Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃
Nuclear magnetic resonance and secondary ion mass-spectroscopy have been used to study the surface charge and surface chemical compositions of La₀.₇Sr₀.₃MnO₃ nanoparticles of 12 and 50-100 nm size. It is found that the surface of particles is characterized by an increased content of Sr and Mn ions t...
Gespeichert in:
Datum: | 2006 |
---|---|
Hauptverfasser: | , , , , , , |
Format: | Artikel |
Sprache: | English |
Veröffentlicht: |
НТК «Інститут монокристалів» НАН України
2006
|
Schriftenreihe: | Functional Materials |
Online Zugang: | http://dspace.nbuv.gov.ua/handle/123456789/144371 |
Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
Назва журналу: | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
Zitieren: | Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ / I.A. Danilenko, T.E. Konstantinova, G.E. Shatalova, V.N. Krivoruchko, V.D. Doroshev, V.A. Stupak, G.K. Volkova // Functional Materials. — 2006. — Т. 13, № 2. — С. 9. — Бібліогр.: 288-292 назв. — англ. |
Institution
Digital Library of Periodicals of National Academy of Sciences of Ukraineid |
irk-123456789-144371 |
---|---|
record_format |
dspace |
spelling |
irk-123456789-1443712018-12-21T01:23:14Z Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ Danilenko, I.A. Konstantinova, T.E. Shatalova, G.E. Krivoruchko, V.N. Doroshev, V.D. Stupak, V.A. Volkova, G.K. Nuclear magnetic resonance and secondary ion mass-spectroscopy have been used to study the surface charge and surface chemical compositions of La₀.₇Sr₀.₃MnO₃ nanoparticles of 12 and 50-100 nm size. It is found that the surface of particles is characterized by an increased content of Sr and Mn ions than the bulk, while the difference depends on particle size. The surface segregation process is considered to be a possible mechanism for cation rearrangement. Thus, the observed magnetically dead layer on a particle surface may be formed due to increase in the Sr and Mn ions concentrations up to values corresponding to an antiferromagnetic state. Методами ядерного магнитного резонанса и вторичной ионной масс-спектроскопии проведены исследования зарядового состояния и химического состава поверхности наночастиц La₀.₇Sr₀.₃MnO₃ с размерами 12 и 50-100 нм. Обнаружено, что для поверхности частиц характерно повышенное содержание ионов Sr и Mn по сравнению с объемом, причем это различие зависит от размера частиц. В качестве возможного механизма перераспределения катионов рассматривается процесс поверхностной сегрегации. Таким образом, наблюдаемый немагнитный слой па поверхности частиц может быть сформирован в результате увеличения концентрации ионов Sr и Mn в поверхностном слое до величин, соответствующих антиферромагнитному состоянию. Методами ядерного магнітного резонансу і вторинної іонної мас-спектроскопії проведено дослідження зарядового етапу та хімічного складу поверхні наночастинок La₀.₇Sr₀.₃MnO₃ з розмірами 12 і 50-100 нм. Виявлено, що для поверхні частинок характерний підвищений склад іонів Sr і Mn, а їхня концентрація залежить від розміру частинок. Як можливий механізм перерозподілу катіонів розглядається процес поверхневої сегрегації. Таким чином, немагнітний шар, що спостерігається на поверхні частинок, може бути сформований в результаті збільшення концентрації іонів Sr і Mn у поверхневому шарі до величин, що відповідають антиферомагнітному етапу. 2006 Article Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ / I.A. Danilenko, T.E. Konstantinova, G.E. Shatalova, V.N. Krivoruchko, V.D. Doroshev, V.A. Stupak, G.K. Volkova // Functional Materials. — 2006. — Т. 13, № 2. — С. 9. — Бібліогр.: 288-292 назв. — англ. 1027-5495 http://dspace.nbuv.gov.ua/handle/123456789/144371 en Functional Materials НТК «Інститут монокристалів» НАН України |
institution |
Digital Library of Periodicals of National Academy of Sciences of Ukraine |
collection |
DSpace DC |
language |
English |
description |
Nuclear magnetic resonance and secondary ion mass-spectroscopy have been used to study the surface charge and surface chemical compositions of La₀.₇Sr₀.₃MnO₃ nanoparticles of 12 and 50-100 nm size. It is found that the surface of particles is characterized by an increased content of Sr and Mn ions than the bulk, while the difference depends on particle size. The surface segregation process is considered to be a possible mechanism for cation rearrangement. Thus, the observed magnetically dead layer on a particle surface may be formed due to increase in the Sr and Mn ions concentrations up to values corresponding to an antiferromagnetic state. |
format |
Article |
author |
Danilenko, I.A. Konstantinova, T.E. Shatalova, G.E. Krivoruchko, V.N. Doroshev, V.D. Stupak, V.A. Volkova, G.K. |
spellingShingle |
Danilenko, I.A. Konstantinova, T.E. Shatalova, G.E. Krivoruchko, V.N. Doroshev, V.D. Stupak, V.A. Volkova, G.K. Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ Functional Materials |
author_facet |
Danilenko, I.A. Konstantinova, T.E. Shatalova, G.E. Krivoruchko, V.N. Doroshev, V.D. Stupak, V.A. Volkova, G.K. |
author_sort |
Danilenko, I.A. |
title |
Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ |
title_short |
Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ |
title_full |
Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ |
title_fullStr |
Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ |
title_full_unstemmed |
Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ |
title_sort |
surface segregation and charge state of la₀.₇sr₀.₃mno₃ |
publisher |
НТК «Інститут монокристалів» НАН України |
publishDate |
2006 |
url |
http://dspace.nbuv.gov.ua/handle/123456789/144371 |
citation_txt |
Surface segregation and charge state of La₀.₇Sr₀.₃MnO₃ / I.A. Danilenko, T.E. Konstantinova, G.E. Shatalova, V.N. Krivoruchko, V.D. Doroshev, V.A. Stupak, G.K. Volkova // Functional Materials. — 2006. — Т. 13, № 2. — С. 9. — Бібліогр.: 288-292 назв. — англ. |
series |
Functional Materials |
work_keys_str_mv |
AT danilenkoia surfacesegregationandchargestateofla07sr03mno3 AT konstantinovate surfacesegregationandchargestateofla07sr03mno3 AT shatalovage surfacesegregationandchargestateofla07sr03mno3 AT krivoruchkovn surfacesegregationandchargestateofla07sr03mno3 AT doroshevvd surfacesegregationandchargestateofla07sr03mno3 AT stupakva surfacesegregationandchargestateofla07sr03mno3 AT volkovagk surfacesegregationandchargestateofla07sr03mno3 |
first_indexed |
2025-07-10T19:16:26Z |
last_indexed |
2025-07-10T19:16:26Z |
_version_ |
1837288657109647360 |
fulltext |
6XUIDFH�VHJUHJDWLRQ�DQG�FKDUJH�VWDWH�RI�/D���6U���0Q2�,�$�'DQLOHQNR��7�(�.RQVWDQWLQRYD��*�(�6KDWDORYD�9�1�.ULYRUXFKNR��9�'�'RURVKHY��9�$�6WXSDN
��*�.�9RONRYD
$�*DONLQ�'RQHWVN�,QVWLWXWH�IRU�3K\VLFV� �(QJLQHHULQJ��1DWLRQDO�$FDGHP\
RI�6FLHQFHV�RI�8NUDLQH�����5�/X[HPEXUJ�6W���������'RQHWVN��8NUDLQH
'RQHWVN�1DWLRQDO�8QLYHUVLW\�����8QLYHUVLW\�6W���������'RQHWVN��8NUDLQH�
1XFOHDU� PDJQHWLF� UHVRQDQFH� DQG� VHFRQGDU\� LRQ� PDVV�VSHFWURVFRS\� KDYH� EHHQ� XVHG� WR
VWXG\� WKH� VXUIDFH�FKDUJH� DQG�VXUIDFH�FKHPLFDO� FRPSRVLWLRQV�RI�/D���6U���0Q2�� QDQRSDUWL�FOHV�RI����DQG�������QP�VL]H��,W�LV�IRXQG�WKDW�WKH�VXUIDFH�RI�SDUWLFOHV�LV�FKDUDFWHUL]HG�E\
DQ� LQFUHDVHG� FRQWHQW� RI�6U� DQG�0Q� LRQV� WKDQ� WKH� EXON�� ZKLOH� WKH� GLIIHUHQFH� GHSHQGV� RQ
SDUWLFOH�VL]H��7KH�VXUIDFH�VHJUHJDWLRQ�SURFHVV�LV�FRQVLGHUHG�WR�EH�D�SRVVLEOH�PHFKDQLVP�IRU
FDWLRQ� UHDUUDQJHPHQW�� 7KXV�� WKH� REVHUYHG�PDJQHWLFDOO\� GHDG� OD\HU� RQ� D� SDUWLFOH� VXUIDFH
PD\� EH� IRUPHG� GXH� WR� LQFUHDVH� LQ� WKH� 6U� DQG� 0Q� LRQV� FRQFHQWUDWLRQV� XS� WR� YDOXHV
FRUUHVSRQGLQJ�WR�DQ�DQWLIHUURPDJQHWLF�VWDWH��
lË�º�ÈäÒ�«�˯Ӻ�º�äÈ�ÓÒ�Óº�º� ¯ËϺÓÈÓ°È� Ò� m�º¯Ò�Óº®�ÒºÓÓº®�äȰ°�F¹Ë}�¯º°}º¹ÒÒ
¹¯ºmË�ËÓ©�Ò°°ãË�ºmÈÓÒ«�Ïȯ«�ºmº�º�°º°�º«ÓÒ«�Ò�²ÒäÒ�˰}º�º�°º°�ÈmÈ�¹ºm˯²Óº°�Ò�ÓÈ�
Óº�Ȱ�Ò��/D���6U���0Q2��°�¯ÈÏä˯ÈäÒ����Ò���Ü����Óä��|Óȯ�ÎËÓº����º��ã«�¹ºm˯²Óº°�Ò�Ȱ�Ò�� ²È¯È}�˯Ӻ� ¹ºm©�ËÓÓºË� °º�˯ÎÈÓÒË� ÒºÓºm� 6U� Ò�0Q� ¹º� °¯ÈmÓËÓÒ
� °� º�Ëäºä�
¹¯Ò�Ëä� ª�º� ¯ÈÏãÒ�ÒË� ÏÈmÒ°Ò�� º�� ¯ÈÏä˯È� �Ȱ�Ò��� {� }È�˰�mË� mºÏäºÎÓº�º� ä˲ÈÓÒÏäÈ
¹Ë¯Ë¯È°¹¯Ë�ËãËÓÒ«� }È�ÒºÓºm� ¯È°°äÈ�¯ÒmÈË�°«� ¹¯º�˰°� ¹ºm˯²Óº°�Óº®� °Ë�¯Ë�È�ÒÒ�
�È}Òä� º¯ÈϺä�� ÓÈã
�ÈËä©®� ÓËäÈ�ÓÒ�Ó©®� °ãº®� ÓÈ� ¹ºm˯²Óº°�Ò� �Ȱ�Ò�� äºÎË�� ©�
°Áº¯äÒ¯ºmÈÓ� m� ¯ËÏ�ã �È�Ë� �mËãÒ�ËÓÒ«� }ºÓ�ËÓ�¯È�ÒÒ� ÒºÓºm�6U� Ò�0Q� m� ¹ºm˯²Óº°�Óºä
°ãºË��º�mËãÒ�ÒÓ��°ºº�mË�°�m�
�Ò²�ÈÓ�ÒÁ˯¯ºäÈ�ÓÒ�Óºä��°º°�º«ÓÒ
�
7KH� GRSHG� ODQWKDQXP� PDQJDQLWHV
/D�±[�&D�6U�%D�[0Q2�� �/'02�� DUH� XQGHU� D
NHHQ� VFLHQWLILF� LQWHUHVW� IRU� PRUH� WKDQ
���\HDUV�EHFDXVH�RI�D�VXUSULVLQJ�FRUUHODWLRQ
EHWZHHQ�HOHFWULFDO�FRQGXFWLYLW\�DQG�PDJQHW�
LVP�REVHUYHG�WKHUHLQ�>�@��$�SDUWLDO�VXEVWLWX�
WLRQ� RI� WKH� WULYDOHQW� UDUH�HDUWK� LRQ� IRU� D
ELYDOHQW�DONDOLQH�HDUWK�LRQ�UHVXOWV�LQ�WKH�DS�
SHDUDQFH� RI�0Q� LRQV� RI� YDULRXV� YDOHQFHV� LQ
HTXLYDOHQW�FU\VWDOORJUDSKLF�SRVLWLRQV��DQG�LQ
WKH� HPHUJHQFH� RI� D� IHUURPDJQHWLF� RUGHULQJ
>����@� LQ� WKHVH� FRPSRXQGV�� )HUURPDJQHWLF
H[FKDQJH� HIILFLHQF\� EHWZHHQ� WKH� DGMDFHQW
VSLQV� GHSHQGV� RQ� WKH� 0Q��±2±0Q��� FKDLQ
VWDWH�� VLQFH� DQ\� GLVWXUEDQFH� RI� WKH� FU\VWDO�
OLQH� VWUXFWXUH� FDXVHV� D� VSLQ� GLVRUGHU� DQG
KLQGHUV�WKH�GRXEOH�H[FKDQJH�>�@�
$�QDWXUDO�DUHD�RI�WKH�VWUXFWXUDO�DQG�VSLQ
GLVRUGHU� LV� WKH� FU\VWDO� VXUIDFH� RI� VRPH� HOH�
PHQWDU\� FHOOV� LQ� WKLFNQHVV� ZKLFK� DFWV� DV� D
EXIIHU�EHWZHHQ�WKH�UHJXODU�VWUXFWXUH�RI�WKH
LQWHUQDO� YROXPH� DQG� WKH� HQYLURQPHQW�� $
FRQWULEXWLRQ� RI� WKH� VXUIDFH� LQWR� WKH� PDWH�
ULDO� SK\VLFDO� SURSHUWLHV� KDV� EHHQ� FOHDUO\
GHPRQVWUDWHG� LQ� WKH� FRXUVH� RI� /'02� UH�
VHDUFK��:KHQ� WKH� VXUIDFH� OD\HU� IUDFWLRQ� LQ
WKH� WRWDO� YROXPH� LV� VPDOO�� VLQJOH� FU\VWDOV
DQG� ILOPV� RI� WKHVH� FRPSRXQGV� H[KLELW� WKH
FRORVVDO� QHJDWLYH� PDJQHWRUHVLVWDQFH� HIIHFW�
,QWHUJUDQXODU�ERXQGDULHV�LQ�FHUDPLF�PDWHUL�
DOV� PDNH� WKH� PDJQHWR�UHVLVWDQW� FKDUDF�
WHULVWLFV�ZRUVH��,Q�WKH�FDVH�RI�QDQRSDUWLFOHV
RI� OHVV� WKDQ� ���� QP� VL]H�� WKH� WUDQVSRUW
SURSHUWLHV� DUH�PDLQO\� LQIOXHQFHG�E\� WKH� LQ�
WHUJUDQXODU� PDJQHWRUHVLVWDQFH� �ORZ� ILHOG
PDJQHWRUHVLVWDQFH���,Q�YHU\�WKLQ�QDQR�SDUWL�
FOHV��WKH�VXUIDFH�UROH�EHFRPHV�SUHGRPLQDQW�
0DJQHWLF� VWXGLHV� RI� WKH� XOWUDILQH� SRZGHUV
VKRZ�D�VXSHU�SDUDPDJQHWLF��630��EHKDYLRU�
ZKLOH�QR� ORZ� ILHOG�PDJQHWRUHVLVWDQFH� LV� RE�
VHUYHG� DERYH� WKH� 630� WHPSHUDWXUH�� 7KH
)XQFWLRQDO�0DWHULDOV�����1R��������� ��������,QVWLWXWH�IRU�6LQJOH�&U\VWDOV
��� )XQFWLRQDO�PDWHULDOV�������������
SXUSRVH� RI� WKLV� ZRUN� LV� WR� VWXG\� WKH� UHOD�
WLRQVKLS�EHWZHHQ�WKH�PDJQHWLF�SURSHUWLHV�RI
WKH� /D���6U���0Q2�� �/602�� QDQR�SRZGHUV
DQG� WKH�VWUXFWXUH�SHFXOLDULWLHV�RI� WKH�JUDQ�
XOH�H[WHUQDO�OD\HU�
7KH�PDJQHWLVP� RI� QDQR�VL]HG�/602�ZDV
VWXGLHG� E\� WKH� QXFOHDU� PDJQHWLF� UHVRQDQFH
�105��� EHFDXVH� LW� SUREHV� ORFDOO\� VSLQ� DQG
FKDUJH� VWDWHV� DQG� WKH� G\QDPLFV� WKHUHRI�
&KDQJHV� RI� WKH� VXUIDFH� OD\HU� VWDWH� LQ� WKH
PDQJDQLWH� QDQR�SDUWLFOHV� DW� WKH� SDUWLFOH
VL]HV� FKDQJLQJ� ZHUH� VWXGLHG� E\� WKH� VHFRQ�
GDU\�LRQ�PDVV�VSHFWURVFRS\��6,06��
7KH�6�� �WKH� SDUWLFOH� VL]H����QP�� DQG�6�
�ELPRGDO�GLVWULEXWLRQ�RI�SDUWLFOHV�RI����DQG
������� QP� VL]H�� VDPSOHV� ZHUH� REWDLQHG
FKHPLFDOO\� E\� FR�SUHFLSLWDWLRQ� XVLQJ� WKH
6+)� KHDWLQJ� DQG� XOWUDVRXQG� WUHDWPHQW� >�@�
:KHQ� PDNLQJ� SRZGHUV�� FKHPLFDOO\� SXUH
/D�2���0Q�12������+�2��DQG�6U&O����+�2�ZHUHWDNHQ�DV�LQLWLDO�UHDJHQWV�LQ�DFFRUGDQFH�ZLWK
WKH�ILQDO�SURGXFW�VWRLFKLRPHWU\��1+�2+�DQG1D�&2�� ZHUH� XVHG� DV� SUHFLSLWDWRUV� RI� WKHPHWDO� VDOW� VROXWLRQ�� /DQWKDQXP� R[LGH� ZDV
SUHOLPLQDU\� GLVVROYHG� LQ� QLWULF� DFLG�� 7KH
SUHFLSLWDWLRQ�ZDV�FDUULHG�RXW�XQGHU�VWLUULQJ
IRU� �� KRXU� DW� URRP� WHPSHUDWXUH�� 7KH� ZD�
WHUHG� SUHFLSLWDWH� REWDLQHG� ZDV� ZDVKHG� LQ
GLVWLOOHG� ZDWHU� WR� UHPRYH� WKH� UHDFWLRQ� E\�
SURGXFWV��$IWHU�ILOWUDWLRQ��WKH�K\GURJHO�ZDV
WUHDWHG� E\� XOWUDVRXQG� DQG� GULHG� LQ� WKH�PL�
FURZDYH�NLOQ� ������*+]������:��WLOO�D�FRQ�
VWDQW� VDPSOH� PDVV�� $� PRQRSKDVH� /602
QDQR�SRZGHU�ZDV�V\QWKHVL]HG�DW�����v��7KH
SKDVH�FRPSRVLWLRQ�ZDV�VWXGLHG�E\�WKH�;�UD\
DQDO\VLV�� 8VLQJ� WUDQVPLVVLRQ� HOHFWURQ� PL�
FURVFRS\� �7(0��� WKH� PRUSKRORJLFDO� VWUXF�
WXUH� SHFXOLDULWLHV� RI� WKH�SKDVHV� LQYROYHG� LQ
WKH�V\QWKHVLV�ZHUH�VWXGLHG��)RU�FRPSDULVRQ�
D�FHUDPLF�VDPSOH��6���ZLWK�SUHGRPLQDQW�YRO�
XPH� SURSHUWLHV� ZDV� XVHG� REWDLQHG� E\� VROLG
SKDVH�V\QWKHVLV�IROORZHG�E\�DJJORPHUDWLRQ�
7KH� 105� VWXGLHV� RI� WKH� ��0Q� QXFOHL� LQ
WKH�QDQR�SRZGHU�/602�VDPSOHV�KDYH�VKRZQ
WKDW� QDQR�VL]HG� FU\VWDOV� ZHUH� FKDUDFWHUL]HG
E\� WKH� H[LVWHQFH� RI� WZR� DUHDV� GLIIHULQJ� LQ
PDJQHWLF� SURSHUWLHV� Û� WKH� JUDLQ� VXUIDFH
DQG� LWV� LQWHUQDO� YROXPH� >����@�� ,W� IROORZHG
IURP� WKH� H[SHULPHQW� WKDW� WKH� DERXW� �� QP
WKLFN�VXUIDFH�OD\HU�RI�WKH�6��DQG�6��VDPSOH
SDUWLFOHV� LV� QHLWKHU� PDJQHWLF� QRU� FRQGXF�
WLYH��%HVLGHV�� LQ� WKH� VDPSOH�6��� DORQJ�ZLWK
WKH� VWDWH� RI� WKH� 0Q������ LRQ� W\SLFDO� RI� D
IHUURPDJQHWLF�ODQWKDQXP�PDQJDQLWH��DQ�DG�
GLWLRQDO� OLQH� ZDV� REVHUYHG� LQ� WKH� VSHFWUD
WKDW� FRUUHVSRQGV� WR� WKH� ORFDOL]HG� VWDWH� RI
WKH�0Q��� LRQV� LQ� WKH� VXUIDFH� OD\HU�RI�QDQR�
JUDQXOHV� �)LJ������ 7KLV� OLQH� ZDV� DEVHQW� LQ
WKH� 6�� FHUDPLFV� DQG� QDQR�VL]HG� 6�� VDPSOH
�)LJ������ 7KH� SUHSDUDWLRQ� WHFKQRORJ\� EHLQJ
WKH�VDPH�IRU�DOO�WKH�VDPSOHV��WKH�GLIIHUHQFH
LQ�PDJQHWLF�SURSHUWLHV�FRXOG�EH�FDXVHG�RQO\
E\� WKH� GLIIHUHQW� SDUWLFOH� VL]H�� WKDW� LV�� LW� LV
GXH� PDLQO\� WR� WKH� VXUIDFH� OD\HU� FRQWULEX�
WLRQ�� 7R� GHWHUPLQH� WKH� VXUIDFH� FRPSRVLWLRQ
RI�WKH�/602�SDUWLFOHV�RI�GLIIHUHQW�VL]HV��WKH
PHWKRG� 6,06�ZDV� XVHG� WKDW� LV� VHQVLWLYH� WR
WKH�VXUIDFH�FRPSRVLWLRQ��)LJ������7KH�DQDO\�
VLV�KDV�VKRZQ��7DEOH��WKDW�LQ�DOO�WKH�VDPSOHV
)LJ����� ��0Q�105�VSHFWUD� RI�6��/602�SRZ�
GHUV�DW����.�
)LJ����� ��0Q� 105� VSHFWUD� UHFRUGHG� IRU� 6�
�VROLG�OLQH��DQG�6���q��/602�VDPSOHV�DW����.�
,QVHW��WKH�VDPH�VSHFWUD�LQ�DQ�H[SDQGHG�VFDOH�
VKRZLQJ�WKH�GHWDLOV�RI�105�VSHFWUD�DW�DERXW
����0+]�
,�$�'DQLOHQNR�HW�DO����6XUIDFH�VHJUHJDWLRQ�DQG�FKDUJH����
)XQFWLRQDO�PDWHULDOV������������� ���
XQGHU� VWXG\�� WKHUH� LV� DQ� LQFUHDVHG� FRQWHQW
RI�6U� LRQV� LQ� WKH� �� QP� WKLFN� VXUIDFH� OD\HU
�WKH� VWRLFKLRPHWULF� FRPSRVLWLRQ� YDOXH� LV
�������,W�LV�RI�LPSRUWDQFH�WKDW�D�FRUUHODWLRQ
EHWZHHQ� WKH� SDUWLFOH� VL]H� DQG� WKH� VXUIDFH
FRPSRVLWLRQ� KDV� EHHQ� H[SHULPHQWDOO\� RE�
VHUYHG�� WKH� VPDOOHU� WKH�SDUWLFOH� VL]H� LV�� WKH
ODUJHU� LV� WKH�6U� DQG�0Q� LRQ� DPRXQW� LQ� WKH
VXUIDFH� OD\HU�� 7KH� YDOXHV� RI� WKH� 0Q��/D��
6U��UDWLR�SUHVHQWHG� LQ�WKH�7DEOH�DUH�QRW�DE�
VROXWH� �GXH� WR� D� ZHDN� VHQVLWLYLW\� RI� WKH
PHWKRG� WR�0Q�� LWV� TXDQWLW\� LV� XQGHUUDWHG�
EXW� WKH\� UHSUHVHQW� FOHDUO\� D� WUHQG� WR� WKH
VXUIDFH�FRPSRVLWLRQ�FKDQJH�DV�D�IXQFWLRQ�RI
WKH�SDUWLFOH�VL]H�
7KUHH� SRVVLEOH� SKHQRPHQD� DUH� NQRZQ
ZKLFK�FDQ�FRQWULEXWH�WR�WKH�FRPSRVLWLRQ�LQ�
KRPRJHQHLW\� LQ� FHUDPLFV�� SKDVH� VHSDUDWLRQ�
DEVRUSWLRQ�� DQG� VXUIDFH� VHJUHJDWLRQ� �LQWHU�
QDO�DGVRUSWLRQ���3KDVH�VHSDUDWLRQ�EHORQJV�WR
WKH�VSDFH�HIIHFWV�DQG� LV�GHVFULEHG�E\�D�FRU�
UHVSRQGLQJ� SKDVH� GLDJUDP�� $EVRUSWLRQ� DQG
VHJUHJDWLRQ� DSSHDU�DV�D� UHVXOW�RI�PDLQWDLQ�
LQJ� HTXLOLEULXP� DW� WKH� VROLG� VXUIDFH�HQYL�
URQPHQW� ERXQGDU\� RU� DW� WKH� JUDLQ� VXUIDFH
DQG�DUH�PDLQO\�GHILQHG�E\�WKH�QDWXUH�RI�WKH
DWRP�RU� LRQ�ERQGV� LQ� WKH� LQWHUIDFH�DUHD�� ,Q
WKH� FDVH� RI� DEVRUSWLRQ�� HTXLOLEULXP� LV� DW�
WDLQHG� GXH� WR� FRQWDFW� EHWZHHQ� WKH� YDSRU
SKDVH�DQG�WKH�VXUIDFH��ZKLOH�HTXLOLEULXP�DW
WKH�LQWHUQDO�DGVRUSWLRQ�LV�DWWDLQHG�E\�D�GLI�
IXVLRQ� FRQWDFW� EHWZHHQ� D� VROLG� YROXPH� DQG
DQ� LQWHUIDFH� DUHD�� 7KH� VXUIDFH� VHJUHJDWLRQ
RI�DONDOLQH�HDUWK�DWRPV�LQ�WKH�FHUDPLF�VDP�
SOHV� RI� SHURYVNLWHV� %D7L2�� DQG� 6U7L2�� ZDVIRXQG� LQ� H[SHULPHQW� DQG� GHVFULEHG� LQ� >�@�
7KH� DXWKRUV� KDYH� VXJJHVWHG� D� WKHRUHWLFDO
PRGHO� ZKHUH� D� VWUHVV� VWDWH� RI� WKH� FU\VWDO
ODWWLFH� DW� WKH� ERXQGDU\� ZLWK� WKH� HQYLURQ�
PHQW�LV�FRQVLGHUHG�DV�D�PRWLYH�IRUFH�RI�WKH
FDWLRQ� UHDUUDQJHPHQW� EHWZHHQ� WKH� SDUWLFOH
EXON�DQG�VXUIDFH��$V�WKH�ODWWLFH�KDV�ORVW�LWV
WKUHH�GLPHQVLRQDO� WUDQVODWLRQ� V\PPHWU\� LQ
WKHVH� LRQLF� FU\VWDOOLQH� FRPSRXQGV�� D� QHJD�
WLYH� VSDFH� FKDUJH� RFFXUV� VLGH� E\� VLGH� ZLWK
WKH�LQWHUIDFH�ZKLFK�PXVW�EH�FRPSHQVDWHG�E\
D� OD\HU� RI� SRVLWLYHO\� FKDUJHG� LRQV� DW� WKH
VXUIDFH�� 7KH� DXWKRUV� KDYH� VKRZQ� DQ� LQIOX�
HQFH� RI� WKH� DOOR\LQJ� DWRPV� RQ� WKH� VHJUHJD�
WLRQ� FKDUDFWHULVWLFV� Û� ZKHQ� DOOR\LQJ� E\
DWRPV� RI� DQRWKHU� YDOHQFH� DQG� RWKHU� LRQLF
UDGLL�� D� SUHYDLOLQJ� UHDUUDQJHPHQW� RI
GRSDQWV�LQWR�WKH�VXUIDFH�DUHD�ZDV�REVHUYHG�
,Q� WKLV� FDVH�� WKH� PRWLRQ� LV� GRQH� QRW� RQO\
GXH� WR� WKH� HOHFWURVWDWLF� IRUFHV� EXW� DOVR� WR
WKH�LQIOXHQFH�RI�HODVWLF�IRUFHV�RI�WKH�FU\VWDO
ODWWLFH� ZKLFK� RFFXU� EHFDXVH� RI� WKH� GLIIHU�
HQFH�RI�WKH�LRQLF�UDGLL�
)URP� WKH� GDWD� RI� RXU� H[SHULPHQWV�� WKH
DUUDQJHPHQW�RI�FDWLRQV�EHWZHHQ�WKH�VXUIDFH
OD\HU� DQG� WKH� LQWHUQDO� YROXPH� RI� ��� DQG
��� QP� VL]H� SDUWLFOHV� ZDV� HVWLPDWHG�� 7KH
SDUWLFOH� ZDV� DVVXPHG� WR� EH� VSKHULFDO� DQG
DWRPV� LQ� WKH� VXUIDFH� OD\HU� WR� EH� DUUDQJHG
KRPRJHQHRXVO\��L�H��ZLWKRXW�DQ\�UDGLDO�FRQ�
FHQWUDWLRQ�JUDGLHQW��7KH�FDWLRQ�UDWLR�LQ�WKLV
FDVH�ZDV�GHWHUPLQHG�E\�WKH�DYHUDJH�FRQFHQ�
WUDWLRQ�YDOXH�LQ�WKH�OD\HU�
$V�WKH�XQLW�YROXPH��D�FXEH�YROXPH�RI�WKH
UHGXFHG� SHURYVNLWH� FHOO� $%2�� �È|�����QP�SHU� RQH� IRUPDO� XQLW� ZDV� WDNHQ�� %DVLQJ� RQ
WKH�SDUWLFOH�VL]H�DQG�WKH�VXUIDFH�OD\HU�WKLFN�
)LJ�����6,06�VSHFWUD�RI�6��VDPSOH�
�DEOH��7KH�FRPSRVLWLRQ�RI�WKH�VXUIDFH�OD\HU�/D���6U���0Q2��DV�GHWHUPLQHG�E\�6,06�
6DPSOH 3DUWLFOH�VL]H��QP 6U�/D 0Q��/D���6U� /D�±[6U[0Q2�
6� �� ���� ���� /D����6U����0Q2�
6� ������� ���� ���� /D����6U����0Q2�
6� FHUDPLFV ���� ���� /D����6U����0Q2�
,�$�'DQLOHQNR�HW�DO����6XUIDFH�VHJUHJDWLRQ�DQG�FKDUJH����
��� )XQFWLRQDO�PDWHULDOV�������������
QHVV�� WKH� QXPEHU� RI� WKH� IRUPXOD� XQLWV� EH�
ORQJLQJ� WR� HDFK� DUHD� FDQ� EH� FDOFXODWHG�
.QRZLQJ� WKH� FDWLRQ� FRQFHQWUDWLRQV�� LW� LV
SRVVLEOH�WR�GHWHUPLQH�DQG�FRPSDUH�WKH�QXP�
EHU� RI� FHOOV� RFFXSLHG�E\� WKH�/D� DQG�6U� LRQV
ERWK�DW�WKH�VXUIDFH�DQG�LQ�WKH�EXON�
$VVXPLQJ�WKDW�WKH�UDWLR�RI�WKH�FRPSRQHQWV
IRU� HDFK� SDUWLFOH� ODLG� DW� V\QWKHVLV� VKRXOG� EH
UHWDLQHG� RQ� DYHUDJH�� WKH� VXUIDFH� HQULFKPHQW
LQ�WKLV�RU�WKDW�HOHPHQW�VKRXOG�SURFHHG�DW�WKH
H[SHQVH� RI� LWV� FRQWHQW� GHFUHDVH� LQ� WKH� EXON�
$V�WKH�FDOFXODWLRQV�VKRZ��WR�DWWDLQ�DQ�H[SHUL�
PHQWDO�FRQFHQWUDWLRQ�LQ�WKH�VXUIDFH�OD\HU�RI
WKH� VDPSOHV� ZLWK� ��� QP� SDUWLFOHV�� 6U� LRQV
VKRXOG�EH�ZLWKGUDZQ�RXW�RI�WKH�LQWHUQDO�YRO�
XPH�LQ�WKH�DPRXQW�FRUUHVSRQGLQJ�WR�����RI
WKH�QXPEHU�RI�ODQWKDQXP�VXEODWWLFH�FU\VWDO�
ORJUDSKLF� SRVLWLRQV� EHORQJLQJ� WR� WKDW� YRO�
XPH��6XFK�D�GHIHFWQHVV�LQ�WKH�FDWLRQ�VXEODW�
WLFH�LV�TXLWH�SRVVLEOH��VR�WKDW�DW�SDUWLFOH�VL]H
t��� QP�� ZH� KDYH� LQ� WKH� YROXPH� D� FKDUJH
EDODQFH� /D�����9����6U������0Q�����0Q�����2��9��6U�YDFDQF\��FRUUHVSRQGLQJ�WR�D�PHWDOOLF
VWDWH�
$�GLIIHUHQW�VLWXDWLRQ�LV�REVHUYHG�IRU�SDU�
WLFOHV� RI����QP�VL]H�� ,Q� WKLV� FDVH��RQO\�RQH
IRXUWK� RI� WKH� ZKROH� SDUWLFOH� YROXPH� DF�
FRXQWV�IRU�WKH�LQWHUQDO�YROXPH��7KH�DPRXQW
RI� VWURQWLXP� LQ� WKH� LQWHUQDO� YROXPH� LV� LQ�
VXIILFLHQW�WR�ILOO�WKH�H[WHUQDO�OD\HU�XS�WR�WKH
FRQFHQWUDWLRQ� REVHUYHG� LQ� WKH� H[SHULPHQW�
3HUKDSV�WKHVH�PLVVLQJ������PLJKW�EH�FRP�
SHQVDWHG�E\�H[LW�RI�PDQJDQHVH�LRQV�RQWR�WKH
VXUIDFH��7KH�H[SHULPHQWDO�GDWD� �7DEOH��FRQ�
ILUP�WKLV�DVVXPSWLRQ��7KH�PD[LPXP�PDQJD�
QHVH�TXDQWLW\�LQ�WKH�VXUIDFH�OD\HU�LV�VHHQ�WR�EH
REVHUYHG�MXVW�IRU�QDQRSDUWLFOH�RI����QP�VL]H��
7KH�UHVXOWV�REWDLQHG�DOORZ�WR�H[SODLQ�WKH
UHDVRQ� IRU� WKH� QRQ�PDJQHWLF� OD\HU� DSSHDU�
DQFH�DW� WKH� VXUIDFH�RI�/D���6U���0Q2��QDQR�SDUWLFOHV�� 7KH� H[LW� RI� VWURQWLXP� LRQV� LQWR
VXEVXUIDFH� OD\HU� FKDQJHV� WKH� UDWLR� RI� WKH
VROLG� VROXWLRQ� FRPSRQHQWV� DQG� WDNHV� LW� RXW
RI� WKH� OLPLWV�RI� WKH� IHUURPDJQHWLF� VWDWH� UH�
JLRQ��:KHQ� HVWLPDWLQJ��ZH� SURFHHGHG� IURP
WKH� DYHUDJH� YDOXH� RI�6U� FRQFHQWUDWLRQ� RYHU
WKH� VXUIDFH� OD\HU� WKLFNQHVV�� ,Q� IDFW�� DV
VKRZQ�LQ�>�@��WKHUH�LV�D�FRQFHQWUDWLRQ�JUDGL�
HQW� WRZDUGV� WKH� SDUWLFOH� VXUIDFH�� .QRZLQJ
WKH� DYHUDJH� VWURQWLXP� FRQFHQWUDWLRQ� DW� WKH
VXUIDFH�DQG�LWV�YDOXH�LQ�WKH�LQWHUQDO�YROXPH
DQG� DVVXPLQJ� DV� WKH� ILUVW� DSSUR[LPDWLRQ
WKDW�WKH�GHSHQGHQFH�LQVLGH�WKH�VXUIDFH�OD\HU
LV� OLQHDU�� WKH� 6U�/D� UDWLR� DW� WKH� LQWHUIDFH
FDQ� EH� GHWHUPLQHG�� $V� WKH� HVWLPDWHV� VKRZ�
WKHVH� YDOXHV� IRU� SDUWLFOHV� RI� ��� DQG����QP
VL]H� DUH� ���� DQG� ����� UHVSHFWLYHO\�� ,Q� WKH
SKDVH� GLDJUDP� /D�±[6U[0Q2�� VXFK� FRQFHQ�WUDWLRQV� FRUUHVSRQG� WR� DQWL�IHUURPDJQHWLF
VWDWH�>�@�
$V� LV� VKRZQ� LQ� >�@�� WKH� QDQR�SDUWLFOH
PDJQHWLF� GRPDLQ� VWUXFWXUHV� RI� WKH� 6�� DQG
6�� VDPSOHV� GLIIHU� HVVHQWLDOO\� IURP� RQH� DQ�
RWKHU�� 7KH� 6�� VDPSOHV� DUH� VLQJOH� PDJQHWLF
GRPDLQ� SDUWLFOHV�� ZKLOH� WKH� 6�� RQHV� DUH
FKDUDFWHUL]HG� E\� D� PXOWL�GRPDLQ� VWUXFWXUH�
7KH�SUHVHQFH�RI�ORFDOL]HG�0Q���VWDWHV�LQ�WKH
6�� VDPSOHV� FDQ� EH� H[SODLQHG� E\� WKH� HIIHFWV
RI�SDUWLWLRQLQJ�LQWR�GRPDLQV�DQG�E\�WKH�VXU�
IDFH� VHSDUDWLRQ� RI�6U� LRQV�� ,Q� WKLV� FDVH�� DQ
DUHD� FRQWDLQLQJ� RQO\� 0Q��� LRQV� PD\� ZHOO
DSSHDU�RQ�D�JUDQXOH�VXUIDFH��6R��WKH�DSSHDU�
DQFH� RI� WKH� ORFDOL]HG�0Q��� VWDWHV� LQ� WKH� 6�
VDPSOHV�FDQ�EH�H[SODLQHG�E\�WKH�QDQR�SDUWL�
FOH�VXUIDFH�HQULFKPHQW�LQ�VWURQWLXP�
7KH� UHVXOWV� REWDLQHG� LQ� WKLV� ZRUN� JLYH
LQIRUPDWLRQ� RQ� WKH� PDJQHWLF� DQG� FU\VWDO
VWUXFWXUHV� RI� WKH� RI� WKH� QDQR�SRZGHU� VXU�
IDFH��7KH�FRPSOH[�VWXGLHV�RI�WKH�VDPSOHV�E\
WKH� ��0Q� 105� DQG� 6,06� PHWKRGV� KDYH
VKRZQ� WKDW� WKH� IRUPDWLRQ� RI� D� �� QP� WKLFN
PDJQHWLFDOO\�GHDG� OD\HU�DW�WKH�SDUWLFOH�VXU�
IDFH� LV�D�UHVXOW�RI� LWV�HQULFKPHQW� LQ�6U�DQG
0Q� LRQV�XS�WR�FRQFHQWUDWLRQV�FRUUHVSRQGLQJ
WR�WKH�DQWL�IHUURPDJQHWLF�VWDWH�
5HIHUHQFHV
� ���*�+�-RQNHU�� -�+�9DQ� 6DQWHQ�� 3K\VLFD�� ���
�����������
� ���-�%�*RRGHQRXJK��3K\V��5HY�������������������
� ���(�2�:ROODQ�� :�&�.RHKOHU�� 3K\V��5HY��� ����
�����������
� ���&�=HQHU��3K\V��5HY������������������
� ���,�$�'DQLOHQNR�� 7�(�.RQVWDQWLQRYD�
9�1�.ULYRUXFKNR�HW�DO���)XQFWLRQDO�0DWHULDOV�
���������������
� ���0�0�6DYRVWD�� 9�1�.ULYRUXFKNR�� ,�$�'DQL�
OHQNR�HW�DO���3K\V��5HY��%���������������������
� ���9�.ULYRUXFKNR�� 7�.RQVWDQWLQRYD�� $�0D]XU� HW
DO���-��0DJQ��0DJQ��0DWHU��������������������
� ���6�%�'HVX�� '�$�3D\QH�� -��$P��&HUDP��6RF��� ���
������������
� ���-�+HPEHUJHU��$�.ULPPHO��7�.XU]�HW�DO���3K\V�
5HY��%��������������������
,�$�'DQLOHQNR�HW�DO����6XUIDFH�VHJUHJDWLRQ�DQG�FKDUJH����
)XQFWLRQDO�PDWHULDOV������������� ���
�ºm˯²ÓËmÈ�°Ë�¯Ë�È�L«��È�Ïȯ«�ºmÒ®�°�ÈÓ�/D���6U���0Q2��,�k�iÈÓÒãËÓ}º������zºÓ°�ÈÓ�ÒÓºmÈ������bÈ�ÈãºmÈ�{�s�z¯Òmº¯��}º��{�i�iº¯º�Ëm��{�k�v��¹È}����z�{ºã}ºmÈ
lË�º�ÈäÒ�«�˯Ӻ�º�äÈ�ÓL�Óº�º�¯ËϺÓÈÓ°�� L�m�º¯ÒÓÓº�� LºÓÓº��äȰ�°¹Ë}�¯º°}º¹L��¹¯º�
mË�ËÓº� �º°ãL�ÎËÓÓ«� Ïȯ«�ºmº�º� °�ÈÓ�� �È� ²LäL�Óº�º� °}ãÈ��� ¹ºm˯²ÓL� ÓÈÓº�Ȱ�ÒÓº}
/D���6U���0Q2��Ï�¯ºÏäL¯ÈäÒ����L���Ü����Óä��{Ò«mãËÓº���º��ã«�¹ºm˯²ÓL��Ȱ�ÒÓº}�²È¯È}�
�˯ÓÒ®� ¹L�mÒ�ËÓÒ®� °}ãÈ�� LºÓLm� 6U� L� 0Q�� È� �²Ó«� }ºÓ�ËÓ�¯È�L«� ÏÈãËÎÒ� � mL�� ¯ºÏäL¯�
�Ȱ�ÒÓº}��Ð}�äºÎãÒmÒ®�ä˲ÈÓLÏä�¹Ë¯Ë¯ºÏ¹º�Lã��}È�LºÓLm�¯ºÏ�ã«�ȼ� °«�¹¯º�˰�¹ºm˯²�
ÓËmº�� °Ë�¯Ë�È�L����È}Òä��ÒÓºä��ÓËäÈ�ÓL�ÓÒ®��ȯ���º�°¹º°�˯��ȼ� °«�ÓÈ�¹ºm˯²ÓL��Ȱ�
�ÒÓº}��äºÎË���Ò� °Áº¯äºmÈÓÒ®� m�¯ËÏ�ã �È�L� ÏLã �ËÓÓ«�}ºÓ�ËÓ�¯È�L�� LºÓLm�6U� L�0Q� �
¹ºm˯²ÓËmºä���ȯL��º�mËãÒ�ÒÓ���º�mL�¹ºmL�È
� �ÈÓ�ÒÁ˯ºäÈ�ÓL�Óºä��°�ÈÓ��
,�$�'DQLOHQNR�HW�DO����6XUIDFH�VHJUHJDWLRQ�DQG�FKDUJH����
��� )XQFWLRQDO�PDWHULDOV�������������
|