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Letter
Molecular Ion Formation by Photo-Induced Electron Transfer at the Tetracyanoquinodimethane/Au(111) Interface David Gerbert, and Petra Tegeder J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.7b01897 • Publication Date (Web): 12 Sep 2017 Downloaded from http://pubs.acs.org on September 14, 2017
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The Journal of Physical Chemistry Letters is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
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The Journal of Physical Chemistry Letters
∗ !" #$% & '
!" ### $ % & $ ' & ()
* $ & $
+
$ $ $ & !" ### $ & $ , & $ - ()
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hn
e-
!! """ #$! $ %" ! "&' ! " "" $"(
) *" "$$* "+! +$"
%! + ! " * %" ," - "$ $$"( ."!" " $ ! " ! !%$+ - "$ $$" $ + !!"' !$! $*"" ! / - $+* """ $$* !! " " !! +/ -+ - $ !%"(
0$$ !' + ! ! %* +1
!" 2 ""% "( +' $$+ !" " " * ! !" % 2 & +1 +3" "!" !! """ +$" $1 ! $$ " 4$!(
5&%' $* $$! #+$ !" ! &$$ !4! "+$"
1$ %" - -!+$ *"$ ! +$ """ " " - " !! "- -"( ) " 6 & "!! !! "- *7!+
89 :; -( 89 " 3& 1 %$* ! %" +$ " -"
! " $ ,* EA < (= > " +$ +$$ $
"-' 1 "*" +" $3$* $ ; ( ? $ +"*
?0 ! @ * $ ""* @ ? "!" "" $* !! &3 - &3$* !"1! 89 +$$" ; ' & " "1$/! 1* +$$ *! 1!"( 8%$""' !" " &$$ !4! +$$ !" +
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*' 1! - &3 - Φ %$" -+ ( > ( > % 1 ! - " $ -( ;" " %$" "! - &!" " "- " ; &3 - Φ < ( > $" +!!$ - " ' & " 3* $ ! " +% + " "!* - $ " $ &3 - - 89:; -( A" * "$%! & +""
B & !+! $
"' ((' ! ! ! $ "" " &$$ " &3 - - +$* 06 89 ; ( " &$$ !4! !"1:"1" "*"+ & +"! Φ - (±( >' %$ & $$* " " "- ( ?"$*' $$+ "+$ & A> " "$!
Φ
"
(±0.05 >' &$ !4! 89 !%! $ "" C!( " Φ
%$ """ "- * ( +$ % !" %"
"" $! $ Φ %$ - $$+! "+$ (±( > ( D "" 1"%! C" & (( $ "- -+ +$ "1" 89 +$$"' % "( ) ! +$$" $" 1! 1* &3 $ 1( "&" B " - 06 89 ; !! & !C "( * !!! +"+" !! "" 1"%! +"" -" ! ! $ "" - !$" " E-"( ( &3 - - 06 89 ; +" (±( > $& * C -
B " ( ; -+ 13! 1$& EF inal −EF < ( > EF + *
" -+ $! ! 1!"' 4% +"" -" 1 1"%!( ;
B 3
F" 1$& + ! $! ( ±(> & " B 1 ""! "-! ; "- " ??G ( "- " - 1 ; "- " $! ( >( " !"1 !! "- - Δ = 160 ± 30 +> " -! " $" 1! " $ ""* ?? ( ;! ;+1"
) " "+$$ !"1 !! "- - "- " 1 ""! & =
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10 IPS m = 1.2 ± 0.2
a)
q = 1.0±0.1 ML
SS‘ m = 1.9 ± 0.1 EFinal - EF [eV]
2PPE Intensity [normalized]
9 8 7
UMO m = 1.2 ± 0.1 HOMO m = 2.0 ± 0.1
IPS1
FS m = 0.1 ± 0.2
6 4.0
4.2 4.4 4.6 4.8 Photon Energy [eV]
5.0
SS‘
5
6
b)
hn = 4.79 eV 4.61 eV 4.42 eV 4.30 eV 4.19 eV
UMO
s ure eat MO df an HO d-b FS + +
7 8 9 E Final - EF [eV]
10
2PPE Intensity [normalized]
q = 1.0±0.1 ML increasing hn = 4.75 eV photon dose IPS1 FS HOMO
es
tur
ea
df
an
d-b
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
5
6
SS‘ UMO
7 8 9 E Final - E F [eV]
10
* !! B " - 06 89:; ( * #" %$" 4$ " * EF inal - +! $" & " EF EF inal − EF = Ekin + Φ "' $& * C "!" &3 -
Φ - !"1:"1" "*"+( )" * !! 3 "" "" 3" 1"%! B "+ !' ! +! 4$ $ ""( ; "$ - """ 3 " -+ ! "' "$ - & " $! 3" -+ ! ""' &$ * !! 3 " "$" -+ ! 4$ ""' $! 1% %+ $%$( % +"" -" & 1 ""! 50' "-! ?3$* "- " ??G ' ! +$$ !! $ " A0 ' 4" + $ " ) ?1 ! 4$ " ? 1"%!( 1 A> $ #" - 06 89 ; $!" &3 - "(
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-$ +$ +$$ !" - 1 =( H' & + 1 ! - "+$$ -$ &% - %$' $& +$:+$$ " ! "4 "- 89:; -( ) !!' +"" - -+ ! " 1 ""! " ! +$$ 1$
50 ( )" " " (±( > 1$& BF ( "' / $
) " (±( > + & $ %$"(
0%' & ! $
"" 1"%! * C -
B "( +""
- 1 ""! ! +$$ !%! $ " A0 ( ) " $$* $! =(±( > 1% BF ! + " -+ $* ! +$$ 1$ - 89( ; "! +"" - 1 ""! 4" + $ " ) ?1 $$* $! −0.75 ± 0.05 > & " B ( ;$ "$%! B "&" $ !"" - ) ? ! "& ( * !! B - 1 ""! & ! 4$ " ? $$* $! 5.72 ± 0.05 > 1% B ( 8
B $" 1 !
$ "" 1% %+ $%$( * 1 %&! " " " % & #! $ "!" "$* +$$ "' -$$&! 1* !+ ! !( A" &! - !C " & ! 1"% - +"" -" * !+ & $&" ! +$$ 1$ 6A0 - 89 " #!' & " ( > & "
EF
"
!+! & ??( " + 1 ! &3 &% - %$ " !$ ++ ( )$$+ "+$ &
hν
< ( > "+$ + - I $!"
! " &3 -( ;" "& ( 1
Φ
"" & "
!" -+ (±( > " $+ - (±( >( "' - +> " -! ! %$ & % #!"
Φ
- 1 ; "-( 8
&3 - %$ -! - $$+ "!" %$ - 06 89:; !+! 1* $%$ +"" A ? "!" 3& -+
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q = 1.0±0.1 ML hn = 4.52 eV
2PPE Intensity [normalized]
a)
IPS1+SS‘
before illumination (F B ) after illumination (FA ) increasing annealing temperature (FC (T))
s ture fea FS + and d-b OMO +H UMO
5
6
7 8 E Final - E F [eV]
9
b) ln[ln(FB -FA )-ln(FC (T)-FA )]
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
0 -2 -4 -6
q = 1.0±0.1 ML hn = 4.52 eV EA= 43±11 meV
-8 4
6 8 -3 -1 1/T [10 K ]
10
!! "$ +!4" B " 89:; - 1 %"! 1* +$$* %! ""( 1 ;" $ - +$ "$ -+ "" "& ( ; +" - &3 -
" # - !$" " $! % %" $ +( 5 Φ " " "! &3 - - $$+' Φ "" &3 - 1- $$+ ! Φ (T ) !" &3 - - $ $ ""( $( 1%"$*' "
Φ
%$ "!" 89:; "+$' & "
1 +!4! 1* $$* !! ""( J Φ $" +"" - " -+ ) ? "-" " ) ?" ! %+ $%$( ) !!' ??G " 7! & " !"( )+$*' $$ 89 !%!
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+"" -" 2! 1* $ #"' ((' * "" "*( +' & - " " " "$ - $$+( )" "1" + $!" Φ !" " 1 " ( ( 1* -$$* %"1$ "" " !4! - ", $'
*) Φ %$ - $$+! "+$ " 1!( ) ! 7% " % 1 % +$$* !! 13 ' & "!! " &3 - ! $ - 10 + $ +" -+ 100 I 325 I( % * EA " !+! -+ $% Φ ( A" &3 - ΦC (T )' & !!" $ + ' " +" - "" - 13 $% +1 - +$$" & & 13 $ ""' ((' 1- $$+ ' ΦA ! ΦB &3 - - ! 1- $$+' "%$*' & 1 -$$& #"" ln[ln(ΦB − ΦA ) − ln(ΦC (T ) − ΦA )] = EA /kB T + const.
&3 - %$" - $ "' ΦC (T )' "& -+ - 7 " - - %" + ( 1 ' *$! % * - +$$* !! "" - EA < =± +>( ; !""" 1 % * &$$ 1 % 1$&( = "++/" 1"%! %"1$ "" 06 89:; ' ((' !! &3 - "- ! +$$* %! 13 ' & 1 % 2 "" - +$$ $ ""( 8&' & % !""" ""1$ !$* """ - 1"%! +( 1*' "%$ """ 1 "!! !"" +$ ' !"' !! "$ + - !"1' ! % $$* !! -$ "-( ? & ! 1"% * " " "* - 1"%! +"" - ! $$+' & #$!
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DF 0.30 = eV
5.72 eV
4.45 eV
F = 5.50 eV
E i -EF
EVac
3.71 eV
FS
= DF eV 5 6 -0. 5.10 eV 1 IPS UMO
hn kBT
EF
EBind -EF
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
SS
-0.26 eV
SS’
HOMO -2.48 eV
Au(111)
1 ML TCNQ
= B$ " - 06 89:; $$" !! &3 - " ! +$$* "+$! 13 ' &$ "" - +$$ !! "" C!( !"" +$ " &$$ " !"( ;!!$$*' " " % 1 -$$* %"1$ +$ %' & " %* $3$*( 0%' 89 " $' "*++ +$$ & !$ ++ ! !"1" 2 !" +* ; "-( ; + -+ " !" " + $! 4 " $$* -%1$( +' + " - 89 &$! "$ - "- " ! !$* ; "- " "$! "*' 1 " & -! ??G " """! 1* $$+ ( )"!' & " !! "- 1 ""1$ - 1"%! C"( ; $ "- -+ ; "1" ! +$$ " % &$! #$ " - &3 -( % " $* +"1$' " +$ % $! !* - " + $ & &3 - !"( 8 489:; - " ??G " -!' & " 1! -$ "-' ((' " - %$* ! ""(
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$*/ !! $ "- + !$' & 74! "" ! -+! !" ! * !! +"+"( ;" - +$$* %! ' & "! &3 - - "+$ " 7% 1+3 - "" - "+$! ( Φ " - - !" " !! #+$$* - - !C " ( ( &3 - " " - - !" np ' +1 - " -$$&" "*+ 1% & "" Φ = 5.20 ± 0.05 > ! "" " %$ - Φ = 5.85 ± 0.05 >( ) 1 4! 1* "+$ + #$ " - Φ = Φ + ΔΦ exp( σ · np )
& " "! !+ C% "" " σ( 8 - " 1% ( > % &3 - %$" - ! > -!' ((' &3 - +"! - hν < ( > !" " ( > " ( ( )- " "" &" -$$* %"1$' & & 1 !"" "( 5&%' "" " "" & " * $" 10−21 +2 - " ( >( A" 1! %* - " !+ "" "" - $$&" " !& $"" 1 !$* # ""( 1 !"$*" " * !! - "" ""( " $ 4.25 ± 0.05 > " ! "" " #1" #$$* " ,* & " *( +"' 06 489:; !! &3 - "- " 1"%!( E! -$ !! $ "-' " - %$%! +$$ " " 1 %* -
4.25 ± 0.05 >
1%
EF (
A-$*' & ! 1"% 89 !%!
$ " " * ( ;" - $ " -+ 6A0
" 1% ' 1"% - +$$ $ "" B + 1 ! %" &% - %$( 5&%' #$$* " "" " &
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Work Function [eV]
a) 5.8 TCNQ/Au(111) q = 1.0±0.1 ML
5.6
hn = 4.42 eV -23 2 s = 5.5±0.2 10 cm hn = 4.52 eV -22 2 s = 1.2±0.1 10 cm hn = 4.79 eV -22 2 s = 8.8±0.1 10 cm hn = 4.86 eV -22 2 s = 7.7±0.2 10 cm
5.4 5.2 0
2 4 6 22 -2 Photon Dose [10 cm ]
b) 10 Cross Section [10-22cm2 ]
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
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8 6
TCNQ/Au(111) q = 1.0±0.1 ML F4TCNQ/Au(111) q = 1.0±0.1 ML
4 2 0 2.5 3.0 3.5 4.0 4.5 5.0 Photon Energy [eV]
D3 - & " !" ! $$+ 4! & #$ - ! 7 !+ C% "" ""
σ ( 1 * !! - C% "" "" - 06 89:; ( +" !! C " -! - 06 489:; ( " * " &!" $ - +$$ " 1* $" " ""( $ &$! 1 - " ! +$$ " (( 50 6A0 "1" +!! ! ""' & (( $" -+ $! "- " "$* $ ! +$$ "( !' & " * $ - $"' & " & ! +$$ $%$ $! ! ( >' "$!
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" $$* ! " 11$* - -+ - % "$! 1 !( ; 489:; - +$$" $!* %$* ! - !"' - $ "- " -"1$( ;" "+$$* "& "+ ' & "" -$$& """ 1 ""1$ - %"1$ &3 - " 89:; - 6 #" & " - hν>( > $!" $ $ - ! +$$ " % $ "- -+ +$$ "1"( ; $& +" ! % " "1$ ! +" $3$* !$! -+ "1" " 13 "- - $" " """!( 8 $ -
n
< ) ? -$$&! 1* "- +$$
" +* $" ""1$ " - % -+(
$" 1!
1* "+$$ $ 1' & 1 - EA < =± +>( D 1$% "1$/ - % " "! 1* " $ - +$$( " + - - % " ! " !" "$" &3 - " " %$( ; "+$ +"' % " !* % 13 "- - $" +$ & " !$* -$$&! 1* ! &3 - 13 " $ %$( ) "++*' & !+"! - 89:; - "- " ' &$ A> $ #" !! "1" +!! "- -+ +$ ! 89 !%! $ "( " $! - %$* ! 89 +$$" ! !$* ! " - &3 -( 1* &3 - - 89:; "*"+ 1 "$* ! "" 1 "1" %$ 1* $$+ & A> $ & "1$"" & $ ""1$" - 89 +$$" - #+$ " !% !! $ F $* A> $ ""( $$*' "!* $$"" !! "- """ : -" $ - " $ +$$" % 1 "!! ! !-* -$ "- " 1"" - &3 - %$" !+! +"" #+"(
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E hn > 4.25 eV
hot e -
EA 4.25 eV
EF
Au(111)
TCNQ
?+ "! " 89:; - $! %"1$ &3 - "( 5 $ !! ! "- -+ +$$ "1" ! +$$ " ! +$$* %! 13 "- - $"(
"+$ 89 +$$" & %! -+ C" $$ $! + - 390 I ! !"! ; "$ *"$ $! + + & &" %"$* $! 1* "%$ " ;+ ' + + ! $ *$" 800 I' 30 + ( J4! +$* % &" "! 1* ", !" + ! "1"7 $ " 370 I' & $!" !" - +$ $*" " 1 -$$&! 1* + ++! !" J " " -+ ( ?+$ " &$$ " J ! $ %+ +1 1" "" -
B #+" & -+!
5.3 · 10−11 +1(
&
+"" B #+" & -+! $7! + " " & &" #$$* !"1! $"&( ) ! "+$-* +" -
B " 3 !C " " !"$*! " -
- 4$ " * 1% + $%$ B
= 0 '
B − B
=
B − Φ( "
" " &3 - Φ "!" " - "!* ! $& * C ( $$*' B $$&" %" - 1' ! "
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&$$ " ! $ ""( "% ""+ &" %! 1* "!* * !! - " - !$" " E-"( ) ! % $ " - $$+! 89:; -'
B +
"+" & -+! & $$+ + - 10 " -+$* $$+! "( ? $$! $$+ "" & 3 " "1"7 "" - " $" B +"+"' ! 1 1$ "$% $$ "$ -"' "+ " $ " - &3 - %$ &" !( $" " 4$ &" /! 1* J + $! " "! A5> +1' & " 7%$ "+$ " " "/ ! - 150 μ+2 ( & - $" 1+ &" " "%$ D:+2' !! *( I& $" " "/ ! & $$&" - $$ - ! !" - * $$+ +(
+ ++! !" +"+"' & +"" ! - 1 ; "-(
! 1* + E" ! J $$1% " ?. F . " -$$* 3&$!!( J(( 3&$!" 4$ " -+ 5!$1 ! ?$ - !+$ *""(
?-' 8( ?(K ?+$&/' 6(K 5' ;( L(K D!$' ( !! B$ "- -+ ! $*+ .3+"-$$( + ' !,' M (
=
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E1$' )(K .3' .( ;(K I+' ( >( ?$ D$$! 1 81 !? 8+ "" " 6 5%" ;""+1$"
!! "- )"(
-) .) ' %/' M =(
= 6+' >(K ?$' 0(K .$F' J(K .N!"' L( 6(K $' L( !! ! E+1 J*+" 0!$ J:; " - ?$ $$ ;$" ; $$ 9+ +$ +( 0) -) ) +() ' % /' M (
I' 6( B(K 6' I(K ' ( I(K ;$$!-' 0(K > J*' E( (K 5' L( ( 0$M +&3 0$" " +$ ?""( ) ) ' %% ' M(
!' ( $$* ! +$$* )!! 0$$ ?& """ 0$ ?-"( 0) )1 ( ) . ' 2' = (
1' ;( (K D' ?( (K )%' L( (K ;%"' ;( L(K ."' L( (K ?! !' L( (K /*1&"3' .( ;( ?&" - ?-" ! J%"( -) .) '
!' ==M=(
J6+' J( 0( +(( . 3( +( ((( K ?' K M (
"' ?( E( A17" ! 6& " B$ ;$" $"( ' 2 ,' M (
?%' E( ( $3 ." - $" ?$ $$"( + ' "" ' =M =(
' 0( ;(K B+*' I(K 5"3&' O(K D' D(K J$' B( J(K 6%' J( 5(K 5 .$$' ;( D( ?$ $$ B,* 1$" %" ( (
((( 1
- ( ' !' =M=(
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;!+"' J( 0(K ."' 6(K !"*' ( B(K ' ?(K /' (K I' ( E(K I +' ( >(K 61+' 0(K 6!"*' ?(K 0"' E( ;(K $(' "- 8"$ ?"( 0 ) ) 4 ' %&/'
M
(
6!"+' ( J(K P' @( O( !! B$ "- 0$$ 0$ ) -"( ) ) ' %' M=(
= P' @( O(K O' 9(K 0&$' 0( "- B#" ?+ ! ?-" ! )-"( -) ) ) ' 2 ' M(
0' ( 6( ;( A!"! )-$ B$ ? ! "- ; B$" "%( 0) ) ) 5) ' "' =M=(
L$13%' ;( B(K D$$!' ;( (K "' L( E(K ' D( 6(K ?' 8(K 1' E(K I3' 6( (K D$$+"' I( L(K 6' I(K E""3*' ( L(K P' @( O( 5 "- B#" ? + 6+ - ? J:; )-" %$"( .) ' % '
M=(
I' 8(K ' J(K D1' E( 6(K .Q&' 8(K D' .(K D3' 0(K 6"' (K 5 $' )( >(K .' D( E! )!! J! ! ?- - $+" A$%$ +"" ?"*( 6 +( ' "$%' M(
D"1*' J(K D' 8(K 6"%*F' O(K I"+' )(K "' ;( 8(K ' J(K .$' L(K >"%' B(K J&1' ( ;( E! )!! J+" - 0$ 0$$ ." * '' ' +*$ =' ! )) ( - ) +3)
+) ' !!' = M=(
D3+' J(K 0*' 0(K E' (K D$-' 0(K ?R$' L( !! D3 0!4" ! BC $ ?"*( - ) ) 5) ' %&"' =(
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0!*' E( L(K ?$3' D( E( )F . 5" ;"" 0$$* $+"( 0) 0) -) ) ' 22' =M= (
"' ( (K A1' (K D' O(K ' E(K ' ?( 6(K ;$+S' 0(K TF' J(K $3' 0(K $$' L( 0(K 6' 8(K $(' "- )!! ?$ E +" . ?!" - :0$ )-"( ) ' ' =M= (
DR3$' (K )%' (K *$3' J(K ""' (K L' ( ;(K .$$%' 8( ;""+1$* - J ) 6*" 1* E - ;$3$ 5$!" & B$$ ''' * 7!+ 89 ( ) () ' 2/' M (
3' (K EF"' ( ;(K L' ?(K I$$*' ?( L(K ?+' ?( (K ?+' .( (K O' 0(K 03"*+%*' ( D3 + )" $ ;""+1$* - ?$* .!! 89 ) ; 0$$" ?$% ?-"( ) ) 4 ' $&' =(
= J$$ ' ;(K E$$' 0(K ?""' J(K L"' ( ?(K .-/' J(K J >' ;(K " ' ( & J+"$ ?$$ J ; ;""+1$" 0$ ) -" +! 1* ?- 0!! "-( ( ' ,' M =(
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The Journal of Physical Chemistry Letters
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The Journal of Physical Chemistry Letters
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