J . r l d l t e s i o r rS c i . l e t l t r t o l .V r l . ( r . N o . l l . p p .

l - 1 9 7 - l - l l 0 ( 1 9 9 1 )
o vsP 199t.

Self-assembled
monolayersof alkanethiolson gold:the
adsorptionand wetting propertiesof monolayersderived
from two componentswith alkane chainsof different
lengths
J O H N P . F O L K E , R SP, A U L E . L A I B I N I Sa n dG E O R G E M . W H I T E S I D E S *
Departntertt tl Chentistr\', Harvard Uttiyer.sin',('untbridgt', X'lA 021.18,{-/.\,4
R e v i s e c vl e r s i o n r e c e i v e c l2 7 J u l . v1 9 9 2
A b s t r a c t - ' l ' h i s p a p c r d c s c r i b c s t h e p r e p a r a t i o n a n d w c t t i n g p r o p c r t i c s o f t u o - c o r . n p o n c n ts c l l a s s c n t b l e - dm o n o l a v c r s ( S A M s ) o b t a i n c d h v t h e c o m p c t i t i v c a i l s o r p t i o n o l ' o n c s h o r t - c h a i n
(HS(CHr)r,,Sha
) n d o n c l o n g - c h a i n ( H S ( ( ' H : ) : , 1 - g )a l k a n e t h i o lo n t o g o l c i l ' r o m c l i l u t c c t h a n o l i c
s o l u t i o n s .T h e ' f o u r p o s s i b l c c o m b i n a t i o n s o l t h c t a i l g r o u p s C H , a n c l C H . ( ) H w c r c i n v e s t i g a t e d :
S h - C H r / L g - C H . O H . S h : C H . O H / L g : C H . . S h : ( ' H . O H / L g : C H . O H . a n d S h : C ' lI . / L u : C ' H , .
T h e c o m p o s i t i o t - tosf t h c s c S A M s a r c n o t t h c s a m c a s t h c c < l m p o s i t i o n so l t h c s o l u t i o n sI r o m r v h i c h
they we're formed. Although thc rclationship bctw'cen the composition ol'thc SAM and thc
c o m p o s i t i o n < l f t h e s o l u t i o n s u c g e s t st h a t s o m e p h a s c s c p a r a t i o nm a v b c o c c u r r i n q
thc SAM.
"r'ithin
c o n t a c t a n g l c s w i t h w a t e r i t n d h e x a d e c a n cs h o w t h a t s i g n i f i c a n tc l i s o r c l c rs t i l l r c m a i n s i n t h e i n t e r facialrcgion.
K c t ' w o r d . s :W c t t a b i l i t r ' : c r ' r t t t p o s i t i o ns: e l f - a s s e r n b l c dm o n o l i r v e r : a l k a n c t h i o l a l c ; g o l d . [ \ \ ' o c o m p o n e n t s ;c o n t a c ta n g l c :c l i s < l r c l e r .
I. INTRODUCTION

In t his paper , w c d e s c ri b e th e a d s o rp ti o n and w etti ng properti es of tw ocom ponent s el f-a s s e mb l e dmo n o l a y c rs (SA Ms) prepared by the adsorpti on of
alkancthiols with different lengths of alkyl chzrins-HS(CHr),/,Sh and
H S ( C H r ) , u L gw
, h c r e s h : l 0 a n d l g : 2 1 , a n d S h a n d L g a r e e i t h e rC H , O H o r
C Hr - ont o f r es h l y e v a p o ra te dg o l d s u b s tra tes.W e have studi ed the four possi bl e
c o m b i n a t i o n s o f S h a n d L g ( S h: C H . , / L g : C H , , S h : C H , / L g : C H . O H ,
Sh: CH,OH/Lg: CH., and Sh: CH.,OH/Lg: CH,OH). We have described
s om e of t he deta i l s o f th e s e s y s tc m sp re v i o u sl y [, 2l ; i n thi s paper. w e focus on
th e c om pos it io n o f th e SA M : i ts d e p e n d e nceon the condi ti ons for adsorpti on
a nd it s ef f ec t o n th e w e tti n g p ro p e rti c s . We i ntroduce thi s w ork w i th a bri ef
o v er v iew of t h e a rc a o f S AMs o f a l k a n e thi ol s on gol d. W e then di scuss the
relat ions hip lr e tw e e n th e c o mp o s i ti o n o f the S A M and the composi ti on of the
s olut ion. I n t he fi n a l s e c ti o n ,w e d e s c ri b es ome of the w etti ng properti es of these
tw< l- c om ponen tSA M s , c o n c e n tra ti n g o n t he rel ati onshi p betw een w ettabi l i ty
a nd t hc c om pos i ti o no f th e SA M .
2. BACKGROUND
Am ong t he m an y s y s te msc u rre n tl y a v a i l a b lefor the formati on of sel f-assembl ed
m onolay er s [ 3- 1 4 ], SA M s o b ta i n e d b y th e adsorpti on of al kanethi ol s (general
* T o w h o m c o r r e s p o n ( l e n c es h o u l d l r e a d d r e s s e d .

r'

l39lJ

f o r m u l a H S ( C H . ) , , X )o n t o g o l d ( a n d ,p e r h a p s o
. n t o s i l v e rt l l . l 2 l ) a r e t h e m o s t
ver s at ile:t he s t re n g th z rn d s p e c i fi c i ty o f th e metal -sul fur i nteracti on al l ow s the
i n t r o d u c t i o n o f m a n y i m p o r t a n t t e r m i n a l f u n c t i o n a lg r o u p s ( X ) i n t o t h e m o n o l a y e r s i l 0 . l - 5 - 2 1 1 .T h e h i g h l y o r d e r e d s t r u c t u r e o f t h e s e S A M s h a s b e e n
e s t a b l i s h e du s i n g a v a r i e t y o f t e c h n i q u e s .i n c l u d i n g p o l a r i z e d i n f r a r e d e x t c r n a l
r e f l c c t a n c es p e c t r o s c o p y( P I E R S ) [ 9 . l l . 1 2 . 1 5 . 2 2 1 , e l e c t r o n d i f f r a c t i o n t 2 3 ] ,
h e l i u m s c a t t e r i n g[ 2 4 , 2 5 ] , X - r a y s c a t t e r i n g1 2 5 . 2 6 1 , s c a n n i n gt u n n e l i n s a n d
a t o m i c f o r c e m i c r o s c c t p i e [s2 7 ] , a n d s u r f a c eR a m a n s p c c t r o s c o p y[ 2 S ] ( F i g . l ) ,
m o l e c u l z t rd y n a m i c s c a l c u l a t i o n sy i e l c l a g c n c r a l s t r u c t u r e i n a s r e e m c n t w i t h
t h e s e t e c h n i q u e s[ 2 9 ] . T h e c x p e r i m e n t a l l r c l c t e r m i n e ds t r u c t u r e e x p o s e s t h e
t e r m i n a l f u n c t i o n a l g r o u p s ( X ) a t t h e m o n o l a v c r - a i r i n t e r f a c e .a n d t h u s a l l o w s
the int er f ac ial p rt-rp e rti e so f th e m o n o l z rv cr to be control l ed by changi ng X .
M o d e l s v s t e m sb a s e d o n t h e s e S A M s h a v c b c c o m e i n c r e a s i n g l yi m p o r t a n t i n
f u n c l a m e n t a ls t u d i e s o f e l e c t r o c h e m i s t r vt l 9 . 3 0 1 . p r o t e i n a d s o r p t i o n t 2 0 1 .
X - r a y - i n d u c c dd a m a g et o o r g a n i cm a t e r i a l s[ 3 1 ] . a n r l v , ' c t t i n g1 1 , 2 . 1 0 , 1 3 . l 6 1 , 32. 0 , 3 2 - 3 5 1 .
O u r i n t e r e s t i n t h e s c S A M s i s b a s c c lo n i u r i n t c r e s t i n t h e p h y s i c a l - o r g a n i c
chcmistryof orsanic interfacese
. s p e c i a l l vt h c r c l u t i o n s h i p sb e t w e e n m o l e c u l a r
structureand wetting tl. 2, 13, l6-ls. 10. .tll SAMs derived from rhe
ads or pt ion of a l k a n e th i o l s o n to g o l d p ro v i cl c l r ntol ccul ar basi s for sturJi esof
w e t t a b i l i t y .I n o u r i n v e s t i g a t i o nos f t h e w e t t a b i l i t r o t ' S A M s . w e h a v c u t i l i z c d t w o
a p p r o a c h e s :f o r m a t i o n c t f s i n g l e - c o m p o n e n tS , \ \ l s u i t h t e r m i n a l f u n c t i o n a l
g r o u p s o f v a r i a b l e h y d r o p h i l i c i t y[ 0 , 1 3 . l 6 - l S . ] 0 1 . a n c l f o r m a r i o n o f r w o 'l'hc
c o m p o n e n to r ' m i x e d ' S A M s 1 1 . 2 , 1 3 , 1 6 , l t t . l O l
l u t t c r m c t h o c lp r o v i d e sa
g r eat erdegr eetl f c o n tro l o v e r th e p ro p e rti e s of thc i ntcrt' l rcc.l rcczrusc
the rel ati ve
conc ent r at ionso f th e tw o c o m p o n e n tsi n th e S A \l cl rn l -rcl rrl j ustccl .
W h e n t w o - c o m p o n e n tS A M s a r e u s e dt o f o r m s L r r f u c cost ' s p c c iifc v n ' c t t a b i l i t i e s ,
t w o r e l a t i o n s h i p s d e t e r m i n e t h e w e t t a b i l i t r ' : t h c r c l r r r i o n s h i l ' br et w e e n t h e
w e t t a b i l i t yo f t h e s u r f a c ea n d t h e c o m p o s i t i o no f t h c S . ^ \ \ 1 .a n t l t h c r e l n t i o n s h i p

a = 4.078A

Au (111). AUSR
{5x {g R 30'
F i g u r e l . T h e s t r u c t u r co f a l k a n c t h i o l a t cas c l s o r b c do n s o l r l r l l l t . ' f h i o l a t c s a r c a c l s o r b c calt t h r c e f o l d h o l l o w s o n t h c s u r f a c e f o r m i n g a c o m m c n s u n r t c \ . 1 r , - R - 1 0 "s t r u c t u r c [ 2 3 J 6 l . T h c a l k v l
c h i r i n s a r e i n t r t r u n s z i g - z a ga r r a v ( t h c s m a l l c o n c c n t n l t i o n o f g u t r c h e c o n f o r m c r s i s l o c a l i z c d n c a r
t h e e n d s o f t h e c h a i n s [ 1 2 , 2 1 , 2 9 ] ) a n d a r c o r i e n t e c la l - r o u 3
r 0 " f r c m t h c s u r f a c en o r m e r l[ 9 . 1 2 . 1 5 .
2 2 1 . B e c a u s co f t h i s h i g h l y o r d c r e d s t r u c t u r c .t h c t a i l s r ( ) L r p s( X ) a r e l o c a l i z e da t r h e m o n o l z r y c r - a i r
interface.

.tA,!1.sof' u I ku net hiols otr glt ld

I3 e 9

b e tw eent he c om pos i ti o n o f th e S AM a n d th e c o mposi ti on of the sol uti on.In thi s

p a p e r we dis c us s b o th o f th e s e re l a ti o n s h i p s try presenti ng data for S A Ms
6 e i i ved f r om t wo a l k a n e th i o l s w i th a l k y l c h a i ns of di fferent l engths. W e al so
d i scus s t he wet t ing re s u l ts i n te rms o f th e e ffe ct of di sorder i n the i nterfaci al
re g i o n on t he wet t ab i l i ty o f th e s etw o -c o m p o n e n tS A Ms t I . 2, I 31.
In m ix ed S A M s co n ta i n i n g o n e l o n g -c h a i n c omponent and one short-chai n
co mponent , t he r eg i o n c l o s e to th e g o l d s u b s tratcthat i s cl ccupi edl oi ntl y by the
sh o rt c hains anc l t he c o rre s p o n d i n gs e c ti o n so f t he l ong chai ns i s w el l ordered:
th e re gion f ur t her a w a v fro m th e g o l c l th a t i s o c cupi ed onl y by the remai nder of
th e l o ng c hains is d i s o rd e re d (a s l o n g i l s th e components have not phasc
s e p a r a t e ds; e eF i g . 2 ) t 3 6 1 .T h c r e s u l t sr e p o r t e c il n t h i s p a p e r i n d i c a t et h a t . u n d e r
co n d i t ions c om m on l y u s e d i n fo rm i n g mi x c c l SA Ms. there appears to be some
p h a s e s e p a r a t i o n o f t h e t u o c ( ) m p o n r - n t si n t h e S A M , b u t c n o u g h d i s o r d e r
r e m a i n st o a f f e c tt h c c o n t a c ta n s l c st l . 2 l
We hav e c hos en .r/r: l 0 a n c l I.g ,:2 l i rt o u r w ork; these cl assesof thi tl l s are
s y n t h e t i c a l l ya c c e s s i b l ca r n csl o l u t - r lier t c t h a n o la t m i l l i m o l a r c o n c e n t r a t i o n st l . 2 1 .
s f S A M s c o n t a i n i n gm i x t u r e so f t h e s e
W e c a n e a s i l yd e t c r m i n c t h c c o m p o s i t i c l n o
l o n g a n d s h o r t t h i o l a t c s b r s c v e r a l t e c h n i q u e s [ 2 ] . X - r a y p h o t o e l ec t r o n
spectroscopy (XPS) is thc most useful singlc technique: XPS provides
i n fo rmat ion per t ain i n gttt e l c me n ta lc o mp o s i ti o n and oxi dati on statcsi n acl di ti on
t 9 t h e r e l a t i v ec o n c c n t r a t i o n so f t h e t w o c o m p o n c n t si n a S A M . I n t h i s p a p c r . w c

= Sh = CH2OHor CH3
= (CH2)1q

=S-

= L g = C H 2 O Ho r C H 3

= (CH2) 21

=S-

F i g u r c 2 . S c h c m a t i cr c p r c s c n t a t i o no f a m i x e c lS A M u ' i t h e c l u a lc t t n c c n t r a t i o n so f a l r ; i t s - c h a i n( l - g )
l:
a n c l a s h e r t - c h a i n( S h ) t h i o l a t c ( r a t i o o f t h e t \ \ ' o c o m p ( ) n c n t si n t h c S A M : R r . r , : [ [ - g J ' [ S h ] :
m e l e f r a c t i o no f t h c l o n g e r c o m p o n e n ti n t h c S A M : / r " s r r r : t l - g l l ( t [ - g l + [ S h ] ) : 0 . 5 ) . T h c t o p
c l r a r v i n gs h o w s a m o n o l a y c r w i t h t h c c o m p o n c n t s r a n d o m l v m i x e d . a n d t h e b t l t t o m s h o w s t h c t r " ' t l
c ( ) m p o n c n t s p h a s c s e p a r a t c d .W e b c l i e v e t h a t o u r S A M s a r c s o m e w h c r e b c t w e c n t h e s c t r , r ' t l
cxtrcmes.

I+()(l

. 1 . l ' . I b l k t r , s e - la l

h a r c g s c d t h c n a t u r a ll o g a r i t h mo f t h e r a t i o o f t h e c a r b o n I s i n t e n s i t yt o t h e g o l d
- + l i n t c n s i n ' ( c l e n o t e da s l n t C ( l s ) / A u ( a f ) l i n t h i s p a p e r ) t o d e t e r m i n e t h e
c i r n r p r 6 s i t i o nosf t h e S A M s l 2 l . O u r g r o u p h a s s h o w n p r e v i o u s l v t h a t t h i s
(luant it \ c an b e u s e d to d e te rm i n e th e c o mposi ti ons of S A Ms i ncorporati ng
t h i 6 l l t e s 6 f c l i f f e r e n tl e n g t h s[ 1 , 3 7 ] . T h i s m e t h o d i s e x c e l l e n tf o r c h a r a c t e r i z i n g
t h c c o m p o s i t i o n so f a g r o u p o f m i x e d S A M s b e c a u s ei t m i n i m i z e se r r o r d u e t < l
c l r i f ti n t h e i n t e n s i t yo f t h e X - r a y s o u r c e . x
T hc g' 1lr k c l e s c ri b e dh e re i s fo c u s e d o n the tai l groups methyl and hydroxyrnc t hr l: t hes e g ro u p s p ro v i c l e a l a rg e d i ffc rence i n the w ettabi l i ti esof the si ngl e., , nr 1r , ' , n. ntS AMs a n d a l a rg e ra n g e o f w e ttabi l i ti esfor the mi xed S A Ms l l . 2.
1 0 . 1 6 l T h e o x y g e n o f t h e h y d r o x y m e t h y lg r o u p a l s o p r o v i d e s a ' t a g ' f o r
m o n i t o r i n gc o m p o s i t i o nb y X P S [ 2 ] .
AND
OF TH E S OI,T]TION
B ET W E ENT H E (-OMP OS ITION
.1.T HE RE LA T ION SH IP
O F T H E S AMI
T HE CO M P O S IT IO N
When t wo- c omp o n e n t S AMs z rrefo rme d from thi ol s of di fferent l engths under
' n r t r m a l a d s o r p t i o n c o n c l i t i o n s ' ( g o l c l - c o a t e ds i l i c < l n s u b s t r a t e si m m er s c d i n
e t hanglic s c llu ti < tn sc o n ta i n i n g a to ta l c o ncentrati on tl f thi tl l tl f l rl l M: l day;
r o o m t e m p e r a t u r e ) .t h e r a t i o o f t h c c o n c e n t r a t i t t n so f t h e t w t l t h i o l a t c s i n t h e
S A M ( R r ^ r , : I A u ( l ) S ( C F I . ) r , L g ] , ' I A u ( lS) ( C H r ) , / , S h ]a) n d t h c r r t t i o o f t h e
:
c o n c e n t r a t i o n so f t h c r e s p e c t i v e t h i o l s i n s t t l u t i t t n ( R , , , r , , I t i S ( C H ] ) , . r L g ] /
\
\
'
c
(
F
i
g
.
3
)
.
harc plotted the
F
i
g
.
3
.
I
I
r
I H S ( C H ] ) , / , S h l )a r e n o t t h e s e r m e
l
t
lnger ctlmponent
o
f
t
h
c
f
r
a
c
t
i
o
r
t
c c t m p o s i t i o n so f t h e S A M s a s t h e m o l c
i
t
n
c
l
( X , . * . r , r nw,h. e r c / r * . s , r r , r : I L g ] r . . r r r / ( [ L g l s r r r + [ S h ] r r . , , ){ , * , : , r r , * X s r r s r \ r :l )
a g a i n s t R r o ' t l . 2 1 . T h c c l e v i a t i o no f t h i s c L r r \ c f r o m i d e a l i t , v( / i . . \ y : R , , , r n ,
in F i g . 3 ) i n c l i c a te sa p re fe re nce of the l onger comportctl t for the
c las hecline
l
s u r f a c e ;t h e s h a r p n e s so f t h e t r a n s i t i o n r e g i o n s u u g e s t st h a t m i x i n g o l ' t h e t w o
c o m p o n e n t s i s n o t e n t h a l p i c a l l vf a v o r c d w i t h i n t h e S A M . p o s s i b l v l c a d i n g t t r
p h a s es e p a r a t i g ni n t h e S A M s . ; F r o m t h e r e l a t i o n s h i pb e t w e e nt h c c o m p o s i t i o n
of the SAM ancl thc composition of the solution. we infer thc following
SAM:
thc
interactions within
for
ranking
qualitative energy
c
n
c
r
g
i e sf o r
, e t e r m i n ea b s o l t r t
t .o w e v c r d
L g . L g > S h . S h > L g . S h . W e c a r n n oh
t hes eint er ac t i o n sb e c a u s eth e s es y s te msa re not at equi l i bri um.
E v en t hough w e c l o n o t k n o w th e c l e ta i i edmol ecul ar mechi tni srttof tormati on
of S A M s . or t h e me c h a n i s m (s )o f e x c h a n gebetw een thi ol atcs otl tl tc sttrfaccand
t h i o l s i n s o l u t i o n [ 3 9 ] . w e k n o w t h a t t h e s e S A M s a r e n o t i t t c t l L r i l i l r r i u mt:h e
r e l a t i o n s h i pb e t w e e n t h e c o m p o s i t i o n o f t h e S A M a n d t h c c o n t p o s i t i o n< l f t h e
s olut ion is nc tt s ta b l e to c h a n g e s i n th e condi ti ons usccl t' or rtcl sot' pti tl n.For
ex am ple, inc r e a s i n g th e to ta l c o n c e n tra ti on of thi ol i n sol ttti ol l rcsul tccli n an

' F F o rd e t a i l sc o n c e r n i n gt h e e x p e r i m e n t a lp r o c e c l u r e ss, e e r c t . l .
t o i l l L t s l r r t ttch c r c l a t i o n s h i p
t l n t h i s s e c t i o n .u , e h a v e u s c d t h e s y s t e m S h : C H . " l - g : ( ' H . O l l
b e t w e e n t h e c o m p o s i t i o n o f t h e S A M s a n d t h e c o m p o s i t i o n o f t h c s o l r t t i o n s t. h e g e n c r a l t r e n d s a r e
t h e s a m ef o r t h e o t h e r s y s t e m st h a t w e h a v e s t u c l i e dt 2 . 3 8 1 .
tlf the
;At present,we do not have experimentalresults that explicitlv detcrmine the <lri.uin
p r e s c n t a t h o r t l u g h i r n a l y s i so f
i n f e r r e d p h a s es e p a r a t i o ni n t h e s e S A M s . I n a s e p a r a t cp a p e r . w c
"rill
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I o r n r c c lt:h e c l ' f c c to l ' c h a n g i n qt h c t o t a l c ( ) n c c n t r a t i oonl t h i o l i n s o l u t i o r rI.: r l l c dc r r el es : \ l i r c d S A M s
t o r n t c c lf ' r o n tt h c c o m p c t i l i v ea d s o r p t i o no l ' H S ( C ' t l . ) r r ( ' H . O H a n d H S ( ( ' H . ) ( l l l r o n t c t h a n o l i c
s o l t t t i o n su ' i t h t o t a l c o n c c r t t r a t i o t tosl ' t h i o l o l ' l ( ) n r M i l l r ( ) o l l tt c m p c r a t u r ct o r i t l l r r . ( ) p c n c i r c l c s .
N I i r c d S A M s l i r r m e c lf r o n r t h c c o n r p c l i t i v cu c l s o r p t i o no f I l S t ( ' H . ) r r ( ' H . O t { r r n r l l l s r ( t l . ) r , , ( ' H ,
t r o r n c t h a n o l i c s o l u t i o n su i l h t ( ) t a l c o n c c n t n t t i o n so f t h i o l o l ' 0 . 0 1 m M a t r ( ) ( ) l nl f l n l ) e r u t u r cf o r '
I r i a l ' .A x i s l a b c l sa r c c l c s c r i b c ci nl t h c c a p t i o nt o F - i q . 3 . ' l ' h cc u r \ . c st h r o u g hl h c c l l r t rrrr r eo n l v g u i r l c s
t t l t h c e y c . T h c c l a s h c dc t t r v c b c t u ' c c n t h c t \ \ ' o s c l s o l ' c l a t t rr e p r c s c l l l st l r c c u r r c t h r , r r r L l tr h c c l a l i ri r r
F i s . 3 : t h e c l a s h c cclu r v c o n t h e r i g h t r c p r c s c n t s/ ? , , r , : / ? . , , , , , .

d e t e i m i n e c lu s i n g s c a n n i n s t u n n e l i n g m i c r o s c o p v I 2 ] . I f w c \ \ , c r c t o u s e g o l c l
s u b s t r a t e sw i t h l a r g e , a t o m i c a l l y s m o o t h t e r r a c e s [ : t 0 ] . w c n t i c h t o b s c r v e a
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h e x a d e c a n ei s s e n s i t i v ep r i m a r i l y t o c h a n - e eisn t h c p o l a r i z a h i l i t ro f r h e g r ' o L l past
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c o n t a c t a n g l e o f w a t e r o n t h e s e S A M s . H y s t c r c s i si n e ( ) t ) t i r elrr r r g l c si s s t i l l
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u s ef ulinf or m ati o n a b o u t th e h e te ro g e n e i tvc tfsurfaccs.
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u n d e r n o r m a l a d s c l r p t i o nc o n d i t i o n s . U p t o n o \ \ . \ \ c h l r r c l t ( ) t o [ ' r s c r v c cal n y
g e n e r a l t r e n d s i n t h e c o n t a c t a n g l e sa s a f u n c t i o n o f t h c c o n d i t i o n s u s c d f o r
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t h e d a t a i n t h c t o p p l o t * ' e r c r i c t c r m i n e c ib y a l e a s t - s q u a r e fsi t . T h e c u r v e s t h r o u c h t h e c l a t ai n t h c
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c o m p o s i t i o no f t h e S A M ( i . c . X r . g . S AFNi4g;. 5 . t o p ) . T h e s e d a t a m i g h t s u g g e s t h a :
t hc c ont ac t an g l e sa re n o t a ffe c te db y d i s o rder i n the i nterfaci alregi on or that tht
m ix ed S A M s a re n o t d i s o rd e re d ,b u t s i n c e methyl enegroups are as hydrophohi .
a s m e t h y l g r o u p s ( s e eb e l o w ) , u s i n g w a t e r a s a p r o b e l i q u i d , w e c a n n o t r e l i a b l r
dif f er ent iat eb e tw e e n a S AM th a t h a s p h a se separatedi nto macrcscopi c i sl ancl .
and a S A M w i th ra n d o m l y d i s p e rs e d h v d rcxymethyl groups i n a sea of methr
a n d m e t h y l e n eg r o u p s .
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a n e l e o f w a t e r a g a i n s tX r g . s a Hi s, r c u r v e d ( F i e . 6 ) . T h e s e d a t a i l l u s t r a t et h e h i g h
s en s i t i v i t yo f t h e c o n t a c ta n g l e st o t h c m o l e c u l a rs t r u c t u r eo f t h e i n t e r f a c e: i f t h i ,
s v s t c m w e r e m a c r o s c o p i c a l l yp h a s e s e p a r a t e d w
. e would expectthe advancinr:
a n s l c st o b e r e l a t e d l i n e a r l y i n t h e c o m p < - r s i t i oonf t h e S A M . T h i s r e s u l t i m p l i c s
s ienif ic ant dis o rd e r a t th e i n te rfa c e : th e l onser chai ns are fl oppi ng over thc
s h t t r t c r c h a i n s w h i l e t h e d r o p o f w a t e r i s a d v a n c i n g ,b u t w h i l c t h c d r o p i :
r e c e d i n c .t h e S A M c t t u l d r e o r s a n i z ct o u n c o v e rt h e h y d r o x v m c t h v ls r ( ) L l p s .
W h e n b o t h t a i l s r o u p s a r e h v c l r o x v m e t h y( li . c . S h : C H , O H ' [ - s : C H . O H ) .
t h e m i x e c lS A M s a r e c o n s i c l e r a b l r l,o r c h v c l r o p h o t - r ti h
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p u r e S A M s t o 5 4 " f < l rt h e S A M u ' i t h 7 r r \ \ \ r = 0 . 5 . T h i s c h u n g ce ( ) l ' l . c \ p o n dt os i r
d e c r c a s ei n t h e i n t e r f a c i a fl r e e e n e r g vo f t h c s \ \ t c n t ( ) , r r - 1 , , ,) o 1 - l 5 r n . l / m l ( o r
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-l-hc
clf the mtllc fraction tlf the longcr componcnt in thc SAI\1.
n r o l e t n l e r r o l r ' \ i t , r t , . i c t c r m i n e da s
d e s c r i b e di n t h e c a p t i o n t o F i g . 3 . T h e s t r a i g h tl i n c t h r o u g h t h c r c c c d r n gr r n g l c ,\ \ . r \ r l e t c r n t i n c db y a
l e a s t - s q u a r e fsi t . T h e c u r v e t h r o u g h t h e d a t a o f t h c a c l r a n c i n gc ( ) n t a c tl n g l e r l s o n l r r r g u i c l ct o t h c
eye.

SAM.sof'ulkunethiols on gold

oCHeOH

1.10-5

Au-S(CH2)21CH2O
H

60

cose

40
30

^/
ALg, SAM
l ' i g u r c 7 . A c l v a n c i n g( f i l l c c l c i r c l c s ) a n c l r c c e d i n g ( o p e n c i r c l e s ) c o n t a c t a n g l e s
or watcr on mixecl
S A M s o t r t a i n e d b y t h c a c l s o r p t i o no f H S ( C H 1 ) r , , ( ' H , f ) F {a n d H S ( C H , ) , , C l H . O H
onro solcl as a
lunction of' the molc fraction of lhc lclngcr comp()nentin thc SAM.
The m.lc lracti.ns r.l,ere
d c t e r m i n c d a s c l e s c r i b c di n t h e c a p t i o n t o F i g . 3 . T h c c u r v c s t h r o u g h t h e d a t a
a r c t t r . r l vs u i d e s t o t h e
cyc.

s i n g l ec o l n p o n c n tS , ' \ \ l s ( " , ,
l ' : r r l c c r e a s cbs v l 7 n t . l / m ro r 0 . 5 k c a l / m o l ) [ l ] . *
F o I t h c c ( ) l l t l l citt l l g l ct o i n c r c a \ c( ) n t h c s cn t i r c r l S , \ \ 4 s .t h c r c m u s t
be significant
l l l l c r l l c l i ( ) l l r c t $ e c l ' t h c p r o b c l i q u i c lu n c l t h c r r c t h r l c n c g r o u p s o f
the longer
.l-hcsc
chrtttlr.
r c s u l t s i m p l y ' s i g n i f i c a n tc l i s o r d c r z r t t h c m g n 1 1 l a l c r - w a t e r; c l
ttttl tl t llay ' er - v aporin te rfa c e s . W e c a n n o t, h o w e ver, i nterpret thc
changes i n
co n tac t angle on t hi s s e t o f S AMs i n te rms o f a model for mi xi ne
of the comp o n cn t s bec aus ewe d o n o t k n o w th e e x te n t to whi ch these
components may tre
fo rmi ng is landson t h e s u rfa c e .
N { i r c c lp h a s e so f S h : C H . / L g : C H :
a r e a s h y c l r o p h o b i c( a s d e t e r m i n e db y t h e
Ittl i rttr c ingc ont ac t an g l e o f w a te r) a s th e h i g h l y o r dei ed, si ngl e-componcnt
S A Ms
(Fi s. '\t . W hile t he c o n ta c t a n g l c so f h e x a d e c u :rncleearl y
shc,wthat the i nterfacc i s
d i s o r i l e r c dt s c c F i g . 9 ) , t h e a d v a n c i n gc o n t a c ta n g l eo f w a t e r i s u n a f f e c t c d
by the
p re senc cof m c t ir v le n eg ro u p s a t th e i n te rfa c e .Gcneral l y,
a surfacecomposed of
methyl group\ hus a /sv of about 20mJ/mr, and one of
m e t h y l e n eg r o u p s ,
/ s v = 3 0 m J m i t c . g 'p o l y e t h y l e n e )[ 4 7 ] ; t h i s d i f f e r c n c es h o u l d l e a d t o a d e c r e a s e
i n th c equilibr iunt co ttti tc t a n g l e o f w a te r b y -tl " usi ng Fow kes' s
equati on for
norr-polar surfaccs [4li]: /sr : /sv* ytv-2,[y*i{,,.
* h . . . t h e s u p e r s c r i p td
rcfe rs t o t he < iis p c rs i v c c o mp o n e n t o f th e surface tensi on
of the ti qui d
(yi v= 22m J / m r f or u ' a te r a t ro o m te mp e ra tu re
t42l ). The recedi ng coni act
a n g l e o f wat er dec r c a s e do n th e mi x c d p h a s e sb y about 8' , suggesti ng
that the
cq u i l i b r ium c ont ac t a n g l e o f w a te r p ro b a b l y al so decreased; thi s resul t
is
'iWe
c o m m o n l y t t h s e r v et h a t t h e r a l u c o f t h e a d v a n c i n gc o n t a c t
anglcof watcr on hydroxvmethylt er m t n a t c d m o n o l a y c r s c l u i c k l y i' n c r c a s e su ' i t h t h e a m o u n t
of time bctween removal of thc sample
fronr solution and the tirne that thc contact an{les are
t a k e n . W e a t t r i b u t e t h i s i n c r e a s e( w h i c h i s
r e l a t i v c l y s m a l l i n t e r m s o f c o s d ) t o t h c a d s o r p t i c l no f
a i r b c l r n ec o n t a m i n a n t st o t h i s h i g h - e n e r g 1 ,
s t t r t a c e 'a n c l n o t t o r e c o n s t r u c t i o t to f t h e m o n o l a y e r a i r
i n t e r f a c e o f t h e s i n g l c - c o m p o n e n tS A M s
t.l(il.

14 0 6

.1.l'. Folkers cl al.

Au-S(CHz)roCHg

Au-S(CHzl21CHg
120.

110

cos e

0
100

^l

llLg,sAM

F i g u r c 8 . A c l v a n c i n g( l ' i l l c r lc i r c l e s ) a n d r c c c c l i n g( o p c n c i r c l c s ) c ( ) n t l r c lr r n s l c so l . $ , a t c r o n m i x c c i
SAMs obtzrined
h v t l r c a d s o r p t i o no f F I S ( f l H . ) r , , ( ' H a. n d H S ( ( ' H . ) . r ( l l , o r r l o g o l t l r r su f u n c t i o no l .
t h c m < l l e f r a c t i o n o f t h e l o n g c r c ( ) m p o n c n t i n t h c S A M . T h c m < l l c l r l r c t r r r n r\ \ r . t . . '( l c t c r n t i n c c l
as
d c s c r i b e d i n t h c c a p t i t ) n t o F i g . 3T .' h e c u r v c s t h r o u g h t h c c l a t a a r c o n l r , ! , u i d c s l o t | 1 . , . , r . ,

c o n s i s t e n tw i t h t h e i n t r o c l u c t i o no f s o m c m e t h y l e n eg r o u p s a t t h e s r r er l , c c . I l t a
s y s t c mw i t h t h c a b i l i t y t o r e o r g a n i z cs u c h a s S A M s , t h e s e r c s L l l t s( i u r r lt h r s c f o r
S h : C H ' O H / L g : C H , ) m i g h t i m p l y t h a t t h e s y s t e mm i n i m i z e S
l , r r t l L r r i n st h e
m e a s L l r e m c not f t h e a d v a n c i n gc o n t a c t a n g l c o f w a t e r a n d m i n i m i z c s
;,,, rluring
the m c as ur em e n to f th e re c e d i n gc o n ta c t a n gl eof w atcr.
4.2. Wettability with hexadecane
T he m os t int ere s ti n gd e ta i l s a b o u t c l i s o rc l e ri n these S A Ms that can bc i nferrcd
f r o m t h e c o n t a c t a n g l e o f h e x a d c c a n ew e r c o b t a i n e c lo n L g : C H . , / S h : C H , .
W hen t hc t wo m e th y l -te rm i n a te dc o m p o n e nts w ere mi xed on the surface, the
zr dv anc ingc onta c t a n g l e o f h e x a c l e c a n cd ecreased from - 45" on the si ngl ec o m p o n e n t S A M s t o 1 6 ' ( F i g .9 ) o n t h e m i x e d S A M w i t h
l r g . S A:r0\ r. 2 . I f w e
a s s um et hat t hi s d e c re a s ei s a n a l o g o u sto th e decreasei n the equi l i bri um contact
a ngle' we c an u s e F o w k c s ' s e q u a ti o n t4 ttl to determi ne the sol i cl -vapor and
s olid- liquid inte rfa c i a l te n s i o n s o f th e s e S AMs (Fi g. 9, bottom). The maxi mum
dec r eas ein t hc a d v a n c i n g c o n ta c t a n g l e o f hexacl ecanefrom the val ues on the
s ingle- c om pon e n tSA M s c o rre s p o n d sto a n i ncreasei n
)rsv by about 6.5mJ/m2
( 0- 20 k c al/ m ol o f s u rfa c e g ro u p s ) a n d a d ecreasei n
?rsr by about 0.6mJ/m2
( 0. 02 k c al/ m ol o f s u rfa c eg ro u p s ).*Ob v i o u sl y, di sorder i n thi s systeml eadsto
an
i n c r eas ein t he n u m b e rs o f m e th y l e n eg ro u ps at the i nterface.W hi l e hexadecane
i s m os t s ens it iv eto th e me th y l e n eg ro u p s & t
/r_g.sav:0.2,rvateri s most sensi ti ve
to dis or der bet w e e n .Xrg .s n v :0 .4a n d 0 .8 ; w e do not have an expl anati onfor thi s
d if f er enc cin beh a v i o r.
*Thc advancing
c o n t a c t a n g l c s o f h e x a d c c a n co n S h : C H r / L g : C H . O H
and Sh:CH.OH/
L g : C H . s h o w s i m i l a r t r e n d s [ 2 ] , b u t s i n c c t h e h y d r o x y m e t h y l - t e r m i n a t e dm o n o l a v e r sa r e w c t t a b l e .
t h c d a t a a r e n o t a s i l l u s t r a t i v eo f d i s o r d e r i n t h e i n t e r f a c ea s t h c y a r e f o r S h : C H , / L s : C l l . .

\AMs o.fulkunethiols on ,qold

l4('t7

Au-S(CHdzrCHa

0.s

60
I
I
I

0.6

o.7

cos 0

\I
0.8

50
400
30

0.9

20

1.0

0
0.9

0.6
mJ/m2

kcal/mol
0.3

0.0

Xtg,sAM
F i g u r e 9 . T t l p : A d v a n c i n g ( f i l l e d c i r c l c s ) a n d r e c e d i n g ( o p c n c i r c l e s ) c o n t a c t a n g l e so f h c x a c l c c a n e
on
mixed SAMs obtained by the adsorption of IIS(CH.)rlcHr and HS(ClH,),,CH.,onre gelcl
as a
function of thc molc fractionof thc longercomponentin the SAM. Bottom: Solid-vapor (yrrlfilted
c i r c l e s ) a n d s o l i d - l i q u i d ( y . , ; f i l l c d s q u a r e s )i n t c r f a c i a l t e n s i o n s d e t e r m i n e d u s i n g t h e a c l v a n c i n g
c o n t a c t a n g l e so f h c x a d e c a n ea n d F o w k e s ' se q u a t i o n [ 4 t t ] . V a l u e so f y . , h a v e b e c n m u l t i p l i e d b y
l0
t o b r i n g t h e m o n s c a l e .T h e m o l e f r a c t i o n s w c r e d c t e r m i n c d a s d e s c r i b c d i n t h e c a p t i o n t o F i g . 3 . T h e
curvcs through thc data are only guidcs to the eyc.

4.3. Hysteresisin the contact angle of water

The hysteresis in the contact angle of water (defined here as A cos 7tt{) c<rs0fJ'o- cos 0'^"n to give positive values) increases in magnitude as the
in te rfa c ebec om esm or e d i s o rd e re d .F i g u re 1 0 s h o w s the hysteresi si n the contact
an g l e o f wat er f or t he m i x e d SA M s o f S h : C H ,OH /Lg: C H ., pl otted agai nstthe
composition of the SAM. The origin of this increase in hysteresisis probably the
disorder in the interface, but we will not be able to quantify this effect until we
can repr(lducibly control the roughnessof our substratesand reduce the error in
the measurementof the contact angles [2]. Theoretical and experimental studies
of hysteresis have not addressed the problem of molecular-icale rnicroscopic
h e te ro geneit yat t he in te rfa c e [4 3 ,4 4 ], b u t o n c e w e understand the di stri buti on
of the two thiolates on the gold surface, SAMs derived from the types of
components used in this study will be a useful tool for understanding fully the
origins of hysteresis.

r40B

.1.P. Folker.r'et al.

Au-S(CH2)1sCH2O
H

0.4
0.3
Acos et'o 0.2

^f

AL g, S A M
F i g u r e 1 0 . H y s t e r c s i si n t h c c o n t a c t a n g l c o f w a t c r o n m i x e d S A M s o b t a i n e c lb v t h c u c l s o r p t i o no f
HS(CHr)r.CH,OII and HS(tlH.).rCHr onto gold as a function of the mole fractior.o
r t rhe lonscr
c o m p o n e n t o n t h c s u r f a c e .V a l u c s o f h y s t c r c s i sc a n n o t b e d e t e r m i n e d w h e n t h c r c c c c l i n sl r n g l c o f
w a t e r i s z e r o , a n d t h e r e f o r e ,t h e r e a r e n o v a l u c sc l f h y s t c r c s i sb c l o w / r o s , r r =
r 0 . l . T h c c r r r re t h r o u g h
t h c c l a t ai s o n l y a g u i d e t o t h e c y c .

5. CONCI,T]SIONS

The dat a s umma ri z e c li n th i s p a p e r i l l u s tra te that formati on of tw o-cr)mponcnt

s elf - as s em ble dmo n o l a y e rs o f a l k a n e th i o l ateson gol d i s an excel l entmethoclfor
for m ing s ur f ac e sw i th c o n tro l l e d w e tta b i l i ti es.W hen usi ng S A Ms to form such
s ur f ac es ,t he c o m p o s i ti o n o f th e S AM may not equal the composi ti on of the
s olut ion, and th e re l a ti o n s h i p b e tw e e n these tw o may be dependent on the
condit ions us e d to fo rm th e m o n c l l a y e rs F
. actors such as the total concentrati on
o f t hiol in t he s o l u ti o n , th e l e n g th o f ti m e that the sampl esw ere l eft i n sol uti on,
the t em per at u reo f th e s o l u ti o n , a n d th e s o l vent used are extremel y i mportant i n
d e t e r m i n i n gt h e c o m p o s i t i o no f t h e S A M [ 1 , 1 6 , 3 U ] .
T he dat a als o i l l u s tra te th a t tw o -c o m p o n ent S A Ms of al kanethi ol ateson gol d
a r e im por t ant to o l s i n u n d e rs ta n d i n gw e tti ng. C ontact angl es usi ng w ater and
h c x adec anear e s e n s i ti v eto d i s o rd e r i n th e i nterfaci alregi onsof mi xed S A Ms of
alkanethiolateswith alkyl chains of different lengths, but this sensitivity depends
o n t he t ail gr ou p s o f th e c o mp o n e n ts a n d on the probe l i qui d: w ater i s sensi ti ve
to t he inc r eas ei n th e c o n c e n tra ti o no f m e th yl enegroups i n the i nterfaci alregi ons
o f m ix ed S A M s o f Sh :C H ,OH /L g :
C H .,OH , but i s onl y sl i ghtl y sensi ti veto the
i nc r eas e in t he c o n c e n tra ti o n o f m e th y l e n e groups i n the i nterfaci al regi ons of
mixed SAMs of Sh : CH./Lg: CH:. Hexadecane is, however, very sensitive to
changes in the relative concentrations of methyl and methylene groups in the
i nt er f ac ial r eg i o n i n mi x e d SA M s o f S h : C H . /Lg: C H .. H ysteresi s i n the
c ont ac t angle o f w a te r i n c re a s e so n th e mi x ed S A Ms. Thi s observati on suggests
that hy s t er es isi s a l s o s e n s i ti v eto m i c ro s c o p i cdi sorder i n the i nterfaci alregi on.
W e do not be l i e v eth a t th e s eSA M s a re c o mpl etel ydi sordered:the rel ati onshi p
between the composition of the SAM and the composition of the solution
s ugges t st hat t h e s e S AMs h a v e p a rti a l l y phase separated under normal con-

SAM.s o.f'alkunethil[.s 0n ,!old

1409

d i ti o ns f or ads or pt io n (s e el a s t fo o tn o te
o n p . 1 4 0 1).w e are conti nui ng to
expl ore
th e wet t ing and ads o rp ti o np ro p e rti e s
o f th e s e ,S Av, * i ttr th. gout, of determi ni ng
a n d cont r olling t he si z e o f th e
i s l a n d sw i th i n S AMs, and then rel ati ng
the w etti ng
properties (especiallyhysteresis)
to the heterogeneityof the interfaces.
Acknowledgements
This research was supported
in part by the office of Naval
Research, the
Defense Advanced Research
ag.n.y, and the National Scheme
^lrgjects
Fo u n d at ion ( G r ant D M R -| 9 -2 0 4 9 0
to ,i . H arvard U ni versi ty Materi al s
R e se a r c hLabor at or y )' J ' P ' F .a c k n o w l e d g e s
th e N a ti onal Insti tutesof H eal th
for a
tra i n i n g gr ant in bio p h y s i c s (1 9 g 9 _
tg g O l . W e woul d especi al l y l i ke
ro rhank
Co l i n B ain f or init iat in g i tu c ti e s
i n th i s a re a .
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R (i. Nuzzo,
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[1llili;rL,,?;;,..|iii|ji;nt,
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sot..
"/.
tt
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Y.-r.
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^T;tlir",l,i!i;,?rti]"
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.t.Ant.(.hent.
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Bain anci G. M
' Int Erl'I:ngt28'

Y!;:;;,t,i::;.^;fiir,r'l,ent

-5tir,
rresqr;c nalwnitesides
andp E Laibinis,

l4' For backgroundinformati.n

on SAMs; sce:A. Ulman, An Irttroducti.n
ro Llrrruthinorgani.
Filmsfrom I'angmuir-rlrodgettut
Serf-Asse
ntbr1,.Ac:itdemic
p.css,SanDiego,
l ' 5 ' R ' G . N u z z o ,I - . H . D u b . i i
CA ( r 99 r ).
a n d D . L . A t a r a ' .J . A m . ( . r t e n t . J o c .
r 1 2 . . 5 5 1(3r 9 9 0 ) ;c . E . D .
C h i d s e ya n dD . N . I o i a c o n
o , L a n g m u i r6 , 6 g 2( 1 9 9 0 ) .
l 6 ' c ' D ' B a i na n d G ' M ' w h i t e s i o . r ' " , r '
A n t . c h e m .s o c . 1 1 0 , 6 5 6 0( l g g u ) ;
c . D . B a i n ,J . E v a l la n d
G ' M ' w h i t e s i d e si b' i ( t 'l l l ' 7 1 - 5 5 ( 1 9 u 9 ) ;
P .E . L a i b i n i sa n d G . M . w h i t e s ir J e s .
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