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  • J. rldltesiorrSci. letltrtol. Vrl. (r. No. ll. vsP 199t.

o

pp. l-197-l-ll0 (1991)

Self-assembledmonolayers of alkanethiolson gold:the adsorptionand wettingproperties of monolayersderived from two componentswith alkanechains of different lengths

JOHN P. FOLKE,RS,PAUL E. LAIBINISand GEORGE M. WHITESIDES*

Departntertt tl Chentistr\', Harvard Uttiyer.sin', ('untbridgt', X'lA 021.18,{-/.\,4

Reviseclversion receivecl27 Jul.v1992

Abstract-'l'his papcr dcscribcs the preparation and wctting propcrtics of tuo-cor.nponcntscll-

asscntble-dmonolavcrs (SAMs) obtaincd hv the compctitivc ailsorption ol'onc short-chain

(HS(CHr)r,,Sh) and onc long-chain (HS(('H:):,1-g) alkanethiolonto golci l'rom clilutccthanolic

solutions.The'four possiblc combinationsol thc tail groups CH, ancl CH.()H wcrc investigated:

Sh - CHr/Lg - CH.OH. Sh : CH.OH/Lg:

CH ..

Sh : ('H.OH/Lg: CH.OH. and Sh : C'lI./Lu: C'H,.

The compositiot-tsof thcsc SAMs arc not thc samc as thc c<lmpositionsol thc solutionsIrom rvhich

they we're formed. Although thc rclationship bctw'cen the composition ol'thc SAM and thc

composition<lf the solution sucgeststhat some phascscparation mav bc occurrinq

thc SAM.

"r'ithin contact anglcswith water itnd hexadecancshow that significantclisorclcr still rcmains in the inter-

facialrcgion.

Kct'word.s:Wcttabilitr': cr'rtttposition:self-assernblcd monolirver: alkancthiolalc; gold.

ponents;contact anglc: clis<lrcler.

[\\'o com-

  • I. INTRODUCTION

In this paper, wc describe the adsorption and wetting properties of two- component self-assembledmonolaycrs (SAMs) prepared by the adsorption of alkancthiols with different lengths of alkyl chzrins-HS(CHr),/,Sh and HS(CHr),uLg,whcre sh: l0 and lg:21, and Sh and Lg are eitherCH,OH o r CHr-onto freshly evaporatedgold substrates.We have studiedthe four possible combinations of Sh and Lg (Sh : CH.,/Lg : CH,, Sh : CH,/Lg : CH.OH, Sh: CH,OH/Lg: CH., and Sh: CH.,OH/Lg: CH,OH). We have described some of the detailsof thesesystcms previously [, 2l; in this paper. we focus on the composition of the SAM: its dependenceon the conditions for adsorption and its effect on the wetting propertics. We introduce this work with a brief overview of the arca of SAMs of alkanethiols on gold. We then discuss the relationship lretweenthe composition of the SAM and the composition of the solution.In the final section,we describesome of the wetting propertiesof these tw<l-componentSAMs, concentrating on the relationship between wettability and thc compositionof the SAM.

2. BACKGROUND

Among the many systemscurrently availablefor the formation of self-assembled monolayers [3-14], SAMs obtained by the adsorption of alkanethiols (general

*To whom correspon(lenceshould lre addressed.

l39lJ

r'

formulaHS(CH.),,X) onto gold (and,perhaps. onto silver tll. l2l) are the most

versatile:the strength zrndspecificity of the metal-sulfur interaction allows the

introductionof many important terminal functionalgroups (X) into the mono-

layers il0.

l-5-211.The

highly ordered structure of these SAMs

has been

establishedusing a variety of techniques.including polarized infrared extcrnal

reflcctancespectroscopy (PIERS) [9. ll. 12. 15.221,electron diffraction t23],

helium scattering [24,25],

X-ray scattering 125.261, scanningtunnelins and

atomic force microscctpies [27], and surfaceRaman spcctroscopy [2S] (Fig. l),

moleculztrdynamics calculationsyielcl a gcncral structure in asreemcntwith

these techniques [29]. The cxperimentallr clcterminedstructure exposesthe

terminal functionalgroups (X) at the monolavcr-air interface.and thus allows

the interfacial prt-rpertiesof the monolzrvcrto be controlled by changing X.

Model svstemsbased on these SAMs havc bccome increasinglyimportant in

funclamentalstudies of

electrochemistrv tl9.

301. protein adsorption t201.

X-ray-induccddamage to organicmaterials [31]. anrl v,'ctting 11,2. 10, 13. l6-

1,3.20, 32-351.

Our interestin thesc SAMs is bascclon iur intcrestin the physical-organic

chcmistryof orsanic interfaces.especiallv thc rclutionshipsbetween molecular

structureand wetting tl.

2,

13, l6-ls.

10.

.tll

SAMs derived from rhe

adsorption of alkanethiolsonto gold proviclc lr ntolccular basis for sturJiesof

wettability.In our investigationsof the wettabilitrot'SAMs. we havc utilizcdtwo

approaches:formation ctf single-componentS,\\ls

uith terminal functional

groups of variablehydrophilicity [0, 13. l6-lS.

componentor'mixed'SAMs 11.2, 13, 16, ltt. lOl

'l'hc ]01. anclformarion of rwo-

luttcrmcthocl provides a

greaterdegree tlf control over the propertiesof thc intcrt'lrcc.lrcczrusc the relative

concentrationsof the two componentsin the SA\l clrnl-rc lrrljustccl.

When two-componentSAMs are usedto form sLrrfuccsot'spccif ic vn'cttabilities,

two

relationshipsdetermine the

wettabilitr': thc

rclrrrionshil'rbe tween the

wettabilityof the surfaceand the compositionof thc S.^\\1.antl thc relntionship

a = 4.078A

Au(111) . AUSR

{5x

{g R 30'

Figure l. The structurcof alkancthiolatcsaclsorbcd on solrl rlllt.'fhiolatcs arc aclsorbccl at thrce-

fold hollows

on thc surface forming a commcnsunrtc \.1 r ,- R-10"structurc [23 J6l. Thc alkvl

chirins are in tr truns zig-zagarrav (thc small conccntnltion of gutrcheconformcrs is localizcd ncar

the ends of the chains [12,21,29])

and arc orienteclal-rour 30" frcm thc surfacenormerl [9. 12. 15.

221.Becausc of this highly ordcred structurc.thc tail sr()Lrps (X) are localizedat rhe monolzrycr-air interface.

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

I3e9

betweenthe composition of the SAM and the compositionof the solution.In this

paper we discuss both of these relationships try presenting data for SAMs

6eiived from two alkanethiolswith alkyl chains of different lengths.We also

discussthe wetting results in terms of the effect of disorder in the interfacial

regionon the wettabilityof thesetwo-component SAMs t I . 2, I 31.

In mixed SAMs containing one long-chain component and one short-chain

component,the region close to the gold substratcthat is

clccupiedlointly by the

short chains anclthe correspondingsections of the long chains is well ordered:

the region further awav from the golclthat is

occupied only by the remainder of

the long chains is disordered (as long ils the components have not phasc

separated;see Fig.2) t361. Thc resultsreportecl in this paperindicate that.

under

conditions commonly used in forming mixccl SAMs. there appearsto be some

phase separationof the tuo

c()mponr-ntsin the SAM,

remainsto affectthc contactanslcs t l. 2l

but cnough disorder

We have chosen .r/r :

l0 ancl I.g,:2l

irt our work; these classesof thitlls are

syntheticallyaccessiblc arncl solut-rle irt cthanolat millimolarconcentrations tl. 21.

We can easilydetcrminc thc compositiclnsof SAMs containing mixturesof these

long and short thiolatcs br

scveral techniques [2].

X-ray

photoelectron

spectroscopy (XPS) is thc most useful singlc technique: XPS provides

information pertainingttt elcmentalcomposition and oxidation statcsin acldition

t9 the relativeconccntrations of the two componcntsin a SAM. In this papcr.wc

= Sh = CH2OHor CH3

= (CH2)1q

=S-

=Lg= CH2OHor CH3

= (CH2) 21

=S-

Figurc 2. Schcmaticrcprcscntation of a mixeclSAM u'ith eclualcttnccntrations of a lr;its-chain (l-g) ancla shert-chain (Sh) thiolatc (ratio of the t\\'o comp()ncnts in thc SAM:Rr.r,:[[-gJ'[Sh]: l :

mele fractionof

thc longercomponent in thc SAM:/r"srrr:tl-gll(t[-gl +[Sh]):0.5). Thc top

clrarvingshows a monolaycr with thc componcnts randomlv mixed. and the btlttom shows thc tr"'tl

c()mponcnts phasc separatcd.We bclieve that our SAMs arc somewhcre bctwecn thesc

tr,r'tl

cxtrcmes.

I +()(l

.1.l'. Iblktr,s e-lal

harc gscd thc naturallogarithm of the ratio of the carbon I s intensityto the gold

-+l intcnsin' (clenoted as lntC(ls)/Au(af)l in this paper) to determine the

cirnrpr6sitions of the SAMs l2l. Our group has shown previouslv that this

(luantit\ can be used to determine the compositions of SAMs incorporating

thi6lltes 6f clifferentlengths [1, 37]. This method is excellentfor characterizing

thc compositionsof a group of mixed SAMs becauseit minimizeserror due t<l

clriftin the intensityof the X-ray source.x

Thc g'1lrk clescribedhere is focused on the tail groups methyl and hydroxy-

rncthrl: thesegroups proviclea large diffcrence in the wettabilitiesof the single-

.,,nr1r,',n.ntSAMs and a large range of wettabilitiesfor the mixed SAMs ll.

2.

  • 10. 16l

The oxygen of the hydroxymethyl group also provides a'tag'for

monitoringcomposition by XPS [2].

.1.THE RELATIONSHIPBETWEEN THE (-OMPOSITION OF THE SOI,T]TIONAND

THE COMPOSITIONOF THE SAMI

When two-component SAMs zrreformed from thiols of different lengthsunder

'nrtrmal

adsorption conclitions' (golcl-coatedsilic<ln substrates imme rscd in

ethanglic sclluti<tnscontaining a total concentration tlf thitll tlf l rllM: l day;

room temperature).the ratio of thc concentratittnsof the twtl thiolatcsin the

SAM (Rr^r,:IAu(l) S(CFI.)r,Lg],'IAu(l)S(CHr),/,Sh]) and thc rrttio of the

concentrationsof thc respective thiols in sttlutittn ( R,,,r,, :

ItiS(CH]) ,.rLg]/

IHS(CH]),/,Shl) are not the serme (Fig.3). IIr Fig.3. \\'c harc plotted the

cctmpositionsof

the SAMs

as the molc fractiort of

thc ltlnger ctlmponent

(X,.*.r,rn,. wherc /r*.s,rr,r:ILg]r

againstRro'

tl.

..

rrr/([Lglsrrr+[Sh]rr.,,) itncl {,*,:,rr,*Xsrrsr\r:

idealit,v (/i

..

\y:

l)

21. Thc cleviationof this cLrr\cfrom

R,,,rn,

clasheclline in Fig. 3) inclicatesa preferenceof the longer comportctlt for the

surface;the sharpnessof the transitionregion suugeststhat mixing ol'the two

componentsis not enthalpicallvfavorcd within the SAM. possiblv lcading ttr

phaseseparatign in the SAMs.; From the relationshipbetween thc composition

of the SAM ancl

thc composition of

the solution. we infer thc following

qualitative energy ranking for interactions within thc SAM:

Lg.Lg>Sh.Sh> Lg.Sh. We carnnot. howevcr, determine absoltrtc cncrgies for

theseinteractions because these systems are not at equilibrium.

Even though we clo not know the cletaiiedmolecular mechitnisrttof tormation

of SAMs. or the mechanism(s)of exchangebetween thiolatcs otl tltc sttrfaccand

thiols in solution [39]. we know that these SAMs are

relationshipbetween the compositionof the SAM and

not itt ctlLrililrrium:the

thc

contposition<lf the

solution is nctt stable to changes in the conditions usccl t'or rtclsot'ptitln.For

example, increasingthe total concentration of thiol in soltttioll rcsultcclin an

'FFor detailsconcerning the

experimentalproceclures, see rct. l.

tln

this section.u,e have uscd the systemSh:CH."l-g:('H.Oll

to illLtslrrttcthc rclationship

betweenthe compositionof the SAMs and the compositionof thc solrttions.the gencral trends are

the samefor the other systemsthat we havestuclied t2. 381.

;At present, we do not have experimental results that explicitlv detcrmine the <lri.uintlf the

inferred phaseseparation in theseSAMs. In a separatcpaper. wc

"rill the experimentallyobserved relationship between the compositionof

prescnta thortlughirnalysis of

the SAM and the composititln

of the solutionin comparisonto a theorcticalmodcl of thc formationof mixed SAMs [381.

^!A,'\/.sctf' u I ku rte t h i o l s o rt go Id

l-t0l

Au-S(CHilzrCHzOrF

o'1

xug,sAM lll

o.rl

/-

Au-s(cHz)rocHgl+

|

I

,

|

I

iLRrou =t*'"

f

I

0 0.01

0.1

1

10

oo

h

Flsorn=

[HS(CH2)zrCHzOH]

tnSrcn1toCttsl

Figure

3.

C'ompirrison

ol

thc

corr.rJ'lositions ol

S,.\\1s irncl ol'the

solutions

front

uhich

tlrcV ucrc

I.rmcci:

mirecl

SA\lS

t()r'ntcrl tront

thc

corlltctitivc

aclstlrptitlt.ttlf

t{S(('H.).rC'Fl'OH

antl

HS(CH.)r,,CFI .

(crpcrinrcpllrl conclilions: cthanolic solutions uith

it t0tal concclllrlltitln tlt thitll tll

I mM: r()om tempcriltrlre : I rllrr t. f hc .r-aris is R,,,,,,.clcfinccl as thc ratio tlf thc conce ntrlttirlns of thc

I9lgcr componcnt unrl thc shortcr c()nrponcnt in solution. Thc r'-aris is the nltllc lraclitln of thc Irlngcr c1;1mp()ncntitt lhc S.'\\l rlrr:rrr. u'hcrc.Zr" sr' * /r,, r,r, : l).clctcrnlinctl fronl tlrc logttrithnl

.f

thc ratig 9f thc illcrrrirr

pl

 

pcak in

XPS to that of thc gold ('4f ) pclrk [.171. Somc

clata pgints mav

hirrc

7

lhc car[er1 (ls) or

.r',(0

7,"rr.,

)

I

bccausc

of

crrtlrs

intcnsitics 9f l-rgth1[]g r'1s11161 rIr)signll

irnclthc gold (-i/) signal varl'bv

in

thc

mcitstlrcmcnts. Il thc

ttbout t5"i,-

thctr thc vltlucs

 

har"clclt

9f'ln(('r'Au) var\'[.rr +-",,. rcsultipg in a minimr.lntcrr()r of *7"1, in the vitlucs tll 7,! \\\r.Wc

thcsc clata ptlints 11utsitle 7, .r., :0 ancl Xrr\\\r : I (rathcr thitrl mtlvitrg thcnl ttl thc cndpoints) ttr

shgw the crr()r ln thc lrcusurcntcnts.'I-hc curvc thrt,ugh thc clata is tlnlv a gtridc ttl thc crc.'fhc clashcd cLlrvc rcprcscrtt. /?, r., : /?.,,,,.

increasein the prcfcrcnce fur the longer component in the SAM. ancl ellsoan

increase in the shlrpncss of the transition region (Fig.'1). When the total

concentrationof thiol \\'ilsdecreased. the preferencefor the ltlngcr component

and the sharpncssof the transition region decreased (Fig.a). The cffect of

increasingthe timc for adsrlrptic-rnwas similar to raising the total concentratitln

of thiol in solutir-rn [3fi]. In somecases, increasing the temperatureof the solution

also affected the rclationship betrveenthe composition of the solutitln and the

composition of the SAN,I in a manner suggestingthat SAMs formccl undcr

normal conditions are not

at

equilibrium:for

Sh:CH'OH/Lg:CH,.

the

transition region becamc nearly an abrupt stcp when the tempcrature of the

solutionswas raiseclfrom l-5"C to 60'C t38].From thesechangcs.''' we conclude

that the SAMs are not in thermodvnamicequilibrium: exchange between species

in solutionand speciesin the completedSAM is slow at room temperature.

We emphasizehere rhat theseresults may be a function of the crystallinityancl

morphology of our gold substrates.These substrates-formed hy electron-beam

evaporation of 2000 A

of gold at room temperature onto chromium-primed

s,iliconwafers-are rough on the atomic scale:they consistof crystallitesof golci

rhat have u,idths of approximately 100 nm and heights of 20-30 nm. as

*We have not systematicallyaddressed the

influencc

of

the

solvent

on

the

character

of

twtl-

componentSAMs. but qualitativestudies have

suggestecl that the sttlvent has a large influcncc

on

the

compositionand structureof theSAM [1. l6].

l 40l

.1.['. I't,lkt'rr ct ltl.

Au-S(GHz)zr CHzO H

0.8

^l

tvLg,

0.6

SAM g.4

0.2

Au-S(CHz)roCHs

0 0.01

0.1

1

10

oo

'sorn-

D

- [HS(CHzlztCH2OH]

tnqcHr)tocnrl

Figure 4. ('omparison ol thc compositionsot SAMs anclof lhc solulionslrorrr uhich thcy u'cre

Iornrccl:the cl'fcctol'changinq thc totalc()nccntration ol thiol in solutiorr.I:rllcd crre le s: \lircd SAMs

torntcclf'ront thc compctiliveadsorption ol'HS(C'tl.)rr('H.OH and HS(('H.)

(

soltttionsu'ith total conccrttratiottsol'thiol ol' l() nrM ill r()ollttcmpcraturc tor i

ll

lront cthanolic

tllrr. ()pcn circlcs.

NIircd SAMs lirrmeclfronr thc conrpclitivcuclsorption of IlSt('H.)rr('H.Ot{ rrnrlllsr( tl.)r,,('H,

trorn cthanolicsolutions uilh

t()talconccntnttions of thiol ol'0.01 mM

at r()()lnlflnl)eruturc for'

  • I rial'.Axis labclsarc clcscribccl in thc captionto F-iq.3.'l'hccur\.cs through lhc cllrtrrrrre onlv guirlcs

ttl thc eyc. Thc clashcdcttrvc bctu'ccnthc t\\'o scls ol'clattrreprcscllls tlrc currc thr,rrrLltrhc clalirirr

Fis. 3: the clashccl curvc on the right rcprcscnts/?,,r, : /?.,,,,,.

deteimineclusing scanninstunneling microscopv I2]. If wc \\,crc to use golcl

substrateswith large, atomically smooth terraces [:t0]. wc nticht obscrve a

diffcrent relationshipbetween Rr,rn, ancl rR.,,r,,.

4. THE REI,ATIONSHIPBETWEEN WETTABILITY AND THE ('OMPOSI I

 

I()\ ()F THE

i.rrr'o()m

i1

..poiur

inter-

nrrrer i: rhcrcfore

l)ollrr

lirnetionality.

sAM ll,2l

We havc used watcr and hcxaclecancas our probc licluiclsbccirrrse ,rt thc largc

diffcrencein their surfacetcnsions (t,l{*t'=73 mJ/mr: yfll)= l8 nr.l nr

temperature tl l ])

and

in

thc

origins of

the forces

that rlete rnrinc thcm.

Approximately 70"/,,of the surfacetension of wllter originatcsin

actions,predominantly hydrogen bonding l42l: wcttins

bl

stronglyaffccted by changesin the polarityof the interfacc. -l-hc :rrr-l,reetcnsion

of hexadecanehas no polar component:in the abscnceol'an\

hexadecaneis sensitiveprimarily to chan-eesin thc polarizahilitrof rhe gr'oLlpsat

the interface.In this section.we first discussthe contactilltglc of ulrler ()n the set

of SAMs that we have studied.We follow with a discussionof et)ntlrctilngles

involving hexadccaneon mixed SAMs withrtr.rtpolar gr()uP\ri.e .

Sh: CH,/

Lg:CH.).

We concludewith an incomplctediscussion ol

hr.,tereris in the

contact angle of water on these SAMs. Hystcrcsisin e()t)tirerlrrrglcs is still

incompletelyunderstood [43.441, but has the potcntiirlrt)l'rr.,rritle substantial

usefulinformation about the heterogeneitvctf surfaccs.

All of the contactangles discussed in his section\\crc tltkcnon S

..

\\ls formed

under normal adsclrptionconditions. Up

to no\\. \\c hlrrc lt()t o['rscrvcclany

generaltrends in the contact anglesas a function of thc conditions uscd for

adsorption t3|l. In this work, we have takcn maximum aclvancins (0,) and

.!,'l't/.sol'ulkrtnethiolsttrrgold

l;103

nrinimum rececling (0,) contact

angles [0.

-1;t]. In presentingour data. we plot

thc cosineof the contactangle as in Youns'scquation [;1-5]: cos0:

(/r,

-

Tsr\/

.,,r. where the /.\.).refers to the interfacialfree energv per unit area between

interfacesX and y (S: solid.L:

liquid.V:

r'apor).

  • 1.1. Wettability with woter

When only one of the tail uroupsis hyclrt)x\tllcthvl (i.c.Sh:CH, /Lg: CH.OH

rrr Sh:CH.OH/Lg:CH,).

the wettabiliticsof the rnixeclSAMs spanthe rangc

bctween hyclrophobicancl hl'clrophilic. Sirrcc llrr'

is nttt simply rclated to R.,,,,,.

pct correlation existsbet\\'ecn the u'cttabilin of thc SAM and the ctlmp<lsititlnof

the solution (Fig.5. bottom).Irr this st'stcnr (Sh:CH./Lg:CH.OH). both the

aclvancingancl the

reccclingcontact anglcs arc. httwevcr.linearlv relatedttl the

Au-S(CHz)roCHs

Au-S(CHz)zrCHzOH

 

-0.5

-0.0

cos e

 

0.5

1.0

 

X',,,SAM

 
 

-0.5

 

. el"o

o el"o

 

-0.0

 

I

cose

I

I

I

 

0.5

I

 

I

!---J

 

1.0

) L

 

0.2

0:4

0.6

0.8

120

90

e

60

30

0

HS(CHz)roCHg "{

rvLg, soln

HS(CHz)zrCHzOH

Figure 5. Advancing (fillcd circlcs) and reccding (opcn circles) contact anglcsof watcr tln mirccl

SAMs obtainedby thc compctitircadsorption of HS(CH,)r(,CHrancl tIS(CHr).rCH.OH

tlnto solcl

as a functign of the molc lraction of the longcr componentin thc SAM. /r*srrr

(top). and as a

functionof the molc fractiorrot thc longercomponent in solution, .Xru,,,r,,

(b<lttom).Values tlf ;'"

r,n,

were determineclas dcscrit'rccl in thc captionto Fig.3t /ru.,,,rn: R.,,,,,r'(l +

R,,,r,,). Straight lines through

the data in thc top plot *'erc rictcrmineciby a least-squaresfit. The curvesthrouch the clatain thc

boltom plot are only guiclcsto thc cl'c.

l;10-t

J. I'. Folker.sct al.

compositionof the SAM (i.c.Xr.g.SAN4; Fig.5. top). Thesedata might suggesttha:

thc contactangles are not affectedby disorder in the interfacialregion or that tht

mixed SAMs are not disordered,but sincemethylene groups are as hydrophohi.

as methyl groups (see below),using

water as a probe liquid, we cannot reliablr

differentiatebetween a SAM that has phase separatedinto macrcscopicislancl.

and a SAM with randomly dispersedhvdrcxymethyl groups in a sea of methr

and methylenegroups.

For Sh:CH.OH/Lg:

CH.,, only the recedinc contact anglesof water arr

linearlv relatedto the compositionof the SAM: the plot of advancingcontacr

anele of water against Xrg.saH,r

is

curved (Fie.6). These data illustratethe high

sensitivity of the contactangles to thc molecularstructure of the interface: if thi,

svstcmwere macroscopicallyphase separated. we would expectthe advancinr:

anslcsto be relatedlinearly in the comp<-rsitionof the SAM. This resultimplics

sienificant disorder at the interface: the lonser chains are flopping over thc

shttrtcr chains while the drop of water is advancing,but whilc thc drop i:

recedinc.the SAM cttuldreorsanizc to uncoverthe hydroxvmcthvlsr()Llps.

When both tail sroupsare hvclroxvmethyl

(i.c. Sh:CH,OH'[-s:CH.OH).

the mixeclSAMs are consiclerablr,

rlorc hvclrophot-ricthan thc sinslc-componenr

SAMs (Fig.7). The advancingcot'ltilct arrglc incrcascs from ut'rorrt10" for thc

pure SAMs to 54" f<lrthe SAM u'ith 7rr \\\r = 0.5.This chungce()l'l.c\ponds

to ir

decrcasein the interfacialfree energvof

-0.8 kcal/mol

thc s\\tcnt (),rr -

1,,,

) o1 -

l5

rn.l/ml(or

of surfacegroups. assunrins ir constantc()lrecntnrtion of surfacc

sroups of 8 x l0-ro mol/cmr [23. ]+. lZlr. \\'c ol'rscrrcilprcriorrslr that thc

advancin-e contact

angle

of

water

on

nti.rctl

S.\ \lr

tlerir cd

from

HS(CHr)r6CH.,OHand HS(CHr)rsCH.OH incrcuscdto -11' lronr - 10"on the

Au-S(CH2)1sCH2OH

-0.s

-0.0

cos e

0.5

Au-S(CH zlz,GHs

120

1.0

^/

lvlg, sAM

Figure 6. Advancing (fillcd circlcs) and receding (opcn circlcst c()nrlct rrngle. ()l \\irlcr on mixed

SANIsobtaincd by the adsorptionof HS(CH.)r,,CH.OFlancl

clf the mtllc fraction tlf the longcr componcnt in thc SAI\1.

HSt('tl.r

-l-hc

(

tl

()nt() !(,lti us u functictn

nrole tnlerrolr'\it,rt, .ictcrminedas

describedin the caption to Fig.3. The straightlinc through thc rcccdrngrrnglc, \\.r\ rletcrntincdby a

least-squaresfit. The curve through the data of thc aclrancingc()ntact lngler ls onlr rr guiclcto thc

eye.

SAM.sof'ulkunethiols on gold

oCHeO H

Au-S(CH2)21CH2OH

1.10-5

 

60

cos e

40

30

^/

ALg, SAM

l'igurc 7. Aclvancing(fillccl circlcs) ancl rcceding (open circles) contact

anglesor

watcr on mixecl

SAMs otrtained by thc aclsorptionof HS(CH1)r,,('H,f)F{ and HS(CH,),,ClH.OH onro solcl as a

lunction of' the molc fraction of lhc lclngcr comp()nent in thc SAM.

The m.lc

lracti.ns r.l,ere

dctermincdas clescribcdin the caption to Fig.3. Thc curvcsthrough the data arc ttr.rlv suidesto the

cyc.

singlecolnponcnt S,'\\ls (",,

l':r

rlccreascsbv l7 nt.l/mror 0.5 kcal/mol) [l].*

thcscntircrl S,\\4s. thcrc must be significant

rrcthrlcnc groups of the longer

mgn11lalcr-water ;cl

changes in

FoI thc c()lltllctitllglc to incrca\c()n

llllcrllcli()lllrct$ecl't thc probc liquicluncl thc

chrtttlr.

.l-hcsc

rcsults imply' significant clisordcrzrt thc

ttttltltllay'er-vapor interfaces. We cannot, however, interpret thc

contact angle on this set of SAMs in terms of a model for mixine of the com-

poncnts becausewe do not

know the extent to which thesecomponents may tre

forming islandson the surface.

N{ircclphases of Sh:CH./Lg:CH:

Ittlirttrcing contact angle of water) as

(Fis. '\t. While the

are as hyclrophobic(as determinedby the

single-componcnt SAMs

the highly ordeied,

contact anglcsof hexadecu:rneclearly shc,w that the interfaccis

disorilercdtscc Fig.9), the

advancing contactangle of water is unaffectcd by the

interface. Gcnerally,a surfacecomposed of

20mJ/mr, and one of methylenegroups,

this differcnceshould lead to a decrease

using Fowkes'sequation for

...

the superscriptd

presenccof mctirvlenegroups at the

methyl group\ hus a /sv of about

/sv=30 mJ

mi tc.g'polyethylene) [47];

in thc equilibriunt cotttitct angle of water by -tl"

(yiv= 22mJ/mr for u'ater at room temperature

norr-polar surfaccs [4li]: /sr : /sv* ytv-2,[y*i{,,. *h

rcfers to

the

<iispcrsivc component of

the

surface tension of the tiquid

t42l).

The receding coniact

8',

suggestingthat the

angle of water decrcasedon the mixcd phasesby about

cquilibrium contact angle of

water probably also decreased; this result is

'iWe commonly tthservethat the raluc of the advancingcontact

termtnatcd monolaycrs cluickly'incrcases u'ith

anglc of

watcr on hydroxvmethyl-

removal of thc sample

the amount of time bctween

fronr solution and the tirne that thc contact an{les are taken. We attribute this increase(which is

relativcly small in terms of cosd) to thc adsorpticln of airbclrnecontaminants to

this high-energ1,

sttrtace'ancl not to reconstructiott of the monolayer air interfaceof the singlc-component SAMs

t.l(il.

1406

.1.l'.

Folkers cl al.

Au-S(CHz)roCHg

Au-S(CHzl21CHg

120.

cos e

110

0

100

^l

llLg,sAM

Figurc 8. Aclvancing(l'illcrl circles) and rccccling(opcn circlcs) c()ntlrclrrnslcs ol.$,atcr on mixcci

SAMs obtzrinedhv tlrc adsorptionof FIS(flH.)r,,('H. and HS(('H.).r( ll, orrlo goltl rrsu functionol.

thc m<llefraction of the longcr c()mponcntin thc SAM. Thc m<llc lrlrctrrrnr\\r.t

..

' (lctcrntinccl as

dcscribedinthccaptit)ntoFig.3.

T'hecurvcsthroughthcclataarconlr,!,uidcslot|1.,.,r.,

consistentwith the introcluctionof somc methylenegroups at the srrerl,cc. Ilt a

systcmwith thc ability to reorganizcsuch as SAMs, thesercsLllts (iurrl thrsc for

Sh: CH'OH/Lg: CH,) might imply that the

systemminimizeS l,rr tlLrrinsthe

and minimizcs ;,,, rluring

measLlremcntof the advancingcontact anglc of water

the mcasurementof the recedingcontact angle of watcr.

  • 4.2. Wettability with hexadecane

The most interestingdetails about clisorclerin theseSAMs that can bc inferrcd

from the contact angle of hexadccanewerc obtaineclon Lg:CH.,/Sh:CH,.

When thc two methyl-terminated components were mixed on the surface,the

zrdvancingcontact angle of hexaclecanc decreasedfrom - 45" on the single-

component SAMs to 16' (Fig. 9) on the mixed SAM with

lr g.SAr\r

:0.2.If

we

assumethat this decreaseis analogousto the decreasein the equilibrium contact

angle' we can use Fowkcs's equation t4ttl to

determine the solicl-vapor and

solid-liquid interfacial tensionsof these SAMs

(Fig. 9, bottom). The maximum

decreasein thc advancingcontact angle of hexaclecanefrom the values on the

single-componentSAMs correspondsto

an increasein )rsv by about 6.5mJ/m2

?rsr by about 0.6mJ/m2

(0-20 kcal/mol of surface groups) and a decreasein

(0.02 kcal/mol of surfacegroups).* Obviously, disorder in this systemleads to an

increasein the

numbers of methylenegroups at the interface.While hexadecane

is most sensitiveto the methylenegroups &t

/r_g.sav:0.2,rvater is most sensitive

to disorder between.Xrg.snv:0.4 and 0.8; we do not have an explanationfor this

differenccin behavior.

*Thc

Lg:CH.

advancingcontact anglcs of

hexadccanc on

Sh:CHr/Lg:CH.OH

and Sh:CH.OH/

show similar trends [2], but sincc the hydroxymethyl-terminated monolaversare wcttable.

thc dataare not as illustrative of disorderin the interfaceas thcy are for Sh : CH,/Ls : Cll

..

\AMs o.fulkunethiols on ,qold

Au-S(CHdzrCHa

l4('t7

 

0.s

60

 

I

I

 

0.6

I

o.7

+

50

cos 0

0.8

\

I

o

400

 

30

 

0.9

 

20

 

1.0

0

 

0.9

0.6

mJ/m2

kcal/mol

0.3

0.0

Xtg,sAM

Figure 9. Ttlp: Advancing (filled circlcs) and receding (opcn circles) contact anglesof hcxaclccaneon

mixed SAMs obtained by the adsorption of IIS(CH.)rlcHr and HS(ClH,),,CH.,onre gelcl as a

function of thc molc fraction of thc longer component in the SAM. Bottom: Solid-vapor (yrrlfilted

circles) and solid-liquid (y.,; fillcd squares)intcrfacial tensionsdetermined using the aclvancing

contactangles of hcxadecaneand Fowkes'sequation [4tt]. Valuesof y., have becn multiplied by l0

to bring them on scale.The mole fractions wcre dctermincd as describcd in the caption to Fig. 3. The

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

interfacebecomes more disordered.Figure 10 showsthe hysteresisin the contact

angleof water for the mixed SAMs of Sh: CH,OH /Lg: CH., plotted againstthe

composition of the SAM. The origin of this increasein 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

heterogeneityat the interface [43,44], but once we understandthe distribution

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)1sCH2OH

0.4

0.3

Acos et'o 0.2

^f

ALg, SAM

Figure 10. Hystercsisin thc contact anglc of watcr on mixed SAMs obtaineclbv thc uclsorptionof

HS(CHr)r.CH,OII

and HS(tlH.).rCHr

onto gold as a function of the mole fractior.rot rhe lonscr

component on thc surface.Valucs of hystcrcsiscannot be determinedwhen thc rcccclinslrnglc of

water is zero, and therefore,there are no valucsclf hystcrcsisbclow /ro s,rrr = 0. l. Thc crrrre through

thc clatais only a guideto the cyc.

5.

CONCI,T]SIONS

The data summarizeclin this

self-assembledmonolayers of

paper illustrate that formation of two-cr)mponcnt

alkanethiolateson gold is an excellentmethocl for

forming surfaceswith controlled wettabilities.When using SAMs to form such

surfaces,the composition of the SAM may not equal the composition of the

solution, and the relationship between these two may be dependent on the

conditions used to form the moncllayers.Factors such as the total concentration

of thiol in the solution,the length of time that the sampleswere left in solution,

the temperatureof the solution,and the solventused are extremelyimportant in

determiningthe compositionof the SAM [ 1, 16,3U].

The data also illustratethat two-component SAMs of alkanethiolateson gold

are important tools in understandingwetting. Contact angles using water and

hcxadecaneare sensitiveto disorder in the interfacialregions of mixed SAMs of

alkanethiolateswith alkyl chains of different lengths,but this sensitivity depends

on the tail groups of the componentsand on the probe liquid: water is sensitive

to the increasein the concentrationof methylenegroups in the interfacialregions

of mixed SAMs of Sh:CH,OH/Lg: CH.,OH, but is only slightlysensitive to the

increasein the concentrationof methylenegroups in the interfacial regions 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

interfacial region in mixed SAMs of Sh: CH. /Lg: CH ..

Hysteresis in the

contact angle of water increaseson the mixed SAMs. This observationsuggests

that hysteresisis alsosensitive to microscopicdisorder in the interfacialregion.

We do not believethat theseSAMs are completelydisordered: the relationship

between the composition of the SAM and the composition of the solution

suggeststhat these SAMs have partially phase separatedunder normal con-

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

1409

ditions for adsorption (see

the wetting and adsorption

lastfootnote

properties of

these,SAv,

within

SAMs,

on p. 1401). we are continuing to

explore

and controlling the sizeof the islands

*ittr th. gout, of determining

and then relating

the wetting

properties (especially hysteresis) to the heterogeneity of the interfaces.

Acknowledgements

This

research was supported

Defense

Advanced

in

part

by

the office

of

Naval Research,

the

Research

DMR-|

Foundation (Grant

^lrgjects

9-20490

to

ag.n.y,

,i.

and

the

National

Scheme

Materials

for a

Research Laboratory)' J'P'F.

training

Harvard

University

acknowledges the National Institutes of Health

grant in biophysics (19g9_

tggOl. We would especially like ro rhank

area.

Colin Bain for initiating itucties in this

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