 SEMimage so f( a)ZnO ( 200c l e),( b)AZO1 g. yc ( /Al /Al 1),5l ZnO( 1), ZnO( 40) oops),( 20) c)AZO2( 2O3( 2O3( oops),c a l c i neda t500℃ 10l /Al2O3 ( l 1)10 oops),and ( c) AZO2 (ZnO ( 20) l oops).The o r i i na ls t ruc t ur e cons i s t so f ZnO o r g AZO po r ous s t ruc t ur ea sar ep l i c ao ft he po r ous i 1 Fabr i c a t i ons chema t i co fZnOand AZOt h i nf i lms F g. s t he s i z edby ALD.( a)Pho t oo fpo r ouspo l e t hanet emp l a t e. yn yur ( b)SEMimageo ft hedepo s i t edt emp l a t ebe f o r ec a l c i na t i on. ( / c)Pho t oo ft het h i nf i lma f t e rc a l c i na t i on,( r t h i nf i lm d)Powde f o rmeda f t e rpu l ve r i z a t i ono ft hes t r uc t ur eshowni nF i 1( c) g. F i e2show t he SEM image so fz i nc ox i de- gur ba s edt h i nf i lmso f( a)ZnO ( 200c l e s),Al-doped yc /Al2O3 ( 1)5 z i nc ox i de o f( b) AZO1 ( ZnO ( 40) l e t hanet emp l a t e,wh i cht hen wa st r ans f o rmed po yur i n t ot h i nf i lmsbypu l ve r i z i ngpr oc e s s( F i 2( a)~2 g. ( c)). i e3shows XRD pa t t e rnso fZnO and AZO F gur t h i nf i lms.I t wa sshownt ha tt hes t r ongandsha r p aksl oc a t eda t2θo f31. 7,34. 4,and36. 2 °,f r om pe ( 101)p l ane s,r e spe c t i ve l f 100), ( 002),and ( yo [, ] wur t z i t es t ruc t ur eo fZnO 1 25-26 .Ot he rpe aksf ound a t2θo f47. 5,56. 6,62. 9,66. 4,67. 9,and69. 2 ° 材料科学与工程学报 · 708 · 2018 年 10 月 [ , , ] co r r e spondt o( 102),( 110),( 103),( 200),( 112), [ , ] 1 26-29 .I l ane s,r e spe c t i ve l 201) p tc l e a r l and ( y y 16 34 44-46 .Thes r e spe c t i ve l l i t l i f ti nt hetwo y gh ysh shownt ha tt he r ei s no add i t i ona lpe aks duet ot he a l umi num i ns e r t i on, wh i ch i nd i c a t e s t ha t t he r ea f f e c t edby env i r onmen tbe c aus et heZn-O bondsa [ 47] t hesubs t i t u t i ono fAla t omsa tZns i t e s .F i 4( c) g. [, ] showst hespe c t r ao fAl2po fAZOt h i nf i lms.I twa s wi t h shown t ha t wi t hi nc r e a s i ng Al conc en t r a t i on t he i n t ens i t fAl2ppe aksi nc r e a s e s,andt heAla t omi c yo f abr i c a t ed AZO a r ei ns i ng l e pha s e cond i t i on1 16 . 2+ Thedop i ngo fZnOt h i nf i lm byr ep l a c i ngZn h i l enc ea t omso fAl3+ l e adst os t r e s sf o rma t i on ghva i nt he c r t a l l i ne s t ruc t ur e and i s known t o be ys r e spons i b l e f o r de t e r i o r a t i on i n ZnO , .Asar e su l t AZOt h i nf i lmsshow [ 30-33] c r t a l l i n i t ys y s amp l e sc an bea t t r i bu t edt ot he d i f f e r en tchemi c a l we ake r c r t a l l i n i t wi t h r educ i ng ak ys y pe [ 34-37] ,a i n t ens i t i e s sshowni nF i b)~3( c).The gs.3( conc en t r a t i onsa r ec a l cu l a t edt obe1. 3 % and7. 2% f o rAZO1and AZO2,r e spe c t i ve l aksh i f t s y.Thepe t oh i rb i nd i ng ene r r e be l i evedt o be duet o ghe gy a [ ] mo r eAl-O bonds39 . f e a s i b i l i t f Ali nco r r a t i oni n t o ZnO imp l i e st he yo po ab i l i t ocon t r o lt hec r t a l l i n i t swe l la st a i l o r i ng yt ys ya [ ] t ha s be en known t ha tt he o ft he band gap37 .I exc e s so ft he Al so l ub i l i t imi ti n ZnO l e ads t o yl Fo rma t i on wi o f ZnAl2O4 t h sp i ne l-t ype ,and i nd i c a t i on o ft he f o rma t i on o f [ 38-40] s t ruc t ur e ZnAl2O4 c s ec an be s e l e c t ed a st he r t a l l i ne pha ys [ , ] c r i t e r i onf o rso l i dso l ub i l i t imi t30 41-42 .Thecur r en t yl expe r imen t a lr e su l t si nd i c a t et ha tt he AZOf o rmedi s s t i l li nt her angeo fso l i dso l ub i l i t imi t. yl F i 3 XRDpa t t e r nso f( a)ZnO ( 200c l e s)a swe l la sAZO wi t h g. yc /Al va r i ousAldop i ngc onc en t r a t i ono f( b)AZO1 ( ZnO( 40) 1), 2O3( /Al 5l 1),10l oops),( ZnO( 20) oops) c)AZO2 ( 2O3( Chemi c a lcompos i t i ons o f Al-doped ZnO we r e me a sur edbyXPS.F i e4showst heXPSspe c t r ao f gur Zn,O,and Alo f AZO t h i nf i lms.I t wa sshowni n / / F i 4( a)t ha tt he Zn 2p3 2 and Zn 2p1 2 pe aksa r e g. a lmos tt hes amef o rt hetwo AZO s amp l e s,andt he /Al F 1),5l i 4 XPSspe c t r ao fAZO1 ( ZnO( 40) oops), g. 2O3( /Al 1),10l ZnO( 20) oops). and AZO2 ( 2O3( ( a)Zn2p,( c)Al2p b)O1s,and ( F i e5( a)shows t he op t i c a lt r ansmi t t anc e gur a s c r i bed t o wur t z i t e .F i e 4 (b)shows t he Gaus s i an gur spe c t r ao ft heZnO and AZO t h i nf i lmspr epa r edon de convo l u t ed XPS O 1sspe c t r ao f AZO t h i nf i lms. t r ansmi t t anc e o f AZO t h i n f i lms wa s s l i t l gh y enhanc edwi t hi nc r e a s i ngAlconc en t r a t i on, i nd i c a t i ng ak pe i t i ons pos a r e [ 16, 43] s t ruc t ur e Thetwope akso fO1and O2c anbea s s i ot he gnedt Zn-O bond,and t he Al-O bond/adso rbed oxygen, r t z subs t r a t e s.I ti s shown t ha tt he op t i c a l qua t ha ti nt he AZO, mo r ef a c i l ee l e c t r on t r ans i t i ons 第 36 卷第 5 期 t o,等 .原子层沉积制备铝掺杂氧化锌纳米薄膜及其光催化特性 EDY Ri yan [ · 709 · ] ex i s tt oabso rbpho t ons48-49 .Theop t i c a labso r t i on p coe f f i c i en t,α,c an be c a l cu l a t ed us i ng Lambe r t’s [ ] equa t i on50-51 : α= 1 1 (t )ln(T ) whe r eT i st he op t i c a lt r ansmi t t anc e andti st he t h i ckne s s.The op t i c a lband gap ( Eg)o f ZnO and [ , ] AZOc anbeeva l ua t edby Taucr e l a t i on47 52 : hν-Eg)m αhν=A ( whe r eA andhνa r et hepr opo r t i ona l i t t an tand ycons t on ene r e spe c t i ve l sa i nc i den t pho gy,r y and m i cons t an twi t ht heva l uei sequa lt o1/2f o ra d i r e c t ft he bandgaps emi conduc t o r.Thed i r e c tbandgapso 2 ox i de sc anbee s t ima t edf r om t hecur veo f( αhv) - ( hν)byex t r apo l a t i ngt hel i ne a rr eg i ono ft hecur ve s [ 47, 53] ,a t oi n t e r c ep tt hex-ax i s sshowni nF i 5( b). g. The e s t ima t ed op t i c a l band gaps i nc r e a s e wi t h i nc r e a s i ng Al conc en t r a t i on a st he va l ue so ft he undoped ZnO,AZO1,and AZO2a r e3. 13,3. 30, and3. 33eV,r e spe c t i ve l r e,t hebandgapo ft he y.He ZnO ( 3. 13eV)i si nag r e emen tt oar e a sonab l eex t en t 2 i 5 ( a)Op t i c a lt r ansmi t t anc espe c t r a,and ( b)p l o t so f( F αhv) g. /Al 1), aga i ns t( hv)f o rZnO ( 200ALDc l e s),AZO1 ( ZnO( 40) yc 2O3( /Al 1),10l oops),and AZO2 ( ZnO( 20) oops) 5l 2O3( wi t ht he a c c ep t ed l i t e r a t ur e va l ue o f ~ 3. 18 t o [ , , ] 3. 22eV 16 51 53-54 .Thei t h nc r e a s eo ft hebandgap wi i nc r e a s i ng Aldop i ngi sa t t r i bu t ed t ot he Bur s t e i n- Mos se f f e c t,c aus ed by ani nc r e a s ei nf r e ee l e c t r on [ , ] conc en t r a t i on due t o Al dop i ng48 54-58 .ZnO t h i n f i lmsa r ena t ur a l l i des emi conduc t o r sdue ypeox y n-t t ona t ur a le l e c t r on dono r sgene r a t ed by O va c anc i e s [ ] andZni n t e r s t i t i a l s48 .Theadd i t i on o fdono r Al3+ c a t i onsr a i s e st heFe rmil eve lo ft he AZO t h i nf i lms i n t o t he conduc t i on band, c aus i ng comp l e t e degene r a t i on, and t he r e f o r et he abso r t i on edge p [ , ] 48 55 . move st oh i rene r ghe gy F i e 6 (a ) shows t he pho t oc a t a l t i c gur y r f o rmanc eo fZnO and AZOt h i nf i lmsanne a l eda t pe 500℃ wi t h MO so l u t i on us ed a s at i c a lo r i c yp gan l l u t an t.Thei n i t i a l MO conc en t r a t i oni s10mg/L po and ZnO o r AZO pho t oc a t a l t s conc en t r a t i on i s ys 0. 25mg/mL.I twa sshownt ha tt hepr e s enc eo fAli n F i 6 ( a)Pho t o c a t a l t i cpe r f o rmanc e so ft h i nf i lms:ZnO g. y ZnO g i ve s a pos i t i ve e f f e c tt ot he pho t oc a t a l t i c y h i nf i lmswi t hh i rAl a c t i v i t i e s( F i 6( a)).AZOt ghe g. ( /Al 200ALDc l e s),AZO1 ( ZnO( 40) oops),AZO2 1),5l yc 2O3( dop i ngconc en t r a t i on (AZO2)ha s a wi de r op t i c a l ( ( ) ) band gap F i t t e r pho t oc a t a l t i c and be g.5 b y r a t e s,c a l cu l a t edf r om ( a) r f o rmanc et han no andl owe r dop i ng,e.g.ZnO pe ( 200ALDcyc l e s)and AZO1i nF i 6( a)and6( b). gs. ( /Al ZnO( 20) 1),10l oops).( b)Co r r e spond i ngdeg r ada t i on 2O3( I tc an beexp l a i neda sf o l l ows.The mos timpo r t an t f a c t o r t ha t c an con t r i bu t e t o i nc r e a s e o f t oc a t a l t i ca c t i v i t st he pr e s enc eo fa h i pho y yi gh 材料科学与工程学报 · 710 · 2018 年 10 月 · · e l e c t r i cconduc t i vepha s e s,wh i chl e adst oani nc r e a s e H2O2 +O2 - →OH +O2 +OH- o ft he pr obab i l i t ft he c a r r i e r sr e a ch i ng t he y o [ 19, 59] /so .When asma l l t oc a t a l t l u t i oni n t e r f a c e pho ys OH +dye → dye mi ne r a l i z a t i on amoun to fAlwa si n t r oduc edi n t ot heZnOt h i nf i lm, l u s i on 4 Conc 3+ 2+ t heonei on i z ed Al subs t i t u t ef o rone Zn · ( 6) ( 7) i v i ng g onef r e ee l e c t r ont ot heconduc t i on bandf o reve r y [ , ] 2+ 3+ 53 60-61 , wh i t e r ep l a c ed by t he Al i ch Zn s [ 53] even t ua l l nc r e a s e st he conduc t i v i t n t he yi y .I t oc a t a l i sr e spe c t, Al dop i ng i nc r e a s ed t he pho ys t oc a t a l t i ca c t i v i t c c e l e r a t i ngt het r ans f e ro f pho y ybya ZnO and AZO t h i nf i lms c an be suc c e s s f u l l y depos i t edby ALD onpo r ouspo l e t hanet emp l a t e. yur Ca l c i na t i onf o l l owi ngt hedepos i t i on make st het h i n f i lmsf o rmt het hr e e-d imens i ona l l r ouss t ruc t ur e s ypo e l e c t r ons t o d i s so l ved oxygen mo l e cu l e s . The a sar ep l i c ao ft hes t ruc t ur eo fo r i i na lt emp l a t e.By g r ouss t ruc t ur e s we r ebr okeni n t o l ve r i z i ng,t hepo pu t o-gene r e comb i na t i on o ft he pho r a t ed c a r r i e r s wa s sma l lp i e c e s and f o rm ZnO and AZO t h i nf i lms. e f f e c t i ve l r e s s edl e ad i ngt o ani nc r e a s ei nt he y supp Expe r imen t a lr e su l t sshow t ha tt he wur t z i t ec r t a l ys s t ruc t ur eo f ZnO c an be ma i n t a i ned by Aldop i ng, [ 1] [ 1] t o-ox i da t i one f f i c i enc pho y . The pho t ogene r a t ed e l e c t r ons and ho l e s have be enf ound t o deg r ade many t so fo rgan i c and ype s i b l et osugge s tt ha t i no rgan i cpo l l u t an t swh i chi spos - + t hee l e c t r on-ho l epa i r( e -h )i sgene r a t eda tt he sur f a c eo ft h i nf i lms,l e ad i ng t ot he f o rma t i on o f oc e s si s r e a c t i veox i da t i vehyd r ox i der ad i c a l s.Thepr [ ] de s c r i bed a sf o l l ows62 : when t he ZnO/AZO i s r a t i on o fe l e c t r ons and ho l e s i l l umi na t ed,t he gene beg i ns (Eq (1)) and, a st he s emi conduc t o ri s imme r s ed i n a l i i d med i um, spon t aneous qu adso r t i ono ft he mo l e cu l e si nal i i doc cur s;t hen p qu i nd i c a t i ngas i ng l epha s es t ruc t ur e.Fur t he rmo r e,by e s enc e and i nc r e a s i ng o f Al dop i ng,t he op t i c a l pr t oc a t a l t i c band gaps en l a r s wi t h t he pho y ge r f o rmanc eenhanc ed.The en l a r to f op t i c a l pe gemen t hi nc r e a s i ng Alconc en t r a t i oni sduet o bandgap wi Ali onst end i ng t o oc cupy ZnO l a t t i c ep l ane s,and t h cons equen t l e ad i ngt ot hei nc r e a s ei nt r anspo r tpa yl o fcha r a r r i e r si n ZnO l a t t i c e.Thet r anspo r to f gec t ogene r a t ed e l e c t r onst ot he ou t e rsys t ems wi l l pho even t ua l l c c e l e r a t ed, r e su l t i ng i n h i y be a gh r f o rmanc e. t oc a t a l t i cpe pho y an e l e c t r oni st r ans f e r r ed t ot he a c c ep t o r mo l e cu l e Re f e r enc e andt hedono rmo l e cu l eg i ve sane l e c t r ont ot heox i de [ 17] · .The ho r a t e OH byr l e sgene e a c t i ng wi t ht he wa t e r mo l e cu l e s (Eq.( 2)),and t he O2 mo l e cu l e a c c ep t san e l e c t r ont of o rm t he supe r-ox i der ad i c a l ·- ·- 3)).The O2 (Eq.( s e O2 r ad i c a l sa c ta ss t r ong ox i d i z i ng agen t s and t hey a l so con t r i bu t et ot he [ 17] f o rma t i ono fhyd r ogenpe r ox i de ( Eqs.( 4)- ( 7)) . 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