HAL Id: tel-01308533
https://tel.archives-ouvertes.fr/tel-01308533
Submitted on 28 Apr 2016
HAL is a multi-disciplinary open access archive for the deposit and dissemination of sci-entific research documents, whether they are pub-lished or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers.
L’archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d’enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.
orthophosphates for optical applications
Aristeo Garrido-Hernandez
To cite this version:
Aristeo Garrido-Hernandez. Synthesis by hydrothermal process of lanthanide orthophosphates for optical applications. Other. Université Blaise Pascal - Clermont-Ferrand II, 2015. English. �NNT : 2015CLF22564�. �tel-01308533�
1G¶2UGUH'8
UNIVERSITE BLAISE PASCAL
U.F.R Sciences et Technologies
Ecole Doctorale des Sciences Fondamentales
N° 821
THESE EN COTUTELLE
Présentée pour obtenir le grade de
Docteur D’université
Spécialité : Chimie, Sciences des Matériaux
Par
Aristeo GARRIDO-HERNÁNDEZ
7LWXODLUHGX0DVWHURI6FLHQFHRQ&KHPLVWU\³6\QWKHVLVE\K\GURWKHUPDOSURFHVVRIODQWKDQLGHRUWKRSKRVSKDWHVIRU
RSWLFDODSSOLFDWLRQV´
6RXWHQXHSXEOLTXHPHQWOH0DUVGHYDQWODFRPPLVVLRQG¶H[DPHQ 3UpVLGHQW 0RKDPHG%RXD]DRXL 5DSSRUWHXUV)UDQFLV9RFDQVRQ /HWLFLD(VSHUDQ]D+HUQiQGH]&UX] ([DPLQDWHXUV'DPLHQ%R\HU $XGUH\3RWGHYLQ )HOLSHGH-HV~V&DUULOOR5RPR $QWRQLHWD*DUFtD0XULOOR 5LFDUGR&XHQFDÈOYDUH]
'(',&$7,21
I dedicate this thesis to: GOD
For His blessing that continue to flow into my life, and because of You, I made this challenge.
MY PARENTS
Aristeo Garrido Cruz, Hilaria Hernández Vargas For their love and their advices.
My Wife Lidia Chavez Geronimo
For her comprehension, love and spending her life with me.
Brothers
Alejandro, Mayra Isabel, Sandra y Mirna Eulalia.
$FNQRZOHGJHPHQWV
7KLV ZRUN ZDV UHDOL]HG LQ FRWXWHOOH EHWZHHQ FHQWHU RI UHVHDUFK DQG WHFKQRORJLFDO LQQRYDWLRQ RI 1DWLRQDO 3RO\WHFKQLF ,QVWLWXWH RI 0H[LFR DQG ,QRUJDQLF 0DWHULDO /DERUDWRU\RI%ODLVH3DVFDO8QLYHUVLW\RI)UDQFH
, DP JUDWHIXO WR &21$&<7 ILQDQFLDO VXSSRUW RI SURMHFWV (&261RUG $18,(6 &21$&<7 03 WR ,31 WKURXJK WKH SURMHFWV 6,3 6,3 DQG ,QVWLWXWLRQDO 3URJUDP E\ WKH 5HVHDUFKHU¶V )RUPDWLRQ %(,),,31 IRU WKH ILQDQFLDO VXSSRUW $OVR , ZRXOG OLNH WR DFNQRZOHGJH WR &21$&<7 IRU WKH VFKRODUVKLS JUDQW UHFHLYHGGXULQJDOOWKH3K'VWXGLHVDQGWKHVWDJHLQWKH,QRUJDQLF0DWHULDOV/DERUDWRU\ RI%ODLVH3DVFDO8QLYHUVLW\LQ&OHUPRQW)HUUDQG)UDQFH
,ZLVKWRH[SUHVVP\LQQHUWKDQNIXOQHVVWRP\VXSHUYLVRUV'DPLHQ%R\HUDQG)HOLSHGH -HV~V &DUULOOR5RPR IRU WKHLU YDOXDEOH DQG NLQG VXJJHVWLRQV WKURXJKRXW DOO WKLV UHVHDUFK
, DP JUDWHIXO WR 3URIHVVRU )UDQFLV 9RFDQVRQ5HVHDUFKHU RI -HDQ 0RQQHW 8QLYHUVLW\ )UDQFH DQG 3URIHVVRU /HWLFLD (VSHUDQ]D +HUQiQGH]&UX] 5HVHDUFKHU RI 8QLYHUVLGDG $XWRQRPD GHO (VWDGR GH +LGDOJR IRU WKH DFFHSWDWLRQ RI H[DPLQLQJ WKLV ZRUN DV UHSRUWHUVDQGPHPEHUVRIWKHMXU\
,ZRXOGOLNHWRH[SUHVV P\JUDWHIXOQHVVWRPHPEHUVRIWKHMXU\WKDWWKH\DFFHSWHGWR MXGJH WKLV ZRUN 0RKDPHG %RXD]DRXL )UDQFLV 9RFDQVRQ /HWLFLD (VSHUDQ]D +HUQiQGH]&UX] 'DPLHQ %R\HU $XGUH\ 3RWGHYLQ )HOLSH GH -HV~V &DUULOOR5RPR $QWRQLHWD*DUFLD0XULOOR5LFDUGR&XHQFDÈOYDUH]
, ZRXOG DOVR OLNH WR VD\ WKDQN \RX WR WKH GLIIHUHQW LQVWLWXWLRQV DQG SURIHVVRUV ZKR VXSSRUWHGWKLVZRUNLQWKHVLGHRIH[SHULPHQWDODQGFKDUDFWHUL]DWLRQWHFKQLTXHV
Content
/LVWRIILJXUHV /LVWRI7DEOHV $EVWUDFW 5pVXPp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±'7DQDO\VHV +HDWWUHDWPHQWHIIHFWRQVWUXFWXUHDQGPRUSKRORJ\ 3KRWROXPLQHVFHQFHVWXG\RI*G32(XDQG*G327ESRZGHUV &RQFOXVLRQ &KDSWHU93KRWROXPLQHVFHQWSURSHUWLHVRI*G[<[327EXSRQ989H[FLWDWLRQ ([SHULPHQWDO 5HVXOWV 6WUXFWXUDODQGPRUSKRORJLFDOFKDUDFWHUL]DWLRQVRI*G[<[32SRZGHUV 6WUXFWXUDO FKHPLFDO DQG PRUSKRORJLFDO FKDUDFWHUL]DWLRQV RI *G[<[327E SRZGHUV &RQFOXVLRQ 5HIHUHQFHV
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
$)RXULHU7UDQVIRUP,QIUDUHG)7,5VSHFWURVFRS\ $5DPDQVSHFWURVFRS\ $7KHUPRJUDYLPHWULFDQDO\VHV$7*'7$ $6FDQQLQJ(OHFWURQ0LFURVFRSH6(0 $7UDQVPLVVLRQHOHFWURQPLFURVFRS\7(0 $/XPLQHVFHQFHVSHFWURVFRS\ 3URGXFWV $UWLFOHV ,QWHUQDWLRQDODQGQDWLRQDOFRQJUHVV *ORVVDU\ 1RPHQFODWXUH
/LVWRIILJXUHV
)LJD[HQRWLPH<<E32FRS\ULJKW'3UHLWHEPRQD]LWH&HFRS\ULJKW/DYLQVN\ )LJ D &KXUFKLWH< <32ā+2 FRS\ULJKW / 3HUORII E 5KDEGRSKDQH/D /D&H32ā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³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
)LJ 6(0 PLFURJUDSK RI <327E PRO SRZGHUV ZLWK KH[DJRQDO SKDVH V\QWKHVL]HGDWS+ &KRXUV )LJ 6(0 PLFURJUDSK RI <327E PRO SRZGHUV ZLWK 7HWUDJRQDO SKDVH V\QWKHVL]HGDWS+ &KRXUV )LJ+LJK5HVROXWLRQ7(0LPDJHVRIKHDWWUHDWHG&IRUKRXUV<327E PROSRZGHUVZLWKWHWUDJRQDOSKDVHDQG)RXULHUWUDQVIRUPVIRUDQGSODQHVIURP KH[DJRQDOSKDVHEIURPWHWUDJRQDOSKDVH )LJ'VFDQHPLVVLRQDQGH[FLWDWLRQVSHFWUDRI<327E )LJ([FLWDWLRQVSHFWUDRI<327EPRQLWRULQJWKH')WUDQVLWLRQDWQP )LJ(PLVVLRQVSHFWUDRI<327EH[FLWHGXSRQ89
)LJ0LFURJUDSKLPDJHVRIGH*G32(XDQG*G327ESRZGHUV )LJ3UREDEOHPRUSKRORJ\IRUPDWLRQ )LJ'LIIUDFWLRQSDWWHUQVRI*G32(XPRODQG*G327EPROSRZGHUV )LJ,QIUDUHGVSHFWUDRI*G32(XPRODQG*G327EPROSRZGHUV )LJ7*$'7$RI*G32(XPROSRZGHUVREWDLQHGE\K\GURWKHUPDOPHWKRG )LJ;5'SDWWHUQVRI*G32(XPROSRZGHUV )LJ,QIUDUHGVSHFWUDRIGH*G32(XPROSRZGHUV )LJ7(0PLFURJUDSKVRIKHDWWUHDWHG*G32(XSRZGHUVDQDQRZLUHVEQDQRSDUWLFOHV )LJ([FLWDWLRQVSHFWUDRIKHDWWUHDWHG&*G32(XPROSRZGHUVFU\VWDOOL]HG LQKH[DJRQDOSKDVH )LJ([FLWDWLRQVSHFWUDRIKHDWWUHDWHG&KRXUV*G327EPROSRZGHUV ZLWKKH[DJRQDOSKDVH )LJ D (YROXWLRQ RI'
)WUDQVLWLRQE (PLVVLRQ VSHFWUD RI *G327E PRO QDQRZLUHV )LJD(YROXWLRQRI' )WUDQVLWLRQVE(PLVVLRQVSHFWUD*G32(XPRO )LJ(PLVVLRQVSHFWUDRIKHDWWUHDWHG&KRXUV*G32(XPROSRZGHUV ZLWKKH[DJRQDOSKDVH )LJ(PLVVLRQVSHFWUDRIKHDWWUHDWHG&KRXUV*G32(XPROSRZGHUV ZLWKKH[DJRQDOSKDVH )LJ /XPLQHVFHQW QDQRFRPSRVLWH ILOPV ZLWKRXW H[FLWDWLRQ XSRQ XOWUDYLROHW H[FLWDWLRQ DW QP )LJ(PLVVLRQVSHFWUDRI1S(XDQG1Z(XLQVLOLFRQHSRO\PHUXSRQH[FLWDWLRQDWQP )LJ(PLVVLRQVSHFWUDRI1S7EDQG1Z7ELQVLOLFRQHSRO\PHUXSRQH[FLWDWLRQDWQP
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
)LJ(QHUJ\WUDQVIHUEHWZHHQ*G DQGGRSDQWLRQV )LJ &KURPDWLF FRRUGLQDWHV RI KHDWWUHDWHG *G32(X7E'\ DQG *G<32(X 7E
'\SRZGHUVDW&IRUKRXUV )LJ ([FLWDWLRQ VSHFWUD RI KHDWWUHDWHG *G32(X7E'\ DQG *G<32(X 7E
'\SRZGHUVDW&IRUKRXUV )LJ(PLVVLRQVSHFWUDRIKHDWWUHDWHG*G32(X*G327EDQG*G32'\SRZGHUV DW&IRUKRXUV )LJ (PLVVLRQ VSHFWUD RI KHDWWUHDWHG *G32(X7E'\ DQG *G<32(X7E '\SRZGHUVDQQHDOHGDW&IRUKRXUV )LJ (PLVVLRQ VSHFWUD RI KHDWWUHDWHG *G32(X7E'\ DQG *G<32(X7E '\SRZGHUVW&IRUKRXUV )LJ3RO\PHULFILOPVRID*G32(X7E'\E*G<32(X7E'\ )LJ(PLVVLRQVSHFWUDRI)*DQG)*0ILOPVDQG*G<32(X7E'\SRZGHUV )LJ(PLVVLRQVSHFWUDRI)*<DQG)*<0ILOPVDQG*G<32(X7E'\SRZGHUV
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
)LJ;5'SDWWHUQVRIV\QWKHVLVHYROXWLRQRI/X32REWDLQHGE\VROLGVWDWHUHDFWLRQ )LJ;5'SDWWHUQVRI/X32REWDLQHGE\VROLGVWDWHUHDFWLRQ )LJ;5'SDWWHUQVRI/X32&HSRZGHUVREWDLQHGE\VROLGVWDWHGUHDFWLRQ )LJ;5'SDWWHUQVRI/X32&HSRZGHUVREWDLQHGE\K\GURWKHUPDOPHWKRGDWS+ &IRUKRXUV )LJ ;5' SDWWHUQV RI KHDW WUHDWHG & KRXUV /X32&H SRZGHUV REWDLQHG E\ K\GURWKHUPDOPHWKRGDWS+ FIRUKRXUV
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¶3HUW3URGLIIUDFWRPHWHU )LJ$7KHUPR1LFROHWVSHFWURSKRWRPHWHU )LJ$-RELQ<YRQODE5DP+5895DPDQVSHFWURSKRWRPHWHU )LJ$6HWHUDPPRGHOR6HWV\VHYROXWLRQ )LJ$-60/96FDQQLQJHOHFWURQPLFURVFRSH )LJ$+LWDFKL+7UDQVPLWLRQHOHFWURQPLFURVFRSH )LJ$/XPLQHVFHQFHVSHFWURSKRWRPHWHU
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
7DEOH 6\QWKHVLV FRQGLWLRQV DQG PRUSKRORJ\ RI *G32(X DQG *G327ESRZGHUV JO\FHURODQGGLVWLOOHGZDWHUZHUHXVHGDVVROYHQW 7DEOH:HLJKWORVVRIQDQRSDUWLFOHVDQGQDQRZLUHV 7DEOH &RPSDULVRQ RI WKH OXPLQHVFHQFH LQWHQVLWLHV EHWZHHQ FRPSRVLWH ILOPV DQG WKH SRZGHUVXVHGDVILOOHUV
7DEOH&RPSDULVRQRI'
)WUDQVLWLRQDWGLIIHUHQWKHDWWUHDWPHQWV
7DEOH FKURPDWLF FRRUGLQDWHV DQG HIILFLHQF\ RI *G32(X7E'\ DQG *G<32 (X7E'\ 7DEOH3DUWLFOHVL]HDQGGRSLQJLRQFRQFHQWUDWLRQLQWKHRSWLPDOHPLVVLRQRI/X32(X
$EVWUDFW
5DUH HDUWK 5H GRSHG ODQWKDQLGH RUWKRSKRVSKDWHV /Q32 DUH FRQVLGHUHG OLNH SURPLVLQJ SKRVSKRUV IRU RSWLFDO DSSOLFDWLRQV 3KRVSKRUV DUH OXPLQHVFHQW PDWHULDOV ZKLFKFRQYHUWFHUWDLQW\SHVRIHQHUJ\;UD\XOWUDYLROHWYLVLEOHLQIUDUHGPDLQO\LQWR YLVLEOHOLJKW
,Q WKLV UHVHDUFK (X HXURSLXP &H FHULXP 7E WHUELXP (U HUELXP 7P WKXOLXP DQGRU <E \WWHUELXP GRSHG /X32 OXWHWLXP RUWKRSKRVSKDWH <32 \WWULXP RUWKRSKRVSKDWH *G32 JDGROLQLXP RUWKRSKRVSKDWH DQGRU *G[<[32 \WWULXPJDGROLQLXPRUWKRSKRVSKDWHZHUHV\QWKHVL]HGE\VROYRWKHUPDOSURFHVV
%\YDU\LQJWKHV\QWKHVLVFRQGLWLRQVWKHFU\VWDOOLQHSKDVHSDUWLFOHVL]HDQGPRUSKRORJ\ ZHUH FRQWUROOHG E\ WKH V\QWKHVLV FRQGLWLRQV WKHVH SDUDPHWHUV DIIHFW WKH SKRWROXPLQHVFHQW SURSHUWLHV 7KH VDPSOHV ZHUH FKDUDFWHUL]HG E\ PHDQV RI ;UD\ 'LIIUDFWLRQ ;5' )RXULHU WUDQVIRUP ,QIUDUHG )7,5 7KHUPRJUDYLPHWULF $QDO\VLV 7*$ 5DPDQ 6SHFWURVFRS\ 6FDQQLQJ (OHFWURQLF 0LFURVFRS\ 6(0 7UDQVPLVVLRQ (OHFWURQLF 0LFURVFRS\ 7(0 DQG SKRWROXPLQHVFHQFH VSHFWURVFRS\ HPLVVLRQ DQG H[FLWDWLRQVSHFWUDTXDQWXP\LHOGVDQGIOXRUHVFHQFHGHFD\WLPHV
,QSDUWLFXODUQDQRZLUHVDQGQDQRSDUWLFOHVQDQRZLUHVDQGQDQRSDUWLFOHVRI*G32(X
*G327EKDYH EHHQ GHYHORSHG DV ZHOO DV SRZGHUV RI<327ESRZGHUV ZLWK PRQRFOLQLF KH[DJRQDO RU WHWUDJRQDO SKDVHV ,W KDV EHHQ GHPRQVWUDWHG D VLJQLILFDQW LQIOXHQFH RI WKH FU\VWDOOLQH VWUXFWXUH DQG PRUSKRORJ\ SKRVSKRUV RQ WKHLU RSWLFDO SURSHUWLHV
3RZGHUV ZLWK GLIIHUHQW PRUSKRORJ\ ZHUH XVHG DV ILOOHUV IRU SUHSDULQJ OXPLQHVFHQW FRPSRVLWHSRO\PHUSKRVSKRUVILOPV%\DGMXVWLQJWKHRUWKRSKRVSKDWHVIRUPXODWLRQDQG GRSDQWQDWXUHRILRQVSKRVSKRUVSURYLGLQJQHDUSHUIHFWZKLWHOLJKWXQGHU89H[FLWDWLRQ FRXOGEHREWDLQHG $OORIWKLVZRUNFOHDUO\VKRZVWKHSRWHQWLDO DSSOLFDWLRQVRIWKHVHPDWHULDOVLQGHYLFHV EDVHGRQDSODVPDH[FLWDWLRQVRXUFHRUOLJKWHPLWWLQJGLRGHWHFKQRORJ\
5pVXPp
/HV RUWKRSKRVSKDWHV GH ODQWKDQLGHV GRSpV DYHF GHV 7HUUHV 5DUHV 75 /Q32 VRQW FRQVLGpUpV FRPPH GHV OXPLQRSKRUHV LQWpUHVVDQWV SRXU GHV DSSOLFDWLRQV RSWLTXHV /HV OXPLQRSKRUHVVRQWGHVPDWpULDX[OXPLQHVFHQWVTXLWUDQVIRUPHQWFHUWDLQVW\SHVGpQHUJLH UD\RQV;XOWUDYLROHWYLVLEOHLQIUDURXJHSULQFLSDOHPHQWHQOXPLqUHYLVLEOH
'DQV OH FDGUH GH FHWWH WKqVH OHV PDWULFHV <32 RUWKRSKRVSKDWH G\WWULXP /X32 RUWKRSKRVSKDWH GH OXWpWLXP *G32 RUWKRSKRVSKDWH GH JDGROLQLXP HW *G[<[32 RUWKRSKRVSKDWHG\WWULXPHWJDGROLQLXPGRSpHVDYHFOHVLRQV(XHXURSLXP&H 7E WHUELXP (U HUELXP 7P WKXOLXP HW RX <E \WWHUELXP RQW pWp V\QWKpWLVpVSDUSURFpGpVROYRWKHUPDO
(QMRXDQWVXUOHVFRQGLWLRQVGHV\QWKqVHODSKDVHFULVWDOOLQHODWDLOOHHWODPRUSKRORJLH GHVSDUWLFXOHVREWHQXHVRQWSXrWUHFRQWU{OpHV/HVpFKDQWLOORQVRQWpWpFDUDFWpULVpVSDU GLIIUDFWLRQGHVUD\RQV;'5;VSHFWURVFRSLHLQIUDURXJHGH7UDQVIRUPpHGH)RXULHU DQDO\VH WKHUPRJUDYLPpWULTXH 7* VSHFWURVFRSLH 5DPDQ PLFURVFRSLH pOHFWURQLTXH j EDOD\DJH0(%PLFURVFRSLHpOHFWURQLTXHjWUDQVPLVVLRQ0(7HWVSHFWURVFRSLHGH OXPLQHVFHQFH VSHFWUHV G¶pPLVVLRQ G¶H[FLWDWLRQ UHQGHPHQWV TXDQWLTXHV HW GpFOLQV GH IOXRUHVFHQFH
(QSDUWLFXOLHUGHVQDQRILOVHWGHVQDQRSDUWLFXOHVGH *G32(X*G327ERQWpWp pODERUpV DLQVL TXH GHV SRXGUHV GH <327E DYHF GHV SKDVHV PRQRFOLQLTXH KH[DJRQDOHRXTXDGUDWLTXH ,O DpWpPLV HQ pYLGHQFHXQHLQIOXHQFHVLJQLILFDWLYHGHOD VWUXFWXUHFULVWDOOLQHHWGHODPRUSKRORJLHGHVOXPLQRSKRUHVVXUOHXUVSURSULpWpVRSWLTXHV 'HVSRXGUHVDYHFXQH PRUSKRORJLHGLIIpUHQWH RQW pWpXWLOLVpV FRPPHFKDUJHVSRXUOD SUpSDUDWLRQGHILOPVFRPSRVLWHVSRO\PqUHOXPLQRSKRUHV (QMRXDQWVXUODIRUPXODWLRQ GHV RUWKRSKRVSKDWHV HW OD QDWXUH GHV LRQV GRSDQWV GHV OXPLQRSKRUHV IRXUQLVVDQW XQH OXPLqUHSURFKHGXEODQFLGpDOVRXVH[FLWDWLRQ89RQWSXrWUHpODERUpV
/¶HQVHPEOH GH FH WUDYDLO PRQWUH FODLUHPHQW OHV SRWHQWLDOLWpV G¶DSSOLFDWLRQV GH FHV PDWpULDX[ GDQV GHV GLVSRVLWLIV EDVpV VXU XQH VRXUFH G¶H[FLWDWLRQ SODVPD RX VXU OD WHFKQRORJLHGHVGLRGHVpOHFWUROXPLQHVFHQWHV
,QWURGXFWLRQ
3KRVSKRUV DUH OXPLQHVFHQW PDWHULDOV ZKLFK FRQYHUW FHUWDLQ W\SHV RI HQHUJ\ ;UD\ XOWUDYLROHW YLVLEOH LQIUDUHG PDLQO\ LQWR YLVLEOH OLJKW /XPLQHVFHQW PDWHULDOV DUH FRQVWLWXWHGRIDKRVWODWWLFHDQGGRSDQWLRQVLQVPDOODPRXQWZKLFKDUHUHVSRQVLEOHRI OLJKW HPLVVLRQ &RPSRXQGV FRQWDLQLQJ UDUHHDUWK LRQV DUH ZLGHO\ IRXQG LQ OLJKWLQJ GHYLFHV >@ ODVHUV >@ VFLQWLOODWRUV >@ DPSOLILHUV LQ RSWLFDO ILEHU >@ GLVSOD\LQJ ELRODEHOLQJ>@HWF
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³DQ\ KRPRJHQHRXV RU KHWHURJHQHRXV FKHPLFDO UHDFWLRQLQ WKHSUHVHQFHRIDVROYHQWZKHWKHU DTXHRXV RUQRQ DTXHRXVDERYH URRP WHPSHUDWXUHDQGDWSUHVVXUHKLJKHUWKDQDWPLQDFORVHGV\VWHP´%\WKLVPHWKRGWKH ILQDO SURSHUWLHV DUH FRQWUROOHG E\ PRGLI\LQJ WKH V\QWKHVLV FRQGLWLRQV LH S+ WHPSHUDWXUHVXUIDFWDQWVDQGFRVROYHQW
$V UHJDUGV WKLV UHVHDUFK /X32 OXWHWLXP RUWKRSKRVSKDWH <32 <WWULXP RUWKRSKRVSKDWH *G32 JDGROLQLXP RUWKRSKRVSKDWH DQG *G[<[32 *DGROLQLXP \WWULXP RUWKRSKRVSKDWH ZHUH VWXGLHG $FFRUGLQJ WR WKHLU FU\VWDOOLQH VWUXFWXUHV ODQWKDQLGH RUWKRSKRVSKDWHV FDQ EH FODVVLILHG OLNH K\GUDWHG PRQRFOLQLF FKXUFKLWH WHWUDJRQDO[HQRWLPHK\GUDWHGKH[DJRQDOUKDEGRSKDQHDQGPRQRFOLQLFPRQD]LWH
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
*HQHUDOREMHFWLYH
7RV\QWKHVL]HDQGFKDUDFWHUL]HSXUHDQG(X7E&H (U<E \R7PGRSHG <32 *G32 /X32 SRZGHUV E\ XVLQJ WKH K\GURWKHUPDO PHWKRG PRGLI\LQJ LWV OXPLQHVFHQWSURSHUWLHVWREHFDQGLGDWHVDVOXPLQHVFHQWPDWHULDOV
6SHFLILFREMHFWLYHV ¾ 7RGHWHUPLQHWKHHIIHFWRIWKHV\QWKHVLVFRQGLWLRQVWHPSHUDWXUHS+VXUIDFWDQWVDQG FRVROYHQWRQSDUWLFOHVL]HPRUSKRORJ\DQGFU\VWDOOLQHVWUXFWXUHRI<32*G32DQG /X32
¾ 7R PHDVXUH WKH OXPLQHVFHQW SURSHUWLHV RI <327E PRO DV D IXQFWLRQ RI FU\VWDOOLQHVWUXFWXUH
¾ 7R GHWHUPLQH WKH HIIHFW RI OXPLQHVFHQW SURSHUWLHV RI *G32(X *G327E (XPRODQG7EPROSRZGHUVZLWKGLIIHUHQWPRUSKRORJLHV
¾ 7R PHDVXUH WKH OXPLQHVFHQW SURSHUWLHV RI 7E PRO GRSHG *G[<[327E [ XQGHUDYDFXXPXOWUDYLROHWOLJKWH[FLWDWLRQQP
¾ 7RREWDLQWKHZKLWHOLJKWWKURXJK(X7EDQG'\GRSHG*G32DQG*G[<[32
SRZGHUVZLWKVSHFLILFFRQFHQWUDWLRQXQGHUDYDFXXPXOWUDYLROHWOLJKWQPDQG QPH[FLWDWLRQ
¾ 7R PHDVXUH WKH OXPLQHVFHQW SURSHUWLHV RI *G32<E7P DQG *G32<E (UXQGHUDQLQIUDUHGOLJKWQPH[FLWDWLRQ
7KLVZRUNLVSUHVHQWHGLQGLIIHUHQWFKDSWHUVYDULRXVFKDUDFWHUL]DWLRQWHFKQLTXHVVXSSRUW WKH LPSRUWDQFH RI WKLV UHVHDUFK &KHPLFDO VWUXFWXUDO PRUSKRORJLFDO RSWLFDO FKDUDFWHUL]DWLRQV RI GLIIHUHQW VDPSOHV REWDLQHG E\ K\GURWKHUPDO PHWKRG ZHUH FDUULHG RXWE\)7,5;5'5DPDQ7*$'7$6(07(0DQGOXPLQHVFHQFHVSHFWURVFRS\ WHFKQLTXHV
7KH&KDSWHU,LVGHYRWHGWRWKHVWXG\RIWKHWKHRUHWLFDOIUDPHZRUNVXFKLQIRUPDWLRQLV WKHEDVLVIRUWKHUHVXOWGLVFXVVLRQ
,Q &KDSWHU ,, WKH HIIHFWV RI V\QWKHVLV FRQGLWLRQV WHPSHUDWXUH UHDFWLRQ WLPH S+ VXUIDFWDQWVDQGFRVROYHQWRQWKHPRUSKRORJ\DQGSDUWLFOHVL]HVRIWKH<32/X32 DQG*G32REWDLQHGE\WKHK\GURWKHUPDOPHWKRGDUHSUHVHQWHG
&KDSWHU ,,, GHDOV ZLWK WKH OXPLQHVFHQW SURSHUWLHV RI <327E ZLWK GLIIHUHQW FU\VWDOOLQHVWUXFWXUHV
7KH&KDSWHU,9SUHVHQWVWKHOXPLQHVFHQWSURSHUWLHVRI*G327EDQG*G32(X QDQRSDUWLFOHV DQG QDQRZLUHV WKLV FKDSWHU GLVFXVVHV WKH PRUSKRORJ\ HIIHFW RQ WKH SRO\PHULFILOPSUHSDUDWLRQ
7KH&KDSWHU9LVGHYRWHGWROXPLQHVFHQWSURSHUWLHVRI*G[<[327EH[FLWHGXQGHU YDFXXPXOWUDYLROHWOLJKW ,Q&KDSWHU9,SRZGHUVDQGSRO\PHULFILOPVRI(X7EDQG'\GRSHG*G32DQG *G[<[32ZHUHSUHSDUHGIRUREWDLQLQJZKLWHOLJKW
&KDSWHU 9,, GHVFULEHV WKH XSFRQYHUVLRQ SURSHUWLHV RI *G32<E7P DQG *G32<E(USRZGHUV
&KDSWHU 9,,, SUHVHQWV WKH 6FLQWLOODWLQJ SURSHUWLHV RI WKH /X32&H V\QWKHVL]HG E\ K\GURWKHUPDODQGVROLGVWDWHUHDFWLRQPHWKRG
)LQDOO\WKHJHQHUDOFRQFOXVLRQVDUHSUHVHQWHG
&KDUDFWHUL]DWLRQ WHFKQLTXHV XVHG LQ WKLV ZRUN DQG WKH VDPSOHV SUHSDUDWLRQV DUH GHVFULEHGLQ$SSHQGL[$)LQDOO\WKHSURGXFWVRIWKLVUHVHDUFKDUHOLVWHGLQ$SSHQGL[ % 5HIHUHQFHV .$:LFNHUVKHLP5$/HIHYHU/XPLQHVFHQWEHKDYLRURIWKHUDUHHDUWKVLQ\WWULXPR[LGHDQGUHODWHG KRVWV-(OHFWURFKHP6RF -52¶&RQQRU8QXVXDOFU\VWDOILHOGHQHUJ\OHYHOVDQGHIILFLHQWODVHUSURSHUWLHVRI<92±1G$SSO 3K\V/HWW *%ODVVHVFLQWLOODWRUPDWHULDOV&KHP0DWHU '%%DUEHU&53ROORFN$PSOLILFDWLRQE\RSWLFDOFRPSRVLWHV2SW/HWW ),VNDQGDU1DQRSDUWLFOHSURFHVVLQJIRURSWLFDODSSOLFDWLRQV$GYDQFHG3RZGHU7HFKQRORJ\ ± 33DYHO)HGRURY1DQRIOXRULGHV-RXUQDORI)OXRULQH&KHPLVWU\±
1&ODYLHU 3RGRU 5 'DFKHX[ &U\VWDO FKHPLVWU\ RI WKH PRQD]LWH VWUXFWXUH -RXUQDO RI WKH (XURSHDQ &HUDPLF6RFLHW\±
0LNKDLO6ROLGVWDWHUHDFWLRQVRIDONDOL PHWDOFKORULGHV ZLWKDFLGWDQWDOXPSKRVSKDWHDFLG]LUFRQLXP SKRVSKDWHDQGYDQDGLXPR[\SKRVSKDWH6ROLG6WDWH,RQLFV±±
. 5DMHVK 3 0XNXQGDQ +LJK6XUIDFH$UHD 1DQRFU\VWDOOLQH &HULXP SKRVSKDWH WKURXJK DTXHRXV 6ROí*HOURXWH&KHP0DWHU
-01HGHOHF&0DQVX\50DKLRX-0RO6WUXFW-0RO6WUXFW
. 5LZRW]NL + 0H\VVDP\ +DQGERRN RQ WKH SK\VLFV DQG FKHPLVWU\ RI UDUH HDUWKV 2SWLFDO 6SHFWURVFRS\&KHP,QW(G(QJO
.5LZRW]NL+0H\VVDP\/LTXLGSKDVHV\QWKHVLVRIGRSHGQDQRSDUWLFOHVFROORLGVRIOXPLQHVFLQJ /D32(XDQG&H327ESDUWLFOHVZLWKDQDUURZSDUWLFOHVL]HGLVWULEXWLRQ-3K\V&KHP%
< 3 )DQJ $: ;X 6\VWHPDWLF V\QWKHVLV DQG FKDUDFWHUL]DWLRQ RI VLQJOHFU\VWDO ODQWKDQLGH RUWKRSKRVSKDWHQDQRZLUHV-$P&KHP6RF
+0H\VVDP\.5LZRW]NL:HWFKHPLFDOV\QWKHVLVRIGRSHGFROORLGDOQDQRPDWHULDOVSDUWLFOHVDQG ILEHUVRI/D32(X/D32&HDQG/D32&H7E$GY0DWH
&KDSWHU,7KHRUHWLFDOIUDPHZRUN
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
/DQWKDQLGHRUWKRSKRVSKDWHPLQHUDOV
,W H[LVWV RYHU RUWKRSKRVSKDWHV PLQHUDOV ZKLFK KDYH EHHQ FODVVLILHG LQWR GLIIHUHQW JURXSV GHSHQGLQJ RI WKHLU FDWLRQLF HOHPHQWV >@ WKLV ZRUN RQO\ GHDOV WR ODQWKDQLGH HOHPHQWV RU UDUH HDUWKV /DQWKDQLGH HOHPHQWV DUH IRUPHG E\ ODQWKDQXP /D FHULXP &H SUDVHRG\PLXP 3U QHRG\PLXP 1G SURPHWKLXP 3P VDPDULXP 6P HXURSLXP(XJDGROLQLXP*GWHUELXP7EG\VSURVLXP'\KROPLXP+RHUELXP (U WKXOLXP 7P \WWHUELXP <E DQG OXWHWLXP /X DQG DOVR DUH FRQVLGHUHG VFDQGLXP6FDQG\WWULXP<ZKLFKDUHLQWKHVDPHVXEJURXS
7KHUH LV D YDULHW\ RI PLQHUDOV WKDW FRQWDLQ GLIIHUHQW ODQWKDQLGH HOHPHQWV 7DEOH UHSRUWVWKHODQWKDQLGHRUWKRSKRVSKDWHVLQUHODWLRQRIWKHURFNV¶VQDPHZKHUHWKH\FDQEH IRXQG>@ 7DEOH/DQWKDQLGHRUWKRSKRVSKDWHVPLQHUDOVFODVVLILFDWLRQ>@ 0LQHUDO *HQHUDOIRUPXOH /Q /DQWKDQLGHV &U\VWDOVWUXFWXUHVSDFHJURXS 0RQD]LWH /Q32 /Dെ'\ 0RQRFOLQLF3Q ;HQRWLPH /Q32 <7Eെ<E 7HWUDJRQDO,DPG
5KDEGRSKDQH /Q32Q+2 ݊ /Dെ'\ +H[DJRQDO3RU3
&KXUFKLWHRU ZHLQVFKHQNLWH /Q32Q+2 ݊ <'\ (Uെ<E 0RQRFOLQLF$D 2UWKRUKRPELF /Q32Q+2݊ ݊ '\+R 2UWKRUKRPELF3
7KH GDWD UHSRUWHG LQ OLWHUDWXUH LQGLFDWH WKDW ODQWKDQLGH RU UDUH HDUWK RUWKRSKRVSKDWHV PLQHUDOV GLVSOD\DYDULHW\ RIFU\VWDO VWUXFWXUHV7KH\ DSSHDULQ KH[DJRQDO WHWUDJRQDO
RUWKRUKRPELF DQG PRQRFOLQLF SKDVHV 'HSHQGLQJ RQ WKH FU\VWDOOLQH IRUP WKH\ DUH GHQRPLQDWHG PRQD]LWH PRQRFOLQLF [HQRWLPH WHWUDJRQDO UKDEGRSKDQH K\GUDWHG KH[DJRQDOFKXUFKLWHRUZHLQVFKHUNLWHK\GUDWHGPRQRFOLQLF>@
5HJDUGLQJWKLVUHVHDUFK<32/X32DQG*G32FDQEHFODVVLILHGLQ IRXUPLQHUDOV PRQD]LWH [HQRWLPH UKDEGRSKDQH DQG FKXUFKLWH 7KH IHDWXUHV RI WKHVH PLQHUDOV DUH SUHVHQWHGIRUEHWWHUXQGHUVWDQGLQJRIWKHLUSURSHUWLHV
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x PRQD]LWH&H&H/D3U1G7K<32 x PRQD]LWH/D/D&H1G3U32 x PRQD]LWH1G1G/D&H3U32 x PRQD]LWH6P6P*G&H7K32 a) E) 5 mm 5 mm
7KHHOHPHQWVLQSDUHQWKHVHVDUHOLVWHGLQWKHRUGHUZKLFKWKH\DUHLQUHODWLYHSURSRUWLRQ ZLWKLQ WKH PLQHUDO WKXV FHULXP LV WKH PRVW FRPPRQ UDUH HDUWK LQ PRQD]LWH&H VXFFHVVLYHO\ F5KDEGRSKDQHLVUHSUHVHQWE\³032Q+2´ZKHUH0FDQEHFDOFLXPFHULXPOHDG ODQWKDQXPQHRG\PLXPWKRULXPLURQDQGXUDQLXPDQGQKDVYDOXHVEHWZHHQQ >@7KHVHDUHWKHPHPEHUVRIWKH5KDEGRSKDQH*URXS x %URFNLWH+\GUDWHG&D7K&H32 x *UD\LWH+\GUDWHG7K3E&D32 x 1LQJ\RLWH+\GUDWHG8&D&H32 x 5KDEGRSKDQH&H+\GUDWHG&H/D32 x 5KDEGRSKDQH/D+\GUDWHG/D&H32 x 5KDEGRSKDQH1G+\GUDWHG1G&H/D32 )LJD&KXUFKLWH<<32Â+2FRS\ULJKW/3HUORII>@E5KDEGRSKDQH/D /D&H32Â+2FRS\ULJKW$/DUVRQ>@
G &KXUFKLWH LV DOVR NQRZQ DV ZHLQVFKHQNLWH 7KH QDPH RI WKH FKXUFKLWH PLQHUDO LV
DFFRUGLQJWR SUHGRPLQDQW HOHPHQW LQ LWVFRPSRVLWLRQ IRUH[DPSOHFKXUFKLWH<ZKLFK FRUUHVSRQGVWR<'\(U*G32·+2DVZHOODVUKDEGRSKDQHFRQWDLQV FRRUGLQDWHGZDWHUPROHFXOHV
/DQWKDQLGH RUWKRSKRVSKDWHV KDYH LQWHUHVWLQJ DSSOLFDWLRQV GXH WR VRPH LQWHUHVWLQJ SK\VLFDO DQG FKHPLFDO SURSHUWLHV KLJK IXVLRQ WHPSHUDWXUH RSWLFDO HPLVVLYLW\ KLJK UHVLVWDQFHWRDTXHRXVDQGPROWHQJODVVFRUURVLRQRUWRUDGLDWLRQGDPDJH
D) E)
&U\VWDOORJUDSKLFVWUXFWXUHVRIODQWKDQLGHRUWKRSKRVSKDWHV
/DQWKDQLGHRUWKRSKRVSKDWHVFDQKDYHGLIIHUHQWVWUXFWXUDOSKDVHVGHSHQGLQJRQV\QWKHVLV PHWKRGV DQG WKHUPDO WUHDWPHQWV >@ ;HQRWLPHW\SH FRPSRXQGV FU\VWDOOL]H LQ WHWUDJRQDO SKDVH IURP 7E WR /X >@ 'LIIHUHQW FU\VWDOOLQH VWUXFWXUHV DQG VSDFH JURXSVDUHOLVWHGLQWKH7DEOH 7DEOH&U\VWDOVWUXFWXUHVDQGVSDFHJURXSVRIODQWKDQLGHRUWKRSKRVSKDWHV /Q /Q32 /Q32Q+2 &U\VWDOOLQH VWUXFWXUH 6SDFHJURXS 1 &U\VWDOOLQH VWUXFWXUH 6SDFH JURXS /D 0RQRFOLQLF 3Q ݊ +H[DJRQDO 3
&H 0RQRFOLQLF 3Q ݊ +H[DJRQDO 3
3U 0RQRFOLQLF 3Q ݊ +H[DJRQDO 3
1G 0RQRFOLQLF 3Q +H[DJRQDO 3
3P 0RQRFOLQLF 3Q ݊ +H[DJRQDO 3
6P 0RQRFOLQLF 3Q ݊ +H[DJRQDO 3RU
3 (X 0RQRFOLQLF 3Q +H[DJRQDO 3 *G 0RQRFOLQLF 3Q ݊ +H[DJRQDO 3 7E 0RQRFOLQLF 7HWUDJRQDO 3Q ,DPG ݊ +H[DJRQDO 3 '\ 7HWUDJRQDO ,DPG ݊ +H[DJRQDO 2UWKRUKRPELF 0RQRFOLQLF 3 3 $D +R 7HWUDJRQDO ,DPG 2UWKRUKRPELF 3 (U 7HWUDJRQDO ,DPG 0RQRFOLQLF +H[DJRQDO $D 3 7P 7HWUDJRQDO ,DPG 0RQRFOLQLF $D <E 7HWUDJRQDO ,DPG 0RQRFOLQLF $D /X 7HWUDJRQDO ,DPG < 7HWUDJRQDO ,DPG 0RQRFOLQLF +H[DJRQDO $D 3 6F 7HWUDJRQDO ,DPG
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c 9ROc /X32 7HWUDJRQDO ,DPG Į Ȗ ȕ D E F <32 7HWUDJRQDO ,DPG Į Ȗ ȕ D E F <32+2 +H[DJRQDO 3 Į ȕ Ȗ D E F <32+2 0RQRFOLQLF 3Q Į Ȗ ȕ D E F *G32 0RQRFOLQLF 3Q Į Ȗ ȕ D E F *G32+2 +H[DJRQDO 3 Į ȕ Ȗ
7KH PRQD]LWHW\SH FRPSRXQGV FU\VWDOOL]H ZLWK PRQRFOLQLF VWUXFWXUH LQ 3Q VSDFH JURXS 7KLV VWUXFWXUH ZDV UHSRUWHG IRU WKH ILUVW WLPH E\ 0RRQH\ >@ 0RQRFOLQLF VWUXFWXUH KDV D VWUXFWXUDO DUUDQJHPHQW EDVHG RQ WKH QLQHIROG FRRUGLQDWLRQ RI WKH PHWDOOLFFDWLRQ)LJDQGLWLVXVXDOO\GHVFULEHGDVDQHTXDWRULDOSHQWDJRQIRUPHG E\R[\JHQDWRPVEHORQJLQJWRPRQRGHQWDWHDQLRQLFWHWUDKHGURQVLQWHUSHQHWUDWHGE\D WHWUDKHGURQEXLOWE\R[\JHQDWRPVEHORQJLQJWRWZRELGHQWDWHWHWUDKHGURQV
&DUURQHWDO>@UHSRUWHGWKDWDQK\GURXVODQWKDQLGHRUWKRSKRVSKDWHVKDYHDPRQD]LWH VWUXFWXUHZKHQWKHLRQLFUDGLXVRIWKHODQWKDQLGHLVJUHDWHUWKDQJDGROLQLXPUDGLXVDQG WKH\ KDYH D [HQRWLPH VWUXFWXUH ZKHQ WKH UDGLXV LV VPDOOHU WKDQ JDGROLQLXP UDGLXV +RZHYHU WKHYDOXHRIWKHODQWKDQLGHLRQLFUDGLXVZLOOGHSHQGRQLWVFRRUGLQDWLRQDV 6KDQQRQREVHUYHG>@
)LJ7KHFRRUGLQDWLRQVWDWXVRIWKHFHQWUDOLRQDQGWKHFU\VWDOVWUXFWXUHRI 0RQD]LWHW\SH>@ 7KH[HQRWLPHW\SHFRPSRXQGVFU\VWDOOL]HZLWKWHWUDJRQDOSKDVHLQ,DPGVSDFH JURXS,QWKLVFU\VWDOOLQHSKDVHWKHODQWKDQLGHHOHPHQWKDVHLJKWIROGFRRUGLQDWLRQ7KH /Q2SRO\KHGURQFDQEHGHVFULEHGDVWZRRUWKRJRQDOWHWUDKHGURQVIRUPLQJDGHIRUPHG GRGHFDKHGURQ7KHSKRVSKDWHJURXSDOVRIRUPVDGLVWRUWHGWHWUDKHGURQ 7KHUKDEGRSKDQHW\SHFRPSRXQGVFU\VWDOOL]HZLWKKH[DJRQDOSKDVHLQ3RU3 VSDFH JURXS 7KLV NLQG RI FRPSRXQGV SUHVHQW FRRUGLQDWHGZDWHU PROHFXOHV LQWR WKHLU
VWUXFWXUHZKLFKYDULHVIURPWR5KDEGRSKDQHKDVDKH[DJRQDOVWUXFWXUHZLWKODUJH FKDQQHOVLQWKHFGLUHFWLRQ>@ZKLFKDUHDEOHWRLQFRUSRUDWHQRQVWRLFKLRPHWULFZDWHU ,QUKDEGRSKDQHFRPSRXQGVWKHODQWKDQLGHHOHPHQWVSUHVHQWDQHLJKWIROG)LJ
'HSHQGLQJRQV\QWKHVLVWHPSHUDWXUHWKHK\GUDWHGKH[DJRQDOIRUPRI/Q32/Q /DWR '\ >@ FDOOHG UKDEGRSKDQH DUH VWDEOH DW ³ORZ´ WHPSHUDWXUH 5KDEGRSKDQH LV WUDQVIRUPHGLQWRPRQRFOLQLFIRUPE\KHDWLQJDWKLJKWHPSHUDWXUH
'X )RX GH .HUGDQLHO DQG FRZRUNHUV UHSRUWHG WKDW UKDEGRSKDQHV RI /D&H RUWKRSKRVSKDWHVDUHREWDLQHGIURPLRQVLQVROXWLRQEHORZ&%\DTXHRXVPHWKRGV ODQWKDQLGH RUWKRSKRVSKDWHV ZKLFK FRQWDLQ WKH HOHPHQWV /Dĺ7E FU\VWDOOL]H LQ KH[DJRQDO PRGLILFDWLRQ 5HJLQD .LMNRZVND >@ GHPRQVWUDWHG WKDW WUDQVLWLRQ RI GHK\GUDWLRQSKDVHDQGVKHIRXQGE\7*DQDO\VHVWKDWKH[DJRQDOSKDVHRIODQWKDQLGHV RUWKRSKRVSKDWHV FRQWDLQLQJ /Dĺ7E GHK\GUDWH EHORZ & DQG WUDQVIRUP LQWR PRQRFOLQLFIRUPDWWHPSHUDWXUHVKLJKHUWKDQ&0RUHRYHULWLVLPSRUWDQWWRQRWH
WKDW PRQD]LWH FRPSRXQGV FRXOG EH REWDLQHG IURP UKDEGRSKDQH E\ PHFKDQLFDO WUHDWPHQWW\SLFDOO\PLOOLQJ>@ )LJ&RRUGLQDWLRQRIWKHFHQWUDOLRQDQGFU\VWDOVWUXFWXUHRIUKDEGRSKDQHW\SH FRPSRXQGV>@ 7KLVZRUNLVIRFXVHGRQWKHVWXG\RIWKUHHGRSHGUDUHHDUWKODQWKDQLGHRUWKRSKRVSKDWHV <32 *G32 DQG /X32 'HSHQGLQJ RQ WKH GRSDQW LRQ DQG WKH KRVW PDWUL[ WKHVH FRPSRXQGV KDYH XQLTXH SURSHUWLHV ZKLFK DUH RI JUHDW LPSRUWDQFH IRU WKH ILQDO DSSOLFDWLRQ7KHUHIRUHWKHGRSDQWLRQQDWXUHLVHVVHQWLDOWRNQRZWKHPDWHULDOEHKDYLRU
/DQWKDQLGHHOHPHQWV &KHPLFDODVSHFWV
,Q WKH JURXQG VWDWH WKH HOHFWURQLF FRQILJXUDWLRQ RI DQ DWRP LV GHWHUPLQHG IRU LWV SULQFLSDOTXDQWXPQXPEHUQDQGWKHDQJXODUTXDQWXPQXPEHUO7KHUHDUHWZRW\SHVRI HOHFWURQLF FRQILJXUDWLRQ IRU WKH ODQWKDQLGH HOHPHQWV >;H@IQVDQG >;H@IQGV
:KHUH>;H@UHSUHVHQWVWKH[HQRQHOHFWURQLFFRQILJXUDWLRQDQGQLVDQXPEHUIURPWR /DQWKDQXPFHULXPDQGJDGROLQLXPDUHRI>;H@IQVW\SHZKLOHSUDVHRG\PLXP QHRG\PLXPSURPHWKLXPVDPDULXPHXURSLXPWHUELXPG\VSURVLXPKROPLXPHUELXP WKXOLXP\WWHUELXPDQGOXWHWLXPEHORQJVWR>;H@IQíGVFRQILJXUDWLRQ6FDQGLXPDQG \WWULXP GR QRW KDYH I HOHFWURQV EXW WKH\ KDYH VLPLODU FKHPLFDO SURSHUWLHV WR ODQWKDQLGHV EHFDXVH WKHLU RXWHUPRVW HOHFWURQV KDYH WKH Q GQV FRQILJXUDWLRQ 7KHUHIRUHWKH\DUHJHQHUDOO\FRQVLGHUHGLQWKHODQWKDQLGHVIDPLO\7DEOHVKRZVWKH ODQWKDQLGH HOHFWURQ FRQILJXUDWLRQV DV ZHOO DV WKH DWRPLF UDGLXV GHSHQGLQJ RQ WKH FRRUGLQDWLRQQXPEHU
7DEOH(OHFWURQLFFRQILJXUDWLRQRIODQWKDQLGHHOHPHQWV>@
=
(OHPHQW $WRPLFZHLJKW $WRPLFUDGLXVc (OHFWURQLFFRQILJXUDWLRQRIQHXWUDODWRPV FRQILJXUDWLRQRI(OHFWURQLF WULYDOHQWDWRPV &Q &Q I V S G V /D >;H@I &H >;H@I 3U >;H@I 1G >;H@I 3P >;H@I 6P >;H@I (X >;H@I *G >;H@I 7E >;H@I '\ >;H@I +R >;H@I (U >;H@I 7P >;H@I <E >;H@I /X >;H@I G V S G V 6F >$U@ < >.U@ &Q &RRUGLQDWLRQQXPEHU &Q
/DQWKDQLGH HOHPHQWV FDQ IRUP FKHPLFDO ERQGV ZLWK PRVW QRQPHWDO HOHPHQWV 6RPH ORZYDOHQFH ODQWKDQLGH HOHPHQWV FDQ IRUP FKHPLFDO ERQGV LQ RUJDQRPHWDOOLF FRPSRXQGV'XHWRWKHODFNRIHOHFWURQVRIODQWKDQLGHHOHPHQWVWKH\VKRZDUHSXOVLRQ IRUFHWRZDUGVDSRVLWLYHFKDUJH
)URP D VRIW±KDUG DFLG±EDVH SRLQW RI YLHZ ODQWKDQLGH HOHPHQWV DUH KDUG EDVHV 7KXV WKH\WHQGWRIRUPFKHPLFDOERQGVZLWKDWRPVWKDWEHORQJWRWKHKDUGDFLGJURXS)RU H[DPSOH R[\JHQ DQG ODQWKDQLGH HOHPHQWV WHQG WR IRUP 5(±2 ERQGV /DQWKDQLGH HOHPHQWVFDQDOVRIRUPFKHPLFDOERQGVZLWKQLWURJHQJURXSDWRPV
/DQWKDQLGHHOHPHQWVFDQVKRZGLIIHUHQWFRRUGLQDWLRQQXPEHUVIURPWR7KHPRVW FRPPRQ FRRUGLQDWLRQ QXPEHU LV HLJKW RI WKH FRPSRXQGV UHSRUWHG &RPSDUHG ZLWKWUDQVLWLRQPHWDOVODQWKDQLGHHOHPHQWVKDYHWZRGLVWLQFWFKDUDFWHULVWLFVLQWHUPVRI WKHLUFRRUGLQDWLRQQXPEHU
/DUJHFRRUGLQDWLRQQXPEHUV)RUH[DPSOHWKHFRRUGLQDWLRQQXPEHURIGWUDQVLWLRQ PHWDOV LV JHQHUDOO\ IRXU RU VL[ +RZHYHU WKH PRVW FRPPRQ FRRUGLQDWLRQ QXPEHU RI ODQWKDQLGHFRPSOH[HVLVHLJKWRUQLQH7KLVQXPEHULVFORVHWRWKHVXPRIVSDQGG
RUELWDOV$QRWKHUUHDVRQIRUWKHODUJHFRRUGLQDWLRQQXPEHURIODQWKDQLGHFRPSOH[HVLV WKHODUJHLRQLFUDGLXVRIWKHODQWKDQLGHHOHPHQWV
9DULDEOH FRRUGLQDWLRQ QXPEHUV 7KH VWDELOL]DWLRQ HQHUJ\ IRU FRRUGLQDWLRQ DSSUR[LPDWHO\N-ÂPRORIODQWKDQLGHLRQVLVPXFKVPDOOHUWKDQWKHVWDELOL]DWLRQ HQHUJ\ RI FU\VWDO ILHOG RI WUDQVLWLRQ PHWDOV W\SLFDOO\ N-ÂPRO 7KHUHIRUH FRRUGLQDWLRQ ERQGV RI ODQWKDQLGH FRPSOH[HV DUH QRW GLUHFWLRQDO DQG WKH FRRUGLQDWLRQ QXPEHUUDQJHVIURPWR
2[LGDWLRQVWDWHVRIODQWKDQLGHHOHPHQWV
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
$FFRUGLQJWR+XQG¶VUXOHHOHFWURQVKHOOVDUHVWDEOHZKHQWKH\DUHHPSW\IXOORUKDOI IXOO )RU H[DPSOH WKH FRQILJXUDWLRQV I /D I*G DQG I/X DUH VWDEOH &H3UDQG7EKDYHRQHRUWZRPRUHHOHFWURQVWKDWUHTXLUHVIRUDVWDEOHHOHFWURQLF FRQILJXUDWLRQVVRWKH\FDQEHIXUWKHUR[LGL]HGWRDVWDWH,QFRQWUDVW6P(XDQG <EKDYHRQHRUWZRPLQXVHOHFWURQVWKDWUHTXLUHVIRUDVWDEOHHOHFWURQLFFRQILJXUDWLRQ WKHUHIRUHWHQGWRUHFHLYHRQHRUWZRHOHFWURQVDQGXQGHUJRDUHGXFWLRQWRDVWDWH)RU WKHVHUHDVRQVVXFKHOHPHQWVKDYHDEQRUPDOYDOHQFHVWDWHV 6\QWKHVLVPHWKRGVRIODQWKDQLGHRUWKRSKRVSKDWHV
,W LV ZHOO NQRZQ WKDW PDWHULDOV SHUIRUPDQFH LV FORVHO\ UHODWHG WR WKH ZD\V WKDW DUH SURFHVVHG >@ /DQWKDQLGH RUWKRSKRVSKDWHV KDYH EHHQ V\QWKHVL]HG E\ WKH VROLG VWDWH