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Hindawi Publishing CorporationResearch Article Effect of Electron Beam Irradiation on Optical Properties of Manganese Tungstate Nanoparticles

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Hindawi Publishing CorporationResearch Article Effect of Electron Beam Irradiation on Optical Properties of Manganese Tungstate Nanoparticles
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  Hndw Psn CopoonJon o Nnocnooy Vom 2013, Ac ID 580308,6psp://dx.do.o/10.1155/2013/580308 Research Article Effect of Electron Beam Irradiation on Optical Properties of Manganese Tungstate Nanoparticles K.P.Priyanka, 1 N.AloysiusSabu, 1  AnuTresaSunny, 2 P.A.Sheena, 3 andThomasVarghese 1 1 Department of Physics, Nanoscience Research Centre (NSRC), Nirmala College, Muvattupuzha, Kerala 66 661, India 2 School of Chemical Sciences, M.G. University, Kottayam 66560, India 3  M.E.S. Asmabi College, P. Vemballur, Kerala 60671, India Cospondnc sod  ddssd o homs Vs; nnoncm@m.comRcvd 2 My 2013; Rvsd 20 Jn 2013; Accpd 25 Jn 2013Acdmc Edo: M R. SnCopy © 2013 K. P. Pynk  . hs s n opn ccss c dsd nd  Cv Commons Aon Lcns,wc pms nscd s, dson, nd podcon n ny mdm, povdd  on wok s popy cd.Mnns ns (MnWO 4 ) nnopcs w synszd  oom mp y cmc pcpon mod. h fco  ny con m (EB) don on  opc pops o MnWO 4 nnopcs ws nvsd. h soponspc, poomnscnc nnsy, nd Rmn nds o  dd smps w modid, wc s n d odcs nd pc sz von. h psn nvson ond   m don s  nw nd cn mod onnc  opc sopon pomnc nd poocvy o MnWO 4 nnopcs. 1. Introduction Nnoscdnsmsvosdmcn-scsomnscncvo,scpop-s, nd pon ppcons. MnWO 4 s k cccondcvy, vy ow mn pon, nov mncpopy, nd poocyc popy [1,2]. h opc nd mnscnc pops o MnWO 4 v cvd non s y  wdy sd s scnn dcosn -ny pc pyscs, -vn scs, ndmdc dnoss [3]. h cc condcvy o MnWO 4 s so snsv o cns n mdy, y mkn s s  mdy snso w pon ppcons kmoooy, mdcn, ood podcon, c, ndndsnddomscnvonmn[,5].hnm-  o pocsss sd o synsz nnocysn MnWO 4 ,sc s mcowv-sssd synss [1], scn-sssdcompxon-pcpon mod [2], m soon po-css[6],sovomo[7],qossmssc- on [8], so- cnq [,9], mn mp synss [10], nd sod s mc ppoc [11]. In  psn wok, mnns ns nnopcs synszd y c cono o  con kncsoqospcpon.As-ppdMnWO 4 nnopcs cczd y X-y dfcon [XRD], nsmssoncon mcoscopy [TEM], UV-Vs sopon spc-oscopy, poomnscnc [PL] spcoscopy nd Rmnspcoscopy. In ddon,  opc pops o  pnd EB dd smps o MnWO 4 nnopcs wvd n conx o  nd p. 2. Experimental Details Mnns cod (MnC 2 ⋅ H 2 O) (99.8%, Sm Adc)nd sodm ns (N 2 WO 4 ⋅ 2H 2 O) (99.9%, A As)w sd wo  picon o  synss o MnWO 4 .Dsdwwssdnsynsspocds. 2.1. Preparation of the Samples. h synss pocds o ppon o MnWO 4 nnopcs sd n s wok s n dscd sw [12]. Nnocysn mn-ns ns smps w ppd y cn qossoonsomnnscodndsodmns(0.1Mc)  oom mp, kpn  pH = 7 . hpcp omd ws cnd, id, wsd wdsd w  nm o ms, nd dd n n ovn o   2 Jon o Nnocnooy  Na 2 WO 4 ·2 H 2 OMnCl 2 ·4 H 2 ORefluxion ( 70 ∘ C, 20 hrs)Calcination PrecipitationMnWO 4 nanoparticlesChemical precipitationpH = 7 Fgure 1: h scm o ppon o MnWO 4 nnopcs y cmc pcpon mod. in powds o mnns ns. h ond powdsmps w ccnd o 3 os n  nc  50 ∘ C n noc mosp. h low c sown  scm o ppon o nnocysn MnWO 4 s sown nF 1.h MnWO 4 smps w kn n mcos ndxposd o EB don   dsnc o 30cm om m x po. h smps w dd   dos o 5kGy nd 10kGy w n con m o 8MV ny ond om  v ny Mcoon  MnoUnvsy, Ind. S1 s p smp o MnWO 4 ; S2 nd S3 dd smps w dos s o 5kGy nd 10kGy,spcvy. h smps md snicn modicons on pysc pops d o m don. 2.2. Characterization. h sc ccscs o p nd dd mnns ns nnopcs wsdd y X-y powd dfcon sn Bk D8Advnc X-y dfcom (  = 1.5406 ˚A) w CK  don n 2 n om 20 ∘ o 70 ∘ . Fom  XRD nyss  pks o MnWO 4 w w mcd w  X-y pn o JCPDS Cd no. 80-0135. hs nyss wcd o o  dnicon o  cys ps nd smon o  v cys sz. h  v wssmdomDy-Sc qon[9].hDy-Sc qon s vn y   =0.9 cos , (1)w  s  X-y wvn,  s   wd  -mxmm (FWHM) o  pk, nd  s  B’s n.Tnsmsson con mcoscopy s  nq oo o dcmonnopcs,vndsonn  nnocys nd on s sc. H mniconmn w c cons ows  dmnon o ndvdcysmopooy.FoTEMsds,MnWO 4 powd ws dspsd n no sn n sonc . Adop o  sspnson ws pcd on  copp d codwconim.Atdyn,coppdconnnnnopcswspcdonodomnpocss. S3S2S1     (   0   1   0    )    (   1   0   0    )    (   0   1   1    )    (   1   1   0    )            (          ̄             1           1          1           )     (   1   1   1    )    (   0   2   0    )    (   0   0   2    )    (   2   0   0    )    (   1   0   2    )    (   1   2   1    )    (   1   1   2    )    (   0   2   2    )    (   2   2   0    )    (   1   3   0    )    (   2   0   2    )    (   2   2   1    )    I  n   t  e  n  s   i   t  y    (  a .  u .    ) 10 20 30 40 50 60 2 (degrees) Fgure 2: XRD spc o MnWO 4 smps. TEM poopso  pnnocysnMnWO 4 pow-d smps w kn sn  Tcn 30 G2 Swn (mod),FEI mk 300KV H Rsoon Tnsmsson EconMcoscop (HRTEM).hsoponspcopndddsmpsn  n o 200–800nm w codd sn  dom UV-Vs Spcopoom (UV 2600 mod, S-mdz). Fo msmn,  nnopcs w pssdno  ck p nd pcd   nnc po o nn sp sn  smp od. Con o  sonc sc ws don sn sndd ncms.Poomnscnc spcoscopy s n fcv wy onvsconcscndopcccscso nnoms. hs nyc cnq vs no-mon sc s sc dcs nd oxyn vcncs sw s  spon nd comnon o poo-ndcdc cs [13]. PL spc o  p nd EB ddsmps o MnWO 4 w msd  oom mp y  Foomx3 Spcopoom.Rmn spcoscopy s  pow oo o  nvs-on o  sc pops o nnopcs cs vons n Rmn spc w dcss n pcsz cn  sy dcd. Rmn spc o  p nddd smps o MnWO 4 w ond  oom m-psnBkFRA106/SRmnspcomwxcon n o 785nm. 3. Results and Discussion F 2sows  powd X-y dfcon pns o pnd EB dd smps o MnWO 4 nnopcs. Fom  Jon o Nnocnooy 3 () () Fgure 3: TEM ms o MnWO 4 nnopcs ccnd  50 ∘ C. XRDpns,vpcszos-ppdnddd smps s n smd sn Dy-Scqon. Av cys szs ond o smps S1,S2, nd S3  26nm, 23.nm, nd 2.5nm, spcvy.h v cys sz o smp S2 ws dcsd om26nm o 23.nm d o EB don (5kGy). Howv, sz o smp S3 ws dcsd ony p o 2.5nm t dos o 10kGy don. h pncp “  ” vs knom  JCPDS i no. 80-0135 o MnWO 4  n cosmn w  osvd “  ” vs. h XRD sssowd  cys sz nd pcn o cysny dcsd t don. I conims mopzon o smp d o don wc s spons o  cnn opc pops. h ss sow  v pcsz dcss w  EB don dos nd ss poss cono o  sz nd  dnsy o  MnWO 4 nnopcs y EB don.A XRD pns o MnWO 4 smps cospond o wom-ypmonocncsc,wcsnmnw  spcv Inonc Cys Sc Ds(ICSD) no. 67907. Un c pms w  = 0.4787 nm,  = 0.5809 nm,  = 0.4999 nm, nd  = 91.19 ∘ o smpS1,  = 0.4843 nm,  = 0.5869 nm,  = 0.5035 nm, nd  = 91.23 ∘ o smp S2, nd  = 0.4823 nm,  = 0.5826 nm,  = 0.5021 nm, nd  = 91.22 ∘ o smp S3. A smpssowd c pms sy  n  ccdnd xpmn vs o  k smps pod n  [1,15]. hs dvon m occ d o sm pc sz o  smps [16].TEM ws sd o  xmn  pc sz, cys-ny, nd mopooy o MnWO 4 smps. TEM id ms o MnWO 4 nnopcs (ccnd  50 ∘ C) sown nF 3. I cn  nod om  TEM m(F 3)   pcs  omd nd x-k sp. Scd  con dfcon (SAED) ssown n  ns o F 3, wc cy ndcs  MnWO 4 nnopcs w y cysn n n.As cn sn om TEMm, vpcsz    I  n   t  e  n  s   i   t  y    (  a .  u .    ) 1.81.61.41.210.80.60.4S2S2S3S3S1S1200 300 400 500 600Wavelength (nm) Fgure : UV-Vs sopon spc o MnWO 4 smps. so26nm,wcsnmnwcysszond om XRD d.F sowsUV-Vssoncspcopnd dd smps o MnWO 4 nnopcs. Fom ss,cnosvdsoponpkosmpsS2 nd S3 sts owds  so wv n on. hsstnsoponpksis-ndsno snicn sz dcon o  nnopcs sn omEBdon.hstnsoponpkosmpS3 s ss s compd o smp S2. I ndcs   sznd sz dsono  pc ncs yond  cnEB don dos v.hopcndpvsondomsoponps o smps S1, S2, nd S3 w 2.3V, 2.58V, nd2.51V, spcvy. I s sn   nd p o MnWO 4 nnopcs std om 2.3 o 2.58V s pc szdcd om 26 o 23.nm nd om 2.3 o 2.51V s   Jon o Nnocnooy  Tabe 1: Compson o xpmn nd p vs o MnWO  w  vs.E (V) E (V) E (V)Psn wok Expmn hoc2.3 (S1) 2.5 [18,19] 1.83 [1] 2.58 (S2) 2.37 [1]2.51 (S3) sz dcd om 26 o 2.5nm. hs ncs n  ndp m occ d o sc nd ndn w szdcon o  nnopcs sn om EB don[16]. An ddon dvn o sz dcon s   sc  o vom o mks poss my zonopoo-ndcsnncpocsss[17]. Moov, m don ppd o mpov opc sopon pomnc o MnWO 4 nnopcs.In ddon, o p nd dd smps  s opoocyccvscsndpnyvs comp o  ny o vs o UV  poons.T 1comps psn xpmn nd p vsoMnWO 4 wxpmnndccdvspodn   [1,18,19]. h psn xpmn vs   s compd o  vs, wc cn d o  dcon n pc sz o  smps.Poomnscnc sds povd nomon no dfn ny ss v wn vnc ndnd condcon nd spons o dv comn-on. Lmnscnc spcm o MnWO 4 nnopcs w293nm xcon s sown nF 5. h PL mssonspc o  nondd smp sow msson nds 23, 7, 60, 85, nd 529nm. hs msson nds d o  nson om  1 A 1 ond s o  von v o  1 T 2 nd om  ow von vo  1 T 2 o  1 A 1 ond s wn  on WO 42− ops [20,21]. hpndddsmpsoMnWO 4 codxovos PL sn w sm cv sps (F 5).h PL spc o dd smps w sown o v nnss v o nondd smp, wc wso o s om dcs nd pc sz von[22]. Inmd ny vs  omd w voccscs d o EB don, wc  ncssy o comnon pocss (con/o), spons o mpovmn o  PL msson  oom mp.Dn  xcon pocss, mdm n dcs n monocnc c csd y dsoon o ocd [WO 6 ]css  spons o  PL msson. Iny, somcons om ow nmd ny vs (oxyn—2p vs) n  vnc nd so  poon ny ( h ] )  s wvn (  = 293 nm) nd s nccons  pomod o  nmd ny vs(nsn—5d vs) ocd n  condcon nd [21].h ns nn om  dxcon pocss convdopoons( h ] 1 ).Svpoonsonnom pcpon o dfn ny ss dn  c-oncnsonssponsonnsPLmsson. 300S2S1S3350 400 450 500Wavelength (nm)6004002000    I  n   t  e  n  s   i   t  y    (  a .  u .    ) Fgure 5: Room mp PL spc o MnWO 4 smps. h ws  sm  st o PL spc o  EBdd smps S2 nd S3 (F 5). h  st o nd p w sz dcon cod  d o sc ndndnwscscmodicons[16].Icnso sn  PL spc o  dd smps S2 nd S3w odnd. hs odnn o MnWO 4 nnopcsm on om  sc nd ndn nd cxpnson w pc sz dcon csd y  EBdon [16].I cn  sn nF 5  PL nnsy ncssny p o 5kGy dos nd n s of   doss o don. h n ncs s d o  ncsn  p ss  v s o  mnscnc. hncs n PL nnsy o n dd smp s do  comnon o s-ppd xcons, wc s comnd fc o dc cns nd y oxyn vcncs, sm pc sz, nd ncsd sopon ovUVndvsn[21,22].hncsnPLnnsy  s so n ndcon o  poocyc cvy.Wn  EB don dos  s ncsd ov cndosv,pcsom,ydcnnmoloopos.hspossydsodconn  loscnc nnsy (smp S3,F 5). Fncs n  don dos pps o v ss fcon  p ss  sowy cns  sz o  pc,y csn  st n  loscnc d o onwvn sd.Rmn spc o MnWO 4 nnopcs o p nddd smps  sown nF 6. A  nRmn mods w osvd n  n 50–1200cm −1  oom mp. h mos nns nd osvd 886cm −1 ond om  symmc scn v-on o  so mn W–O ond, w  symmcscn von o  so mn W–O ond ppd 775cm −1 . O nds  cond y symmcscn von mods o on W–O ond, symmcscn vons o on W–O ond, domon vonosoW–Oonds,vonmodsoMn-O,ndncn domon mods nd c mods [16,23,2]. I cn  osvd  Rmn pks w sy std o  Jon o Nnocnooy 5    I  n   t  e  n  s   i   t  y    (  a .  u .    ) 250002000015000100005000S1S3S20 200 400 600 800 1000 1200Raman shi (cm −1 ) Fgure 6: Rmn spc o MnWO 4 smps. ddsmpsS2ndS3,ndstwsondo  smp S2.I cn  sn nF 6 Rmn pks o smpsS2 nd S3 w xmy odnd. h von modo smp S2  886cm −1 odnd om 15.5 o 30.2cm −1 ,w o  smp S3,  n wd odnd om 15.5o 23.9cm −1 . h odnd Rmn nds cod  d o qnm coninmn fc [18]. Bsds  qnmconinmn, c xpnson my so con o odnd Rmn pks. h ncsd c vom oMnWO 4 nnocyss  sm pc szs wod v nd v n o W–O onds, wc my dcs oc consn o  W–O ond [25,26]. As  s, RmnpksoMnWO 4 nnopcscmodndspc sz dcd.PsnxpmnRmnmodsoMnWO 4 nnop-cspsndnT 2onwpvosxpmn- nd ccd vs [23,27]. Psn ss  sy   n  pod vs, nd s von cod csd y  nnosc sz o  smps.h sc cczon nd opc sds o MnWO 4 nnopcs conim  sz dcon nd sc- modicons csd y  EB don, wc nn s n  st n  soponnd PL spc, ndnncd nd odnd PL s w s Rmn spc. 4. Conclusions MnWO 4 nnopcs w synszd y smp cmcpcpon mod, nd  fc o  ny EBdononopcpopswssddnodompov opcsoponpomncnd poocv-y. h EB don my v sd n sz dcon,wc n n csd n ncs o  opc nd ps w s poomnscnc nnsy nd odnn o Rmn nds. Fmo,  d ond  wodsm o sow   mod o EB don my consddscnmnsonncopcspons Tabe 2: Compson o Rmn mods o MnWO  w .ModPsn vsL vs[23,27] Ccd vs [23,27] S1 S2 S3B  90 79 82 89 95A  130 119 123 129 129B  162 151 15 160 165B  168 157 161 166 171B  182 171 17 177 183A  205 193 198 206 226B  276 265 269 272 278A  259 22 252 258 26B  297 290 293 29 296A  330 317 320 327 338B   361 39 35 356 373A ∗  399 393 395 397 389B  51 506 508 512 509A ∗  57 528 535 55 58B ∗  675 633 62 67 662A ∗  702 688 695 698 69B ∗  776 762 769 77 775A ∗  888 878 882 885 858 nd poocvy o MnWO 4 nnopcs o vd pp-cons.  Acknowledgments h os cknowd  nks o Mcoon Cn-, Mno Unvsy, Mno, nd Nm Co,Mvpz, o povdn  oppony o ndks sdy. h innc sppo om  KSCSTE, h- vnnpm, s y cknowdd. References [1] Y. Xn, S. Son, J. Fn, Y. L, M. L, nd H. Zn, “Mco-mson-mdd sovom synss nd poomns-cn popy o 3D lowk MnWO 4 mco/nnocompossc,” Solid State Sciences , vo. 10, no. 10, pp. 1299–130,2008.[2] S. L, K. Tn, Z. Fn, Y. Hn, nd H. Zn, “Synsso MnWO 4 nnois y  scn-sssd compxon-pcpon ppoc nd cono o mopooy,” Nanotech-nology  , vo. 16, no. 10, pp. 207–211, 2005.[3] D. Endon nd F. J. Mnj´on, “Pss fcs on  sc- nd conc pops o ABX scnn cyss,” Progress in Materials Science , vo. 53, no. , pp. 711–773, 2008.[] W. Q, W. Wodsk, nd J. U. My, “Compv sdy onmcomopooy nd mdy snsv pops o n-im nd ck-im mdy snsos sd on smcondcnMnWO 4 ,” Sensors and Actuators B , vo. 6, no. 1–3, pp. 76–82,2000.
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