Phase composition, structure and stress state of magnetron sputtered W-Ti condensates
The effects of elemental composition and deposition temperature on W—Ti ion-plasma condensate structure, substructure characteristics and stress state have been studied. The crystalline state of all phases formed during deposition has been found to be based on the α-W bcc crystalline lattice. In the...
Збережено в:
| Опубліковано в: : | Functional Materials |
|---|---|
| Дата: | 2006 |
| Автор: | |
| Формат: | Стаття |
| Мова: | English |
| Опубліковано: |
НТК «Інститут монокристалів» НАН України
2006
|
| Онлайн доступ: | https://nasplib.isofts.kiev.ua/handle/123456789/135072 |
| Теги: |
Додати тег
Немає тегів, Будьте першим, хто поставить тег для цього запису!
|
| Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| Цитувати: | Phase composition, structure and stress state of magnetron sputtered W-Ti condensates / O.V. Sobol` // Functional Materials. — 2006. — Т. 13, № 4. — С. 577-583. — Бібліогр.: 17 назв. — англ. |
Репозитарії
Digital Library of Periodicals of National Academy of Sciences of Ukraine| id |
nasplib_isofts_kiev_ua-123456789-135072 |
|---|---|
| record_format |
dspace |
| spelling |
Sobol`, O.V. 2018-06-14T14:52:52Z 2018-06-14T14:52:52Z 2006 Phase composition, structure and stress state of magnetron sputtered W-Ti condensates / O.V. Sobol` // Functional Materials. — 2006. — Т. 13, № 4. — С. 577-583. — Бібліогр.: 17 назв. — англ. 1027-5495 https://nasplib.isofts.kiev.ua/handle/123456789/135072 The effects of elemental composition and deposition temperature on W—Ti ion-plasma condensate structure, substructure characteristics and stress state have been studied. The crystalline state of all phases formed during deposition has been found to be based on the α-W bcc crystalline lattice. In the initial stages of solid solution formation under relatively low content of substituting titanium atoms in the lattice (7 to 11 at.%), oriented crystallite growth takes place with (100) planes parallel to the condensate surface. At higher titanium atomic content in the lattice, strongly strained crystallites of (W₁₋ₓ, Tiₓ) solid solution are formed with light preferential orientation of (110) plane parallel to the growth surface. In this case, the deposition temperature elevation from 300°C to 800°C results in concentration stratification of the formed solid solution followed by formation of two solid solutions with different stable elemental composition. The diffusion coefficient in nano-crystalline W—Ti condensates has been estimated and models describing the formed condensate structure state are proposed. en НТК «Інститут монокристалів» НАН України Functional Materials Phase composition, structure and stress state of magnetron sputtered W-Ti condensates Фазовий склад, структура та напружений стан конденсатів системи W-Ti, одержаних магнетронним розпиленням Article published earlier |
| institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| collection |
DSpace DC |
| title |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates |
| spellingShingle |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates Sobol`, O.V. |
| title_short |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates |
| title_full |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates |
| title_fullStr |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates |
| title_full_unstemmed |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates |
| title_sort |
phase composition, structure and stress state of magnetron sputtered w-ti condensates |
| author |
Sobol`, O.V. |
| author_facet |
Sobol`, O.V. |
| publishDate |
2006 |
| language |
English |
| container_title |
Functional Materials |
| publisher |
НТК «Інститут монокристалів» НАН України |
| format |
Article |
| title_alt |
Фазовий склад, структура та напружений стан конденсатів системи W-Ti, одержаних магнетронним розпиленням |
| description |
The effects of elemental composition and deposition temperature on W—Ti ion-plasma condensate structure, substructure characteristics and stress state have been studied. The crystalline state of all phases formed during deposition has been found to be based on the α-W bcc crystalline lattice. In the initial stages of solid solution formation under relatively low content of substituting titanium atoms in the lattice (7 to 11 at.%), oriented crystallite growth takes place with (100) planes parallel to the condensate surface. At higher titanium atomic content in the lattice, strongly strained crystallites of (W₁₋ₓ, Tiₓ) solid solution are formed with light preferential orientation of (110) plane parallel to the growth surface. In this case, the deposition temperature elevation from 300°C to 800°C results in concentration stratification of the formed solid solution followed by formation of two solid solutions with different stable elemental composition. The diffusion coefficient in nano-crystalline W—Ti condensates has been estimated and models describing the formed condensate structure state are proposed.
|
| issn |
1027-5495 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/135072 |
| citation_txt |
Phase composition, structure and stress state of magnetron sputtered W-Ti condensates / O.V. Sobol` // Functional Materials. — 2006. — Т. 13, № 4. — С. 577-583. — Бібліогр.: 17 назв. — англ. |
| work_keys_str_mv |
AT sobolov phasecompositionstructureandstressstateofmagnetronsputteredwticondensates AT sobolov fazoviiskladstrukturatanapruženiistankondensatívsistemiwtioderžanihmagnetronnimrozpilennâm |
| first_indexed |
2025-11-25T20:31:20Z |
| last_indexed |
2025-11-25T20:31:20Z |
| _version_ |
1850521566785306624 |
| fulltext |
3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG�VWUHVV�VWDWHRI�PDJQHWURQ�VSXWWHUHG�:±7L FRQGHQVDWHV
2�9�6RERO�
1DWLRQDO�7HFKQLFDO�8QLYHUVLW\��.KDUNLY�3RO\WHFKQLFDO�,QVWLWXWH���
���)UXQ]H�6W���������.KDUNLY��8NUDLQH
5HFHLYHG�$XJXVW��������
7KH� HIIHFWV� RI� HOHPHQWDO� FRPSRVLWLRQ� DQG� GHSRVLWLRQ� WHPSHUDWXUH� RQ�:±7L� LRQ�SODVPD
FRQGHQVDWH�VWUXFWXUH��VXEVWUXFWXUH�FKDUDFWHULVWLFV�DQG�VWUHVV�VWDWH�KDYH�EHHQ�VWXGLHG��7KH
FU\VWDOOLQH�VWDWH�RI�DOO�SKDVHV�IRUPHG�GXULQJ�GHSRVLWLRQ�KDV�EHHQ�IRXQG�WR�EH�EDVHG�RQ�WKH
D�:�EFF�FU\VWDOOLQH�ODWWLFH��,Q�WKH�LQLWLDO�VWDJHV�RI�VROLG�VROXWLRQ�IRUPDWLRQ�XQGHU�UHODWLYHO\
ORZ�FRQWHQW�RI�VXEVWLWXWLQJ�WLWDQLXP�DWRPV�LQ�WKH�ODWWLFH����WR����DW�����RULHQWHG�FU\VWDO�
OLWH� JURZWK� WDNHV� SODFH� ZLWK� ������ SODQHV� SDUDOOHO� WR� WKH� FRQGHQVDWH� VXUIDFH�� $W� KLJKHU
WLWDQLXP� DWRPLF� FRQWHQW� LQ� WKH� ODWWLFH�� VWURQJO\� VWUDLQHG� FU\VWDOOLWHV� RI� �:�±[�� 7L[�� VROLGVROXWLRQ� DUH� IRUPHG� ZLWK� OLJKW� SUHIHUHQWLDO� RULHQWDWLRQ� RI� ������ SODQH� SDUDOOHO� WR� WKH
JURZWK� VXUIDFH�� ,Q� WKLV� FDVH�� WKH� GHSRVLWLRQ� WHPSHUDWXUH� HOHYDWLRQ� IURP� ����&� WR� ����&
UHVXOWV� LQ�FRQFHQWUDWLRQ�VWUDWLILFDWLRQ�RI�WKH�IRUPHG�VROLG�VROXWLRQ�IROORZHG�E\�IRUPDWLRQ
RI� WZR� VROLG� VROXWLRQV� ZLWK� GLIIHUHQW� VWDEOH� HOHPHQWDO� FRPSRVLWLRQ�� 7KH� GLIIXVLRQ� FRHIIL�
FLHQW� LQ�QDQR�FU\VWDOOLQH�:±7L� FRQGHQVDWHV�KDV� EHHQ� HVWLPDWHG�DQG�PRGHOV�GHVFULELQJ� WKH
IRUPHG�FRQGHQVDWH�VWUXFWXUH�VWDWH�DUH�SURSRVHG�
j°°ãË�ºmÈÓº�mãÒ«ÓÒË�ªãËäËÓ�Óº�º�°º°�ÈmÈ�Ò��Ëä¹Ë¯È��¯©�º°ÈÎ�ËÓÒ«�ÒºÓÓº�¹ãÈÏäËÓ�
Ó©²� }ºÓ�ËÓ°È�ºm� °Ò°�Ëä©�:±7L� ÓÈ� Ò²� °�¯�}��¯��� °�°�¯�}��¯Ó©Ë� ²È¯È}�˯Ұ�Ò}Ò� Ò
Óȹ¯«ÎËÓÓºË�°º°�º«ÓÒË���°�ÈÓºmãËÓº����º�}¯Ò°�ÈããÒ�˰}ºË�°º°�º«ÓÒË�m°Ë²�ÁÈÏ��Áº¯äÒ�
¯�Ë䩲�m�¹¯º�˰°Ë�º°ÈÎ�ËÓÒ«��ÈÏÒ¯�Ë�°«�ÓÈ�|¡z�}¯Ò°�ÈããÒ�˰}º®�¯Ë�Ë�}Ë�DÜ:��sÈ
ÓÈ�Èã Ó©²�°�È�Ò«²�Áº¯äÒ¯ºmÈÓÒ«��m˯�º�º�¯È°�mº¯È�¹¯Ò�º�Óº°Ò�Ëã Óº�äÈãºä�°º�˯ÎÈ�
ÓÒÒ�ÏÈäË�È
�Ò²�È�ºäºm��Ò�ÈÓÈ�m�¯Ë�Ë�}Ë� ��Ü���È�����¹¯ºÒ°²º�Ò��º¯ÒËÓ�Ò¯ºmÈÓÓ©®
¯º°�� }¯Ò°�ÈããÒ�ºm� °� ¹ãº°}º°�
� ������� ¹È¯ÈããËã Óº®� ¹ºm˯²Óº°�Ò� }ºÓ�ËÓ°È�ÒÒ�� �¯Ò
ºãËË� m©°º}ºä� °º�˯ÎÈÓÒÒ� m� ¯Ë�Ë�}Ë� È�ºäºm� �Ò�ÈÓÈ� Áº¯äÒ¯�
�°«� °Òã Óº�ËÁº¯äÒ¯º�
mÈÓÓ©Ë�}¯Ò°�ÈããÒ�©��:�±[��7L[���m˯�º�º�¯È°�mº¯È�°�Ó˺ã �º®�°�˹ËÓ
�°ºm˯�ËÓ°�mÈ�Ë}°��¯©� °� ¹ãº°}º°�
� ������ }¯Ò°�ÈããÒ�˰}º®� ¯Ë�Ë�}Ò�� ¹È¯ÈããËã Óº®� ¹ºm˯²Óº°�Ò
¯º°�È��{�ª�ºä�°ã��ÈË��mËãÒ�ËÓÒË��Ëä¹Ë¯È��¯©�º°ÈÎ�ËÓÒ«�º������&��º�����&�¹¯Òmº�Ò��}
}ºÓ�ËÓ�¯È�ÒºÓÓºä�� ¯È°°ãºËÓÒ
�Áº¯äÒ¯�Ëäº�º� �m˯�º�º� ¯È°�mº¯È����º� °º¹¯ºmºÎ�ÈË�°«
º¯ÈϺmÈÓÒËä��m�²��m˯�©²�¯È°�mº¯ºm�°�¯ÈÏãÒ�È
�Òä°«�°�ÈÒã Ó©ä�ªãËäËÓ�Ó©ä�°º°�È�
mºä�� �¯ºmË�ËÓÈ� º�ËÓ}È� }ºªÁÁÒ�ÒËÓ�È� �ÒÁÁ�ÏÒÒ� m� ÓÈÓº}¯Ò°�ÈããÒ�˰}Ò²� }ºÓ�ËÓ°È�Ȳ
°Ò°�Ëä©�:±7L�Ò�¹¯Ë�ãºÎËÓ©�äº�ËãÒ��ã«�º¹Ò°ÈÓÒ«�Áº¯äÒ¯�Ëäº�º�°�¯�}��¯Óº�º�°º°�º«�
ÓÒ«�}ºÓ�ËÓ°È�ºm�
$� KLJK� LQWHUHVW� LQ�:±7L� ILOP� V\VWHP� LV
GXH�ILUVW�RI�DOO� WR�WKH�JRRG�SURPLVHV�RI�WKH
DSSOLFDWLRQ� WKHUHRI� LQ� PLFURHOHFWURQLFV�� IRU
LQVWDQFH�� DV� GLIIXVLRQ� EDUULHUV� >��@�� 7KH
EHVW�HOHFWULFDO�FKDUDFWHULVWLFV�IRU�WKH�V\VWHP
�WKH� ORZHVW� HOHFWULFDO� UHVLVWLYLW\� RI� EDUULHU
OD\HU� OHVV� WKDQ� ��� P:�FP�� DUH� SURYLGHG� E\
FRQGHQVDWHV� FRQWDLQLQJ� ����� DW���:� DQG
�����DW���7L� >�@��$QRWKHU�SURPLVLQJ�ILHOG
LV�WKH�DSSOLFDWLRQ�RI�FRQGHQVHG�:±7L�PDWHUL�
DOV� DV� ELQGLQJ� OD\HU� LQ�PXOWL�OD\HUHG� ZHDU�
UHVLVWDQW� FRDWLQJV� >�@�� ,Q� WKLV� FDVH�� D� VXE�
VWDQWLDO� WKLFNQHVV� RI� EDUULHU� OD\HUV� ����� WR
����PP�� LQ� FRPELQDWLRQ� ZLWK� :±7L� OD\HU
WKLFNQHVV�RI�WKH�RUGHU�RI�PLFURPHWHUV�LQ�WKH
PXOWL�OD\HUHG� ZHDU�UHVLVWDQW� FRDWLQJV� LPSO\
D� VWURQJ� GHSHQGHQFH� RI� FRQGHQVDWH� IXQF�
WLRQDO� FKDUDFWHULVWLFV� RQ� LWV� VWUXFWXUH� DQG
)XQFWLRQDO�0DWHULDOV�����1R��������� ��������,QVWLWXWH�IRU�6LQJOH�&U\VWDOV
)XQFWLRQDO�PDWHULDOV������������� ���
SKDVH� VWDWH�� ,W� LV� ZHOO� NQRZQ� WKDW� LRQ�
SODVPD�FRQGHQVDWLRQ�UHVXOWV�LQ�IRUPDWLRQ�RI
VWUXFWXUH� DQG� SKDVH� VWDWH� GLIIHUHQW� IURP
WKRVH� H[SHFWHG� IRU� HTXLOLEULXP� IRUPDWLRQ
FRQGLWLRQV� >����@�� 7KXV�� WKH� DLP� RI� WKLV
ZRUN� ZDV� WR� VWXG\� WKH� IRUPDWLRQ� UHJXODUL�
WLHV� RI� VWUXFWXUH�SKDVH� DQG� VWUHVV� VWDWHV� RI
:±7L� FRQGHQVDWHV� DV� IXQFWLRQV� RI� WKHLU� HOH�
PHQWDO� FRPSRVLWLRQ� DQG� VXEVWUDWH� WHPSHUD�
WXUH� XQGHU� GHSRVLWLRQ�� 7KRVH� SUREOHPV� DUH
ERWK�RI�VFLHQWLILF�LPSRUWDQFH�LQ�WKH�ILHOG�RI
SK\VLFDO�PDWHULDO� VFLHQFH� RI� FRQGHQVHG� V\V�
WHPV�DQG�SUHFWLFDO�RQH�IRU�GHYHORSPHQW�RI�D
WHFKQLTXH� IRU� VWUXFWXUH� EDVHG� RSWLPL]DWLRQ
RI�FRQGHQVDWH�IXQFWLRQDO�FKDUDFWHULVWLFV�
,Q� WKLV� FRQQHFWLRQ�� WZR� FKDUDFWHULVWLF
FRQFHQWUDWLRQ�UDQJHV�ZHUH�VWXGLHG��7KH�ILUVW
LV������DW����:�DQG������DW����7L��7KDW
FRQFHQWUDWLRQ� UDQJH�� RQ� WKH� RQH� KDQG�� DO�
ORZV� WR� REWDLQ� LQWHQVH� HQRXJK� GLIIUDFWLRQ
OLQHV�IURP�VROLG�VROXWLRQ�ODWWLFH�QHFHVVDU\�WR
VWXG\� WKH� VWUXFWXUH� DQG� VXEVWUXFWXUH� FKDU�
DFWHULVWLFV�� DQG�� RQ� WKH� RWKHU� KDQG�� DOORZV
WR� DQDO\]H� WKH� LQLWLDO� VWDJHV� RI� VROLG� VROX�
WLRQ�IRUPDWLRQ�GXH�WR�UHODWLYHO\�ORZ�FRQFHQ�
WUDWLRQ�RI�WLWDQLXP�LPSXULW\�DWRPV�LQ�WXQJ�
VWHQ�EDVLF� EFF� ODWWLFH� �WXQJVWHQ� DWRPLF�FRQ�
FHQWUDWLRQ� ZDV� ILYH� WLPHV� VR� KLJK� DV
WLWDQLXP�RQH���7KH�VHFRQG�UDQJH� ������DW�
��:�DQG������DW����7L���SURYLGHV�WKH�EHVW
IXQFWLRQDO� SURSHUWLHV� RI� WKH� V\VWHP�� DV� LW
ZDV�IRXQG�E\�VHYHUDO�DXWKRUV�>����@��WKXV��LW
LV� RI� LQWHUHVW� IURP�SUDFWLFDO� SRLQW� RI�YLHZ�
0RUHRYHU�� WKH� FRQFHQWUDWLRQ� UDQJHV� ZHUH
FKRVHQ� DFFRUGLQJ� WR� SKDVH� GLDJUDP� VR� WKDW
WR� JHW� LQ� WKH� ILUVW� FDVH� LQWR� VROLG� VROXWLRQ
DUHD�VWDEOH�WR�VSLQRGDO�GHFRPSRVLWLRQ��XS�WR
��� DW����7L��� ZKLOH� LQ� WKH� VHFRQG� FDVH�� WR
JHW� LQWR� WKH� DUHD� RI� VROLG� VROXWLRQ� VSLQRGDO
GHFRPSRVLWLRQ�IROORZHG�E\�FRQFHQWUDWLRQ�RU�
GHULQJ�>��@��
7KH� ILOPV� ZHUH� SUHSDUHG� E\� PDJQHWURQ
VSXWWHULQJ� WKH� FRPSRVHG� WDUJHW� �FDVW� WXQJ�
VWHQ� GLVF� �DW� OHDVW� ����� SXULW\�� RI� ���PP
LQ� GLDPHWHU� DQG� LPSRVHG� 7L� VHFWRUV�� XQGHU
RSHUDWLQJ� SUHVVXUH� RI� DUJRQ� DWPRVSKHUH� RI
���� 3D�� $SSOLFDWLRQ� RI� FRPSRVHG� WDUJHW
UDWKHU�WKDQ�VLQWHUHG�RQH�LV�H[SODLQHG�E\�WKH
NQRZQ� IDFW� WKDW� LW� SURYLGHV� SXUHU� FRQGHQ�
VDWH�FRPSRVLWLRQ� >�@��%HIRUH�GHSRVLWLRQ��WKH
VXEVWUDWHV�ZHUH�KROG�LQ�YDFXXP�RI�������3D
DW� ����&� IRU� DQ� KRXU� WR� UHPRYH� JDVHRXV
LPSXULWLHV�IURP�WKH�VXUIDFH��7KH�GHSRVLWLRQ
UDWH� ZDV� QHDU� ���� QP�V��� $V� VXEVWUDWHV�
SODWHV� RI� JODVV� FHUDPLFV� DQG� VLQJOH�FU\VWDO�
OLQH� VLOLFRQ� ZHUH� XVHG�� 7KH� FRDWLQJ� WKLFN�
QHVV�ZDV�����WR�����PP��7KH�VXEVWUDWH�WHP�
SHUDWXUH�ZDV�YDULHG�IURP�����WR�����&�
7KH� ;�UD\� GLIIUDFWLRQ� ZDV� H[DPLQHG
XVLQJ� D�'521��� DSSDUDWXV�ZLWK�&XÜ.D� UD�GLDWLRQ�LQ�GLVFUHWH�UHJLPH�RI�VFDWWHULQJ�UHJ�
LVWUDWLRQ� ZLWK� VFDQQLQJ� VWHS� LQ� WKH� UDQJH
'��T�� RI� ����� WR� ������� GHSHQGLQJ� RQ� WKH
KDOI�ZLGWK� DQG� LQWHQVLW\� RI� GLIIUDFWLRQ
OLQHV��([SRVXUH� WLPH�ZDV���� WR�����V� IRU�D
SRLQW�� 'LIIUDFWLRQ� SURILOHV� ZHUH� VHSDUDWHG
XVLQJ� WKH� VRIWZDUH� GHYHORSHG� DW� 178
�.K3,��� 9ROXPH� IUDFWLRQV� RI� SKDVHV� LQ� WKH
ILOP� ZDV� FDOFXODWHG� XVLQJ� D� VWDQGDUG� WHFK�
QLTXH�WDNLQJ�LQWR�FRQVLGHUDWLRQ�WKH�LQWHJUDO
LQWHQVLW\� DQG� UHIOHFWLYLW\� RI� VHYHUDO� OLQHV
IRU� HDFK� SKDVH� >��@�� 7KH� VWUXFWXUH� SHUIHF�
WLRQ�GHJUHH��Z��ZDV�HVWLPDWHG�E\�PHDVXULQJ
WKH�KDOI�PD[LPXP�IXOO�ZLGWK�RI�GLIIUDFWLRQ
OLQH�UHFRUGHG� LQ�T�VFDQQLQJ�UHJLPH��)RU�WKH
DQDO\VLV�� GLIIUDFWLRQ� OLQHV� IURP� ������ DQG
������FU\VWDOORJUDSKLF�SODQHV�ZHUH�FKRVHQ�
7KH�UHVLGXDO�HODVWLF�VWUDLQ�OHYHO�DQG�FU\V�
WDOOLQH� ODWWLFH� SDUDPHWHUV� IRU� QRQ�VWUDLQHG
VWDWH�ZHUH�FDOFXODWHG�XVLQJ���VLQ�\�SORWV�
7KH�UHIOHFWLRQV�IURP�������SODQHV�DW�WLOW�DQ�
JOHV� \� RI� ��� ���� ������ ���� ���� DQG� �����
ZHUH�FRQVLGHUHG��,Q�EFF�ODWWLFH�LQKHUHQW�ERWK
WR� WXQJVWHQ� DQG� WXQJVWHQ� EDVHG� VROLG� VROX�
WLRQ��WKH���������DQG�����DQJOHV�FRUUHVSRQG
WR�WKH�DQJOHV�EHWZHHQ�������DQG�������SODQHV
ZLWK�LQYHUVLRQ��ZKLOH������DQG��������WR�WKH
DQJOHV� EHWZHHQ� ������ DQG� ������� $W� FRUUH�
VSRQGLQJ� ILOP� JURZWK� WH[WXUH�� VXFK� FKRLFH
RI�\� DQJOHV� DOORZHG� WR� VHSDUDWH� WKH� HIIHFWV
FKDUDFWHULVWLF� RI� GLIIHUHQW� FU\VWDOOLWH� RULHQ�
WDWLRQ�V\VWHPV��7R�VWXG\�WKH�VWUDLQ�GLVWULEX�
WLRQ� KRPRJHQHLW\� RYHU� WKH� FRQGHQVDWH� YRO�
XPH�� WKH�PHDVXUHPHQWV�ZHUH�PDGH� ERWK� WR
WRZDUGV��\�DQG�Ü\�DQJOHV�
7KH� OLQHDU� DSSUR[LPDWLRQ� RI� H[SHULPHQ�
WDO� SRLQWV� LQ� �ÈÜVLQ�\��SORW� JLYHV� VWUDLQ
YDOXH�H�DYHUDJHG�RYHU�WKH�FRDWLQJ�WKLFNQHVV
IURP�WKH�H[SUHVVLRQ�
H� �D\ �����D\ �D� � �D__���DAD�
ZLWK�DA�LV�WKH�ODWWLFH�SDUDPHWHU�LQ�GLUHFWLRQ
QRUPDO� WR� UHIOHFWLQJ� SODQH� �\� ������ D__�� WKH
ODWWLFH�SDUDPHWHU�LQ�WKH�ILOP�SODQH��\� ������
��� WKH� ODWWLFH� SDUDPHWHU� LQ� QRQ�VWUHVVHG
VWDWH�� )URP� WKH� �ÈÜVLQ�\��SORWV�� WKH� YDOXH
��ZDV� GHWHUPLQHG�DVVXPLQJ� LVRWURSLF� V\P�PHWULF� SODQH�VWUHVVHG� VWDWH�� ,W� ZDV� FDOFX�
ODWHG� DW� \�� YDOXH� FRUUHVSRQGLQJ� WR� XQ�VWUDLQHG�VHFWLRQ�RI�VWUDLQLQJ�HOOLSVRLG���
VLQ�\�� � �Q����Q�
2�9�6RERO����3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG����
��� )XQFWLRQDO�PDWHULDOV�������������
7KH� FRDWLQJ� HOHPHQWDO� FRPSRVLWLRQ� ZDV
GHWHUPLQHG� E\� ;�UD\� IOXRUHVFHQW� DQDO\VLV
XVLQJ� �63587�� DSSDUDWXV� �SURGXFHG� E\
�8NUUHQWJHQ���8NUDLQH���7KH�UDGLDWLRQ�IURP
D��VKRRW�WKURXJK�� W\SH�;�UD\� WXEH�ZLWK�$J
DQRGH�DW�H[FLWDWLRQ�YROWDJH����N9�ZDV�XVHG
DV�SULPDU\�H[FLWLQJ�UDGLDWLRQ����
� � � $FFRUGLQJ� WR� SKDVH� GLDJUDP� >�@�� WKH�:
VROXELOLW\�LQ�DÜ7L�GRHV�QRW�H[FHHG�����DW����
ZKLOH�WLWDQLXP�DWRPV�DUH�FRPSOHWHO\�VROXEOH
LQ�WXQJVWHQ�EFF�ODWWLFH�E\�VXEVWLWXWLRQ�W\SH�
,Q� WKLV� FRQQHFWLRQ�� SUHGRPLQDQW� IRUPDWLRQ
RI�EFF�ODWWLFH�EDVHG�VROLG�VROXWLRQ�VKRXOG�EH
H[SHFWHG�LQ�LRQ�SODVPD�FRQGHQVDWHV��$FFRUG�
LQJ� WR�;�UD\� SKDVH� DQDO\VLV� GDWD�� WKH� FRDW�
LQJV� FRQVLVWLQJ�RI� DOPRVW�SXUH� WXQJVWHQ�DÜ
:� DQG� VROLG� VROXWLRQ� �:�±[�� 7L[�� EDVHG� RQDÜ:�EFF�ODWWLFH�DUH�IRUPHG�LQ�WKH�ILUVW�FRQ�
FHQWUDWLRQ� UDQJH� �)LJ����� FXUYHV� ��� � ��� 7KH
UHODWLYHO\�ORZ�GLVVROXWLRQ�RI�WLWDQLXP�DWRPV
UHVXOWV� LQ� IRUPDWLRQ� RI� QRW� RQO\� WH[WXUH
ZLWK� FORVHVW� SDFNHG�SODQHV� ������SDUDOOHO� WR
JURZWK� VXUIDFH� LQKHUHQW� WR� LRQ�SODVPD� FRQ�
GHQVDWHV� >��@�� EXW� RI� DQRWKHU� WH[WXUH� ZLWK
������W\SH�SODQHV�SDUDOOHO�WR�JURZWK�VXUIDFH�
7KH�SHUIHFWLRQ�GHJUHH�RI� WH[WXUH�ZLWK�FU\V�
WDOOLWH� ������ SODQHV� SDUDOOHO� WR� WKH� JURZWK
VXUIDFH� ZDV� VXEVWDQWLDOO\� KLJKHU� WKDQ� WKDW
IRU� ������ RQH�� WKDW� LV� PDQLIHVWHG� DV� GH�
FUHDVHG� Z� �7DEOH����� 7KH� YROXPH� FRQWHQW
UDWLR� RI� ������ WR� ������ WH[WXUHG� FU\VWDOOLWHV
LQ� WKH�VDPSOHV�YDULHG� IURP�������WR������
DW� WKH� VXEVWUDWH� WHPSHUDWXUH� LQFUHDVLQJ
IURP�����WR�����&��UHVSHFWLYHO\��7DEOH����
7KH�VROLG�VROXWLRQ�OLQH�PD[LPXP�DYHUDJH
SRVLWLRQV� REWDLQHG� DIWHU� VHSDUDWLRQ� RI� FRP�
SOH[�GLIIUDFWLRQ�SURILOH�DUH�FORVH�WR�RQH�DQ�
RWKHU� ERWK� IRU� 7V� �����&� DQG� 7V� �����&�7KLV� SRVLWLRQ� FRUUHVSRQGV� WR� WKH� ODWWLFH� SD�
UDPHWHU�DA� �������QP��7R�FRPSDUH�WKH�RE�WDLQHG� ODWWLFH� SDUDPHWHU�ZLWK� FRQFHQWUDWLRQ
RI� WLWDQLXP� DWRPV� GLVVROYHG� LQ� VROLG� VROX�
WLRQ� ODWWLFH�� LW� LV�QHFHVVDU\� WR� WDNH� LQWR�DF�
FRXQW� WKH� HIIHFW� RI� FRQGHQVDWH� VWUHVV� VWDWH
RQ�WKH�GLIIUDFWLRQ�OLQH�SRVLWLRQV��7KH�UHVXOWV
RI� VXFK� LQYHVWLJDWLRQV� ZLOO� EH� JLYHQ� LQ� WKH
VHFRQG�SDUW�RI�WKH�ZRUN��,W�VKRXOG�EH�QRWHG
WKDW� WKH� FRDWLQJ� HOHPHQWDO� FRPSRVLWLRQ� DF�
FRUGLQJ� WR� WKH� ;�UD\� IOXRUHVFHQW� DQDO\VLV
GDWD� VKRZV� WKDW� WKH� FRDWLQJ� FRPSRVLWLRQ
YDULHV� IURP� DERXW�:�7L� ������� WR�:�7L�
������ DV� WKH� VXEVWUDWH� WHPSHUDWXUH� LQ�
FUHDVHV��
:LWKLQ� WKH� VHFRQG� FRQFHQWUDWLRQ� UDQJH�
WKH�FRDWLQJ�PDLQ�SKDVH�FRPSRQHQW�LV��:�±[�7L[�� VROLG� VROXWLRQ� �)LJ����� FXUYHV� ��� ��� ���7KH� FRQGHQVDWLRQ� WHPSHUDWXUH� HOHYDWLRQ� UH�
VXOWV� LQ� LQFUHDVLQJ� UHODWLYH�YROXPH� IUDFWLRQ
RI� VROLG� VROXWLRQ� LQ� WKH� FRDWLQJ�� ZKLOH� LWV
GLVVRFLDWLRQ�LQWR�WZR�FKDUDFWHULVWLF�FRPSRVL�
WLRQV� ZLWKLQ� WKH� VDPH� W\SH� RI� EFF� ODWWLFH
)LJ����� 'LIIUDFWLRQ� VSHFWUXP� IUDJPHQWV� IRU
:±7L� ILOPV� RI� WKH� ILUVW� FRQFHQWUDWLRQ� UDQJH
����WR����DW����7L��SUHSDUHG�DW�VXEVWUDWH�WHP�
SHUDWXUHV���V������&������DQG�����&������DQG�IRUWKH� ILOPV� RI� WKH� VHFRQG� FRQFHQWUDWLRQ� UDQJH
����WR����DW���7L��SUHSDUHG�DW��V� �����&� ��������&� ����� ����&� ����� 7KH� OHWWHUV� � DQG� E
LQGLFDWH� WKH� SRVLWLRQV� RI� WZR� FKDUDFWHULVWLF
PD[LPD�IRU��:�±[��7L[��VROLG�VROXWLRQ�
7DEOH���� 3KDVH� FRPSRVLWLRQ�� FU\VWDOOLWH� WH[WXUH� GHJUHH� �Z��� VXEVWUXFWXUH� FKDUDFWHULVWLFV� �PLFUR�
VWUDLQ� H�� DQG� FU\VWDOOLWH� VL]H� /�� IRU�:±7L� FRQGHQVDWHV� LQ� WKH� ILUVW� FRQFHQWUDWLRQ� UDQJH� ���� WR
���DW���7L���
7V���& 3KDVH 7H[WXUH &RQWHQW�
YRO�� H��� /��QP
SODQH Z��GHJUHHV
��� DÜ: ����� �� �� ��� ��
����� ��� �� ���� ��
�:�±[�7L[� ����� !�� �� ��� ��
��� DÜ: ����� �� �� ��� ��
����� �� �� ��� ��
�:�±[�7L[� ����� !�� �� ��� ��
2�9�6RERO����3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG����
)XQFWLRQDO�PDWHULDOV������������� ���
EHFRPHV� MXVW� REYLRXV� IURP� WKH� GLIIUDFWLRQ
OLQH�VHSDUDWLRQ�LQWR�WZR�FRPSRQHQWV��LQ�)LJ�
���WKH�SRVLWLRQV�DUH�PDUNHG�E\�DUURZV�D�DQG
E���6XFK�VLWXDWLRQ� LV� LQKHUHQW� LQ�VROLG�VROX�
WLRQV� DIWHU� FRQFHQWUDWLRQ� ODPLQDWLRQ�GXH� WR
VSLQRGDO� GLVVRFLDWLRQ� PHFKDQLVP� >��@�� 7KH
FRKHUHQWO\� ERQGHG� DUHDV� RI� VROLG� VROXWLRQV
ZLWK� GLIIHUHQW� DWRPLF� UDWLRV� DUH� IRUPHG� LQ
WKLV�FDVH��WKLV�GLIIHUHQFH�HQKDQFHV�WKHQ�DV�D
UHVXOW�RI�GLVVRFLDWLRQ�DQG�DWRPLF�UHDUUDQJH�
PHQW�GXH� WR�DVFHQGLQJ�GLIIXVLRQ�PHFKDQLVP�
,Q� )LJ����� RQH� H[DPSOH� RI� FRPSOH[� GLIIUDF�
WLRQ�SURILOH�VHSDUDWLRQ�LV�VKRZQ��ZKHUH�WZR
SURQRXQFHG�GLIIUDFWLRQ�PD[LPD�RI� VROLG� VR�
OXWLRQ� DUH� VHHQ� �FXUYHV� ��� �� LQ� )LJ����� LQ
SRVLWLRQV�FRUUHVSRQGLQJ�OLNHO\�WR�WZR�PHWDV�
WDEOH� FRQFHQWUDWLRQ� VWDWHV�� 7KH� FXUYH� �� LQ
)LJ����FRUUHVSRQGV�WR�DÜ:�������GLIIUDFWLRQ�OLQH�
,Q�7DEOH����WKH�GDWD�REWDLQHG�E\�FDOFXOD�
WLRQ� RI� YROXPH� SKDVH� FRQWHQW� LQ� WKH� ILOPV
GHSHQGLQJ�RQ�FRQGHQVDWLRQ� WHPSHUDWXUH�DUH
VXPPDUL]HG�� ,W� LV� VHHQ� WKDW� WKH� FRQGHQVD�
WLRQ�WHPSHUDWXUH�LQFUHDVH�UHVXOWV�LQ�UHODWLYH
GHFUHDVH�RI�WKH�SXUH�DÜ:�SKDVH�FRQWHQW�DQG
LQFUHDVLQJ� FRQWHQW� RI� �:�±[��7L[�� VROLG� VROX�WLRQ� EDVHG� WKHUHRQ�� $� SURQRXQFHG� VHSDUD�
WLRQ� RI� �:�±[�� 7L[�� VROLG� VROXWLRQ� LQWR� WZRVWDEOH�FRPSRQHQWV�LV�REVHUYHG��$FFRUGLQJ�WR
;�UD\� IOXRUHVFHQFH� GDWD�� DYHUDJH� DWRPLF
UDWLR�FKDQJHG�IURP�:�7L� �������DQG������
DW� 7V� ����� DQG� ����&� WR�:�7L� ������� DW�V� �����&�7KH� VXEVWUXFWXUH� FKDUDFWHULVWLFV� DQD�
O\]HG� XVLQJ� WZR� UHIOHFWLRQ� RUGHUV� IURP
^���`��^���`�SODQHV�RI�WXQJVWHQ�DQG�^���`�RI
WXQJVWHQ� EDVHG� VROLG� VROXWLRQ� HYLGHQFHG
PLFUR�VWUDLQV� GHYHORSHG� LQ� WKH� GLUHFWLRQ� RI
ILOP�IRUPLQJ�SDUWLFOH�LQFLGHQFH��QRUPDOO\�WR
JURZWK�SODQH���IURP��������IRU�7V� �����&�
WR� ���� �� �IRU� 7V� �����&�� IRU� FU\VWDOOLWHVZLWK� SUHGRPLQDQW� RULHQWDWLRQ� ������� DQG
IURP� ����� �� �7V� �����&�� WR� ���� �� �7V� ����&��IRU�FU\VWDOOLWHV� ������RULHQWHG�SDUDO�
OHO� WR� WKH� JURZWK� VXUIDFH� LQ� WKH� VDPSOHV
ZLWK�UHODWLYHO\�ORZ�WLWDQLXP�DWRPLF�FRQWHQW
��VW� VHULHV�� �7DEOH�����)RU�DÜ:�SKDVH��FU\V�
WDOOLWH�VL]H�ZDV�IRXQG�WR�EH�DOPRVW�WKH�VDPH
���� WR� ��� QP�� IRU� ERWK� WH[WXUH� W\SHV�� 7KH
VROLG� VROXWLRQ� FU\VWDOOLWHV� ZHUH� PRUH
VWUDLQHG��7KHLU�PLFUR�VWUDLQ�OHYHO�ZDV�DERXW
�������ZKLOH�FU\VWDOOLWH�VL]H�GLG�QRW�H[FHHG
���WR����QP��)RU�WKH�VHFRQG�VDPSOH�VHULHV�
LW� LV� MXVW� WKH� VROLG� VROXWLRQ� FU\VWDOOLWHV
�DERXW� ������ IRU��V� ����� DQG� ����&�� DQG����WR������IRU��V� �����&��WKDW�ZHUH�PRVWVWUDLQHG�� WRR�� EXW� WKRVH�KDG� ODUJHU� DYHUDJH
VL]HV�IURP����WR�����QP��7DEOH����� ,Q�DÜ:
SKDVH�� WKH�PLFUR�VWUDLQ� OHYHO�ZDV� UHODWLYHO\
)LJ����� 7KH� UHVXOW� RI� SURILOH� VHSDUDWLRQ� IRU
;�UD\� GLIIUDFWLRQ� OLQH� ���� LQWR� WKH� FRPSR�
QHQWV� ���������� DQG�RYHUDOO� FRQYROXWLRQ� OLQH
���� IRU� D� FRQGHQVDWH� SUHSDUHG� DW��V� �����&
�&7L|���DW����
7DEOH���� 3KDVH� FRPSRVLWLRQ�� FU\VWDOOLWH� WH[WXUH� GHJUHH� �Z��� VXEVWUXFWXUH� FKDUDFWHULVWLFV� �PLFUR�
VWUDLQ� H�� DQG� FU\VWDOOLWH� VL]H� /�� IRU� :±7L� FRQGHQVDWHV� LQ� WKH� VHFRQG� FRQFHQWUDWLRQ� UDQJH
���������DW���7L���
7V���& 3KDVH 7H[WXUH &RQWHQW�
YRO�� H��� /��QP
SODQH Z��GHJUHHV
��� DÜ: ����� !�� �� ��� �
�:�±[�7L[���W\SH�E
����� �� �� ��� ��
�:�±[�7L[���W\SH�D ����� !�� �� ��� ��
��� DÜ: ����� !�� � ��� �
�:�±[�7L[���W\SH�D ����� �� �� ��� ���
��� DÜ: ����� !�� � ��� �
�:�±[�7L[���W\SH�D ����� �� �� ��� ���
�:�±[�7L[���W\SH�E ����� �� �� ��� ���
��WKH�W\SH�LV�LQGLFDWHG�DFFRUGLQJ�WR�GLIIUDFWLRQ�OLQH�SRVLWLRQ�LQ�)LJ�����
2�9�6RERO����3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG����
��� )XQFWLRQDO�PDWHULDOV�������������
ORZ� ��������������IRU�DOO�WKH�VDPSOHV��ZKLOH
FU\VWDOOLWH� VL]H� EHLQJ� VXEVWDQWLDOO\� OHVV� DQG
GLG�QRW�H[FHHG���WR���QP�
6WXG\LQJ� WKH� PDFUR�VWUDLQHG� VWDWH� E\
�ÈÜVLQ�\���PHWKRG�LQ�WKH�FRQGHQVDWHV�RI�WKH
ILUVW�FRQFHQWUDWLRQ�UDQJH�KDV�VKRZQ�WKDW�DÜ
:�SKDVH�FU\VWDOOLWHV�ZHUH�VXEMHFWHG�WR�FRP�
SUHVVLYH�PDFUR�VWUDLQV��7KH�SUDFWLFDOO\�V\P�
PHWULF�IRUP�RI�WKH�SORW�REWDLQHG�IRU�PDFUR�
VWUDLQ� FDOFXODWLRQV� E\� �ÈÜVLQ�\��� PHWKRG
XVLQJ�VFDQV�ERWK�LQ��\�DQG�Ü\�DQJOH�UDQJHV
LQGLFDWHV� DSSOLFDELOLW\� RI� SODQH�VWUHVVHG
VWDWH�PRGHO�WR�WKH�REMHFWV�XQGHU�VWXG\��7KH
VWUDLQ� YDOXH� ZDV� ���� WR� ������ �WKH� VLJQ
��� LQGLFDWHV� FRPSUHVVLYH� VWUDLQ�� IRU� �����
WH[WXUHG�FU\VWDOOLWHV�REWDLQHG� LQ� WKH����� WR
����&� FRQGHQVDWLRQ� WHPSHUDWXUH� UDQJH�
ZKLOH�IRU�������WH[WXUHG�FU\VWDOOLWHV�� LW�ZDV
D� OLWWOH� ORZHU� ����� WR���������7KH� ODWWLFH
SDUDPHWHU� FDOFXODWLRQ� IRU� QRQ�VWUDLQHG� VHF�
WLRQ� KDV� VKRZQ� D� YDOXH� È�� ��������� WR��������QP� LQ�DÜ:� SKDVH�� WKDW� LV� FORVH� WR
WKH� UHIHUHQFH� YDOXH� IRU� WKH� EXON� >��@�� 7KH
ODWWLFH� SDUDPHWHU� RI� WXQJVWHQ� FU\VWDOOLWHV
ZLWK� ������ WH[WXUH� ZDV� LQFUHDVHG� D� OLWWOH�
������� QP� IRU��V� �����&�� DQG� ������� QPIRU��V� �����&��$FFRUGLQJ�WR�GDWD�RI�>�@�DQGDVVXPLQJ� 9HGDUG� UXOH� WR� EH� YDOLG� IRU� WKH
ODWWLFH�SDUDPHWHU�YDULDWLRQ��WKH�REWDLQHG�SD�
UDPHWHU�FKDQJH�LQ�QRQ�VWUDLQHG�VHFWLRQ�LQGL�
FDWHV� GLVVROXWLRQ� RI� �� DQG� ��� �� WLWDQLXP
DWRPV��UHVSHFWLYHO\�LQ�WXQJVWHQ�ODWWLFH�
,Q� WKH� VHFRQG� VDPSOH� VHULHV� ZLWK� KLJK
FRQWHQW� RI� WLWDQLXP� LPSXULW\� DWRPV�� WKH
PDFUR�VWUDLQ� FRXOG� EH� GHWHUPLQHG� E\
�ÈÜVLQ�\��� PHWKRG� RQO\� IRU� VROLG� VROXWLRQ
FRPSRQHQW��,Q�WKH�VROLG�VROXWLRQ�FU\VWDOOLWHV
RI� FRQGHQVDWH� SUHSDUHG� DW� �V� �����&�� WKHPDFUR�VWUDLQ� ZDV� IRXQG� WR� EH� FRPSUHVVLYH
DQG� WR� DPRXQW� ���� ��� ,Q� WKLV� FDVH�� WKH
ODWWLFH� SDUDPHWHU� LQ� QRQ�VWUHVVHG� VHFWLRQ
ZDV� �� �������� QP� WKDW� FRUUHVSRQGV� WRFRPSRVLWLRQ�:����7L������ ,Q� FRQGHQVDWHV� RE�WDLQHG�DW��V� �����&��WKH�PDFUR�VWUDLQ�YDOXHZDV��������ZKLOH�SDUDPHWHU��� ��������QPFRUUHVSRQGLQJ�WR�FRPSRVLWLRQ�:����7L������$W�V� �����&��FRPSUHVVLYH�VWUDLQV�DERXW�������ZHUH� GHYHORSHG� LQ� D�W\SH� FU\VWDOOLWHV�� ZKLOH
WKH� ODWWLFH� SDUDPHWHU� �� ��������QP� FRUUH�VSRQGHG� WR�:����7L����� FRPSRVLWLRQ�� (VWLPD�WLRQV�PDGH� IURP�E�W\SH� OLQH�SRVLWLRQV�JLYHV
FKDUDFWHULVWLF� FRPSRVLWLRQ� :����7L����� IRUWKH�VHFRQG�VROLG�VROXWLRQ�FRPSRQHQW�
7KH�UHVXOWV�REWDLQHG�VKRZ�WKDW� LQ� LQLWLDO
VWDJHV�RI�VROLG�VROXWLRQ�IRUPDWLRQ��WLWDQLXP
DGGLWLRQ� LQWR� WXQJVWHQ� ODWWLFH� SURPRWHV
JURZLQJ� RI� WH[WXUHG� FU\VWDOOLWHV�ZLWK� �����
SODQHV�SDUDOOHO� WR� WKH�FRQGHQVDWLRQ�VXUIDFH�
6XFK� DUUDQJHPHQW� UHVXOWV� LQ� OHVV� VWUDLQHG
EDVLF� EFF� FU\VWDOOLQH� ODWWLFH�� WKDW� LV� PDQL�
IHVWHG� LQ� UHODWLYHO\� ORZ� PDFUR�� DQG� PLFUR�
VWUDLQLQJ� RI� VXFK� FU\VWDOOLWHV�� $V� WKH� RI
DWRPLF� WLWDQLXP�FRQWHQW� LQ� EFF� WXQJVWHQ� ODW�
WLFH�LQFUHDVHV�XS�WR�������DW��V� �����&���WKHFU\VWDOOLWH�������WH[WXUH�SHUIHFWLRQ�LV�ORVW�
,Q� WKH� ILOPV� FRQWDLQLQJ� DERXW� ��� WR
��� DW��� RI� 7L�� WKH� SUHVHQFH� RI� VHYHUDO
SKDVHV� DPRQJ� ZKLFK� WKHUH� DUH� ERWK� DOPRVW
SXUH� WXQJVWHQ� SKDVH� DQG� �:�±[�� 7L[�� VROLGVROXWLRQ� ZLWK� WLWDQLXP� FRQWHQW� H[FHHGLQJ
WKH� DYHUDJH� YDOXH� IRU� WKH� ILOP� DV� D� ZKROH
LQGLFDWHV� LQKRPRJHQHLW\� RI� HOHPHQWDO� FRP�
SRVLWLRQ�� 7KH� PRVW� SUREDEOH� FDXVH� RI� WKLV
IDFW�LV�WKH�OLPLWHG�WLWDQLXP�DWRPLF�GLIIXVLRQ
OHQJWK� GXULQJ� WKH� ILOP� JURZWK�� 7KH� GLIIX�
VLRQ�OHQJWK�FDQ�EH�HVWLPDWHG�XQGHU�DVVXPS�
WLRQ� WKDW� WKH� LPSXULW\� WLWDQLXP� DWRPV� GLI�
IXVH� IURP� WKH� LQWHU�FU\VWDOOLWH� DUHD� WR� WKH
EXON� RI� VROLG� VROXWLRQ� FU\VWDOOLWH�� WKH� VLWX�
DWLRQ� EHLQJ� FORVH� WR� UHDOLW\� IRU� WKH� FDVH� RI
PDJQHWURQ� VSXWWHULQJ� IURP� WKH� FRPSRVHG
WDUJHW�� $V� WKH� VXEVWUXFWXUH� DQDO\VLV� KDV
VKRZQ��IRU�FRQGHQVDWHV�SUHSDUHG�LQ�WKH�ILUVW
FRQFHQWUDWLRQ�UDQJH�����WR����DW���7L��DW��V �����&�� WKH� VROLG� VROXWLRQ� FU\VWDOOLWHV� KDG
WKH� DYHUDJH� VL]H� RI� ��� QP��8VLQJ� WKH� HVWL�
PDWLQJ� HTXDWLRQ� �/!� ��'W����� >��@�� ZKHUH
�/!� LV� D� KDOI� RI� WKH� JUDLQ� VL]H� DVVXPLQJ
HTXLD[LDO�JUDLQV��W��WKH�GLIIXVLRQ�WLPH�ZKLFK
LV� WDNHQ� ��� V� DFFRUGLQJ� WR� WKH� FRQGHQVDWH
JURZWK�UDWH��RQH�FDQ�REWDLQ�WKH�YROXPH�GLI�
IXVLRQ� FRHIILFLHQW� '|�������FP��V�� IRU
��� QP� VL]H� JUDLQV�� 7KLV� YDOXH� DJUHHV� ZHOO
ZLWK� RWKHU� UHVXOWV� RQ� DWRPLF� GLIIXVLRQ�PR�
ELOLW\� LQ� QDQR�FU\VWDOOLQH� FRQGHQVDWHV� >��@�
,W� LV�ZRUWK� WR� QRWH� WKDW� LQ� EXON�PLFURFU\V�
WDOOLQH� VWDWH�� VXFK�'� YDOXH� LQ�:±7L� V\VWHP
PD\� EH� DWWDLQHG� RQO\� DW� WHPSHUDWXUHV� H[�
FHHGLQJ������&�HYHQ�IRU�JUDLQ�ERXQGDU\�GLI�
IXVLRQ� >��@�� 6XFK�DQ�HIIHFW�RI�GLIIXVLRQ� FR�
HIILFLHQW� LQFUHDVH� LQ� QDQR�PDWHULDOV� LV� ZHOO
NQRZQ�DQG�LV�UHODWHG�WR�GHFUHDVLQJ�GLIIXVLRQ
DFWLYDWLRQ�HQHUJ\�LQ�WKH�JUDLQV�VPDOOHU�WKDQ
���QP�DV�FRPSDUHG�WR�PLFURPHWHU�VL]H�RQHV
>������@�
7KH� KLJK� GLIIXVLRQ�PRELOLW\� RI� WLWDQLXP
DWRPV� LQ� VXE�VXUIDFH� OD\HUV��DV�ZHOO� DV� VHF�
RQGDU\� DWRPLF� VSXWWHULQJ� IURP� WKH� VXUIDFH
DUH�WKH�PDLQ�SUREDEOH�FDXVHV�RI�DWRPLF�UDWLR
YDULDWLRQ� LQ� WKH� ILOP� DV� FRQGHQVDWLRQ� WHP�
SHUDWXUH� LQFUHDVHV�� ,I� DW� FRQGHQVDWLRQ� WHP�
SHUDWXUHV�����DQG�����&��DWRPLF�FRQFHQWUD�
WLRQ� FKDQJH� GRHV� QRW� H[FHHG� VHYHUDO� SHU
FHQW�� VXFK�YDULDWLRQ� DW��V� �����&� LV� DERXW�� �� KLJKHU� WKDW� DW� �V� �����&� �WXQJVWHQUHODWLYH�DWRPLF�FRQWHQW�LQFUHDVHV�IURP����WR
��� DW���� DFFRUGLQJ� WR� ;�UD\� IOXRUHVFHQFH
2�9�6RERO����3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG����
)XQFWLRQDO�PDWHULDOV������������� ���
DQDO\VLV��� 7KH� HOHPHQWDO� FRPSRVLWLRQ� FDOFX�
ODWLRQV�EDVLQJ�RQ�GDWD�RQ�SKDVH�YROXPH�FRQ�
WHQW�LQ�VROLG�VROXWLRQV�RI�GLIIHUHQW�FRPSRVL�
WLRQV�DW�VXFK�WHPSHUDWXUHV�UHVXOWV�LQ�VRPH�
ZKDW� ORZOHU� �QHDU� �� DW���� EXW� DV� ZHOO
UDWKHU� KLJK� UHODWLYH� WXQJVWHQ� DWRPLF� FRQ�
FHQWUDWLRQ�LQ�WKH�ILOP�XQGHU�VXEVWUDWH�WHP�
SHUDWXUH�LQFUHDVH�
,Q�WKH�ILOPV�ZLWK�KLJKHU�WLWDQLXP�DWRPLF
FRQWHQW�����WR����DW������YDULDWLRQV�RI�ERWK
VROLG� VROXWLRQ� YROXPH� FRQWHQW� DQG� DYHUDJH
FRQFHQWUDWLRQ� RI� LWV� FRPSRQHQWV� DUH� RE�
VHUYHG� GHSHQGLQJ� RQ� WKH� FRQGHQVDWLRQ� WHP�
SHUDWXUH�� $FFRUGLQJ� WR� ;�UD\� GLIIUDFWLRQ
GDWD�� WZR� WKH� PRVW� VWDEOH� VROLG� VROXWLRQV
FRQWDLQHG�DERXW����WR������DQG����WR�����
RI� WLWDQLXP�� UHVSHFWLYHO\�� $V� WKHVH� DWRPLF
UDWLRV� GR� QRW� FRUUHVSRQG� WR� DQ\� VSHFLDO
SRLQWV� LQ� HTXLOLEULXP� SKDVH� GLDJUDP�� DS�
SHDUDQFH�RI�VXFK�VWDEOH�FRQFHQWUDWLRQ�VWDWHV
PD\� EH� FDXVHG� E\� FRQFHQWUDWLRQ� RUGHULQJ
DQG� SKDVH� IRUPDWLRQ� SHFXOLDULWLHV� LQ� QRQ�
HTXLOLEULXP� QDQR�FU\VWDOOLQH� VWUXFWXUHV�� 7R
VXFK�SURFHVVHV��ILUVW�RI�DOO��WKH�VSLQRGDO�W\SH
FRQFHQWUDWLRQ� VWUDWLILFDWLRQ� VWLPXODWHG� E\
OLPLWHG�GLIIXVLRQ�PD\�EH�DWWULEXWHG�>������@��
$W�KLJK�DYHUDJH�WLWDQLXP�DWRPLF�FRQWHQW
LQ�WKH�ILOP�� LWV� OLPLWHG�GLIIXVLRQ� OHQJWK� LQ�
IOXHQFHV� YHU\� VWURQJO\�� WKDW� UHVXOWV� LQ� IRU�
PDWLRQ� RI� WKH� SUDFWLFDOO\� LPSXULW\�IUHH� GR�
PDLQV� RI� DÜ:� FU\VWDOOLWHV�� ,W� LV� RI� VLJQLIL�
FDQFH� WKDW�DV�WKH�FRQGHQVDWLRQ�WHPSHUDWXUH
LQFUHDVHV��ERWK�VSHFLILF�YROXPH�DQG�DYHUDJH
VL]H� RI� VXFK� GRPDLQV� LQ� WKH� PDWHULDO� GH�
FUHDVH��$V� WR� WKH� IDFW� RI� IRUPLQJ� VXFK� LP�
SXULW\�IUHH� GRPDLQV� XQGHU� FRQGHQVDWLRQ�� LW
LV� IDYRUHG� WR� D� JUHDW� H[WHQW� E\� VWURQJ�PH�
WDOOLF�ERQG�LQKHUHQW�LQ�WXQJVWHQ�DWRPV�WKDW
UHVXOWV�LQ�GHYHORSPHQW�RI�KLJK�PLFUR�VWUDLQ�
LQJ� LQ� WKH� FU\VWDOOLQH� ODWWLFH� GXH� WR� VXEVWL�
WXWLRQ� RI� WXQJVWHQ� DWRPV� E\� WLWDQLXP� RQHV
KDYLQJ�PXFK�ODUJHU�DWRPLF�UDGLXV��$V�D�UH�
VXOW�� DGGLWLRQDO� VWUDLQ� HQHUJ\� RFFXUULQJ� RQ
WKH�EDFNJURXQG�RI�FRQGHQVDWLRQ�FRPSUHVVLYH
PDFUR�VWUHVVHV� KLQGHUV� WKH� LPSXULW\� WLWD�
QLXP� DWRPLF� GLIIXVLRQ� IURP� VXE�ERXQGDU\
DUHD� LQWR� WKH� FU\VWDOOLWH� EXON� DQG� FDXVHV
PXOWL�]RQH�VWUXFWXUH�RI�WLWDQLXP�DWRPLF�GLV�
WULEXWLRQ�� 7KH� FDOFXODWLRQ� IRU� WKH� FRQGHQ�
VDWHV�RI�WKH�VHFRQG�FRQFHQWUDWLRQ�UDQJH����
WR����DW���7L��GHSRVLWHG�DW�WKH�KLJKHVW�WHP�
SHUDWXUH� �V� �����&� VKRZV� WKDW� ZLWK� RE�WDLQHG� '|�������FP��V� DQG� FKDUDFWHULVWLF
JURZWK� WLPH� RI� ���� QP� VL]H� FU\VWDOOLWHV
W|���� V�� ZH� REWDLQ� GLIIXVLRQ� OHQJWK
�/!|��� QP� ZKLFK� FRUUHVSRQGV� WR� WKH� VL]H
RI� DQ� H[WHUQDO� DUHD� �QHDU� JUDLQ� ERXQGDU\�
ZLWK� VWDEOH� FRPSRVLWLRQ� �:����� 7L����� PRVW
VDWXUDWHG� E\� WLWDQLXP� DWRPV� DFFRUGLQJ� WR
PXOWL�]RQH�JUDLQ�VWUXFWXUH�PRGHO�
7KXV�� EDVLQJ�RQ� WKH� UHVXOWV� RI� VWUXFWXUH
DQG� VXEVWUXFWXUH� DQDO\VLV� RI� WKH� FRQGHQ�
VDWHV�ZLWK�KLJK� FRQWHQW� RI� LPSXULW\�DWRPV�
WKH�PRVW�OLNHO\�VFKHPH�RI�JUDLQ�VWUXFWXUH�LV
WKUHH�OD\HUHG�RQH�LQFOXGLQJ�D���WR���QP�FHQ�
WHU� DUHD� RI� DOPRVW� SXUH� DÜ:�� IROORZHG� E\
WZR� SHULSKHU\� WXQJVWHQ� ODWWLFH� EDVHG� VWDEOH
�:�±[�� 7L[�� VROLG� VROXWLRQ� DUHDV� ZLWK� ORZHUDQG� KLJKHU� WLWDQLXP� FRQWHQW�� UHVSHFWLYHO\�
7KH�]RQH�RI�KLJK�WLWDQLXP�VDWXUDWLRQ�LV�SR�
VLWLRQHG�FORVHU�WR�JUDLQ�ERXQGDU\��ZKLOH�WKH
WLWDQLXP�GHSOHWHG�]RQH�EHLQJ�QHDUHU�WR�FHQ�
WUDO� JUDLQ� SDUW�� ,Q� WKH� ODVW� FDVH�� GXH� WR
OHVVHU� PLFUR�VWUDLQ� FDXVHG� E\� LPSXULW\
DWRPV�� WKH� GLIIXVLRQ� OHQJWK� PD\� EH� LQ�
FUHDVHG����
7KXV�� VWXGLHV� RI� WKH� WZR� FRQFHQWUDWLRQ
UDQJHV� RI� :±7L� V\VWHP� KDYH� VKRZQ� WKDW
ERWK� DW� ORZ� ���� WR� ������ WLWDQLXP� DWRPLF
FRQWHQW� DQG� DW� DERXW� ���� :�7L� UDWLR�� WKH
SKDVHV�EDVHG�RQ�DÜ:�EFF� FU\VWDOOLQH� ODWWLFH
DUH�IRUPHG� LQ�WKH�FRQGHQVDWH��7KH�SUHVHQFH
RI�IHZ�VXEVWLWXWLQJ�WLWDQLXP�DWRPV�LQ�WXQJ�
VWHQ�ODWWLFH����WR����DW����UHVXOWV�LQ�IRUPD�
WLRQ� RI� SUHGRPLQDQWO\� RULHQWHG� FU\VWDOOLWHV
ZLWK�������SODQHV�SDUDOOHO�WR�WKH�FRQGHQVDWH
JURZWK�VXUIDFH��7KH�IRUPDWLRQ�RI��:�±[��7L[�VROLG� VROXWLRQ� ZLWK� D� KLJK� FRQWHQW� RI� WLWD�
QLXP� VXEVWLWXWHG� WXQJVWHQ� VLWHV� LQ� WKH� ODW�
WLFH�UHVXOWV�LQ�KLJKHU�GLVRULHQWDWLRQ�RI�FU\V�
WDOOLWHV� DQG� GHYHORSPHQW� RI� VWURQJ� PLFUR�
VWUDLQV� XS� WR� ���� ��� 7KRXJK� WKH
FRQGHQVDWLRQ� WHPSHUDWXUH� HOHYDWLRQ� XS� WR
����&�UHVXOWV� LQ� UHODWLYH� LQFUHDVH� RI� �:�±[�7L[��VROLG�VROXWLRQ�VSHFLILF�YROXPH�FRQWHQW�DVFRPSDUHG�WR�SXUH�DÜ:�SKDVH��KRZHYHU��WKLV
GRHV� QRW� DOORZ� DYRLGLQJ� PXOWL�]RQH� VWUXF�
WXUH� LQKRPRJHQHLW\� RI� WKH� JUDLQV� GXH� WR
FRQFHQWUDWLRQ� VWUDWLILFDWLRQ� FDXVHG� E\� OLP�
LWHG�GLIIXVLRQ�PRELOLW\�RI�WLWDQLXP�DWRPV�
5HIHUHQFHV
� ���3��+�&KDQJ��+��<�/LX��-�$�.HHQDQ�HW�DO���-��$SSO�
3K\V��������������������
� ���-�%XUVFKLN�� %�$GROSKL�� )UHV��-��$QDO��&KHP��
�����������������
� ���3��+�&KDQJ�� +��0�&KDQJ�� +��<�/LX�
-�*�%RKOPDQ��-��0DW��6FL��������������������
� ���&�(�:LFNHUVKDP��-�(�3RROH��-�-�0XHOOHU��-��9DF�
6FL�� �7HFK��$��9DFXXP��6XUIDFHV�� DQG�)LOPV�
����������������
� ���9�*�*OHERYVN\�� (�$�0DUNDU\DQWV�� (�9�7LWRY�
0DW��/HWW�����������������
� ���$�3�6KSDN�� 2�,�1DNRQHFKQD�� <X�$�.XQ\WVN\�
2�9�6RERO���0HFKDQLFDO�3URSHUWLHV�RI�7LWDQLXP
%DVHG�&RDWLQJV�� ,03�1$68��.\LY� ������� >LQ
8NUDLQLDQ@�
2�9�6RERO����3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG����
��� )XQFWLRQDO�PDWHULDOV�������������
� ���-��3�3DOPTXLVW�� =V�&]LJDQ\�� 0�2GHQ� HW� DO��
7KLQ�6ROLG�)LOPV�����������������
� ���$�$�.R]±PD�� 2�9�6RERO��� (�$�6RERO±� HW� DO��
)XQFWLRQDO�0DWHULDOV����������������
� ���'LDJUDPV� RI� 6WDWH� IRU� 'RXEOH� 0HWDOOLF� 6\V�
WHPV�� HG�� E\� 1�3�/\DNLVKHY�� Y���� 0DVKLQRV�
WURHQLH��0RVFRZ��������>LQ�5XVVLDQ@�
����$�3�6KSDN�� 2�9�6RERO��� 3�*�&KHUHPVNR\� HW
DO��� 1DQRV\VWHPV�� 1DQRPDWHULDOV�� 1DQRWHFK�
QRORJLHV����������������
����6�6�*RUHOLN�� <X�$�6NDNRY�� /�1�5DVWRUJX\HY�
;�UD\� DQG� (OHFWURQ�2SWLF� $QDO\VLV�� 0,6,6�
0RVFRZ��������>LQ�5XVVLDQ@�
����2�9�6RERO���3K00����������������
����6�9HSUHN��0�*�-�9HSUHN�+HLMPDQ��3�.DUYDQN�
RYD�� -�3URFKD]ND�� 7KLQ� 6ROLG� )LOPV�� ����� �
�������
����3URSHUWLHV�RI�(OHPHQWV��Y����3K\VLFDO�3URSHU�
WLHV��HG��E\�*�9�6DPVRQRY��0HWDOOXUJLD��0RV�
FRZ��������>LQ�5XVVLDQ@�
����0�'�*OLQFKXN�� 3�,�%\NRY�� %�.KLOFKHU�� )L]�
7YHUG��7HOD�������������������
����$�,�*XVHY�� $�$�5HPSHO��� 1DQR�&U\VWDOOLQH
0DWHULDOV�� 3K\V0DW/LW�� 0RVFRZ� ������� >LQ
5XVVLDQ@�
����$�3�6KSDN�� 2�9�6RERO��� <X�$�.XQLWVNL\�
3�*�&KHUHPVNR\��6HOI�2UJDQL]DWLRQ�LQ�/RZ�'L�
PHQVLRQ�6\VWHPV��,0)�1$68��.\LY��������>LQ
5XVVLDQ@�
nÈϺmÒ®�°}ãÈ���°�¯�}��¯È��È�Óȹ¯�ÎËÓÒ®�°�ÈÓ�}ºÓ�ËÓ°È�Lm�°Ò°�ËäÒ�:±7L�º�˯ÎÈÓÒ²�äÈ�ÓË�¯ºÓÓÒä�¯ºÏ¹ÒãËÓÓ«ä�
|�{�vººã �
iº°ãL�ÎËÓº� m¹ãÒm� ËãËäËÓ�Óº�º� °}ãÈ��� �È� �Ëä¹Ë¯È��¯Ò� º°È�ÎËÓÓ«� LºÓÓº�¹ãÈÏäºmÒ²
}ºÓ�ËÓ°È�Lm�°Ò°�ËäÒ�:±7L�ÓÈ��²�°�¯�}��¯���°�°�¯�}��¯ÓL�²È¯È}�˯Ұ�Ò}Ò��È�Óȹ¯�ÎË�
ÓÒ®�°�ÈÓ��{°�ÈÓºmãËÓº���º�}¯Ò°�ÈãL�ÓÒ®�°�ÈÓ��°L²�ÁÈÏ��«}L�Áº¯ä�
� °«�¹¯Ò�º°È�ÎËÓÓL�
ÈÏ�¼� °«�ÓÈ�|¡z�}¯Ò°�ÈãL�ÓL®�¯Ë�L��L�mºã Á¯Èä���sÈ�¹º�È�}ºmÒ²�°�È�L«²�Áº¯ä�mÈÓÓ«
�m˯�º�º� ¯ºÏ�ÒÓ�� ¹¯Ò� mL�Óº°Óº� äÈãºä�� mäL°�L� È�ºäLm� �Ò�ÈÓ�� �� ¯Ë�L��L� ��������È����
mL��mȼ� °«� º¯L¼Ó�ºmÈÓÒ®� ¯L°�� }¯Ò°�ÈãL�Lm� Ï� ¹ãº�ÒÓÈäÒ� �Ò¹�� ������ ¹È¯ÈãËã Óº� ¹º�
m˯²ÓL�¹L�}ãÈ�}Ò���¯Ò�Lã �� mÒ°º}ºä��mäL°�L�È�ºäLm��Ò�ÈÓ��mL��mȼ� °«�Áº¯ä�mÈÓÓ«
°Òã Óº�ËÁº¯äºmÈÓÒ²� }¯Ò°�ÈãL�Lm� �:�±[�� 7L[�� �m˯�º�º� ¯ºÏ�ÒÓ�� Ï� ÓËmËãÒ}Òä� °��¹ËÓËä�º°}ºÓÈ㺰�L��Ë}°��¯Ò�Ï�¹ãº�ÒÓº
� ������}¯Ò°�ÈãL�Óº��¯Ë�L�}Ò��¹È¯ÈãËã Óº
�¹ºm˯²ÓL
ϯº°����{�� ºä��mÒ¹È�}��ÏLã �ËÓÓ«��Ëä¹Ë¯È��¯Ò�º°È�ÎËÓÓ«�mL������v��º�����v�¹¯Ò�
Ïmº�Ò� ��º�}ºÓ�ËÓ�¯È�L®Óº�º�¯ºÏ�ȯ�mÈÓÓ«��m˯�º�º�¯ÈÏ�ÒÓ��L���mº¯ËÓÓ«��mº²��m˯�Ò²
¯ºÏ�ÒÓLm�Ï�¯LÏÓÒä�°�ÈLã ÓÒä�ËãËäËÓ�ÓÒä�°}ãÈ�ºä���¯ºmË�ËÓº�º�LÓ}��}ºËÁL�L¼Ó�È��Ò�
Á�ÏL����ÓÈÓº}¯Ò°�ÈãL�ÓÒ²�}ºÓ�ËÓ°È�Ȳ�°Ò°�ËäÒ�:±7L�L�Ïȹ¯º¹ºÓºmÈÓº�äº�Ëã ��ã«�º¹Ò°�
°�¯�}��¯Óº�º�°�ÈÓ��}ºÓ�ËÓ°È�Lm���º�Áº¯ä�
� °«�
��
2�9�6RERO����3KDVH�FRPSRVLWLRQ��VWUXFWXUH�DQG����
)XQFWLRQDO�PDWHULDOV������������� ���
|