Syn hesis and Combina o ial Op imiza ion
o No el S a -Shaped Resis Ma e ials
o Li hog aphic Applica ions
Disse a ion
zu E langung des akademischen G ades eines
Dok o s de Na u wissenscha en (D . e . na .) im Fach Chemie
de Fakul ä ü Biologie, Chemie und Geowissenscha en de Uni e si ä Bay eu h
o geleg on
Flo ian Wiebe ge
gebo en in Scheßli z
Bay eu h, 2012
Die o liegende A bei wu de in de Zei on No embe 2007 bis Mai 2012 am Leh s uhl
Mak omolekula e Chemie I de Uni e si ä Bay eu h un e de Be euung on He n P o . D .
Hans-We ne Schmid ange e ig in enge Koope a ion mi dem Leh s uhl
Ma e ialwissenscha en und Ingenieu wissenscha en de Co nell Uni e si ä , I haca, New
Yo k, USA on He n P o . D . Ch is ophe Kempe Obe .
Da um de Ein eichung de A bei : 09.Mai 2012
Da um des wissenscha lichen Kolloquiums: 28.Sep embe 2012
P ü ungsausschuss:
E s gu ach e : P o . D . Hans-We ne Schmid
Zwei gu ach e : P o . D . Axel H. E. Mülle
Vo si zende : P o . D . S ephan Fö s e
P o . D . Ca lo Un e zag
Meine lieben Familie
We nich s als die Chemie e s eh , e s eh auch die nich ech .
Geo g Ch is oph Lich enbe g (1742 – 1799)
Table o con en s
9
Table o con en s
Summa y 13
Zusammen assung 17
1 In oduc ion 21
1.1 Li hog aphy 21
1.1.1 Li hog aphic pa e ning p ocess 21
1.1.2 Exposu e ools and echniques 24
1.1.3 Resis ma e ials 26
1.2 A om ans e adical polyme iza ion 29
1.2.1 Con olled adical polyme iza ion 29
1.2.2 The ATRP p ocess and i s componen s 32
1.2.3 Polyme a chi ec u es accessible ia ATRP 34
1.3 Combina o ial in es iga ions 36
1.3.1 Combina o ics and high- h oughpu sc eening 36
1.3.2 Combina o ial in es iga ions o hin ilms 37
Re e ences 39
2 Aim and mo i a ion 45
3 O e iew o he hesis 47
3.1 Combina o ial echniques o e icien ly in es iga e and
op imize hin ilm nanopa e ning 48
3.2 Tailo ed S a -Shaped S a is ical Te oligome s ia ATRP
o Li hog aphic Applica ions 54
3.3 Tailo ed S a Block Copolyme A chi ec u e o
High Pe o mance Chemically Ampli ied Resis s 58
4 Publica ions and manusc ip s 63
4.1 Indi idual con ibu ions 63
4.2 Combina o ial echniques o e icien ly in es iga e and op imize
hin ilm nanopa e ning 65
4.3 Tailo ed S a -Shaped S a is ical Te oligome s ia ATRP o
Li hog aphic Applica ions 93
4.4 Tailo ed S a Block Copolyme A chi ec u e o High Pe o mance
Chemically Ampli ied Resis s 115
5 Publica ion lis 137
Danksagung 141
Summa y
16
Zusammen assung
17
Zusammen assung
Go don Ea le Moo e p ognos izie e Mi e de 1960e Jah e eine kos engüns ige
Ve dopplung de T ansis o anzahl on in eg ie en Schal k eisen alle zwei Jah e – bekann
gewo den als „Moo esches Gese z“. Füh ende Un e nehmen o ien ie en sich bei de
En wicklung on in eg ie en Schal k eisen an diesem Moo eschen Gese z und ugen dazu
bei, diese Vo he sage bis heu e zu e wi klichen. Dabei o mulie die Halblei e indus ie
zum E üllen diese Vo aussage alle zwei Jah e ih e Ziele, welche zusammenge ass in de
sogenann en „In e na ional Technology Roadmap o Semiconduc o s“ (ITRS) nachgelesen
we den können. Die ITRS is somi eine Au lis ung on Rich linien, die eine wi scha liche
Wei e en wicklung de Leis ungsme kmale on in eg ie en Schal k eisen e möglichen soll,
wie zum Beispiel die Ges al ung de in eg ie en Schal k eise und die Wei e en wicklung on
Belich ungsmaschinen und – echniken, sowie – eng dami e bunden – Resis ma e ialien.
Diese A bei behandel die En wicklung on neuen Resis ma e ialien und ih e
kombina o ischen Un e suchung hinsich lich de wich igen Leis ungsme kmale de
li hog aphischen S uk u ie ung.
Fü die li hog aphische S uk u ie ung is eine Ab olge on zahl eichen P ozesssch i en
nö ig. Dami beinhal e diese P ozess eine g oße Anzahl on s a k mi einande wechsel-
wi kenden Ve a bei ungsbedingungen. Zum Ve s ändnis und zu um assenden Un e suchung
on de a igen Sys emen, die du ch iele Va iablen beein lussba sind, wa en die
En wicklung und Realisie ung on kombina o ischen Anwendungen ein Schwe punk diese
A bei . Des Wei e en konzen ie e sich diese A bei au die Syn hese on neuen
maßgeschneide en Resis ma e ialien ü die li hog aphische S uk u ie ung. Die S e n-
opologie s ell e sich hie bei als die iel e sp echends e Polyme a chi ek u ü neues
Resis ma e ial he aus und wu de übe eine om Ke n ausgehende „A om T ans e Radical
Polyme iza ion“ (ATRP) Syn hese ou e ealisie . Das li hog aphische Po en ial de neu
he ges ell en Resis ma e ialien au Basis on s a is ischen S e n e polyme e und
S e nblockcopolyme e wu de mi els Elek onens ahlli hog aphie in kombina o ischen
Biblio heken sys ema isch un e such .
Das e s e Kapi el handel on en wickel en, angepass en und e besse en
kombina o ischen Techniken zu Un e suchung dünne Filme im Allgemeinen und de en
Anwendung au die li hog aphische S uk u ie ung im Speziellen. De li hog aphische
Zusammen assung
18
S uk u ie ungsablau on chemisch e s ä k en Resis en beinhal e die olgenden Sch i e:
Filmhe s ellung, einem Tempe ie ungsp ozess zu En e nung des Lösungsmi el („pos apply
bake“; PAB), Belich ung, einem Tempe ie ungsp ozess zu Ak i ie ung de ka aly ischen
Reak ion („pos exposu e bake“; PEB) und En wicklung. Fü diesen komplexen
Gesam p ozess wu den Va iableng adien en ü jeden Ve a bei ungssch i en wickel und
angepass , um das Po en ial neue Resis sys eme zu un e suchen und zu op imie en. Fü die
Filmhe s ellung wu de eine Me hode en wickel um einen Zusammense zungsg adien en zu
p äpa ie en. Diese wu de e wi klich du ch ein G adien enex uda – he ges ell du ch zwei
indi iduell ans eue ba e Sp i zenpumpen – das anschließend ge akel wu de. Zum Nachweis
de Umse zung des Zusammense zungsg adien en wu de Hochleis ungs lüssigkei s-
ch oma og aphie genu z . De zwei e (PAB) sowie de ie e (PEB) li hog aphische
Ve a bei ungssch i sind jeweils Tempe ie ungssch i e des Resis ilms, obgleich sie
un e schiedlichen Zwecken dienen. Zu Un e suchung solche Tempe ie ungsp ozesse
wu den Tempe a u g adien en e zeug , die au de inie e Tempe a u be eiche und -s eigungen
eins ellba sind. Die Eins ellung e olg dabei du ch ak i es Heizen und Kühlen sowie den
gewähl en Abs and und de A de e wende en dazwischen liegenden Me allpla e. Zum
d i en Sch i – Belich ung – wu den Me hoden en wickel um de inie e Belich ungsdosis-
g adien en in seh kleinen Flächen des Resis ilms zu ealisie en. Un e schiedliche
Belich ungsdosisg adien en wu den en wo en ü Fo oli hog aphie sowie ü
Elek onens ahlli hog aphie. Fü den Dosisg adien om le z genann en wu de ein
Belich ungsdesign an dem Compu e p og ammie , welche den Elek onens ahl wäh end
des Belich ungsp ozesses s eue . De Dosisg adien ü die o oli hog aphischen
Un e suchungen wu de du ch eine speziell en wo ene Scha enmaske ealisie . Fü den
le z en Ve a bei ungssch i , de En wicklung, wu de eine Vo un e suchung de Löslichkei s-
bedingungen des Resis ilms mi Hil e de Schwingqua zmik owaagen echnologie einge üh .
Basie end au den gemessenen Löslichkei s e hal en wu de das Zei ens e ü En wicklungs-
zei g adien en gese z , de du ch s u enweises ode kon inuie liches Ein auchen de
Resis ilme in de En wickle lösung ealisie wu de. Schließlich wu den zwei bis d ei
Va iableng adien en zu binä en, beziehungsweise e nä en kombina o ischen Biblio heken
e einig . Diese e nä en kombina o ischen Biblio heken e lauben die zei gleiche
Un e suchung on d ei Va iablen eines li hog aphischen S uk u ie ungsp ozesses und
e möglichen so die schnelle und e izien e Op imie ung eines Resis sys ems in Bezug au die
Gü e des Resis s.
Zusammen assung
19
Das zwei e Kapi el handel on de Syn hese on s e n ö migen Te oligome en als
po en iell neue Resis a chi ek u ü li hog aphische S uk u ie ungen. Die Polyme isa ion
e olg e om Ke n weg mi els ATRP. Den Ke n bilde e dabei ein mi ach Ini ia o en
unk ionalisie es Saccha ose-Molekül. Nach diese Rou e wu den ie s e n ö mige
Te oligome e mi un e schiedlichen A mlängen syn he isie . Des Wei e en wu de ein
Saccha ose-Molekül mi eine mi le en Ini ia o anzahl on 3,5 syn he isie und ausgehend
on diesem zwei en Ke n ein S e n e oligome mi eduzie e A manzahl, jedoch iden ischen
Ke n und ähnliche A mlänge he ges ell . Wei e hin wu de ein linea es Te oligome als
Re e enz-Resis ma e ial mi dem Ini ia o E hyl-2-b ombu y a syn he isie . Alle
he ges ell en Polyme e wiesen eine enge und monomodale Molekula gewich s e eilung mi
Polydispe si ä en on kleine 1,1 au . Basie end au zu o e mi el en Monome einwaagen
wu den alle syn he isie en Te oligome e mi den geplan en Monome e häl nissen e hal en.
Dieses anges eb e Monome e häl nis o ien ie e sich an dem eines de zei indus iell
genu z en linea en Te oligome s. Von den syn he isie en S e noligome en wu de eines
ausgewähl und im Hinblick au die g undsä zliche Eignung de S e na chi ek u ü
li hog aphisches S uk u ie en un e such . Dieses neue Resis ma e ial wu de kombina o isch
in eine e nä en Biblio hek mi den Va iablen Belich ungsdosis, PEB Tempe a u und
En wicklungszei in einem Op imie ungsexpe imen un e such . Hie bei wu den op imie e
S uk u en on 100 nm B ei e mi eine exzellen en Kan en auhigkei on 3,1 nm e hal en.
Das le z e Kapi el diese A bei zeig die ziels ebige Wei e en wicklung des
s e n ö migen Resis ma e ials on Kapi el zwei. De s a is ische Monome einbau wu de
hie bei e se z du ch die Ein üh ung de maßgeschneide en S e nblockcopolyme -
A chi ek u . Diese A chi ek u wu de zum e s en Mal übe die om Ke n ausgehende ATRP-
Rou e nach olls ändigen Umsa z eines e s en Monome s und de in si u Polyme isa ion des
danach hinzuge üg en Monome s ealisie . Die e olg eiche Syn hese wu de du ch
Kon ak winkelmessungen bek ä ig . Diese zeig e eine e höh e Hyd ophobizi ä ü S e n-
blockcopolyme e im Ve gleich zu den s a is ischen S e ncopolyme en mi gleichem
Monome einbau. Des Wei e en wiesen die S e nblockcopolyme e eine e höh e Löslichkei im
En wickle au , welche du ch Messungen mi de Schwingqua zmik owaage e mi el wu de.
Zusä zlich zeig en sie eine bis zu ach ach höhe e li hog aphische Emp indlichkei im
Gegensa z zu dem syn he isie en linea en Re e enz-Copolyme . Das iel e sp echends e
S e nblockcopolyme wu de ü die anschließende li hog aphische Un e suchung in eine
e nä en kombina o ischen Biblio hek hinsich lich Belich ungsdosis, S uk u g öße, PEB
Zusammen assung
20
Tempe a u und En wicklungszei ausgewähl . Mi diesem Resis sys em konn en kla e Linien
mi eine B ei e on 66 nm und eine Kan en auhigkei on 6 nm ealisie we den.
Zusammen assend läss sich es s ellen, dass in diese A bei un e schiedliche
s e n ö mige Te polyme e übe die om Ke n ausgehende ATRP-Rou e syn he isie und
e olg eich zum e s en Mal im li hog aphischen S uk u ie ungsp ozess eingese z wu den.
Zusä zlich demons ie e die kombina o ische Op imie ung das du chweg iel e sp echende
Po en ial diese s e n ö migen Resis a chi ek u . Die wesen lichen Ve besse ungen s ellen
dabei die gezeig e he o agende Kan en auhigkei , die e ziel e übe aus hohe Emp indlichkei
und allgemein de e ablie e schnelle und e izien e kombina o ische Op imie ungsp ozess de
zu kla en 66 nm Linien üh e.
In oduc ion
21
1 In oduc ion
1.1 Li hog aphy
The in en ion and de elopmen o compu e s and hei s eady ad ancemen s simpli ied
and changed ou li e o as we know i oday. This de elopmen was mainly con ibu ed om
he minia u iza ion p ocess o in eg a ed ci cui s in mic op ocesso s d i en by new
ad ancemen s in li hog aphy o e he yea s.
1.1.1 Li hog aphic pa e ning p ocess
In he summe o 1958 Jack Kilby made an impo an b eak h ough in he ad ancemen
o ansis o s and in en ed he i s in eg a ed ci cui (IC).
1
This can be seen as he beginning
o he mode n compu e age. Only se en yea s la e he de elopmen o he pe o mance o
ICs g ew so apidly, Go don Moo e made he p edic ion ha he numbe o ansis o s on one
IC doubles e e y wo yea s wi h dec easing cos s pe single ansis o . This desc ibes he so-
called “Moo e’s Law” (Figu e 1).
2
Figu e 1: Le : The minimum cos o a single componen ( ansis o ) is dec easing wi h e olu ion o
ICs. Righ : The numbe o componen s pe IC is p edic ed o be doubled e e y wo yea s.
Moo e was p o ed igh and he de elopmen o ICs p oceeded as he expec ed in he
ollowing decades. This ad ancemen was mainly a ibu ed o he s eady educ ion in
componen ’s size. Fo semiconduc o indus y his p edic ion became mo e and mo e a kind o
In oduc ion
22
business model bu also a challenge. As a esul companies o semiconduc o indus y
inco po a ed na ional and soon in e na ional o s a e hei echnological needs and o
coo dina e de elopmen s o ICs. This ade associa ion mee s e e y yea and epo s o e all
17 scopes on esea ch di ec ions and sugges s hei ealiza ion imelines up o 15 yea s
summa ized in he so-called “In e na ional Technology Roadmap o Semiconduc o s”
(ITRS).
3
Such esea ch di ec ions a e o ins ance u he minia u iza ion o he design o
ansis o s, educed powe consump ion, and inc ease in pe o mance. Recen ly In el
Co po a ion p esen ed he i s demons a ion o a 22 nm mic op ocesso in 2011.
4
This
mic op ocesso – code-named I y B idge – is he i s chip uses 3-D T i-Ga e ansis o s,
which ep esen s a b eak h ough in ansis o pe o mance and ene gy e iciency. The
ealiza ion o such mic op ocesso s is a e y complex p ocess and consis s o abou 500
p ocessing s eps.
5
This la ge numbe comes om epea ing li hog aphy and e ch pa e n
ans e p ocesses up o o y imes. In Figu e 2 a simpli ied pa e n ans e p ocess is
illus a ed.
Figu e 2: A simpli ied illus a ion o he li hog aphic and e ch pa e n ans e p ocess.
A he beginning o his li hog aphic p ocess he subs a e has o be deeply cleaned o
emo e con amina ions and annealed o emo e wa e .
6
In he ollowing s ep (1) a silicon
oxide laye is c ea ed on he silicon wa e . This can be conduc ed, e.g., by he oxida ion o
silicon a e y high empe a u es in he p esence o oxygen o by plasma e ching. Ongoing an
adhesion p omo e solu ion is spin cas on he subs a e. The mos common used adhesion
1.Deposi ion o oxide laye
on silicon wa e
2.Applica ion o pho o esis 3.UV-exposu e h ough
shadow mask
4.De elopmen o esis 5.E ch o oxide laye 6.Remo e emaining esis
Silicon wa e
Pho o esis
Oxide laye
Shadow mask UV ligh
In oduc ion
23
p omo e is hexame hyl disilazane (HMDS) which eac s chemically wi h he su ace hyd oxy
g oups. In he second s ep (2) a pho o esis solu ion is spin cas on he subs a e o ilm
applica ion. The ilm hickness mus no exceed he aspec a io o 3:1 in espec o he
a ge ed line wid h due o ce ain pa e n collapse. The hickness is adjus able ou o he
concen a ion o he solu ion, he pho o esis ma e ial i sel , and he accele a ion and he inal
e olu ions pe minu e ( pm) o he spin cas ing p ocess. Subsequen ly he ilm is annealed o
pos apply bake (PAB) o emo e mos o he emaining sol en in he esis ilm and o
s abilize he ilm. The basic p inciple o he ollowing exposu e s ep (3) is o gene a e a
change in dissolubili y o he esis ilm o he ongoing de elopmen s ep (4). This is he
ac ual li hog aphic pa e n ans e as he esis ilm is exposed h ough a shadow mask. As
al eady men ioned, he whole p ocess is conduc ed many imes in he p oduc ion o ICs and
hus a p ecise alignmen o mask in e e y exposu e s ep o subs a e is equi ed. In he case o
high pe o mance esis sys ems he exposu e alone c ea es no change in solubili y. Fo hese
sys ems a subsequen annealing s ep is necessa y, he so-called pos exposu e bake (PEB). In
he exposed a eas a pho oac i e compound is ac i a ed and a ca aly ic eac ion akes place
du ing he PEB. Fo he ollowing de elopmen s ep (4) an aqueous base (usually e ame hyl
ammonium hyd oxide: TMAH) is used. In his s ep he base-soluble esis ma e ial is
dissol ed and he pa e n – he image o he shadow mask – is le on he subs a e. These
pa e ns a e annealed in a ollowing pos bake o emo e esidual wa e o gas, o imp o e he
adhesion, and o ha den o wi hs anding he upcoming ha sh e ching s ep (5). In his s ep he
ac ual pu pose o he esis ma e ial becomes impo an : The esis ma e ial ‘ esis s’ he
e chan and p o ec s he oxide a eas co e ed by he esis and hus only he unp o ec ed a eas
a e e ched. Such e chan s a e ei he acid solu ion o mo e commonly d y plasma. The las s ep
in his p ocess con ains he s ipping o he emaining esis ma e ial (6). One op ion o
emo e he o ganic ma e ial is o use we chemical as ino ganic acid-based sys ems o phenol-
based s ippe s. Ano he me hod – s anda d in semiconduc o p ocessing – is he use o
oxygen plasma which can e en s ip he e ched esis ma e ial bu lea es he ino ganic su ace
un ouched. Fu he s eps a e, e.g., ion implan ing o al e ing conduc elec ici y (doping),
applying mul iple laye s o me al (coppe ) o elec ical connec ions, and implemen a ion o
low-κ ma e ials, supplemen ing he ac ual pa e ning ans e p ocess. A he end o all
p ocessing s eps he inished mic op ocesso is coa ed wi h a so-called passi a ion laye . This
insula ing laye inc eases elec ical s abili y bu also p o ec s he IC om con amina ions.
In oduc ion
24
Each o hese p ocessing s eps con ains p ocess a iables like ime, concen a ion,
ma e ial, empe a u e, dose, o name bu a ew. A a ia ion o one a iable a he beginning o
his mul i- a iable p ocess o en a ec s nega i ely he ollowing s eps in his ex eme
sensi i e and hus au oma ed p ocedu e. This sensi i i y o p ocess condi ions and u ilized
esis ma e ial inc eases wi h he u he minia u iza ion o ICs and equi es he u he
de elopmen and ime-consuming op imiza ion o exposu e ools, esis ma e ials, addi i es,
and p ocess se -ups.
1.1.2 Exposu e ools and echniques
The unc ional pu pose o an exposu e ool is he li hog aphic pa e n ans e . A
shadow mask is exposed by a ligh sou ce and he passed ligh is ocused h ough a lens
sys em o a subs a e coa ed wi h pho osensi i e ma e ial. Since he de elopmen o ICs in he
end o he i ies he p edomina ed pa e ning p ocess o he p oduc ion o mic oelec onics is
based on op ical li hog aphy.
7
The exposu e ools and echniques o his pa e ning p ocess
e ol ed down o he p esen day. The main d i ing o ce o his e olu ion was o dec ease
ab ica ion cos s o ICs which was pa ially done by cons an ad ancemen s in p oduc i i y
and h oughpu o ICs. Bu imp o ed esolu ion con ibu ed he mos o educe cos s due o
mo e ICs could be ab ica ed on one single wa e . The heo e ically maximum esolu ion o
an exposu e ool can be calcula ed using Equa ion 1.
8
⁄ Equa ion 1
whe e LW ep esen s linewid h ( esolu ion), k1 p ocess-dependen coe icien , λ
exposu e wa eleng h, and NA nume ical ape u e. Fo he imp o emen o esolu ion k1 and
he u ilized wa eleng h λ mus dec ease, while NA mus inc ease. The k1 ac o combines
di e en e ec s o ins ance o he pho o esis ( e lec ion and s anding wa es) o de ec s in
he imaging sys em (s ay ligh , lens abe a ions, and ib a ions).
9
Theo e ically he lowe
limi o k1 is abou 0.25. To come close o his alue ce ain echniques can be u ilized e.g. so-
called phase shi masks, op ical p oximi y co ec ion, o o -axis illumina ion.
10
,
11
NA is
de ined “as he sine o he maximum hal -angle o di ac ed ligh ha can en e he lens imes
he index o e ac ion o he su ounding medium, n” (see Equa ion 2).6
Equa ion 2
In oduc ion
25
This means o inc ease NA he accep ance angle o he lens has o be inc eased and he
medium he ligh passes a e he lens sys em has o be changed o highe n. Wi h a high n
(n=1.44 o wa e a 193 nm), due o ad ancemen s in lens ma e ials, and inc easing o he
po ion cap u ed ligh by he objec i e lens a high alue o 1.3 o NA was epo ed.
12
A e y
impo an pa o esolu ion educ ion con ibu es he exposu e wa eleng h λ as can be seen in
Equa ion 1. High-p essu e Hg discha ge lamps we e used ill he la e 1980s wi h ope a ing
wa e leng hs o 436 nm (g-line), 365 nm (i-line) and 250 nm whe eby he esolu ion
imp o ed om 5 µm down o 0.25 µm.7,
13
The in en ion o excime lase s based on K yp on-
Fluo ide (K F; 248 nm) and A gon-Fluo ide (A F; 193 nm) in he 1990s ended he u iliza ion
o Hg discha ge lamps.
14
The s eadily ad ancemen s o hese lase s in powe and bandwid h
led o highe p oduc i i y, la ge dep h-o - ocus and highe esolu ions om 250 nm down o
82 nm. E en hough an ope a ing ligh sou ce exis ed wi h he F2 lase (157 nm), he ma ke
leade In el Co po a ion ne e ad anced 157 nm li hog aphy beyond he p o o ype s age due
o a lowe powe in compa ison o K F and A F lase s and imma u e lens ma e ials and
pho o esis ma e ials.
15
,
16
Ins ead a huge p og ess happened wi h es ablishing wa e -based
imme sion li hog aphy esul ing in an imp o emen in esolu ion o 30 – 40 %.8 A e wa ds
e o s we e ocused on lowe ing k1 e.g. inc ease o uni o mi y in imaging and image
placemen , uni o mi y in illumina ion, high pu i y op ical elemen s.7 The in oduc ion o
exposu e echniques like double exposu e, double pa e ning, and space double pa e ning
con ibu ed also eno mously o he educ ion o he p ocess cons an k1.
17
Wi h he help o all
hese ad ancemen s, op imized echniques and me hods In el Co po a ion ecen ly ealized a
ull-scale high- olume ab ica ion o 22 nm esolu ion.4
As men ioned abo e educing he wa e leng h u he imp o es esolu ion bu also o he
non-op ical pa e ning echniques a e concei able o achie e his goal. Ex eme ul a- iole
li hog aphy (EUVL; 13.5 nm), maskless li hog aphy (ML2) echniques, nanoimp in
li hog aphy (NIL), and di ec ed sel -assembly a e possible p ospec s.3,13 In con as o he
es ablished 193 nm li hog aphy hese new me hods a e by now imma u e and oo expensi e.
Bu o he ealiza ion o he nex highe esolu ion s eps which he ITRS aims, he
possibili ies o 193 nm li hog aphy d aw o a close. Di ec ed sel -assembly o block
copolyme s and hei possible u iliza ion o ICs ab ica ion a e beyond he beginnings and a
cheape al e na i e bu ye no applicable.
18
NIL is a mechanical eplica ion o a elie pa e n
by de o ming a esis laye unde p essu e o his pa e n. Indeed his pa e n ans e o e s
high h oughpu in ab ica ion o eplicas bu due o de ec and o e lay issues o he elie
In oduc ion
32
An absolu e de e mina ion o capabili y and e iciency is di icul as all o hem ha e
hei ad an ages and limi a ions. So, o ins ance, nea ly all monome s a e polyme izable
using RAFT and in he las decade mo e and mo e monome s we e accessible o ATRP, e en
inyl ace a e.49,
54
,
55
Al hough he e is some p og ess in making he NMP p ocess mo e
adap i e o unc ional monome s, his polyme iza ion echnique exhibi s he mos es ic ions
on his ma e .
56
The expense o polyme iza ion is mainly dependen on monome ’s choice
bu in combina ion wi h applicable ini ia o s ATRP is he mos a o able echnique. F om an
economic poin o iew he di e ences be ween hese h ee echniques a e ma ginal. Bu
las ly i is ai o say ATRP is a e y e sa ile and obus echnique and o many s udies and
applica ions mo e sui able han he RAFT o NMP.
1.2.2 The ATRP p ocess and i s componen s
ATRP is one o he mos powe ul CRP echniques, especially because i is a e y
e sa ile p ocess and he componen s o conduc a success ul polyme iza ion a e easily
a ailable. Besides monome , he polyme iza ion p ocess usually equi es a ansi ion me al
(M n; whe e n is he oxida ion s a e) and a ligand (solubilizing he me al in o ganic sol en s)
oge he se ing as he ca alys sys em. Combined wi h an ini ia o ca ying an ac i e g oup i
can be ans e ed be ween he me al cen e and he chain end and hus e e sibly
ac i a ing/deac i a ing he eac i e chain. Va ious me als like i an, i on, molybdenum, nickel
can be used as ca alys whe eas coppe (Ma yjaszewski e al.) and u henium (Sawamo o e
al.) a e by a he mos equen ly epo ed.
57
Usually he ini ia o is an alkyl halide (chlo ine,
b omine, o a e iodine), bu he usage o o he s, e.g. pseudohalogen molecules, o
hexa luo ophospha e was also demons a ed.
58
Ligands, in luenced by he s uc u e and ype
o ligand, a e used o s abilize he ca alys and hus he a om ans e equilib ium. Ve y o en
amines, py idines and py idineimines a e used as ligands ha a e exempli ied in Figu e 6a.
The ligands show di e en ac i a ion a es depending on opology (cyclic, linea o
b anched), na u e o N-ligands (a yl amine, alkyl amine, py idine, e c), numbe o C-uni s
be ween N a oms, and also on s e ic e ec s.
59
The ini ia o s a e alkyl halides ac i a ed by α-
ca bonyl, phenyl, inyl, o cyano g oups exempla ily shown in Figu e 6b.
60
The eac i i y
depends on he numbe o subs i uen s a he ac i e ca bon a om (p ima y, seconda y,
e ia y), g oups able o s abilize (delocalize) he adical (phenyl, es e , allyl, cyano), and he
In oduc ion
33
halogen a om (b omine, chlo ine, iodine). Fo polyme iza ions nea ly all monome s wi h
ac i a ed double bond can be u ilized o he ATRP p ocess.
Figu e 6: Ligands and ini ia o s equen ly used in ATRP. a) Ligands o coppe based ca alys s o
ATRP wi h an inc easing ca aly ic ac i i y om le o igh . Figu e 6b) ATRP ini ia o s wi h
inc easing ini ia o eac i i y om le o igh .
The basic ATRP p ocess s a s wi h an equi alen concen a ion o ini ia o o ansi ion
me al (M n) and ligand.
61
In he las 15 yea s a ious modi ica ions o his s anda d p ocess
we e c ea ed. An oxida i ely s able ATRP was conduc ed using a ansi ion me al wi h a
highe oxida ion s a e (M n+1).
62
The ca alys was con e ed o an ac i e ca alys (M n) by a
s anda d ee adical ini ia o in si u. Bu he e side e ec s occu as polyme iza ion s a s wi h
a small amoun o he ee adical ini ia o as well as only homopolyme s could be achie ed.
A subs i u ion o he ee adical ini ia o wi h a educing agen o ming no ini ia ing species
sol es his issue o side polyme iza ions. Such educing agen s a e o ins ance asco bic acid,
glucose, phenol, hyd azine, and in (II) 2-e hylhexanoa e.
63
The educing agen can also be
used o elimina e oxygen in he eac ion solu ion. The amoun o ca alys (ac i a o ) can he e
be as low as in he ppm egion as he ac i a o is egene a ed by elec on ans e (ARGET).
This p ocess p o ides ano he ad an age as i supp esses side eac ions caused by he ca alys
i sel due o he small amoun used.
64
This ad an age allows syn hesizing HMW copolyme s.
La ely Fe0, Mg0, and Zn0 we e used as educing agen s.
65
These ze o alen me als showed
di e en eac i i ies and p oceeded in a well-con olled ashion. Recen ly ATRP made a leap
BzCl AllCl E B iB
mo e ac i e
ECPA
Me4-CyclamTPMAPMDETAbpyNPPMI
a)
ligands
b)
ini ia o s
ClAN
mo e ac i e
In oduc ion
34
in e olu ion: he educing agen was eplaced by an elec ical cu en , so-called
elec ochemically media ed ATRP (eATRP).
66
In doing so, he a io o ac i a o o deac i a o
is con olled by cu en , po en ial, and o al cha ge passed and hus he polyme iza ion can be
swi ched on and o e e sibly. This p ocess was s udied on me hac yla es demons a ing low
polydispe si ies e en o HMW polyme s. In en i onmen ally iendly poin o iew
elec odeposi ion o coppe om an ATRP is concei able o emo e he ca alys .
67
Recen ly,
ano he ATRP p ocess was de eloped a oiding me allic ca alys s en i ely, eplacing he me al
by he enzyme ho se adish pe oxidase.
68
Fu he mo e p og esses we e made using wa e as an
inexpensi e and en i onmen ally iendly medium and hus examples o polyme iza ions in
emulsions, suspensions, o dispe sions in aqueous sys ems we e shown.
69
These new
de elopmen s in ATRP u ilizing less ca alys and wa e as he eac ion medium a e pushing
his polyme iza ion me hod owa ds g een and sus ainable polyme chemis y.
1.2.3 Polyme a chi ec u es accessible ia ATRP
The mul i ude o comme cially a ailable eagen s and monome s as well as he
e sa ili y a e he p ominen easons o he widesp ead applica ion o ATRP. Besides
homopolyme s o he polyme composi ions can be ealized such as block, andom,
al e na ing, and e en g adien copolyme s (Figu e 7a). As discussed abo e nea ly all
monome s wi h a adical s abilizing g oup ha e been homopolyme ized ye . These
homopolyme s can be used as mac oini ia o o a subsequen polyme iza ion o ano he
monome leading o block copolyme s. Recen ly i was exempli ied on di e en
me hac yla es ha a successi e polyme iza ion can be epea ed se e al imes yielding, in his
case, well-con olled decablock copolyme s.
70
Fo a andom copolyme iza ion he same e ms
as o a homopolyme iza ion a e applicable bu he e also less eac i e monome s a e
polyme izable demons a ed o 1-oc ene wi h n-bu ylac yla e.
71
Fo he p epa a ion o
al e na ing copolyme s wo monome s wi h s ongly di e en pola i ies/ eac i i ies ha e o be
polyme ized. The monome s s y ene and N-phenyl maleimide o example show such a s ong
endency o al e na e.
72
A new class o copolyme s is ep esen ed by g adien copolyme s,
whe e he composi ion along he polyme chain changes con inuously. Such a g adien
polyme can be yielded by changing he monome eeds as he copolyme iza ion p oceeds.
Fo ins ance such a g adien copolyme was ealized by con inuous addi ion o e -
bu yac yla e o a miniemulsion polyme iza ion o n-bu ylac yla e.
73
In oduc ion
35
Figu e 7: a) Copolyme s wi h con olled composi ions p epa ed by ATRP. b) Examples o polyme
a chi ec u es p epa ed by ATRP. c) End- unc ionaliza ion o di e en polyme a chi ec u es.
ATRP allows he ealiza ion o homopolyme s and copolyme s wi h con ol o e
molecula a chi ec u e, e.g. linea , b ush, ne wo k, hype b anched o den i ic, and s a -shaped
a chi ec u e, oo (Figu e 7b). Especially he s a a chi ec u e imp esses wi h he esul ing
physical and mechanical p ope ies. Thus s a polyme s ound i s way in o indus y o
imp o e engine oils,
74
coa ings,
75
and con ac lenses,
76
o name a ew. E en o such mo e
sophis ica ed a chi ec u es i is possible o an icipa e molecula weigh and o achie e na ow
molecula weigh dis ibu ions o linea and e en o some mo e sophis ica ed
a chi ec u es.
77
B anched polyme s o b ushes can be ealized by polyme iza ions using
mul i unc ional ini ia o s,
78
ini ia o monome s (“inime s”),
79
o b anching agen s.
80
Inc easing he b anching si es will lead o hype b anched polyme s. Polyme s wi h well-
a anged b anching poin s a e called dend ime s. This opology is gi en, e.g., by a
mul i unc ional ini ia o om which polyme iza ion s a s. The ends o he chains a e
unc ionalized wi h wo o mo e ini ia ing si es and he polyme iza ion s a s o e .
81
Se e al
opologies esul om he copolyme iza ion wi h di inyl monome s, which depend on he
concen a ion and on he ime o addi ion. Highe concen a ions a he beginning and ea ly
addi ion a e ini ia ion leads o ne wo k/gels. Is he concen a ion low a he beginning o he
di inyl monome is added some ime be o e he polyme iza ions ends he esul ing
a chi ec u e is a s a o nanogel.
82
O en hese a chi ec u es a e combined wi h a andom o a
block monome composi ion o e en wi h o he a chi ec u es. A wide ange o di e en
opology composi ions a e shown o hype b anched polyme s
83
o polyme b ushes
84
as well
as di e en ypes o dend ime -like polyme s
85
, mik oa m s a polyme s,
86
s a -linea block
homopolyme block copolyme andom copolyme al e na ing copolyme g adien copolyme
s a b anched/b ush ne wo k(hype )b anched/dend i ic
a) Composi ion
b) A chi ec u e
c) Func ionali y elechelic
polyme s
end unc ionalized
polyme s/
mac omonome s
side- unc ional
polyme s
linea
mul i unc ional
polyme s
In oduc ion
36
polyme s
87
and s a block copolyme s.
88
The ealiza ion o s a block copolyme s is a good
illus a ion o he combina ion o a chi ec u es and polyme iza ion echniques. One me hod
desc ibes he p epa a ion o a mac oini ia o ia a co e- i s polyme iza ion om a s a -shaped
ini ia o .
89
Ano he me hod ab ica es a mac oini ia o wi h mul iple ini ia ing si es by an
a ms- i s app oach ia c osslinking o linea homopolyme s anionically polyme ized.
90
In
bo h cases he gene a ed mac oini ia o was used o a second polyme iza ion s ep o design a
s a block copolyme . The p epa a ion o such a chi ec u e was also demons a ed by c oss-
linking o micelles o med by block copolyme s.
91
In Figu e 7c polyme end- unc ionaliza ion o di e en a chi ec u es is shown. These
unc ional g oups can be inco po a ed ia nucleophilc subs i u ion o he alkyl halide on he
end chain.
92
In his way inyl, azide, es e , o hyd oxy g oups and so on can be in oduced o
u he p ocessing. Howe e , hese unc ional g oups can also in oduced by ini ia o s.
Besides he alkyl halide he ini ia o can con ain azides, epoxide, alkene, hyd oxyl, and es e
g oups o name bu a ew. A las monome s p o iding unc ional g oups can also be
copolyme ized egula ed by monome eed.
1.3 Combina o ial in es iga ions
New de eloped and imp o ed ma e ials and hei mul i-s ep p ocessing a e well-known
challenges in li hog aphy. Fo a as and e ec i e implemen a ion combina o ial app oaches
a e a pa icula ly sui able s a egy.
1.3.1 Combina o ics and high- h oughpu sc eening
Business i al y o ce companies o look on p o i abili y o new p oduc s as he
de elopmen o new and he imp o emen o exis ing ma e ials is always a ime-consuming
and cos -in ense p ocess.
93
Due o mos ly complex demands on new ma e ial’s sys ems,
adi ionally a huge amoun o single expe imen s ha e o be unde aken – meaning also lo s
o loss o ma e ial – o achie e desi ed ma e ial ea u es. Bu he numbe o new p omising
chemicals, ma e ial composi ions o syn hesis ou es is oo la ge o such a sys ema ic
in es iga ion.
94
Combina o ial scanning p oduces elie as a as , cos -e icien , and capable
ool o in es iga ion and op imiza ion o ma e ials. Va iable g adien s, he linea a ia ion o
pa ame e s, as well as hei pe pendicula combina ion o so-called combina o ial lib a ies
In oduc ion
37
yields in a high amoun o esul s in a single expe imen . The cha ac e iza ion o hese esul s
and he iden i ica ion o ends in hese combina o ial lib a ies p o ides besides ma e ial’s
de elopmen also undamen al knowledge o in es iga ed sys ems. The i s a emp s o
combina o ial app oaches we e done by Edison and Ciamician a he end and beginning o he
nine een h cen u y, espec i ely.
95
,
96
In 1970 Hanak implemen ed he “mul i-sample concep ”
and hus i s ly epo ed combina o ics using combina o ial lib a ies by au oma ed sample
p epa a ion o ma e ial’s op imiza ion.
97
These new hinking in in es iga ing was
success ully adap ed by he pha maceu ical indus y and e olu ionized his esea ch ield.
98
This e olu ion in d ug esea ch led o a emendously inc eased numbe o compounds which
we e syn hesized and analyzed.
99
,
100
The success o combina o ics is also closely ela ed o
de elopmen s in s anda d binding assays o he iden i ica ion o bioac i e ma e ials and in
analyzing me hods like liquid ch oma og aphy and mass spec ome y.
101
Thus due o hese
me hods yn hesized compounds can be sc eened e icien ly.
102
Bu his high- h oughpu
sc eening echnique was also adop ed by he ield o ma e ials esea ch in he las
decades.
103
,
104
Combina o ial ma e ial esea ch a ge s he combina ion o ela ed expe imen s
in one expe imen o in es iga ion o in e ac ing pa ame e sys ems and o op imiza ion o
ma e ials and p ocesses.
105
Impo an ma e ial esea ch ields a e bioma e ials o d ug
deli e y,
106
sensing ma e ials,
107
polyme ic coa ings,
108
elec onic and unc ional ma e ials,
109
and ca alysis
110
o name a ew. Recen ly, ma e ial esea ch made a g ea leap o wa d in as
and e icien in es iga ion o ma e ial composi ions. On a silicon subs a e 24 combina o ial
lib a ies consis ing o i an, nickel, and sil e we e p epa ed and es ed on e ch beha io .
111
1.3.2 Combina o ial in es iga ions o hin ilms
An in e es ing esea ch ield ep esen s p ope y in es iga ions o hin ilm in e ms o
ce ain a iable g adien s.
112
Fo ilm applica ions in gene al he ilm hickness is a c ucial
pa ame e . The p epa a ion o con inuous ilm hickness g adien s we e success ully
demons a ed ia doc o blading depending on concen a ion, applica ion sol en , gap size o
he doc o blade and accele a ion o he doc o blade.
113
A 2-D combina o ial lib a y
consis ing o a ilm hickness g adien e sus a empe a u e g adien was made o in es iga e
dewe ing beha io o a polys y ene ilm by Amis e al.
114
His g oup also p epa ed a 2-D
lib a y consis ing o a hin ilm wi h an in e nal polyme blend g adien ou o polys y ene and
poly ( inyl me hyl e he ) in combina ion wi h a empe a u e g adien and in es iga ed phase
In oduc ion
38
sepa a ion.
115
Fo he polyme blend g adien a g adien ex uda e was ealized wi h he help
o sy inge pumps and a cus om buil se -up. This ex uda e was applied on a subs a e and
subsequen ly doc o bladed. Such g adien ilm p epa a ions and also hickness g adien s can
also be conduc ed u ilizing physical apo deposi ion. Recen ly combina o ial op imiza ions
ega ding ilm hickness and composi ion was epo ed o he in es iga ion o elec o-op ical
de ices.
116
Fo adhesion in es iga ions in pa icula he chemical su ace ea men o ilms is
an impo an pa ame e and o his g adien s o su ace cha ac e is ics we e de eloped.
Su ace modi ica ions can be ob ained ia elec on beam ea men and we e demons a ed on
a poly (2- inylpy idine) coa ed su ace esul ing in a hyd ophilici y g adien .
117
Ano he
me hod o a su ace hyd ophiliza ion g adien was shown u ilizing a poly ( inyl ca bona e)
ilm con inuously imme sed in an aqueous NaOH solu ion.
118
Li hog aphy is a special ield o esea ch ega ding hin ilm in es iga ions as he whole
li hog aphic pa e n ans e p ocedu e is based on ea ing hin esis ilms. Thus, his
p ocedu e consis s o a la ge amoun o a iables, e.g. esis composi ion, ilm hickness,
annealing empe a u e, exposu e dose, o de elopmen ime o name a ew. The ac ha hese
a iables in e ac s ongly wi h each o he makes li hog aphy an in e es ing esea ch a ea.
Thus combina o ial app oaches ind i s way in o li hog aphy in he las decade. An impo an
a iable in gene al o hin ilms bu especially in he li hog aphic con ex is he bake
(annealing) empe a u e and o cou se he ime. A combina o ial lib a y o hese wo a iables
was c ea ed o deg ada ion in es iga ions o poly ( e -bu oxy-ca bonyloxy-s y ene).
119
Such
annealing s eps a e conduc ed o he nowadays u ilized chemically ampli ied esis sys ems
in he li hog aphic pa e ning p ocess a leas wo imes. Hence, o pe o mance
op imiza ions o a esis sys em wo bake s eps we e in es iga ed o hogonally o each o he
in a 2-D lib a y.
120
Ano he impo an a iable is he ma e ial composi ion as u ilized esis
sys ems consis o mo e han wo componen s. Fo his eason a combina o ial lib a y ou o
di e en composi ions o a molecula glass pho o esis sys em p epa ed ia PVD was
in es iga ed in ega d o exposu e dose.
121
Recen ly a syne gis ic e ec was ound o esis
composi ion and he pos exposu e bake.
122
This was iden i ied due o he in es iga ion in a
e na y combina o ial lib a y. This e na y lib a y was ealized ou o a composi ion g adien
pe pendicula o a empe a u e g adien esul ing in a 2-D lib a y and an exposu e dose
g adien ma ix-like on op o his 2-D lib a y.
In oduc ion
39
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O e iew o he hesis
48
1:1 line/space pa e ns wi h a ea u e size o 100 nm bu di e ing in he exposu e dose
ep esen ing a dose g adien . The esul ing pa e ns we e in es iga ed conce ning ea u e’s
quali y by obse ing images in he scanning elec on mic oscope mode. He e mul iple high-
esolu ion mic og aphs had o be obse ed om each pa e n o e e y sec o o he
combina o ial lib a ies o calcula e and e alua e he line edge oughness using he so wa e
SuMMIT ( . 8.0.4).
In he ollowing he key esul s o he indi idual publica ions a e summa ized. De ailed
desc ip ions o syn hesis and p ocess condi ions as well as measu ed alues a e p o ided in
he espec i e chap e s.
3.1 Combina o ial echniques o e icien ly in es iga e and op imize hin
ilm nanopa e ning
(Submi ed o Molecules, see chap e 4.2)
The i s chap e summa izes all de eloped and implemen ed combina o ial echniques
o a ho oughly in es iga ion o hin ilm p ocessing and p ope ies and we e applied in iew
o he op imiza ion o he complex li hog aphic pa e ning p ocess. The mo i a ion o his
chap e was o in es iga e p ocess condi ions and o es ablish echniques o a as and
e icien op imiza ion o especially new esis sys ems applicable o he mul i-s ep
li hog aphic p ocess. In he ollowing he g adien p epa a ion o ma e ial composi ion,
exposu e dose, empe a u e, and de elopmen ime as well as hei combina ion o
combina o ial lib a ies a e p esen ed.
The sys ems h oughou used in his hesis we e chemically ampli ied esis s (CARs)
sys ems. These sys ems may consis o wo o ou componen s. To in es iga e he p ope ies
o di e en componen a ios and o e alua e he op imized esis composi ion conce ning
ea u e’s quali y, a me hod was de eloped o ealize an in e nal composi ion g adien wi hin a
hin ilm. The p epa a ion o such a g adien was conduc ed in wo s eps: i s a g adien
ex uda e ou o wo solu ions we e applied – ia a sy inge pump sys em wi h wo indi idual
con ollable sy inge pumps and a connec ed mixing de ice – which was di ec ly a e wa ds
O e iew o he hesis
49
doc o bladed o he second s ep (see Figu e 1a) and subsequen ly annealed o emo e
esidual sol en (pos apply bake; PAB). Fo he cha ac e iza ion o he achie ed composi ion
g adien he solid ilm was sec ioned in o segmen s o using luo escence spec oscopy o cu
oge he wi h he subs a e in o pieces which we e hen insed o using high pe o mance
liquid ch oma og aphy (HPLC). The g aph in Figu e 1b shows exempla ily he composi ion
g adien o a nega i e one pho o esis ilm cha ac e ized using HPLC.
Figu e 1a: The g adien ex uda e was ealized on a subs a e ia opposi e low a es o wo solu ions – one
con ains ma ix componen and pho oacid gene a o and he o he c osslinke componen and pho oacid
gene a o – in he i s s ep, subsequen ly doc o bladed and annealed in he ollowing s ep. The esul ing
g adien ilm was sec ioned in segmen s pa allel o he applica ion di ec ion, cu in o pieces (A-N) and analyzed
using high pe o mance liquid ch oma og aphy. Figu e 1b shows he esis ma e ial a ios o each segmen and
he con inuous dec ease o he ma ix componen (□) and he con inuous inc ease o he c osslinke componen
() while he pho oacid gene a o s ays cons an .
The nex s ep in he li hog aphic p ocess a e ilm applica ion and PAB is he exposu e.
Fo CAR sys ems acids a e eleased du ing his s ep which c osslink nega i e one esis s o
dep o ec posi i e one esis s du ing he subsequen pos exposu e bake (PEB). The
dissolu ion beha io o eac ed o un eac ed esis ma e ial causes he de elopmen con as o
exposed o unexposed a eas. The exposu e dose is e y c i ical o high- h oughpu indus ial
applica ions and should be as low as possible. I is s ongly in luenced by he na u e o
applied ma e ials, di e s o e e y indi idual esis sys em, and also is a ec ed by he o he
applied p ocessing condi ions. Thus exposu e dose g adien s applicable o elec on beam
li hog aphy and UV-li hog aphy we e de eloped, espec i ely. Fo he exposu e dose g adien
in he la e case a special designed shadow mask was used o ealize he dose g adien in a
mask-alignmen sys em (Figu e 2a). This shadow mask is composed o 4900 sec o s wi h a
A B C D E F G H I J K L M N
10
20
30
40
50
60
70
80
90
esis ma e ial a io in w .%
segmen
ma ix
c osslinke
pho oacid gene a o
a
2. doc o blading
1. ex uda e
applica ion
g adien
ex uda e
solu ion A
solu ion B
b
O e iew o he hesis
50
sec o ’s size o 1.2 mm x 1.2 mm. One sec o consis s o nine subsec o s and only one ou o
nine pa s has anslucen pa e ns while he emaining pa is coa ed ligh p oo . Thus 4900
dose g adien s a e ealizable in one expe imen ia p ecise ealignmen o he subs a e
be ween di e en exposu es. This is exempli ied by one sec o wi h i e doses using a
posi i e one esis (da k g ey) whe e he subsequen PEB and de elopmen was al eady
pe o med o ealize he ea u es (Figu e 2b). The dose g adien shows ob iously om
unde exposed o op imized o o e exposed ea u es. This is indica ed by he ea u es
becoming ongoing b igh e in g ey scale means mo e and mo e o he posi i e one esis was
dep o ec ed and emo ed du ing de elopmen .
Figu e 2a: A schema ic illus a ion shows he main componen s o a mask-alignmen sys em. One sec o o
o e all 4900 is highligh ed in a schema ic magni ica ion showing nine subsec o s: Only one ou o nine
subsec o s has a anslucen pa e n while he es is ligh p oo coa ed. Thus he p ecise mic ome e adjus men
o he subs a e holde allows he ealiza ion o dose g adien s (Figu e 2b). The SEM image shows one sec o
wi h an exposu e dose g adien o i e di e en subsec o s ealized wi h a posi i e one esis (da k g ey). The
inc easing dose is indica ed by he b igh e g ey scales means mo e o he esis was de eloped and shows he
subs a e (ligh g ey).
Fo a ealiza ion o a dose g adien wi h he di ec w i e echnique elec on beam
exposu e no mask was needed bu wi h he so wa e Elphy Plus a so-called w i e- ield o a
size o 100 µm x 100 µm size was p og ammed. This w i e- ield consis s o mul iple ea u es
each ha ing a di e en dose ep esen ing he dose g adien . Such w i ing ields can be
exposed simila on se e al posi ions o he subs a e o example in a ma ix-like a angemen
esul ing in compa able exposed a eas o pho oli hog aphy in ou capabili ies.
pa e n
ligh p oo by
ch ome coa ing
me cu y
a c lamp
condense lens
shadow mask
( o exposu e
dose g adien )
esis -coa ed
subs a e
a
subs a e is ealigned
be ween exposu es
b
dose (Dx)sec o
ealignmen di ec ions o subs a e o
di e en exposu e doses in one sec o :
123
45
200 µm
D1D2D3
D4D5
obse ed exposu e dose g adien
o one sec o
O e iew o he hesis
51
The subsequen PEB s ep is a o he esul ing pa e n quali y e y impo an s ep in he
case o applying CAR sys ems. The acid which is gene a ed in he p e ious exposu e s ep
ca alyzes dep o ec ion o c osslinking eac ions dependen on he esis ype and hus esul s
in he de elopmen con as o exposed o non-exposed a eas. Especially o he in es iga ion
o new esis s he op imal PEB empe a u e is o conside able alue which con ols he
di usion leng h o he acid molecules and he eac ion a e. A a oo low PEB empe a u e he
dep o ec ion/c osslinking is insu icien while a a oo high PEB empe a u e acids di use
in o non-exposed a eas and ca alyze eac ions. Fo an e icien in es iga ion o he PEB
empe a u e g adien s we e p epa ed ia sel -made se -ups on me al pla es wi h ac i e cooling
agen s on one side and a hea ing sou ce on he o he side. This se -up is adjus able o
pa icula equi emen s o di e en empe a u es and empe a u e slopes. In Figu e 3 wo
empe a u e p o iles wi h di e en empe a u e slopes a e exempla ily shown. A la
empe a u e slope o 0.55 °C/mm (○) was ealized on an aluminum pla e using ice-wa e as
cooling agen on one side and hea ed o 240 °C on he o he side. Howe e a s eep
empe a u e slope o 1.85 °C/mm () was ealized on a s eel pla e using liquid ni ogen o
cooling on one side and hea ed o 300 °C on he o he side.
Figu e 3: Two empe a u e p o iles a e shown o a leng h o 50 mm using di e en cooling agen s, me al pla es,
and hea ing empe a u es. A la empe a u e slope o 0.55 °C/mm (○) in he ange o 85 °C o 112 °C was
achie ed on an aluminum pla e using ice-wa e and 240 °C o empe a u e adjus men . A s eep empe a u e
slope o 1.85 °C/mm in he ange o 39 °C o 130 °C was achie ed on a s eel pla e using liquid ni ogen and
300 °C o empe a u e adjus men .
010 20 30 40 50
40
60
80
100
120 ice-wa e , aluminum, 240 °C
liquid ni ogen, s eel, 300 °C
empe a u e in °C
leng h in mm
O e iew o he hesis
52
The las s ep o he li hog aphic pa e ning p ocess o CAR sys ems is he de elopmen .
In his s ep he non-c osslinked ma e ial o nega i e one esis s and o posi i e one esis s
he dep o ec ed ma e ial is dissol ed and emo ed by he de elope . Fo he de e mina ion o
he dissolu ion beha io o non-exposed and exposed esis ma e ial qua z c ys al
mic obalance (QCM) measu emen s conduc ed plunged in o he de elope solu ion was
es ablished. This me hod allows an es ima ion o he applicable de elope s eng h and he
igh de elopmen ime pe iod o he espec i e esis ilm which plays a chie pa o he
quali y o he esul ing pa e ns. He e a de ia ion o an op imum de elopmen ime pe iod, so
called unde de elopmen o o e de elopmen , esul s in ma e ial esidues be ween pa e ns
espec i ely hinne o e en s ipped o pa e ns. Based on hese p esc eening esul s o he
QCM measu emen s he ime ame o u he de ailed de elopmen in es iga ions on Si-
wa e s was iden i ied. Fo his a esis ilm which al eady passed he li hog aphic pa e ning
p ocess pending de elopmen was s epwise o con inuously imme sed in o he de elope
solu ion using simple se -ups. Fo he s epwise de elopmen o he esis ilm he subs a e
was clamped in o an in e se pai o weeze s and was hen imme sed s ep by s ep in o he
de elope solu ion. Fo he con inuous de elopmen a wi e was a ached o he pai o weeze
and connec ed o an elec ical mo o d i e wi h adjus able speeds. The imme sion ime
pe iods we e iden i ied by he ime ame de e mined by he QCM measu emen s esul ing in
a de elopmen ime g adien .
Fo he in es iga ion and op imiza ion o new esis ma e ials combina ions o he mos
impo an p ocessing pa ame e s we e a anged o bina y and o e na y combina o ial
lib a ies by he use o he abo e lis ed g adien s. Thus i is possible o in es iga e and
op imize wo espec i ely h ee s ong in e ac ing pa ame e s in one expe imen . Fo his wo
linea g adien s a e a anged o hogonally o each o he esul ing in a bina y lib a y. Fo he
p epa a ion o a e na y lib a y a hi d a iable a ia ion has o be conduc ed ei he in he hi d
dimension o in a e y small a ea in which he i s and second a iable a e e ec i ely
unchanged and applied ma ix-like on he bina y lib a y. In Figu e 4 such a e na y
combina o ial lib a y is exempla ily shown applied on a posi i e one esis sys em. This
lib a y is composed o a PEB empe a u e g adien pe pendicula o a de elopmen ime
g adien ep esen ing he bina y lib a y, while an elec on beam exposu e dose g adien is
applied ma ix-like o his bina y lib a y. The obse a ion and e alua ion o his lib a y shows
ha o each w i e- ield only one exposu e dose i s o he applied PEB empe a u e and
de elopmen ime. The pa e ns we e e alua ed ega ding hei ea u e’s quali y which is
O e iew o he hesis
53
desc ibed by he line edge oughness (LER). The clea es lines ou o his combina o ial
lib a y we e obse ed in sec o B2 de e mined by a LER alue o 5.3 nm. The pa e ns
esul ing om a highe and a lowe PEB empe a u e han he iden i ied op imum o 100 °C
bu wi h he same de elopmen ime show clea ly inc eased LER alues. Such inc ease o
LER alues is also e iden a pa e ns wi h a longe and sho e de elopmen ime han he
obse ed op imum o 30 s.
Figu e 4: A schema ic illus a ion o a e na y combina o ial lib a y composed a PEB empe a u e g adien
(95 °C – 102 °C) and o hogonally o i a de elopmen ime s ep g adien (15 s, 30 s, 60 s) ep esen ing he
bina y lib a y. The exposu e dose g adien is conduc ed in w i e- ields (10 µC/cm² – 410 µC/cm²), p o ided in
24 a ays o a 100 nm line/space p o ile and is applied ma ix-like on he bina y lib a y. Selec ed SEM images
demons a e he s ong in luence o he applied a iable g adien s. The espec i e condi ions (PEB empe a u e,
de elopmen ime, and dose plus he LER alues) o hese pa e ns a e lis ed below he illus a ion.
dose
in µC/cm² 182.3 251.6 214.2 155.1 251.6
PEB empe a u e
in °C102 100 100 100 95
de elopmen ime
in s 30 15 30 60 30
LER (3σ)
in nm 6.8 5.8 5.3 7.0 7.6
de elopmen
ime g adien
PEB empe a u e g adien
15 s
95 °C102 °C
30 s
60 s
100 µm
dose g adien
w i e- ield wi h
exposu e dose g adien
10 µC/cm² - 410 µC/cm²
A B C D
1
2
3
A2 B3 B2 B1 D2
200 nm
lib a y size: 30 x 20 mm
O e iew o he hesis
54
In summa y, echniques o he p epa a ion o a iable g adien s ega ding hin ilm
in es iga ions and hei combina ion o combina o ial lib a ies we e p esen ed and hei
powe ul and e icien op imiza ion demons a ed. All a iable g adien s a e comple ely
adjus able o he equi emen s need o in es iga ion and op imiza ion o new esis ma e ials
o o he complex in es iga ion o mul i- a iable dependen hin ilm sys ems.
3.2 Tailo ed S a -Shaped S a is ical Te oligome s ia ATRP o
Li hog aphic Applica ions
(Jou nal o Ma e ials Chemis y, see chap e 4.3)
The second chap e deals wi h he p esen a ion o a s a -shaped e oligome as a new
esis ype. The syn hesis o his new ma e ial was ca ied ou using a om ans e adical
polyme iza ion (ATRP) ia he co e- i s ou e ou o saccha ose molecule wi h eigh
ini ia ing si es. Fo compa ison easons a linea model oligome was syn hesized and a
saccha ose ini ia o was modi ied o hold less ATRP ini ia ing si es. Thus s a e oligome s
we e syn hesized wi h a educed a m numbe bu he iden ical saccha ose co e. The esul ing
e oligome s showed a na ow molecula weigh dis ibu ion as well as a con olled
inco po a ion a io o he h ee monome s and a ge ed molecula weigh s we e p ecisely
achie ed. Finally he mos p omising syn hesized s a -shaped e oligome was in es iga ed in
a combina o ial lib a y o i s li hog aphic pe o mance.
In his s udy he monome s used o he polyme iza ions a e cu en ly indus ially used
in espec o he po en ial applica ion o hese s a oligome s o li hog aphic pa e ning: α-
gamma bu y olac one me hac yla e (GBLMA), me hyl adaman yl me hac yla e (MAMA),
and hyd oxyl adaman yl me hac yla e (HAMA) (see Figu e 5). A linea model oligome (L)
was syn hesized using e hyl 2-b omoisobu y a e as ini ia o . Fo he ealiza ion o he s a
a chi ec u e a saccha ose molecule unc ionalized wi h eigh ATRP ini ia ing si es (1) was
used and ou s a -shaped oligome s wi h a ying a ge a m leng hs we e syn hesized
(S1a-d). In addi ion, a saccha ose molecule was syn hesized wi h ATRP ini ia ing si es as
well as non- eac i e si es (2). The a e age numbe o ini ia ing si es o his co e amoun s o
3.5 and hus esul s in a educed unc ionali y in con as o 1. Thus a s a -shaped e oligome
(S2) was ealized as missing link be ween he linea oligome and he s a e oligome (S1).
O e iew o he hesis
55
Figu e 5: This igu e shows he used monome s α-gamma bu y olac one me hac yla e (GBLMA), me hyl
adaman yl me hac yla e (MAMA), and hyd oxyl adaman yl me hac yla e (HAMA). The polyme s L, S1a-d, and
S2 we e ealized using he linea ini ia o e hyl 2-b omoisobu y a e and he saccha ose ini ia o s 1 and 2,
espec i ely. The o e all e oligome composi ion o GBLMA/MAMA/HAMA (GcMcH) was abou 50/30/20.
Fo all polyme s na ow monomodal dis ibu ions we e de ec ed, GPC/ mul i-angle ligh
sca e ing (MALS) aces exhibi ed symme ical shapes and polydispe si y index alues o
lowe han 1.1 we e de e mined (see Figu e 6). The MALS de ec o e ealed ecombina ion
shoulde s o he aces o S1c and S1d. As he sca e ing de ec o is disp opo ionally
sensi i e (in ensi y ~ diame e 6) hese ecombina ions a e negligible.
Figu e 6: No malized sca e ing in ensi y o GPC aces o L, S1a, S1b, S1c, S1d and S2 measu ed wi h a mul i-
angle ligh sca e ing de ec o . Sligh ecombina ions a e isible by shoulde s o he s a -shaped e oligome s
S1c (dash do ) and S1d (dash do do ). Due o he ac ha he sca e ing de ec o is disp opo ionally sensi i e o
he molecula size (in ensi y ~ diame e 6) hese ecombina ions a e negligible.
OO
OH
OO
+ +
O
O
OO
CuCl/CuCl2
PMDETA
Anisole
1.
2. 1
3. 2
O
O
B
GBLMA MAMA HAMA S2
S1a-d
L
B
O
x
y
z
n
O O O
O O O
O
O
OH
GcMcH
30 32 34 36 38 40 42
0.0
0.2
0.4
0.6
0.8
1.0
no malized sca e ing in ensi ies
elu ion olume in ml
L
S1a
S1b
S1c
S1d
S2
O e iew o he hesis
56
The a ge ed monome composi ion o all e oligome was 50 % GBLMA, 30 %
MAMA and 20 % HAMA due o i s po en ial applica ion as esis ma e ial.
2
Fo he
ealiza ion o his monome composi ion a monome eed o 41 % GBLMA, 41 % MAMA
and 18 % HAMA was iden i ied because o epea ed expe imen a ions. The monome
composi ion was de e mined ia 1H-NMR measu emen s o aken aliquo s ou o he
polyme iza ion solu ion. The shown composi ion was achie ed o e a con e sion ange o
Xp = 30 – 60 % on he example o S1d (see Figu e 7).
Figu e 7: E olu ion o monome inco po a ion (GBLMA (◊), MAMA (□) and HAMA (○)) and also -ln(1-Xp)
() e sus polyme iza ion ime o S1d.
Fo a p oo o p inciple he syn hesized s a esis S1d was in es iga ed o li hog aphic
applica ion as his well-de ined s a oligome has he mos dis inc s a cha ac e , a simila
molecula weigh and he same monome composi ion as he non-con olled a chi ec u e o
he hype b anched polyme esis ma e ial published by Hadziioannou e al.
3
In his wo k he
new s a esis ma e ial was di ec ly op imized in one expe imen conce ning he li hog aphic
a iables exposu e dose, PEB empe a u e, and de elopmen ime. The p epa ed e na y
combina o ial lib a y consis ed o a empe a u e g adien o PEB se pe pendicula o a
de elopmen ime g adien and an exposu e dose g adien o 1:1 line/space 100 nm pa e ns
applied ma ix-like wi h elec on beam li hog aphy (see Figu e 8). Low line edge oughness
(LER: de ia ion o ea u e edge om ideal shape) and also low line wid h oughness (LWR:
020 40 60 80 100
0
10
20
30
40
50
60
70
0
10
20
30
40
50
60
70
80
GBLMA
MAMA
HAMA
- ln (1-Xp)
composi ion in %
polyme iza ion ime in min
Con e sion
Guide o he eye
O e iew o he hesis
57
de ia ion o wid h) alues ga e he in o ma ion on op imized p ocessing condi ions. The
excellen LER alue o 3.1 nm and LWR o 5.9 nm we e obse ed a an elec on beam dose
o 214.2 µC/cm2, a PEB empe a u e o 98 °C, and a de elopmen ime o 60 s.
Figu e 8: The uppe igu e shows a schema ic illus a ion o he e na y combina o ial lib a y consis ing o he
PEB empe a u e g adien , he de elopmen ime s ep g adien , and he elec on beam dose g adien . The able
exhibi s pa e ns om he ou co ne s o he combina o ial lib a y (I, II, IV, V) and he op imized pa e n (III).
The espec i e condi ions (PEB empe a u e, de elopmen ime, and dose) o hese pa e ns and he calcula ed
LER and LWR a e lis ed.
De elopmen
ime g adien
PEB empe a u e g adien
15 s
104 °C95 °C
30 s
60 s
120 s
100 µm
Dose g adien
exposu e dose a ay
10 - 410 µC/cm²
PEB empe a u e
in °C 95 95 98 104 104
de elopmen ime
in s 120 15 60 15 120
dose
in µC/cm² 155.1 408.2 214.2 295.7 132
LER (3σ)
in nm 5.8 4.4 3.1 6.9 7.6
LWR (3σ)
in nm 8.9 6.5 5.8 10.3 13.3
III III IV
300 nm
V
Publica ions and manusc ip s
64
Tailo ed S a -Shaped S a is ical Te oligome s ia ATRP o Li hog aphic
Applica ions
Jou nal o Ma e ials Chemis y 2012, 22, 73-79.
F. Wiebe ge , D. C. Fo man, C. Neube , A. H. G öschel, M. Böhm, A. H. E. Mülle ,
H.-W. Schmid and C. K. Obe
The conduc ed expe imen al wo k and mos o he syn hesized polyme we e done on
my pa . Two polyme s we e syn hesized by D . D ew C. Fo man (Co nell Uni e si y). The
GPC/MALS measu emen s we e conduc ed by Dipl.-Ing. Ma ie a Böhm (Uni e si y o
Bay eu h, Mac omolecula Chemis y II). The manusc ip was w i en mainly by mysel and
join ly inalized wi h he help o all coau ho s.
Tailo ed S a Block Copolyme A chi ec u e o High Pe o mance
Chemically Ampli ied Resis s
Ad anced Ma e ials 2012, 24, 5939-5944.
F. Wiebe ge , C. Neube , C. K. Obe , and H.-W. Schmid
The comple e polyme syn hesis and all expe imen s we e ca ied ou by me. The
manusc ip was w i en by mysel and join ly inalized wi h he help o all coau ho s.
Publica ions and manusc ip s
65
4.2 Combina o ial echniques o e icien ly in es iga e and
op imize hin ilm p ocessing and p ope ies
By Flo ian Wiebe ge ,1) T is an Kolb,1) Ch is ian Neube ,1)
Ch is ophe K. Obe ,2) and Hans-We ne Schmid 1,a)
1Mac omolecula Chemis y I and Bay eu h Ins i u e o Mac omolecula Resea ch (BIMF),
Uni e si y o Bay eu h, D-95447 Bay eu h, Ge many
2Ma e ials Science & Enginee ing, Co nell Uni e si y, I haca, NY 14853
This pape is submi ed o
Molecules
a) Au ho o whom co espondence should be add essed.
Elec onic mail: hans-we ne .schmid @uni-bay eu h.de.
Publica ions and manusc ip s
66
Abs ac : In his a icle we p esen se e al de eloped and imp o ed combina o ial echniques
o op imize p ocessing condi ions and ma e ial p ope ies o hin ilms. The combina o ial
app oach allows in es iga ions o mul i- a iable dependencies and is he pe ec ool o
in es iga e hin ilms ega ding hei high pe o mance pu pose. In his con ex we de elop
and es ablish he eliable p epa a ion o g adien s o ma e ial composi ion, empe a u e,
exposu e, and imme sion ime. Fu he mo e we demons a e he sma applica ion o
combina ions o composi ion and p ocessing g adien s o c ea e combina o ial lib a ies. Fi s
a bina y combina o ial lib a y is c ea ed by applying wo g adien s pe pendicula o each
o he . A hi d g adien is ca ied ou in e y small a eas and a anged ma ix-like o e he
en i e bina y combina o ial lib a y esul ing in a e na y combina o ial lib a y. Te na y
combina o ial lib a ies allow iden i ying p ecise ends o he op imiza ion o mul i- a iable
dependen p ocesses which is demons a ed on he li hog aphic pa e ning p ocess. He e we
e i y conclusi ely he s ong in e ac ion and hus he in e dependency o a iables in he
p epa a ion and p ope ies o complex hin ilm sys ems. The es ablished g adien p epa a ion
echniques a e no limi ed o li hog aphic pa e ning. I is possible o u ilize and ans e he
epo ed combina o ial echniques o o he mul i- a iable dependen p ocesses and o
in es iga e and op imize hin ilm laye s and de ices, o op ical, elec o-op ical, and
elec onic applica ions.
1. In oduc ion
Combina o ial op imiza ion me hods a e widely used abo e all in pha maceu ical
esea ch o sc een new molecules o hei po en ial applica ion as d ugs [1-4]. Especially in
his ield o esea ch he me hod o “high- h oughpu sc eening” was de eloped [5]. Bu he
app oach o combina o ial in es iga ions has been agg essi ely adop ed by he ield o
ma e ials esea ch in ecen yea s [6-8]. Combina o ial ma e ials science pu sues he objec i e
o p epa ing a amily o ela ed samples in a single expe imen , o in es iga e in e ac ing
pa ame e s and, o op imize ma e ials and p ocesses. Due o con inuously a ising challenges
in ma e ials de elopmen , he use o a iable g adien s and he combina ion o g adien s o so
called combina o ial lib a ies, has been d i en o wa d. Impo an esea ch a eas o
es ablished combina o ial app oaches include sensing ma e ials, ca alysis, elec onic and
unc ional ma e ials, and bioma e ials [9]. In he las decade esea ch has add essed he
in es iga ion o p ope ies o hin ilms in ela ion o ce ain a iable g adien s [10]. In
gene al he ilm hickness i sel is an impo an a iable o ilm applica ion. Thus o enable a
Publica ions and manusc ip s
67
combina o ial in es iga ion, ilms o con inuous hickness g adien s we e p epa ed [11]. Amis
e al. ha e demons a ed he dewe ing beha io o a polys y ene ilm by p epa ing a ilm
hickness g adien e sus a con inuous empe a u e g adien a anged in a 2-D combina o ial
lib a y [12]. His g oup also in es iga ed he phase sepa a ion o a hin ilm p epa ed o a
polyme blend g adien in combina ion wi h a empe a u e g adien [13]. The ilm p epa a ion
o his polyme blend g adien was ealized u ilizing a cus om buil se -up. In addi ion o
solu ion cas composi ion as well as laye hickness g adien s, sol en - ee p epa ed g adien s
u ilizing physical apo deposi ion (PVD) a e well-known. He e combina o ial op imiza ions
o elec o-op ical de ices we e in es iga ed in a 2-D combina o ial lib a y in ega d o
composi ion and laye hicknesses [14]. Ano he impo an pa ame e especially o adhesion
in es iga ions is he chemical su ace ea men o a ilm, hus g adien s o su ace
cha ac e is ics we e de eloped. Such a su ace modi ica ion was ob ained ia elec on beam
ea men o a poly(2- inylpy idine) coa ed su ace. This elec on beam exposu e dose
g adien applied o e a leng h o 5 cm gene a es a hyd ophilici y g adien on he su ace [15].
Ma suda e al. ha e shown ano he me hod o he p epa a ion o a su ace hyd ophiliza ion
g adien wi h a poly( inyl ca bona e) coa ed ilm [16]. This ilm hyd olyzes g adually ia a
con inuous imme sion in an aqueous NaOH solu ion.
A special ield o in e es ega ding hin ilms is li hog aphy. In he p ocess o
li hog aphic pa e ning he esis ilm has o pass se e al s eps e.g. ilm p epa a ion, annealing
s eps, exposu e, de elopmen , and e ching. This mul i-s ep p ocess on he o he hand gi es a
a ie y o a iables which in e ac s ongly wi h each o he , such as esis composi ion, ilm
hickness, annealing empe a u e, exposu e dose, o de elopmen ime o name a ew. No
leas he enginee ing and manu ac u ing o new pa e ning ools [17] and he in oduc ion o
new ma e ials [18] leads o a pe pe ual op imiza ion o he ope a ing p ocess [19]. Thus
combina o ial in es iga ions became an in e es ing app oach o li hog aphic issues in he las
decade. Fo ins ance, di e en composi ions o a molecula glass pho o esis we e
in es iga ed in combina o ial PVD p epa ed lib a ies as a unc ion o exposu e dose [20].
Ano he impo an a iable especially in he li hog aphic con ex bu also in gene al o hin
polyme ilms is he annealing (bake) ime and empe a u e. The e o e deg ada ion o
poly( e -bu oxy-ca bonyloxy-s y ene) has been in es iga ed wi h empe a u e and also bake
ime g adien s [21]. Fu he mo e he applied bake s eps o chemically ampli ied esis sys ems
in he li hog aphic pa e ning p ocess ha e o be p ecisely iden i ied o he pos exposu e and
pos apply bake s eps. Hence, o he op imiza ion o esis pe o mance bo h bake s eps we e
Publica ions and manusc ip s
68
pe o med as empe a u e g adien s in esea ch labo a o ies and applied in a manne
o hogonal o each o he [22]. Recen ly we ha e iden i ied a syne gis ic e ec o pos
exposu e bake and esis composi ion. The e o e he composi ion g adien was applied
pe pendicula o he empe a u e g adien o pos exposu e bake and combined wi h an
exposu e dose g adien as e na y g adien [23-25]. These di e en echniques o g adien
p epa a ion o hin ilm in es iga ions demons a e imp essi ely he as and e ec i e
a iable in es iga ion in one expe imen . The p esen ed a icle summa izes ou imp o ed and
newly de eloped combina o ial echniques on hin ilm in es iga ions, he p epa a ion o
bina y and e na y combina o ial lib a ies, and hei cha ac e iza ion.
2. Resul s and Discussion
2.1. Combina o ial Techniques
Fo a combina o ial in es iga ion ypically g adien s o ma e ials and/o p ocess
a iables a e applied. Howe e o new combina o ial app oaches he exis ing echniques
ha e o be adap ed, he se ups modi ied o new echniques de eloped jus o i a pa icula se
o equi emen s. In he ollowing sec ions we show adap ed and newly de eloped
combina o ial echniques and he co esponding se ups ocused on combina o ial app oaches
o solu ion-p ocessed hin ilms.
2.1.1. In e nal Ma e ial Composi ion G adien
Fo he p epa a ion o a ilm including an in e nal composi ion g adien wo indi idual
con ollable sy inge pumps we e used. The sy inge pump sys em allows he p epa a ion o a
g adien ex uda e made o solu ions A & B, when equipped wi h wo sy inges. One sy inge is
illed wi h solu ion A and he o he wi h solu ion B. The sy inges a e connec ed ia PTFE
ubes o he uppe pa o a s a ic mixe . Bo h ubes we e illed comple ely wi h he espec i e
solu ions. The s a ic mixe was insed jus wi h solu ion A o ge he s a ic mixe ai bubble-
ee (see he low a e p o ile in Figu e 1a; pa 1). A e wa ds he sy inge pump sys em was
s a ed o one second (see Figu e 1a; pa 2) o p emix bo h solu ions in he ixed olume o
he s a ic mixe . This s ep is necessa y o ex ude he insing solu ion A ou o he mixing
de ice and o ill i wi h he solu ion o he ini ial g adien ex uda e. Subsequen ly he s a ic
mixe was ixed o he mo able pa o a doc o blade machine o enable he applica ion o he
g adien ex uda e on a subs a e.
Publica ions and manusc ip s
69
Figu e 1a. Schema ic illus a ion o he low a e p o ile con olled by he
neMESYS sy inge pump sys em: Pa 1 se es as he insing s ep wi h solu ion A
o ge he s a ic mixe ai bubble- ee; in pa 2 he p emix inside he s a ic mixe
is p epa ed; pa 3 shows he opposi e low a e g adien s o he wo sy inges
while he ac ual ex usion akes place.
Figu e 1b. The de ailed p epa a ion o a composi ion g adien ilm is
schema ically illus a ed. The g adien ex uda e o solu ion A (blue) and solu ion
B ( ed) (s ep 1: ex uda e applica ion) was ealized as desc ibed o Figu e 1a, pa
3. Subsequen ly he g adien ex uda e was doc o bladed pe pendicula o he
applica ion di ec ion (s ep 2: doc o blading) and annealed o emo e he sol en .
Fo a sys ema ical cha ac e iza ion he yielded ilm wi h he in e nal composi ion
g adien was di ided alongside he g adien in o he sec o s A-P.
The e iciency o his p epa a ion me hod in iew o he cons an change o he esul ing
in e nal composi ion g adien ilm is demons a ed ealizing a PMMA ilm wi h a g adien o
a luo escence dye. This g adien ilm was p epa ed applying wo 10 w .% solu ions o
PMMA in THF, while in solu ion A he luo escen dye N,N’-Di(1-hep yloc yl)-pe ylene-
3,4,9,10-bis(dica boximide) ( o exclude concen a ion quenching: 0.02 mmol in 1 g o
solu ion) was dissol ed. The luo escen dye g adien ilm was cha ac e ized by luo escence
spec oscopy u ilizing a luo escence eade . The acqui ed luo escence spec a exci ed a a
wa eleng h o 455 nm show h ee maxima a 532 nm, 572 nm and 620 nm (see Figu e 2). The
obse ed con inuous in ensi y dec ease o he comple e spec a demons a es he p epa ed
in e nal dye g adien . The in ensi ies o he maximum a 532 nm o all 16 measu ed spec a o
sec o A o P along he composi ion g adien a e summa ized in he inse e i ying he
con inuous dec ease o he luo escence dye concen a ion. In conclusion his echnique o e s
a simple and e icien way o make a sol en -based g adien ex uda e which wi hs ands
b
a
0
5
10
15
20
25
30
30
25
20
15
10
5
0
Solu ion
ASolu ion
B
Pa 1 Pa 2 Pa 3
ime pe iods:
low a e in µl s-1
2. doc o blading
1. ex uda e
applica ion
ex uda e
1s 7s
solu ion A
solu ion B
Publica ions and manusc ip s
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doc o blading as well as an ongoing he mal ea men o ealize a solid ilm wi h an in e nal
composi ion g adien o e a b oad concen a ion ange.
Figu e 2. The cha ac e iza ion o he luo escen dye g adien in PMMA ia
luo escence spec oscopy: 16 luo escence spec a (sec o A – P) along he
applica ion di ec ion wi h an equal gap we e measu ed (only six spec a a e shown
o e he ull measu ed wa e leng h ange o a be e o e iew). The inse o he
g aph shows he in ensi ies o he maximum a 532 nm o he spec a o all 16
sec o s and e i ies dis inc ly he con inuous dec ease o he luo escence in ensi y
gi en by he ma e ial g adien .
2.1.2. Tempe a u e G adien
Va ious well de ined and long- e m s able empe a u e g adien s we e enginee ed in ou
labo a o y on he basis o pla es o di e en me als. On one side o he pla e a essel was
welded and illed wi h, o example, ice-wa e o liquid ni ogen and ep esen s he cooling
sou ce. He e i has o be conside ed ha he essel mus be e illed con inuously o ensu e
cons an cooling. The o he side was placed plana on a ho pla e, se ing as an ac i e hea ing
sou ce, and was adjus ed o a desi ed empe a u e. A e a calib a ion ime o one hou he
empe a u e g adien s ayed cons an and was e i ied by an in a ed came a. Fo his a
e e ence silicon wa e used o measu ing pu poses was placed in he cen e o he se up’s
me al pla e.
In Figu e 3 wo empe a u e g adien s wi h di e en slopes a e shown o e a leng h o
50 mm measu ed using a e e ence silicon wa e . The g adien s demons a e he abili y o
550 600 650
0
500
1000
1500
2000
2500
3000
a.u.
wa e leng h in nm
A
D
G
J
M
P
A B C D E F G H I J K L M N O P
0
500
1000
1500
2000
2500
3000
maxima a 532 nm
532
sec o
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adjus he empe a u e g adien s by de ining app op ia e condi ions: o he mo e la
empe a u e g adien (ci cles) ice-wa e was used o he ac i e cooling, an aluminum pla e
se ed as he moconduc i e me al pla e and o cons an hea ing he ho pla e was adjus ed o
240 °C. A s eepe g adien (squa es) was gene a ed wi h liquid ni ogen as cooling sou ce, a
s eel pla e and he ho pla e adjus ed o 300 °C.
Figu e 3. Two empe a u e p o iles – measu ed using he e e ence silicon wa e
– a e shown u ilizing di e en me al pla es p epa ed o e he leng h o 50 mm.
The i s empe a u e g adien (ci cles) was made on an aluminum pla e applying
o he le side cooling ice-wa e and hea ing on he igh side a he empe a u e
o 240 °C. The achie ed empe a u e g adien shows a s eady slope o
0.55 °C/mm om 85 °C o 112 °C. The second (squa es) was p epa ed unde he
condi ions liquid ni ogen, s eel pla e and 300 °C. I shows an o e all slope o
1.85 °C/mm om 39 °C o 130 °C.
The la e empe a u e g adien (ci cles) esul ed in a s eady slope o 0.55 °C/mm om
85 °C o 112 °C. The second empe a u e g adien (squa es) shows a e y s eep slope o
1.85 °C/mm om 39 °C o 130 °C. Fu he a ia ions in ho pla e empe a u e, pla e ma e ial
o cooling sou ce allow well-de ined empe a u e slopes in a b oad empe a u e ange. The
esul s and cus omizabili y demons a e imp essi ely he applicabili y o his simple
empe a u e g adien se -up and hus o e a e sa ile u ili y o annealing p ocesses e.g.
in es iga ions on mo phology o he mal c osslinking o polyme ilms.
010 20 30 40 50
40
60
80
100
120 ice-wa e , aluminum, 240 °C
liquid ni ogen, s eel, 300 °C
empe a u e in °C
leng h in mm
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2.1.3. Exposu e Dose G adien
The exposu e p ocedu e can be he mos ime-consuming s ep in manu ac u ing
p ocesses including a ligh -induced eac ion. Combina o ial in es iga ions a e an app op ia e
app oach o iden i y he op imized exposu e condi ions o sa e ime and o achie e op imal
esul s. Thus combina o ial exposu e op imiza ion me hods can be used in a e sa ile manne
and implemen ed easily in exposu e in es iga ions o solid ilms. Exposu e dose g adien s a e
concei able o pho ocycloaddi ion, o ien a ion o ch omopho es and pho opolyme iza ion
d i en by pho o exposu e and also e apo a ion-condensa ion and polyme deg ada ion
in es iga ions caused by elec on beam exposu e.
An exposu e dose g adien o UV exposu e was ealized o his wo k wi h a mask-
alignmen sys em and a specially designed qua z glass mask. Figu e 4a shows a schema ic
illus a ion o such an exposu e se -up wi h a me cu y lamp as ligh sou ce and a condense
lens o gene a e pa allel ligh hus a ilm coa ed subs a e is exposed consis en ly wi h a dose
(D) h ough he shadow mask. This mask consis s o 70 x 70 sec o s a anged and numbe ed
in an X/Y coo dina e sys em. Each sec o has a size o 1.2 mm x 1.2 mm. I is designed wi h
eigh ou o nine subsec o s wi h a ligh p oo ch ome coa ing (b own) and one ou o nine
subsec o s o a anslucen pa e n (whi e/b own) wi h an a ea o 300 µm x 300 µm o each
subsec o . The mask-alignmen sys em has an alignmen s age wi h mic ome e adjus men
o he subs a e holde . This allows an accu a e alignmen o subsequen exposu es o
subsec o s in one sec o on he same subs a e. The e o e he subs a e is mo ed by 400 µm
o ealignmen be ween wo exposu es ob aining wo subsec o s; by his he subs a e is
mo ed 100 µm u he han he edge leng h o he anslucen pa e n which a oids a eas o
inad e en double exposu e. Fo he e i ica ion o he UV-exposu e g adien a posi i e one
esis was used. The p ocedu e o a dose-g adien exposu e was conduc ed as ollows: he
ilm-coa ed subs a e was adjus ed o he subs a e holde in he mask-alignmen sys em and
he exposu e o he i s subsec o s in all sec o s was conduc ed. Subsequen ly he subs a e is
ealigned by mo emen o he subs a e holde o 400 µm o he le de ining he posi ion o
he second subsec o s’ exposu e and again 400 µm o he le o he hi d exposu e (see
Figu e 4b). Fo he ou h exposu e he subs a e holde is ealigned o he o igin (800 µm o
he igh ) and hen 400 µm up and o he i h exposu e 400 µm o he le . The dose was
inc eased o e e y exposu e s ep om 80 mJ/cm² o 160 mJ/cm² and as a esul a dose
g adien o i e di e en doses on an a ea o 1.44 mm² was c ea ed. Subsequen ly he ilm-
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coa ed subs a e was he mally ea ed a 105 °C o 30 s o pos exposu e bake. A e wa ds
he ilm is de eloped in an aqueous 0.26 N e ame hylammonium hyd oxide (TMAH)
solu ion o 30 s esul ing in he emo al o he exposed esis i he dose was su icien ly
high. In Figu e 4b (SEM image) he exposu e dose g adien o a selec ed sec o is shown:
Pa e n (D1) exposed wi h he lowes dose is ob iously unde exposed as he con ou s o he
pa e n a e jus sligh ly isible and he esis (da k g ey) is oughly de eloped. Inc easing he
dose esul s in mo e clea de eloped pa e ns indica ed by he s onge con as (da k - b igh )
in he co esponding subsec o s gi en by he unde eloped unexposed esis ma e ial beside
he subs a e su ace (ligh g ey). A he highes dose (D5) he pa e n is o e exposed, which is
ob ious by he beginning o ea u es’ s ipping o .
Figu e 4a. The schema ic illus a ion shows a mask-alignmen sys em consis ing
o he main componen s: a me cu y a c lamp as ligh sou ce, a condense lens o
he p oduc ion o pa allel ligh o exposu e consis en ly a ilm-coa ed subs a e
h ough he shadow mask. One sec o o o e all 4900 sec o s is shown in he
schema ic magni ica ion o he shadow mask, which a e a anged and numbe ed
in an X/Y coo dina e sys em. Each sec o consis s o eigh ou o nine subsec o s
wi h ligh p oo ch ome coa ing (b own) and one ou o nine subsec o s o a
anslucen pa e n (whi e/b own). The subs a e holde is adjus able ia
mic ome e adjus men o allow a p ecise alignmen o subsequen exposu es.
Figu e 4b. Schema ic illus a ion o he ealignmen di ec ions o he subs a e
be ween di e en exposu es: The SEM image shows a selec ed sec o wi h an
exposu e dose g adien o i e subsec o s ealized wi h a posi i e one esis (da k
g ey). The dose was inc eased om D1 o D5 leading om an unde - o an
o e exposu e o he esis shown by he inc easing p opo ion o he b igh
appea ing subs a e su ace (ligh g ey).
anslucen pa e n
in one subsec o
ligh p oo by
ch ome coa ing
me cu y
a c lamp
condense lens
shadow mask
( o exposu e
dose g adien )
esis -coa ed
subs a e
a
subs a e is ealigned
be ween exposu es
b
dose (Dx)Sec o
(≙9 Subsec o s)
ealignmen di ec ions o subs a e o
di e en exposu e doses in one sec o :
123
45
200 µm
D1D2D3
D4D5
obse ed exposu e dose g adien
o one sec o
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Table 1. Ma e ial composi ion a ios o each wa e piece o he h ee componen s
esis g adien ilm analyzed by high pe o mance liquid ch oma og aphy.
wa e piece
A
B
C
D
E
F
G
H
I
J
K
L
M
N
wa e segmen in mm
0-5
5-10
10-15
15-20
20-25
25-30
30-35
35-40
40-45
45-50
50-55
55-60
60-65
65-70
PAG in w .%
5.0
5.0
5.1
5.1
5.3
5.3
5.5
5.5
5.7
5.6
5.9
5.9
6.2
5.9
ma ix in w .%
88.6
83.9
78.6
71.2
65.9
57.1
50.2
48.7
39.7
37.9
29.5
27.3
20.5
18.2
c osslinke in w .%
6.4
11.1
16.3
23.7
28.8
37.6
44.3
45.8
54.6
56.5
64.6
66.8
73.3
75.9
The nex s ep in he li hog aphic p ocess is he exposu e, which ac i a es he PAG. This
s ep was conduc ed wi h he EVG®620 mask-aligne u ilizing a shadow mask wi h a
line/space pa e n. The dose was adjus ed o 60 mJ/cm². Immedia ely a e wa ds a PEB was
applied o pe o m he acid ca alyzed c osslinking eac ion be ween c osslinke and ma ix.
Fo he p epa a ion o a combina o ial lib a y a empe a u e g adien o PEB was applied
pe pendicula o he ma e ial composi ion g adien o 30 s. The applied empe a u e g adien
had a cons an slope o 1.07 °C/mm wi hin he empe a u e in e al om 85 °C o 20 °C.
Subsequen ly he esis ilm was de eloped in a 0.26 N aqueous solu ion o TMAH o 10 s
by dissol ing he esis ma e ials o he unexposed a eas. In Figu e 8 a pho og aph o he
p ocessed ilm wi h he emaining pa e ned esis ma e ial and SEM images o he pa e n o
selec ed sec o s o he combina o ial lib a y a e shown.
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81
Figu e 8. Pho og aph o he pa e ned esis ilm on he silicon wa e a e
applying he ma e ial composi ion g adien (le o igh : column A o N), pos
apply bake o 115 °C o 60 s, pho o exposu e (60 mJ/cm²), PEB empe a u e
g adien ( op o bo om: ow 1 o 40) and de elopmen in a 0.26 N aqueous
solu ion o e ame hylammonium hyd oxide o 10 s. Al eady wi h he naked eye
can be seen ha below ow 15 (60 °C) all pa e ns a e comple ely s ipped o .
The dependence o empe a u e o ma e ial composi ion is ob ious by he SEM
inse s o column E: sec o E7 shows dis inc pa e n while in sec o E2 all lines
a e me ged. Unde he condi ions o a s eady empe a u e ( ow 2) dis inc pa e n
a e ob ious a high ma ix con en (sec o A2) while wi h inc easing c osslinke
con en he pa e ns end o me ge (C2/E2). A end is obse able as o highe
c osslinke con en lowe PEB empe a u es a e needed o dis inc pa e ns (A2,
C4, E7).
The composi ion g adien anges om a high ma ix con en (le : column A) o a high
c osslinke con en ( igh : column N) a anged pe pendicula o he empe a u e g adien om
a high ( op: ow 1) o a low empe a u e (bo om: ow 40). I can be seen wi h he naked eye
ha below ow 15 (60 °C) e en he exposed esis o each ma e ial composi ion is comple ely
s ipped o he subs a e du ing de elopmen . This indica es a minimum empe a u e is
necessa y o c osslink his esis sys em a any ma e ial composi ion. Mos o pa e ns igh o
column F (ma ix ≤ 57.1 w .% / c osslinke 37.6 w .% / PAG 5 w .%) co esponding o high
c osslinke con en s a e s ipped o , oo. The inse SEM images show clea ly he PEB
empe a u e dependence o he esis ma e ial composi ion (column E): While sec o E7
(72 °C) shows dis inc lines, in sec o E2 (83 °C) he lines o he pa e n a e me ged oge he .
D
BFCA
1
5
10
15
A2 C2
C4 E2
E7
E
E2
20µm
C2
20µm
A2
20µm
C4
20µm
E7
20µm
componen s composi ion g adien
empe a u e g adien
ma ix
c osslinke
1 cm
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This is due o he ac ha he highe applied empe a u e esul s in an inc eased acid di usion
o his ma e ial composi ion beyond he exposed a eas. Wi h a highe ma ix componen ( ow
2) he pa e n quali y inc eases om sec o E2 o C2 un il in sec o A2 dis inc pa e ns we e
obse ed. These obse a ions e eal a endency which is con i med by sec o C4: Dis inc
pa e ns we e achie ed wi h dec easing ma ix con en and concu en empe a u e dec eases
beginning wi h sec o A2 o e sec o C4 and ending wi h sec o E7. These esul s show
imp essi ely he s eng h o combina o ial lib a ies in ecognizing a iable dependen ends
o in e ac ing mul i- a iable sys em and so combina o ial app oaches a e an excellen
echnique o op imizing ma e ial composi ion and hei p ocessing condi ions.
2.2.2. Te na y Combina o ial Lib a y
The upg ade o a bina y combina o ial lib a y by a hi d g adien is called e na y
combina o ial lib a y. Fo he p epa a ion o a bina y combina o ial lib a y a iable g adien s
a e ypically a anged o hogonally on wo-dimensional a eas. Thus o he ealiza ion o a
e na y lib a y i is equi ed ha he hi d a iable g adien is implemen ed in he hi d
dimension o a anged in a e y small a ea in which he i s as well as he second a iable a e
e ec i ely cons an wi hin he g adien . To implemen he la e case he hi d a iable is
applied se e al imes – ma ix-like – in one small spo on he bina y lib a y. As desc ibed
abo e he exposu e dose g adien s ha e he abili y o ul ill hese equi emen s and hence i is
possible o in es iga e h ee in e ac ing a iables in jus one combina o ial lib a y.
In he ollowing we p esen he de eloped e na y lib a y o a li hog aphic in es iga ion
as shown schema ically in Figu e 9.
The e na y lib a y consis s o a empe a u e g adien pe pendicula o a de elopmen
ime g adien , which ep esen s he a iable g adien s o he bina y lib a y, while small
sec o s o elec on beam exposu e dose g adien s a e applied ma ix-like o his bina y
combina o ial lib a y. Fo he shown li hog aphic combina o ial in es iga ion a s a -shaped
e oligome [s a is ical copolyme ized ou o α-gamma bu y olac one me hac yla e, me hyl
adaman yl me hac yla e, and hyd oxyl adaman yl me hac yla e (GBLMA-co-MAMA-co-
HAMA)] as posi i e one esis plus he PAG iphenylsul onium pe luo o-1-bu anesul ona e
was used. The esis ma e ial solu ion was cas ia spin coa ing on a hexame hyldisilazane-
p imed ou inch silicon wa e , esul ing in a ilm hickness o abou 90 nm. The ilm-coa ed
subs a e was cu o a ec angle o 30 mm x 20 mm, he mally ea ed a 125 °C o 150 s, and
elec on beam exposed by a dose g adien which was conduc ed in 12 w i e- ields, applied
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83
ma ix-like (see Figu e 9). This ma ix consis s o h ee ows and ou columns while he gap
be ween each ow is 10 mm and be ween each column 5 mm. Each w i e- ield – 100 µm x
100 µm in size – comp ises an exposu e dose g adien o 24 a ays o 100 nm line/space
pa e n be ween 10 µC/cm² o 410 µC/cm². A e wa ds PEB was applied – pa allel o he ows
o he exposed ma ix – by a empe a u e g adien o 30 s. This empe a u e g adien was
p epa ed on an aluminum pla e wi h ice-wa e as cooling sou ce and a ho pla e adjus ed o
220 °C as hea ing sou ce. Thus he empe a u e g adien applied o he subs a e anged om
95 °C o 102 °C wi h a slope o 0.47 °C/mm. A e ha a de elopmen ime s ep g adien was
applied alongside he columns o he exposed ma ix o 15, 30, 60 s in a 0.26 N
e ame hylammonium hyd oxide solu ion. The e o e he subs a e was subdi ided in o h ee
segmen s whe eas each segmen con ains one ow o w i e- ields. Selec ed SEM images o
line/space pa e ns and hei co esponding p ocessing condi ions a e shown in Figu e 9.
Fu he mo e line edge oughness (LER) alues – used as pe o mance c i e ion – o hese
selec ed line/space pa e ns a e also lis ed. LER is a ma hema ical calcula ed alue, desc ibing
he de ia ion o pa e n edges o an ideal shaped pa e n. The LER alues o he line/space
pa e ns we e calcula ed o e a leng h o 15 µm by he so wa e SuMMITTM om EUV
echnology.
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84
Figu e 9. Schema ic illus a ion o he e na y combina o ial lib a y p epa ed on a
subs a e wi h a size o 30 mm x 20 mm. The PEB empe a u e g adien (95 °C –
102 °C) is a anged ho izon al and pe pendicula o i he de elopmen ime s ep
g adien (15 s, 30 s, 60 s). The 12 w i e- ields (100µm x 100µm) wi h he
exposu e dose g adien (10 µC/cm² – 410 µC/cm²) a e a anged ma ix-like in
small sec o s and p o ide 24 a ays o 100 nm line/space p o iles. The selec ed
SEM images demons a e he s ong in luence o he applied h ee a iable
g adien s. The espec i e condi ions (PEB empe a u e, de elopmen ime, and
dose plus he LER alues) o hese pa e ns a e lis ed below.
One in e es ing obse a ion om he e na y combina o ial lib a y is ha o each w i e-
ield only one exposu e dose i s op imized o he o he applied pa ame e PEB and
de elopmen and hus only one pa e n could be e alua ed pe sec o . Fo he applied
neighbo ing lowe dose in a w i e- ield, much hinne lines han 100 nm o e en unde eloped
Publica ions and manusc ip s
85
pa e ns a e obse ed. This is due o an insu icien dep o ec ion a io and hus he poo
de elopmen o he esis in he exposed a eas. Consequen ly he neighbo ing highe dose
esul ed in oo much emo al o esis ma e ial so e en whole a eas a e s ipped o which
indica es o high dep o ec ion occu ed. The pa e n wi h he clea es lines (B2) was obse ed
a a dose o 214.2 µC/cm², a PEB empe a u e o 100 °C, and a de elopmen ime o 30 s
esul ing in a LER alue o 5.3 nm. The pa e ns p epa ed a a PEB empe a u e highe and
lowe han he obse ed op imum empe a u e o 100 °C bu wi h he same de elopmen ime
show clea ly inc eased LER alues o 6.8 nm (A2) and 7.6 nm (D2). No iceable is he
dec easing dose equi ed o achie e pa e n o a highe applied PEB empe a u e (A2) a he
same de elopmen condi ions. Less PAG was ac i a ed due o a lowe dose, bu his is
compensa ed by he inc eased acid di usion and eac ion a e a highe empe a u es and ice
e sa o D2. The inc ease o LER alues a e also obse able o pa e ns annealed a he
same PEB empe a u e bu applied o longe and sho e de elopmen imes han he obse ed
op imum o 30 s wi h he LER o 5.3 nm in sec o B2 (B1: 60 s, LER 7.0 nm, B3: 15 s,
LER 5.8 nm). He e he ope a ion wi h he op imized exposu e dose is dis inc i e and c ucial.
While he exposu e dose o he longes de elopmen ime B1 is abou 25 % lowe han he
dose o he op imum B2, he dose o he sho es de elopmen ime B3 is abou 20 % highe
han he dose o he op imum pa e n in B2. This combina o ial in es iga ion demons a es he
s ong in e dependence and in e ac ion o esis p ocessing a iables and shows he high
e iciency o a e na y combina o ial lib a y o such a complex in es iga ion o a mul i-
a iable sys em.
3. Expe imen al Sec ion
3.1. Chemicals and Ma e ials
Unless o he wise s a ed, all sol en s and chemicals we e pu chased om Sigma-Ald ich
and used as ecei ed. N,N’-Di(1-hep yloc yl)-pe ylene-3,4,9,10-bis(dica boximide) was
kindly p o ided by D . And è Wicklein, MC I, Uni e si y o Bay eu h. Poly (me hyl
me hac yla e) (Mw = 123.4 kg/mol) was pu chased om Degussa. 1,1,1- is(4-
hyd oxyphenyl)-1-e hyl-4-isop opylbenzene was pu chased om ABCR. N,N′,N′′,N′′′-
e a(me hoxyme hyl)glycolu il was pu chased om Wo lée-Chemie.
3.2. In e nal Ma e ial Composi ion G adien
The g adien ex uda e was p epa ed using he sy inge pump sys em neMESYS (ce oni
GmbH) con aining wo indi idual con ollable sy inge pumps which we e connec ed ia
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86
PTFE ubes o a s a ic mixe (Adchem GmbH; MA 3.0-13-S: sho ened o a leng h o 15 mm).
The sy inge pump sys em was p og ammed o s a solu ion A wi h a low a e o 30 µl/s bu
dec easing cons an ly wi h ime, while solu ion B s a s wi h a low a e o 0 µl/s bu
inc easing cons an ly wi h ime. Fo he ac ual ex usion o he homogeneous mixed g adien
he low a es o each sy inge pump a e uned ega ding a summa ized s eady low a e o
30 µl/s, hus a cons an a ia ion o he solu ions A & B is gi en o a ime pe iod o se en
seconds (see Figu e 1a; pa 3). Simul aneously he doc o blade machine o which he s a ic
mixe is ixed has o be ac i a ed wi h a eloci y o 10 mm/s o he same ime pe iod. Bo h
simul aneously unning p ocedu es a e desc ibed in Figu e 1b s ep 1: ex uda e applica ion.
The second s ep akes place a e he subs a e’s o a ion h ough 90 deg ees. The ex uda e is
hen doc o bladed wi h a doc o blade machine (E ichsen Coa mas e 509 MC-1) using a 4-
sided ba (BYK: gap: 50, 100, 150, 200 µm) pe pendicula o i s applica ion di ec ion wi h a
eloci y o 10 mm/s using a doc o blade o co esponding size (see Figu e 1b s ep 2: doc o
blading). A e wa ds he ilm was baked o e apo a e he applica ion sol en and o ix he
composi ion g adien . The yielded ilm wi h he in e nal composi ion g adien was di ided
alongside he g adien in o he sec o s A o P o a sys ema ical cha ac e iza ion.
The PMMA ilm wi h he in e nal g adien o he luo escen dye was e i ied by
Fluo escence Reade Flashscan 530 (Analy ikJena AG). The measu emen was execu ed a
spo s e e y 5 mm pa allel o he g adien . The esis ilm wi h he in e nal composi ion
g adien was e i ied wi h high pe o mance liquid ch oma og aphy (HPLC) (Agilen 1100
se ies HPLC, column: ZORBAX Bonus-RP 4.6 x 150 mm, 5 µm; 1 ml/min o 80 % ACN /
20 % H2O; 201 nm / 278 nm).
3.3. Tempe a u e G adien
The empe a u e g adien s we e adjus ed on me al pla es wi h a leng h o 35 cm, a wid h
o 20 cm, and a hickness o 0.5 cm. On one side o he pla e a essel was welded wi h a
leng h o 10 cm, a wid h o 20 cm, and a heigh o 10 cm se ing as ese oi o he cooling
agen . This cooled side o he me al pla e was placed on co k o insula ion. The o he side o
he pla e was placed plana on a ho pla e (P äzi he m PZ 28-2T; Ha y Ges igkei GmbH)
wi h a de ined con ac a ea o 6 cm x 20 cm. A e e ence silicon wa e – 525 µm hickness,
polished on side, n- ype, highly a senic doped wi h a esis ance o < 0.01 Ωcm, which
exhibi s less in a ed anspa ency – was placed on he pla e a e a calib a ion ime o one
hou . This wa e was moni o ed wi h an in a ed came a (The maCAMTME300; FLIR
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sys ems), which was adjus ed 30 cm di ec ly abo e he wa e . Be o e u ilizing he in a ed
came a, he ex inc ion coe icien o he silicon wa e was calib a ed wi h he help o he
mel ing poin s o s ea ic acid (69 °C), benzyl (1,2-diphenyle hane-1,2-dione) (95 °C) and
benzoic acid (122 °C) [28].
3.4. Exposu e Dose G adien
The UV-exposu e dose g adien using a mask-alignmen sys em (EVG®620; EV G oup)
and specially designed i e inch qua z glass mask (p oduced by ML&C). Fo he e i ica ion
o his UV-exposu e g adien a esis ilm was p epa ed ou o a posi i e one s a -shaped
e oligome [s a is ical copolyme ized ou o α-gamma bu y olac one me hac yla e, me hyl
adaman yl me hac yla e, and hyd oxyl adaman yl me hac yla e (GBLMA-co-MAMA-co-
HAMA)] (95w .%) and he pho oacid gene a o iphenylsul onium pe luo o-1-
bu anesul ona e (5w .%) and was applied om a 2.5 w .% solu ion in 1-me hoxy-2-
ace oxyp opane on a silicon wa e . A e spin coa ing he esul ing ilm was p e-baked and
had a hickness o 90 nm measu ed by a su ace p o ilome e (Dek ak 3030 ST; Veeco). The
wa eleng h ange o he mask-alignmen sys em was adap ed o 240 nm o 290 nm o he
used esis sys em.
The elec on beam exposu e was pe o med using a Zeiss 1530 FESEM equipped wi h a Rai h
Elphy Plus a an accele a ing ol age o 20 kV and doses we e adjus ed om 100 µC/cm² (D1)
o 2516 µC/cm² (D21). The exposu e ook place on a new molecula glass nega i e one esis
u ilizing physical apo deposi ion o ilm p epa a ion and consis ed o 2-
[(me hylsul onyl)oxy]-1H-Benz[de]isoquinoline-1,3(2H)-dione (41%), 1,1'-binaph hyl-2,2'-
diamine (40%), and 2-[(me hylsul onyl)oxy]-1H-Benz[ ]isoindole-1,3(2H)-dione (19%).
A e wa ds he ilm was de eloped 60 s in s i ed cyclohexane.
3.5. Dissolu ion In es iga ion
Fo QCM measu emen s qua z c ys al holde (Max ec CHC-100) and qua z c ys als
(QCs) (1 inch, 5 MHz, polished gold elec odes; pu chased om QT Qua z echnik GmbH)
we e used. Fo he esis ilm p epa a ion on he QCs solu ions ou o a posi i e one s a -
shaped e oligome (GBLMA-co-MAMA-co-HAMA) and he pho oacid gene a o
( iphenylsul onium pe luo o-1-bu anesul ona e) we e spin-coa ed unde equal condi ions
(3.4. Exposu e Dose G adien ) on qua z c ys als esul ing in a ilm hickness o abou 90 nm.
The wa eleng h o UV-exposu e was adjus ed o 240 nm o 290 nm (F300S; Fusion UV).
The PEB was pe o med a a empe a u e o 130 °C o 30 s.
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4. Conclusions
This wo k demons a es se e al me hods o combina o ial in es iga ions on solu ion-
coa ed hin ilms. In his con ex ilm p epa a ion o an in e nal ma e ial composi ion g adien
by a sy inge pump sys em and a s a ic mixing de ice was success ul es ablished o polyme ic
as well as low molecula weigh ma e ials. The cha ac e iza ion by luo escence spec oscopy
as well as HPLC con i med a linea slope o he achie ed ma e ial composi ion g adien . We
ha e also shown he con olled p epa a ion o a ious empe a u e g adien s he e applied o
he mal annealing p ocesses whose slope is adjus able o he pa icula equi emen . In
addi ion, we ha e applied exposu e dose g adien s o UV ligh and elec on beam exposu e
on iny a eas allowing a ma ix-like applica ion and hus he p epa a ion o a e na y
combina o ial lib a y. Fo dissolu ion in es iga ions qua z c ys al mic obalance
measu emen s in combina ion wi h a i a ion p ocess we e shown o p o ide an e icien
sc eening echnique. Based on hese aluable esul s u he combina o ial in es iga ions on
solu ion-coa ed ilms we e conduc ed wi h ei he s epwise o con inuous imme sion g adien s.
Finally hese g adien s we e combined o a bina y and a e na y combina o ial lib a y and
applied o li hog aphic sys ems. He e he esis ma e ial was e icien ly p esc eened allowing
he e alua ion o he in e dependence o he applied a iables. Thus by his me hod also a as
op imiza ion o he esis ma e ial p ocessing was achie ed. These esul s imp essi ely
demons a e he e iciency o combina o ial app oaches on hin ilms applied o complex
mul i- a iable dependen applica ions.
Acknowledgmen s
This wo k was suppo ed by he Semiconduc o Resea ch Co po a ion’s Global
Resea ch Collabo a ion (GRC) P og am [Tasks 1675.001 and 1675.002] and he Deu sche
Fo schungsgemeinscha (DFG), SFB 481 [P ojec No. A6]. In addi ion we hank EUV
echnology o he oughness e alua ion so wa e SuMMITTM. This publica ion was unded
by he Ge man Resea ch Founda ion (DFG) and he Uni e si y o Bay eu h in he unding
p og amme Open Access Publishing.
Publica ions and manusc ip s
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Re e ences and No es
1 D ews, J. D ug disco e y: A his o ical pe spec i e. Science 2000, 287, 1960–1964.
2 Newman, D.J.; C agg, G.M. Na u al P oduc s as Sou ces o New D ugs o e he Las 25
Yea s. J. Na . P od. 2007, 70, 461–477.
3 Kennedy, J.P.; Williams, L.; B idges, T.M.; Daniels, R.N.; Wea e , D.; Lindsley, C.W.
Applica ion o Combina o ial Chemis y Science on Mode n D ug Disco e y. J. Comb.
Chem. 2008, 10, 345–354.
4 Jo gensen, W.L. E icien D ug Lead Disco e y and Op imiza ion. Acc. Chem. Res.
2009, 42, 724–733.
5 Bu baum, J.; Sigal, N.H. New echnologies o high- h oughpu sc eening. Cu . Opin.
Chem. Biol. 1997, 1, 72–78.
6 Thompson, L.A.; Ellman, J.A. Syn hesis and Applica ions o Small Molecule Lib a ies.
Chem. Re . 1996, 96, 555–600.
7 Jandelei , B.; Schae e , D.J.; Powe s, T.S.; Tu ne , H.W.; Weinbe g, W.H.
Combina o ial ma e ials science and ca alysis. Angew. Chem. In . Ed. 1999, 38, 2494–
2532.
8 Buenconsejo, P.J.S.; Siegel, A.; Sa an, A.; Thienhaus, S.; Ludwig, A. P epa a ion o 24
e na y hin ilm ma e ials lib a ies on a single subs a e in one expe imen o
i e e sible high- h oughpu s udies. ACS Comb. Sci. 2012, 14, 25–30.
9 Po y ailo, R.; Rajan, K.; S oewe, K.; Takeuchi, I.; Chisholm, B.; Lam, H. Combina o ial
and High-Th oughpu Sc eening o Ma e ials Lib a ies: Re iew o S a e o he A . ACS
Comb. Sci. 2011, 13, 579–633.
10 Ba be , Z.H.; Blami e, M.G. High h oughpu hin ilm ma e ials science. Ma e . Sci.
Technol. 2008, 24, 757–770.
11 S a o d, C.M.; Rosko , K.E.; Epps, T.H.; Fasolka, M.J. Gene a ing hickness g adien s
o hin polyme ilms ia low coa ing. Re . Sci. Ins um. 2006, 77, 23908/1-7.
12 Me edi h, J.C.; Smi h, A.P.; Ka im, A.; Amis, E.J. Combina o ial Ma e ials Science o
Polyme Thin-Film Dewe ing. Mac omolecules 2000, 33, 9747–9756.
13 Me edi h, J.C.; Ka im, A.; Amis, E.J. High-Th oughpu Measu emen o Polyme Blend
Phase Beha io . Mac omolecules 2000, 33, 5760–5762.
14 Neube , C. B e, M. Thelakka , M. Schmid , H.- . H nsel, H. e l, H. ausch, G.
Combina o ial p epa a ion and cha ac e iza ion o hin- ilm mul ilaye elec o-op ical
de ices. Re . Sci. Ins um. 2007, 78, 72216/1-11.
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96
he esea ch ield o li hog aphy as new esis ma e ials. S anda d esis s a e s ill based on
linea polyme ma e ials.
20
Du ing he las decade, an addi ional a chi ec u e, molecula
glasses (MG), in oduced by Shi o a e al.,
21
has been s udied as a new class o pho o esis
ma e ials.
22
,
23
The main ad an ages o MGs a e he o ma ion o anspa en ilms, hei
monodispe si y, he usage o common o ganic pu i ica ion me hods and he smalle molecule
size, which is abou he same size as addi i es such as a pho o acid gene a o and base
quenche .
24
The ad an ages o common polyme ma e ials a e s able amo phous ilm
o ma ion, obus p ocessabili y and he almos unlimi ed s uc u al lexibili y due o
monome choice and a chi ec u e.22 In con as o MGs, polyme s show chain en anglemen s
and ha e an a e age coil dimension o 5-10 nm. Chain en anglemen s and ex ended coil
dimension a e conside ed o be he main easons o i egula i ies in high- esolu ion pa e ns.
The in oduc ion o s a -shaped polyme a chi ec u e is in ended o o e come issues om
bo h he linea polyme and he MG esis ma e ials. Addi ional esea ch in non-linea
polyme a chi ec u es has included g a
25
o hype b anched
26
polyme esis s ha we e
designed o imp o e he esis ’s dissolu ion beha io o o enhance he sensi i i y o he esis ,
espec i ely. These wo ks demons a e ha swi ching om linea polyme s o mo e complex
a chi ec u es can yield imp o ed pe o mance.
Anionic polyme iza ion is a well-known and well-es ablished me hod o he ab ica ion
o ailo made polyme s wi h p ecise con ol o e molecula weigh (MW) and (low)
polydispe si ies.
27
Howe e , his me hod exhibi s majo d awbacks in mode n ma e ial
esea ch as i is highly suscep ible o impu i ies (especially oxygen and wa e ) as well as
unc ional g oups (elec ophilic, pola and p o ic). Al hough new syn he ic pa hs like RAFT
and NMP o e come some o hese obs acles, hey in ol e long and di icul p epa a i e
e o s and complica ed syn he ic pa hs owa ds s a -shaped polyme s.
28
In he pas wo
decades, a om ans e adical polyme iza ion (ATRP) has eme ged as one o he mos
e sa ile con olled adical polyme iza ion echniques sus aining mos unc ional g oups and
e en small amoun s o oxygen.
29
In addi ion, eac ion condi ions can be easily uned by many
pa ame e s o accu a e polyme syn hesis. Ano he in e es ing ea u e is he s aigh o wa d
p epa a ion o mul i unc ional, b ush- o e en s a -shaped ini ia o s by simple and
inexpensi e one-s ep es e i ica ion o oligo- and polyols wi h halogen bea ing moie ies.
30
,
31
The possibili y o c ea ing a chi ec u es o a wide ange o applica ions is almos in ini e as
he pool o monome s polyme izable ia ATRP is s ill inc easing.28 When ATRP is used o
Publica ions and manusc ip s
97
p epa e copolyme s, di e en con e sions yield di e en composi ions excep o he case o
monome eeds wi h he same eac i i y.
32
Based on his knowledge, we add ess key challenges acing ATRP syn hesis o s a -
shaped s a is ical e oligome s. While con e sion was p e iously u ilized as a p ocess
a iable, in his s udy i will be kep in a na ow ange, while he eac ion a e is con olled by
he [CuI]/[CuII] and [M]:[I] a ios. This allows he syn hesis o s a s comp ised o di e en
co es wi h di e en a m leng hs o be p epa ed a simila con e sions and hence, iden ical
composi ion. In oducing speci ic ac ions o non- eac i e si es in o he saccha ose ini ia o
p o ed success ul in con olling he a e age a m numbe o syn hesized s a e oligome s.
Wi h eac ion condi ions and polyme iza ion kine ics esol ed, one speci ic well-de ined s a
a chi ec u e was used o in es iga e i s po en ial in li hog aphic pa e ning.
Expe imen al Pa
Ma e ials
E hyl 2-b omoisobu y a e (EBiB) (97 %), 2-b omoisobu y yl b omide (98 %), p opionyl
b omide (98 %), 4-(dime hylamino)py idine (99 %), Py idine, Dichlo ome hane , Coppe (I)
chlo ide (>99 %), Coppe (II) chlo ide (>99 %), and N,N,N’,N”,N”- pen ame hyldie hylene-
iamine (PMDETA) (98 %), T iphenylsul onium pe luo o-1-bu anesul ona e (>99%),
P opylene glycol monome hyl e he ace a e (99%), Te ame hylammonium hyd oxide
solu ion (10 w .%), Hexame hyldisilazane (HMDS) we e pu chased om Ald ich and D(+)-
Saccha ose was pu chased om Aldi Süd. Me hyl adaman yl me hac yla e (MAMA) and
hyd oxyl adaman yl me hac yla e (HAMA) we e pu chased om Idemi su Chemicals and α-
gamma bu y olac one me hac yla e (GBLMA) om Ku a ay. MAMA and GBLMA we e
passed h ough a basic alumina column o emo e he inhibi o . HAMA was used as ecei ed.
All sol en s used we e o analy ical g ade.
P epa a ion o Mul i unc ional Ini ia o s
The co e- i s
33
app oach and ATRP we e selec ed o syn hesize s a -shaped oligome s.
2,3,4,6,1’,3’,4’,6’-oc a-O-(2-b omoisobu y yl)-saccha ose (1), which has eigh ini ia ing si es,
was p epa ed om saccha ose as p e iously published.
34
A modi ied mul i unc ional ini ia o wi h ewe ini ia ing si es (2) was p epa ed by
subs i u ing he 2-b omoisobu y yl b omide wi h a 50/50 solu ion o 2-b omoisobu y yl
Publica ions and manusc ip s
98
b omide and p opionyl b omide. 5.0 g (14.6 mmol) D(+)-Saccha ose we e dehyd a ed in a
acuum o en a 80 °C o 1 hou p io o being s i ed wi h 4-(Dime hylamino)py idine in
ca aly ic quan i ies in a solu ion o 200 mL chlo o o m and 90 mL py idine unde ni ogen.
A e cooling he solu ion wi h ice, 26.9 g (116.8 mmol) 2-b omoisobu y yl b omide and
16.0 g (116.8 mmol) p opionyl b omide we e added om a d opping unnel o e a pe iod o 3
hou s. The solu ion was b ough o oom empe a u e and s i ed o e nigh be o e unde going
e lux a 75 °C o h ee hou s. The solu ion was dilu ed wi h die hyl e he and he py idinium
b omide was emo ed by epea ed ex ac ion wi h wa e , sodium hyd ogen ca bona e solu ion
and sodium chlo ide solu ion. The solu ion was concen a ed and pu i ied by column
ch oma og aphy (SiO2; E hyl ace a e), he sol en e apo a ed, hen dissol ed in ho me hanol
and p ecipi a ed a -20 °C o e nigh . The ob ained solid mix u e o p oduc s co esponding o
he saccha ose based mul i unc ional ini ia o 2 has an a e age o 3.5 ini ia ing si es. (6.2 g,
5.6 mmol, 38.1 %)
Eigh si e saccha ose-based ini ia o 1: M (+Li+) = 1.541 g∙mol-1 by MALDI-TOF MS
(DHB:LiCl:ini ia o 10:1:1).34 Reduced si e Saccha ose-based ini ia o 2: M (+Li+) = 889
(5.8 %), 981 (17.6 %), 1.073 (27.6 %), 1.165 (25.8 %), 1.257 (14.5 %), 1.348 (8.7 %) g∙mol-1
by MALDI-TOF MS (DHB:LiCl:ini ia o 10:1:1).
P epa a ion o S a -shaped Te oligome s
A p e ious p ocedu e34 o he p epa a ion o poly( e -bu ylme hac yla e) s a s by
ATRP was modi ied as ollows: 0.20 g (0.13 mmol) 1, 1.76 g (10.4 mmol) GBLMA, 2.43 g
(10.4 mmol) MAMA, 1.22 g (5.2 mmol) HAMA, 0.03 g (0.35 mmol) CuCl and 0.93 g
(0.69 mmol) CuCl2 and 20 g anisole we e added o a 50 mL ound bo om lask sealed wi h a
ubbe sep um, equipped wi h a s i ba , and pu ged wi h ni ogen o 30 min. The solu ion
was hea ed in a 65 °C oil ba h and 0.18 g (1.04 mmol) PMDETA we e added a ime =0. A
cha ac e is ic colo change o anspa en g een indica ed he s a o he eac ion.
Aliquo s we e aken h oughou he eac ion o ollow he con e sion o all h ee
monome wi h 1H-NMR simul aneously. Peak in eg a ion was pe o med on he inyl peaks
o GBLMA, MAMA, HAMA a a chemical shi o δ = 6.39 ppm, δ = 6.27 ppm and δ =
6.22 ppm, espec i ely, and calib a ed o he in eg a ion o he anisole signal a δ = 3.87 ppm.
The hal -loga i hmic ela ionship be ween con e sion and polyme iza ion ime was used o
de e mine he end ime o 50 % con e sion (Equa ion 1).
35
-
37
Publica ions and manusc ip s
99
Cu
CuXPKk
M
MmATRPp
0
ln
(1)
A he calcula ed end ime, a inal aliquo was emo ed o e i y he inal con e sion
and he eac ion was quenched by apid cooling o oom empe a u e wi h liquid ni ogen. The
eac ion solu ion was passed h ough a silica column o emo e he coppe ca alys ,
concen a ed unde educed p essu e while being hea ed o 80 °C and p ecipi a ed in
me hanol. Following g a i y il a ion, he esul ing powde was aken up in 1,4-dioxane and
eeze d ied o ob ain he s a -shaped (GBLMA-co-MAMA-co-HAMA) oligome (S1d) as a
whi e powde (2.75 g, 97 %).
Simila p ocedu es we e aken ou wi h eac an a ios and polyme iza ion imes
modi ied o achie e samples wi h di e en de ined a m leng hs.
Gel Pe mea ion Ch oma og aphy
GPC wi h a Wya DAWN HELEOS mul iangle ligh sca e ing (GPC/MALS) de ec o
equipped wi h a 632.8 nm He-Ne lase and Visco ek Model 250 iscosi y de ec o
(GPC/ iscosi y) we e used o de e mine he absolu e molecula weigh s. THF was used as
eluen a a low a e o 1.0 mL/min: column se , 5 µm PSS SDV gel, 102, 103, 104, and 105 Å,
30 cm each. Fo GPC/ iscosi y, he e ac i e index inc emen , dn/dc, was measu ed on a PSS
DnDc-2010/620 di e en ial e ac ome e in THF a 25 °C.
Li hog aphic Expe imen s
Fo ilm p epa a ion a 5 w .-% solu ion o S1d and iphenylsul onium pe luo o-1-
bu anoylsul ona e (19:1) in PGMEA was spin coa ed on a HMDS p imed silicon wa e and
p ebaked a 125 °C o 150 s which co esponded o a 90 nm ilm hickness. The ilm was
exposed wi h a 100 nm line/space pa e n a doses om 10 o 410 µC/cm² in 24 s eps wi h a
Zeiss 1530 FESEM equipped wi h a Rai h Elphi Plus and an accele a ing ol age o 20 kV.
The ilm was annealed o pos exposu e bake (PEB) wi h a empe a u e g adien om 93 °C
o 104 °C o 30 s and pe pendicula o he empe a u e g adien de eloped in 0.26 N TMAH
o ou ime pe iods o (15, 30, 60, 120) s. A Zeiss 1530 FESEM was used o imaging and
he so wa e SuMMITTM was used o e alua ion and de e mina ion o he line edge
oughness (LER) and he line wid h oughness (LWR) o he line/space pa e n.
Publica ions and manusc ip s
100
Resul s and Discussion
Analysis o Ini ia o Func ionali y
In o de o achie e di e en unc ionali ies om he same saccha ose co e, ac i e
ini ia ing g oups we e eplaced wi h a non- eac i e p opyles e esul ing in educed
unc ionali y. Scheme 1 shows he eac ion pa hway owa d he nea ly comple e
unc ionalized saccha ose based ini ia o 1 and he ini ia o 2 wi h educed unc ionali y.
Scheme 1: Reac ion pa hway owa d saccha ose based ini ia o s 1 and 2. 1 is he maximum
unc ionalized saccha ose based ini ia o , while 2 has a educed unc ionali y ealized by capping wi h
he non- eac i e p opyles e .
Saccha ose con ains eigh possible eac ion si es o 2-b omoisobu y yl b omide and
p opionyl b omide. The syn he ic ou e o ini ia o 1 yields he maximum unc ionalized
saccha ose based ini ia o while he syn hesized ini ia o 2 is no a single ini ia o , bu a he a
mix u e o ini ia o s based on he same saccha ose molecule, each o di e en unc ionali y.
The composi ion o he mul i unc ional ini ia o s was analyzed by MALDI-TOF mass
spec ome y (MS) o de e mine he numbe s o ini ia ing si es and he co esponding con en
in he mix u e o he syn hesized ini ia o 2 (Table 1).
O
CH2OH
OH
OH
OH
O
O
CH2OH
OH
OH
CH2OH
O
CH2O
O
O
O
O
O
CH2O
O
O
CH2O
O
B
O
B
B
CHCl3/Py idine
4-DMAP
0°C → → 75°C
1
2
O
O
B
H
98.4 % 1.6 %
O
B
44.0 % 56.0 %
1:
2:
D(+)-Saccha ose
+
16 eq : 0 eq
8 eq : 8 eq
Publica ions and manusc ip s
101
Table 1: Absolu e numbe s o ini ia ing si es and co esponding con en o ini a o 2 measu ed by
MALDI-TOF MS
Mw (g/mol)a
Ini ia ing
Si esb
Con en (%)c
889
1
5.8
981
2
17.6
1.073
3
27.6
1.165
4
25.8
1.257
5
14.5
1.348
6
8.7
a Molecula weigh o MALDI-TOF MS de ec ed ini ia o + (Li+) b Numbe o b omina ed ini ia ing
si es de e mined by abula ion o molecula weigh o possible combina ions o si es eac ed wi h 2-
b omoisobu y yl b omide, si es eac ed wi h p opionyl b omide, and deb omina ed ini ia o s yielded
by he pu i ica ion p ocedu e. c Con en o co esponding ini ia o de i a i e in he syn hesized
mix u e o ini ia o 2. The con en is calcula ed by he in eg a ed s eng h o he MALDI-TOF MS
peaks.
The MALDI-TOF MS measu emen shows a Gaussian con en dis ibu ion wi h he
main con en in he mix u e o ini ia o 2 be ween h ee (27.6 %) and ou (25.8 %) ini ia ing
si es. As a esul he ini ia o 2 has he o e all a e age o 3.5 b omine based ini ia ing si es
which is gi en by he endcapping o he saccha ose co e wi h p opionyl b omide and by he
loss o b omides du ing pu i ica ion p ocedu e.
The e iciency o he eac i e si es o ini ialize polyme iza ion has o be aken in o
accoun , educing he a m numbe u he . A p ac ical alue o 66 % is well-es ablished by
nume ous epo s on me hac yla e syn hesis wi h ini ia ing si es o iden ical eac i i y and was
also aken in o conside a ion o he ini ia o e iciency. Thus, a inal numbe o a ms o 5.3
o 1 is an icipa ed and in he same manne , he ini ia o e iciency o 2 is an icipa ed o be
2.4. Wi h he ini ia o 1, he e hyl 2-b omoisobu y a e ini ia o and he ini ia o 2 we a e able
o syn hesize polyme s o a s a a chi ec u e con aining mo e han i e a ms, linea polyme s
as well as he co esponding missing links wi h mo e han wo a ms.
Publica ions and manusc ip s
102
Monome Feed Ra ios
Fo his s udy, an a e age monome composi ion o 50 % GBLMA, 30 % MAMA and
20 % HAMA wi hin he p oduc was a ge ed due o i s po en ial applica ion as a esis
ma e ial.30 Th ough epea ed expe imen a ion wi h a s a is ical linea copolyme , a eed o
41 % GBLMA, 41 % MAMA and 18 % HAMA was ound o achie e he a ge composi ion
o e a con e sion ange o Xp = 30 - 60 % (Figu e 1). Fo his pu pose, he composi ion was
moni o ed h oughou he polyme iza ion by he dec ease o he h ee inyl signals, which
co esponded o each monome decaying in 1H-NMR. Excep o he s a o he eac ion, he
composi ion o he g owing polyme emained close o he a ge composi ion. Con e sion
ollowed i s o de kine ics wi hou any ace o side eac ions like ecombina ion o ans e .
Figu e 1: E olu ion o monome inco po a ion (GBLMA (◊), MAMA (□) and HAMA (○)) and also -
ln(1-Xp) () e sus polyme iza ion ime o S1d.
Syn hesis o S a -shaped Te oligome s wi h Modi ied A m Leng hs
Fou s a -shaped oligome s wi h a ying a ge a e age a m leng hs o 7, 10, 19 and 20
uni s and iden ical co e 1, a s a wi h modi ied co e 2 and a linea model oligome ini ia ed
om e hyl 2-b omoisobu y a e we e syn hesized (Scheme 2; Table 2). Fo all ma e ials he
a e age monome composi ion is 50 % GBLMA, 30 % MAMA and 20 % HAMA, which
020 40 60 80 100
0
10
20
30
40
50
60
70
0
10
20
30
40
50
60
70
80
GBLMA
MAMA
HAMA
- ln (1-Xp)
composi ion in %
polyme iza ion ime in min
Con e sion
Guide o he eye
Publica ions and manusc ip s
103
demons a es he e ec i eness o he p oposed me hod. S1c shows he mos dis inc s a
cha ac e , a simila molecula weigh and he same composi ion as a hype b anched polyme
published by Hadziioannou e al.26 Thus S1d was syn hesized wi h a ocus on he same
molecula weigh o S1c bu in a la ge scale o li hog aphic in es iga ions. In addi ion, as
shown in Figu e 1 he desi ed composi ion is independen on he in es iga ed con e sions,
his second ba ch was syn hesized up o a highe con e sion o 60 % o sa e monome .
Scheme 2: Syn hesis o he linea model e oligome L and he s a -shaped e oligome s 1 and 2. The
o e all e oligome composi ion o GBLMA/MAMA/HAMA (GcMcH) was 50/30/20. 1 is he
maximum unc ionalized saccha ose ini ia o , while 2 has a educed unc ionali y.
Table 2: Syn hesis condi ions and s a e oligome speci ics
Code
Polyme a, b
[I]0
(mmol/L)
[M]0c:[I]0:[L]:[CuI]0:[CuII]0
Time
(min)
Mn, heo.d
(kg/mol)
Mn,MALS
(kg/mol)
PDIe
DPn
L
(GcMcH)41
27.0
55 : 1.0 : 1.0 : 0.5 : 0.5
200
7.0
8.4
1.05
41
S1a
((GcMcH)7)5.3
31.4
70 : 1.0 : 8.0 : 0.5 : 7.5
120
8.4
9.1
1.05
38
S1b
((GcMcH)10)5.3
8.9
119 : 1.0 : 8.0 : 1.6 : 6.4
105
12.0
12.5
1.05
55
S1c
((GcMcH)19)5.3
4.5
237 : 1.0 : 8.0 : 4.0 : 4.0
124
22.4
20.6
1.03
98
S1d
((GcMcH)20)5.3
6.5
200 : 1.0 : 8.0 : 2.7 : 5.3
150
22.4
23.9
1.05
104
S2
((GcMcH)14)2.4
25.0
75 : 1.0 : 4.0 : 0.8 : 3.2
45
8.2
8.0
1.08
35
a Fi s subsc ip deno es deg ee o polyme iza ion pe a m; b Second subsc ip deno es a m numbe ;
c Monome eed a io: 41 % GBLMA, 41 % MAMA, 18 % HAMA; d heo e ical a ge ed molecula
weigh ; e polydispe si y index measu ed by MALS de ec ion; o e all deg ee o polyme iza ion
deduced om MALS alues.
OO
OH
OO
+ +
O
O
OO
CuCl/CuCl2
PMDETA
Anisole
1.
2. 1
3. 2
O
O
B
GBLMA MAMA HAMA S2
S1a-d
L
B
O
x
y
z
n
O O O
O O O
O
O
OH
GcMcH
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104
The a io o monome uni s o ini ia o plays a c ucial ole in syn hesizing he desi ed
a m leng h and he a e age monome composi ion o he s a . Reac ion condi ions we e
adjus ed o each polyme iza ion o esul in monome pe cen ages o 50 %, 30 % and 20 %,
o GBLMA, MAMA and HAMA, espec i ely, when con e sion app oached he
p ede e mined egion o 40-60 %. Since he eac ion ime dec eases sha ply when
syn hesizing sho e molecules, he a io [CuI]0/[CuII]0 was dec eased o slow down eac ion
imes signi ican ly. The addi ion o [CuII] deac i a o allows a ge ing e y sho a ms wi hou
losing con ol o e he eac ion. Analysis o he inal aliquo s yielded an o e all composi ion
o (46/32/22), (47/31/22), (50/31/19), (50/30/20), (49/30/21) and (49/31/20)
(GBLMA%/MAMA%/HAMA%) o L, S1a, S1b, S1c, S1d and S2. This is e y well wi hin
he expec ed ange and unde lines p e iously made assump ions.
The con e sion index (Equa ion 1) desc ibes a loga i hmic ela ionship be ween he
con e sion o monome and polyme iza ion ime and he e o e co esponds o a i s o de
kine ic.35-37 By no malizing he con e sion index wi h eac ion quan i ies ha a e p opo ional
o he emaining e ms (Equa ion 2), i can be shown ha all ou eac ions ollow he same
kine ics (Figu e 2) independen o [I]0/[CuI]0 and [CuI]0/[CuII]0 a ios.
I
M
ICu
Cu
M
M
~ln
0
0
0
0
00
(2)
This in o ma ion can hen be used o p edic how changing each eac ion condi ion will
impac he polyme iza ion ime equi ed o achie e he desi ed con e sion.
As al eady men ioned in he in oduc ion, s a e oligome s consis o polyme chains
co alen ly linked o one co e esul ing in educed hyd odynamic adii compa ed o linea
polyme coils, so s anda d GPC does no deli e eliable alues o molecula weigh s wi hou
co esponding calib a ion. Thus GPC measu emen s we e pe o med wi h a mul i-angle ligh
sca e ing (MALS) de ec o o ob ain absolu e molecula weigh s (Figu e 3).
Publica ions and manusc ip s
105
Figu e 2: Plo o he no malized con e sion index e sus polyme iza ion ime o S1a (□), S1b (∆),
S1c (○), S1d (◊).
Figu e 3: No malized sca e ing in ensi y o GPC aces o L, S1a, S1b, S1c, S1d and S2 measu ed
wi h THF as he eluen and a mul i-angle ligh sca e ing de ec o . Sligh ecombina ions a e isible by
shoulde s o he s a -shaped e oligome s S1c (dash do ) and S1d (dash do do ) due o he ac , ha
he sca e ing de ec o is disp opo ionally sensi i e o he molecula size (in ensi y ~ diame e 6).
020 40 60 80 100 120 140
0
5
10
15
20
25
30
35
40
polyme iza ion ime in min
no malized con e sion index [L/mmol]
ln([M]0/[M] )*([Cu(II)]/[Cu(I)]*[I0])*([M]0/[I]0)
S1a
S1b
S1c
S1d
Guide o he eye
30 32 34 36 38 40 42
0.0
0.2
0.4
0.6
0.8
1.0
no malized sca e ing in ensi ies
elu ion olume in ml
L
S1a
S1b
S1c
S1d
S2
Publica ions and manusc ip s
112
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J. H. Adai , T. Li, T. Kido, K. Ha ey, J. Moon, J. Mecholsky, A. Mo one, D. R. Talham,
M. H. Ludwig and L. Wang, Ma e . Sci. Eng., R, 1998, 23, 1-242.
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G. F. Ma z, A. L. Melby, S.-R. T. Chen, and N. F. Vozza, Low molecula weigh wa e
soluble polyme composi ion and me hod o use, 2001, WO 2001006999.
19
L. M. De Leon-Rod iguez, A. Lubag, D. G. Udugamasoo iya, B. P one h, R. A. B ekken,
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C. J. Hawke , Polym. P ep ., 1999, 40, 438-439.
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Hadziioannou, Ad . Ma e ., 2009, 21, 1121-1125.
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Publica ions and manusc ip s
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Publica ions and manusc ip s
115
4.4 Tailo ed S a Block Copolyme A chi ec u e o
High Pe o mance Chemically Ampli ied Resis s
By Flo ian Wiebe ge , Ch is ian Neube , Ch is ophe K. Obe , and Hans-We ne Schmid *
[*] P o . H.-W. Schmid , F. Wiebe ge , D . C. Neube
Mak omolekula e Chemie I
Bay eu he Ins i u ü Mak omolekül o schung (BIMF) and Bay eu he Zen um ü Kolloide
und G enz lächen (BZKG)
Uni e si ä Bay eu h
95440 Bay eu h, Ge many
E-mail: hans-we ne .schmid @uni-bay eu h.de
P o . C. K. Obe
Depa men o Ma e ials Science and Enginee ing
Co nell Uni e si y
I haca, NY 14853, USA
Keywo ds: ailo ed molecula a chi ec u es, s a block copolyme s, a om- ans e
adical polyme iza ion; elec on-beam li hog aphy, esis sensi i i y
This pape is published in
Ad anced Ma e ials 2012, 24, 5939-5944.
Publica ions and manusc ip s
116
The ma e ial pe o mance o polyme s is p ima ily gi en by hei chemical na u e bu
can be uned by he polyme a chi ec u e.[1,2] Tailo ed mac omolecula a chi ec u es ha e
been de eloped o a ge ed ad anced applica ions and a e he ocus o many esea ch
ac i i ies.[3] Typically polyme a chi ec u e is con olled by a bo om-up app oach, hus chain
g ow h opology is de ined by bo h an ini ia ing molecule and he monome s used. In his
con ex he a ailabili y o a numbe ini ia o s uc u es wi h di e en numbe s o ini ia ing
si es sui ed o a a ie y o monome s is especially aluable o con olled adical
polyme iza ion echniques. Due o he a ailabili y o sui able eagen s and he possibili y o
de ined molecula assembly o monome s, ailo ed polyme s and a chi ec u es ha e become
mo e sophis ica ed in ecen yea s.[4] Besides andom, g adien , and block copolyme s, which
simply di e in composi ion, g a copolyme s o b ushes, s a s, (hype )b anched polyme s o
ne wo ks ha e been ex ensi ely in es iga ed. Es ablished and e sa ile me hods o he
syn hesis o such ailo ed mac omolecules include con olled adical polyme iza ion
echniques and he simple o use a om ans e adical polyme iza ion (ATRP) in pa icula .[5]
A la ge numbe o polyme designs ha e been de eloped using p ima ily ATRP o i s
combina ion wi h o he echniques. Recen examples show a wide ange o hype b anched
polyme s[6] o polyme b ushes[7] as well as di e en ypes o dend ime -like[8] and
mik oa m s a polyme s,[9] s a -linea block polyme s[10] and s a block copolyme s.[11] As
an example o s a block copolyme s, he combina ion o wo di e en syn hesis ou es ha e
been demons a ed. One s a egy s a s wi h he syn hesis o a mac oini ia o ia a “co e- i s ”
polyme iza ion om a s a -shaped ini ia o [12] while in he second ou e he “co e” is o med
by an “a ms- i s ” app oach linking linea homopolyme s (a ms).[13] In bo h cases he
esul ing mac oini ia o was used o a subsequen second polyme iza ion o achie e he s a
block copolyme a chi ec u e.
Tailo ed polyme a chi ec u es wi h hei unique p ope ies we e de eloped conce ning
possible applica ions in a ious esea ch ields and mus ul ill pa icula equi emen s. The
p ope ies de ined by he gi en a chi ec u e a e impo an o hei success ul in oduc ion in
opics like d ug deli e y,[14] biomedical applica ions,[15] mic oelec onic ma e ials,[16]
o ganic de ices,[17] coa ings,[18] o li hog aphic pa e ning.[19] The i s polyme s mainly
used o comme cial applica ions as pho o esis we e a linea poly( inylcinnama e) and
c esol- o maldehyde ype polyme s (No olac) bu hey soon e ealed limi s in esolu ion. The
de elopmen o new polyme s se ing as esis s has con inued o p og ess o keep in s ep wi h
u he de elopmen s o pa e ning ools and o he equi emen s.[20] The cu en end in
Publica ions and manusc ip s
117
polyme ic esis s is based on andom e polyme s wi h ailo ed monome composi ions as
chemically ampli ied esis ma e ials.[21] Recen in es iga ions o his class o polyme
esis s ha e epo ed he ad an ages o con olling mac omolecula opology. Te polyme s
wi h a hype b anched a chi ec u e[22] as well as s a opology[23,24] we e epo ed as esis s
o high po en ial and wi h imp o ed pe o mance.
Based on hese esul s we p esen o he i s ime s a block copolyme s o use as high
pe o mance esis ma e ials. In addi ion o hei con olled sphe ical shape hese copolyme s
o e well de ined monome inco po a ion and placemen due o hei shell-like s uc u e. The
ailo ed s a block copolyme s we e syn hesized u ilizing he co e- i s ATRP ou e by he ull
con e sion o a i s monome and in-si u polyme iza ion o addi ional added monome
esul ing in na ow dispe si y (PDIs < 1.2). Thei applica ion o li hog aphic pa e ning was
e icien ly op imized by a combina o ial in es iga ion[25] and he new high pe o mance s a
esis ma e ial ea u es an imp essi e imp o emen in sensi i i y and solubili y in con as o
andomly dis ibu ed s a polyme s o a e e ence linea e polyme .
The chemical s uc u es o he used monome s and o he andom linea e polyme , as
well as o he co e[26] o he s a polyme and he co esponding a ms o he andom s a
copolyme s and also o he s a block copolyme s a e shown in Scheme 1. Cu en
indus ially used high pe o mance polyme pho o esis s o 193 nm li hog aphy consis o α-
gamma bu y olac one me hac yla e (GBLMA) as lac one monome , me hyl adaman yl
me hac yla e (MAMA) as acid-labile lea ing monome , and hyd oxyl adaman yl me hac yla e
(HAMA) as pola monome and a e used no only o 193 nm li hog aphy bu also o
ex eme ul a iole (EUV; 13.4 nm) and elec on beam li hog aphy.[21] Thus we selec ed
hese monome s o he syn hesis o ou e e ence linea e polyme an-L (composed o
GBLMA/ MAMA/ HAMA) as well as he andom s a copolyme s an-S1 (GBLMA/
MAMA/ HAMA) and an-S2 (GBLMA/ MAMA) while he monome a io ollows he
published hype b anched polyme esis monome composi ion.[27] Based on a s a molecula
a chi ec u e we demons a e u he p og ess by syn hesizing he ailo ed s a block
copolyme s block-S1 (GBLMA/ MAMA/ HAMA) and block-S2a and block-S2b (GBLMA/
MAMA) using he ATRP echnique ia ull con e sion o monome s o he i s block and
subsequen in-si u polyme iza ion o subsequen ly added monome s o achie e a ge
con e sions. To inc ease he de elopmen con as he monome HAMA is elimina ed o
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118
block-S2 polyme s and eplaced wi h monome GBLMA (block-S2a) o wi h monome
MAMA (block-S2b).
Scheme 1. Chemical s uc u es o used monome s GBLMA, MAMA, HAMA, he co e o he s a polyme s
( unc ionalized saccha ose), and syn hesized e e ence linea e polyme ( an-L), andom s a copolyme s ( an-
S1, an S2) and ailo ed s a block copolyme s (block-S1, block-S2a, and block-S2b) a e shown. The schema ic
illus a ion o an-S ep esen s he andom monome dis ibu ion (blue and ed squa es) wi hin he polyme a ms,
while he schema ic illus a ion o block-S illus a es he co e-shell-like s uc u e o he block copolyme a ms.
Monome eed and he polyme composi ion analyzed by 1H-NMR a e lis ed in Table 1.
The de ec ion o monome consump ion is possible as he cha ac e is ic 1H-NMR peaks o
inyl p o ons o each monome di e : 6.39 ppm o GBLMA, 6.27 ppm o MAMA, and
6.22 ppm o HAMA (Suppo ing In o ma ion, Figu e S1). The heo e ically calcula ed
molecula weigh s a e lis ed in Table 1. Absolu e molecula weigh s and polydispe si y
indices we e cha ac e ized by GPC u ilizing a mul i-angle ligh sca e ing de ec o and he
e ac i e index inc emen dn/dc. The a ge ed molecula weigh s o he s a polyme a e in
good ag eemen o he heo e ical alues. Assuming ha he molecula size o a linea
polyme is mo e expanded in compa ison o a mo e compac s a polyme he a ge molecula
GBLMA MAMA HAMA
Monome s Random Linea Te polyme
Co e o S a Polyme
Func ionalized saccha ose
an-L
Random S a Polyme s
S a Block Copolyme s
an-S1 an-S2
block-S1 block-S2a and block-S2b
Schema ic
illus a ion
o block-S
Schema ic
illus a ion
o an-S
Publica ions and manusc ip s
119
weigh o he an-L was se one hi d lowe . Fo all polyme s a monomodal dis ibu ion wi h a
symme ical shape was de ec ed (Figu e S2) and all polyme s showed a na ow molecula
weigh dis ibu ion wi h PDIs below 1.2 indica ing hei con olled cha ac e .
Table 1. Monome eed composi ions, co esponding molecula weigh s, polydispe si y indices, and polyme
composi ions o syn hesized linea and s a polyme s.
Samples
Monome Feed
Composi ion
(in mola equi alen )
Ta ge ed
Mn [a]
[kg mol-1]
Mn, MALS
[kg mol-1]
PDI[b]
Polyme composi ion (in %) [c]
GBLMA / MAMA / HAMA
GBLMA
MAMA
HAMA
an-L
40
40
20
13.5
15.5
1.10
46.8 / 29.6 / 23.7
an-S1
40
40
20
22.4
23.9
1.05
48.5 / 30.0 / 21.5
an-S2
50
50
-
23.7
25.8
1.02
62.4 / 37.6 / -
block-S1
30[d]
50[e]
20[e]
25.6
30.8
1.18
54.4 / 28.1 / 17.5
block-S2a
50[d]
50[e]
-
26.3
30.0
1.17
69.0 / 31.0 / -
block-S2b
33[d]
67[e]
-
27.8
32.3
1.19
53.2 / 46.8 / -
[a] Theo e ical calcula ed molecula weigh . [b] polydispe si y index measu ed by MALS de ec ion.
[c] De e mined by 1H-NMR. [d] Con e sion o GBLMA close o 100 %. [e] Addi ion o new monome a e ull
con e sion o GBLMA.
As he s a block copolyme s ha e a co e-shell-like s uc u e – he hyd ophilic lac one
monome uni s a e inco po a ed in o he inne shell and he mo e hyd ophobic adaman yl
monome uni s in he ou e shell – he su ace o ilms p epa ed om he s a block
copolyme s and andom s a copolyme s should di e in pola i y. The e o e he ailo ing
gi en by a chi ec u e is in addi ion suppo ed by wa e con ac angle measu emen o all
epo ed polyme s (Table S1; Figu e S3). The measu emen s yielded con ac angles o a ound
70° o ilms spin-coa ed o an-L and he an-S1 desc ibing a mo e pola su ace. In con as
he con ac angle o nea ly 81° was measu ed o he mo e nonpola an-S2 ilm. This is due
o he ac ha he pola hyd oxyl g oup o he monome HAMA is missing in an-S2 and hus
he su ace has highe hyd ophobici y. The same e ec o hyd ophobici y change o he ilm
su ace was obse ed o he s a block copolyme s. He e he ilm su ace o he block-S1
shows a con ac angle close o 77° and he ilm su aces o spin-coa ed block-S2a and block-
S2b ea u e highe con ac angles o abou 90°. The esul s co espond o he highe amoun o
inco po a ed pola monome HAMA posi ioned in he ou e shell o block-S1 and o he
HAMA ee block-S2a and block-S2b wi h ou e shells o med only by he nonpola
monome MAMA.
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120
Fu he mo e he dissolu ion beha io o he syn hesized polyme s should be in luenced
by molecula a chi ec u e. The e o e ilms o each polyme wi h added pho oacid gene a o
(PAG) we e spin-coa ed on qua z c ys als, lood exposed o PAG ac i a ion, and annealed in
a pos exposu e bake (PEB) o ca alyze he dep o ec ion o MAMA. A solubili y change is
expec ed o he dep o ec ed and hus mo e pola esis ma e ials de elopable in an aqueous
e ame hylammonium hyd oxide (TMAH) solu ion. Fo he sys ema ic in es iga ion o he
de elopmen con as cla i ying he solubili y di e ence be ween p o ec ed and dep o ec ed
esis he qua z c ys al mic obalance (QCM) echnique was used o cha ac e iza ion.[28]
The e o e unexposed and exposed ilms o all in es iga ed ma e ials spin-coa ed on qua z
c ys als we e clamped in he holde and imme sed in he de elope solu ion. The esul ing
aces o ilm hickness a ia ion, calcula ed om he de ec ed QCM equencies, a e shown
in Figu e 1a. All non-exposed ilms () show no signi ican change in ilm hickness o e a
pe iod o i e minu es demons a ing hei comple e insolubili y in he applied de elope
solu ion. The solubili y change o he ilm is p oduced by he elimina ion o 2-me hylidene-
adaman ane (only possible o MAMA uni s) esul ing in pola me hac ylic acid g oups
bonded o he s a . The ou e shell o block-S1 (○) consis s o bo h MAMA and o HAMA
uni s which canno be dep o ec ed; hus only an insu icien pola i y change can be gene a ed
and he ilm swells o a ilm hickness inc ease o 20 %. The exposed e e ence ilm o an-L
(⌂) and he ilm o an-S1 () show a dis inc swelling cha ac e o e 40 s and 63 s,
espec i ely, ollowed by hei comple e dissolu ion. Howe e , an-S2 (), block-S2a (),
and block-S2b (◊) show a ba ely measu eable as swelling ollowed again by comple e
dissolu ion: while dissolu ion akes 60 s o an-S2, he ilms o block-S2a and block-S2b a e
comple ely dissol ed wi hin he i s i e seconds. He e he ou e shell consis s only o
MAMA uni s and hus he pola i y change is well con olled. Based on hese p omising
dissolu ion in es iga ions he polyme s we e exposed o di e en doses o in es iga e hei
sensi i i y. Again ilms o each polyme and PAG mix u e we e spin-coa ed on silicon
subs a es unde equal condi ions. The ilms we e exposed o an elec on beam dose g adien
o 25 inc easing doses, annealed o PEB and de eloped in TMAH. The esul ing pa e ns
we e measu ed in ega d o dose dependen achie ed ilm hickness loss using a s ylus
p o ile . The measu ed ilm hicknesses con i m he esul s gi en by he QCM in es iga ions
(see Figu e 1b). The ilm o block-S1 (○) showed a he highes dose o 397 µC cm-2 only a
20 % loss in ilm hickness. As indica ed by QCM measu emen s, an-L and an-S1 need he
longes de elopmen ime pe iod and equi e ela i ely high doses o clea (160 µC cm-2 o
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an-L (⌂) / 92 µC cm-2 o an-S1 (□)). Howe e , he nea ly iden ical cha ac e s o an-S2,
block-S2a, and block-S2b o he QCM measu emen s disclose di e ences in hei sensi i i y.
Ran-S2 () needs only he dose o 77 µC cm-2 o clea and equi es he e o e a highe dose
han i s s a block copolyme coun e pa s: block-S2a () equi es he clea ing dose o
31 µC cm-2 and block-S2b (◊) o only 21 µC cm-2, espec i ely. This powe ul sensi i i y
inc ease up o eigh imes o he s a block copolyme s in compa ison o e e ence linea
polyme an-L demons a es he ad an ageous and p og ess in ailo ing he molecula
a chi ec u e by ollowing he s a block copolyme s concep .
Figu e 1. a) Qua z c ys al mic obalance measu emen s o non-exposed and lood exposed polyme esis ilms.
All non-exposed ilms () exhibi no signi ican change in ilm hickness while he lood exposed ilms jus
swell (block-S1 ○), swell and subsequen ly dissol e ( an-L ⌂ / an-S1 □), o apidly swell and dissol e wi hin
seconds ( an-S2 / block-S2a / block-S2b ◊).
b) Sensi i i y cu es o in es iga ed polyme esis ilms u ilizing elec on beam exposu e. Block-S1 (○) was
de eloped pa ly e en a he highes dose while he o he polyme s show high de elopmen con as s. The mos
sensi i e polyme is block-S2b (◊) exhibi ed a clea ing dose o 21.5 µC cm-2.
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Syn hesis o s a block copolyme s
A mix u e o GBLMA CuCl, CuCl2, 2,3,4,6,1’,3’,4’,6’-oc a-O-(2-b omoisobu y yl)-
saccha ose and anisole (16 mL) in he case o s a block copolyme block-S1 (see Table S2)
o a mix u e o GBLMA, CuCl, 2,3,4,6,1’,3’,4’,6’-oc a-O-(2-b omoisobu y yl)-saccha ose
and anisole (16 mL) in he case o s a block copolyme block-S2a o a mix u e o GBLMA,
CuCl, 2,3,4,6,1’,3’,4’,6’-oc a-O-(2-b omoisobu y yl)-saccha ose and anisole (15 mL) in he
case o s a block copolyme block-S2b was s i ed in a sc ew cap ial wi h a ubbe sep um
a 65 °C and degassed wi h ni ogen o 30 min. The ligand N,N,N’,N’’,N’’- pen ame hyl-
die hylene iamine (PMDETA) (equimola o CuCl and CuCl2) was dissol ed in 3 mL anisole
and degassed o 30 min, oo. The ligand’s solu ion was added o he monome s’ solu ion wi h
a degassed sy inge a ime called his ime 1 = 0. Th oughou he eac ion aliquo s we e aken
o ollow he con e sion o α-gamma bu y olac one wi h 1H-NMR in CDCl3. Meanwhile a
mix u e o MAMA and HAMA in he case o s a block copolyme block-S1 o MAMA in
he case o s a block copolyme block-S2a o block-S2b was dissol ed in 5 mL anisole and
degassed o 30 min. A e ully con e sion o α-gamma bu y olac one he adaman yl
monome ’s solu ion was added o he eac ion solu ion wi h a degassed sy inge a ime called
2 = 0. Subsequen ly an aliquo was emo ed om he eac ion solu ion o ollow he
con e sion o he added monome s wi h 1H-NMR in CDCl3. The polyme iza ion was ended a
a con e sion o 31 %/47 % (MAMA/HAMA) o block-S1, o 45 %/- o block-S2a, and o
44 %/- o block-S2b. The eac ion was apidly cooled down wi h liquid ni ogen, dilu ed in
THF and passed h ough a silica column o emo e he coppe ca alys s. Then he solu ion
was concen a ed and p ecipi a ed in cold me hanol. The polyme was collec ed ia il a ion,
d ied, eeze-d ied in 1,4-dioxane yielding a whi e powde . The molecula weigh s,
polydispe si y indices and polyme composi ions a e shown in Table 1, he GPC aces a e
shown in Figu e S2.
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Table S2. Amoun s o eagen s o syn hesis o s a block copolyme s block-S1 and block-S2a/b.
Ini ia o
GBLMA
MAMA
HAMA
CuCl
CuCl2
block-S1
198.79 mg
(0.13 mmol)
1.46 g
(8.55 mmol)
3.34 g
(14.25 mmol)
1.35 g
(5.70 mmol)
34.25 mg
(0.35 mmol)
92.85 mg
(0.69 mmol)
block-S2a
141.87 mg
(0.09 mmol)
1.42 g
(8.32 mmol)
1.95 g
(8.32 mmol)
-
80.56 mg
(0.81 mmol)
-
block-S2b
198.62 mg
(0.13 mmol)
1.54 g
(9.06 mmol)
4.25 g
(18.12 mmol)
-
112.60 mg
(1.14 mmol)
-
Figu e S1 1H-NMR spec um (B uke A ance 300) o he monome s GBLMA/MAMA/HAMA in an anisole
solu ion in CDCl3 show he di e en shi ed inyl p o ons o GBLMA (6.39 ppm), MAMA (6.27 ppm), and
HAMA (6.22 ppm).
8 6 4 2 0
6.7 6.6 6.5 6.4 6.3 6.2
GBLMA
MAMA
HAMA
Vinyl p o ons o
Anisole
ppm
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Figu e S2. GPC aces o linea e polyme ( an-L), andom s a polyme s ( an-S1, an S2) and s a block
copolyme s (block-S1, block-S2a, block-S2b).
Wa e con ac angle measu emen s
Solu ions o 2.5 w .% o each polyme in cyclohexanone/cyclohexane 3/2 ( / ) we e
p epa ed and spin cas on silicon wa e and annealed o a subsequen pos apply bake (PAB)
a 125 °C o 60 s achie ing ilm hicknesses o abou 80 nm. Wa e con ac angle
measu emen s we e in es iga ed by a Da aPhysica OCA using deionized wa e .
Table S3. Wa e con ac angle measu emen s on ilms made o linea e polyme ( an-L), andom s a polyme s
( an-S1, an S2) and s a block copolyme s (block-S1, block-S2a, block-S2b) and he a e age o i e uns.
un
an-L
an-S1
an-S2
block-S1
block-S2a
block-S2b
1
71.0°
66.4°
79.3°
76.8°
89.4°
89.1°
2
71.5°
67.1°
80.4°
75.6°
90.5°
90.1°
3
72.0°
67.1°
81.6°
77.1°
90.2°
89.3°
4
71.5°
68.3°
80.7°
77.6°
89.0°
89.4°
5
71.6°
67.8°
81.0°
77.1°
88.8°
90.1°
a e age (1σ)
71.5 ± 0.4°
67.3 ± 0.7°
80.6 ± 0.9°
76.8 ± 0.8°
89.6 ± 0.7°
89.6 ± 0.5°
26 28 30 32 34 36
0.0
0.2
0.4
0.6
0.8
1.0
an-L
an-S1
an-S2
block-S1
block-S2a
block-S2b
no malized e ac i e indices
elu ion ime in ml
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131
Figu e S3. Pic u es o wa e d ople s on spin cas polyme ilm su aces (linea e polyme ( an-L), andom s a
polyme s ( an-S1, an S2) and s a block copolyme s (block-S1, block-S2a, block-S2b)) and hei co esponding
measu ed con ac angles‘.
Dissolu ion in es iga ions
The qua z c ys al mic obalance (QCM) measu emen s ( emo e oscilla o and con olle
ca d: In icon) we e pe o med wi h a sol en -p oo QC-holde (Max ec CHC-100). The
measu emen s we e con olled by adap ed LabView so wa e and he da a densi y was ou
poin s pe second. The QCs (5 MHz) we e spin cas wi h solu ions o 2.5 w .% (each polyme
plus added pho oacid gene a o iphenylsul onium pe luo o-1-bu anesul ona e 19/1 (w/w))
in cyclohexanone/cyclohexane 3/2 ( / ), subsequen ly annealed o PAB a 125 °C o 60 s
achie ing ilm hicknesses o abou 80 nm. In doing so wo o each polyme ilms whe e
p epa ed and one o his pai was lood exposed o UV ligh (248 nm; Fusion UV Sys ems:
F300S) and hen applied o he pos exposu e bake a 95 °C o 30 s. The QCs we e
successi ely moun ed in he QC-holde and imme sed in o he 0.26 N e ame hylammonium
hyd oxide de elopmen solu ions o i e minu es o collec he equency a e.
an-L
an-S1
an-S2
block-S1
block-S2a
block-S2b
71.5
67.3
80.6
76.8
89.6
89.6
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Sensi i i y in es iga ions
The silicon wa e we e spin cas wi h solu ions o 2.5 w .% (each polyme plus added
pho oacid gene a o iphenylsul onium pe luo o-1-bu anesul ona e 19/1 (w/w)) in
cyclohexanone/cyclohexane 3/2 ( / ) subsequen ly annealed o PAB a 125 °C o 60 s
yielding ilm hicknesses o abou 80 nm. Each wa e was exposed o a dose g adien anging
om 5 o 397.5 µC cm-2 – one dose in an a ea o 20 µm x 100 µm – applied wi h a Zeiss LEO
1530 equipped wi h a Rai h Elphy Plus u ilizing an accele a ion ol age o 20 kV. A e a pos
exposu e bake (95 °C; 30 s) he wa e we e de eloped (30 s; 0.26 N TMAH). The yielded
p o ile heigh s o each di e en exposed a ea we e measu ed and epo ed in espec o he
ilm hickness by a s ylus p o ile (Veeco Dek ak 150).
Te na y lib a y o e e ence linea e polyme an-L
The e na y lib a y consis s o a empe a u e g adien pe pendicula o a de elopmen
ime g adien , which ep esen s he a iable g adien s o he bina y lib a y, while an elec on
beam exposu e dose g adien is applied in e y small a eas ma ix-like o his bina y lib a y.
A ilm was spin cas on a silicon wa e ou o a 2.5 w .% solu ion o an-L and he pho oacid
gene a o iphenylsul onium pe luo o-1-bu anesul ona e 19/1 (w/w) in cyclo-
hexanone/cyclohexane 3/2 ( / ). Subsequen ly he ilm was annealed unde acuum o he
pos apply bake (PAB) a 125 °C o 2.5 min esul ing in a ilm hickness o 80 nm. Then he
subs a e was cu o a quad a wi h an edge leng h o abou 30 mm unde A gon-a mosphe e.
As i s applied a iable o he combina o ial lib a y he elec on beam exposu e dose
and ea u e size g adien was p ocessed in 120 w i e- ields s uc u ed ma ix-like applied wi h
a Zeiss LEO 1530 equipped wi h a Rai h Elphy Plus u ilizing an accele a ion ol age o
20 kV. This ma ix consis s o h ee ows imes ou columns o sec o s, each con aining 10
w i e- ields ep esen ing he exposu e dose g adien om 100 – 288.7 µC cm-2, while in a
single w i e- ield – 100 µm x 100 µm in size – he ea u e size a ia ion in s eps o 6 nm om
42 – o 108 nm is gi en. Each sec o has a leng h o 2 mm and a wid h o 100 µm; be ween
each column he gap was 9 mm and 15 mm be ween each ow espec i ely. Subsequen ly he
pos exposu e bake (PEB) was applied by a empe a u e s ep g adien . The subs a e was cu
along he ows in o h ee pieces; one o he pieces was annealed a a empe a u e o 93, 95,
and 97 °C, espec i ely, o 30 s. The de elopmen ime s ep g adien was applied alongside
Publica ions and manusc ip s
133
he columns o he exposed ma ix o 5, 15, 30, 60 s in a 0.26 N e ame hylammonium
hyd oxide solu ion. The e o each subs a e piece was subdi ided in o ou segmen s whe eas
each segmen con ains one ow o w i e- ields.
The de eloped ilm was spu e ed wi h 1.3 nm pla inum and in es iga ed in a scanning
elec on mic oscope (SEM) Zeiss 1530. The obse ed SEM images o he line/space pa e ns
we e e alua ed o line edge and line wid h oughness by he so wa e SuMMITTM om EUV
echnology and he op imized pa e ns a e shown in Figu e S4.
Figu e S4: Selec ed SEM images o e-beam w i en ea u e size g adien in op imized
sec o and co esponding LER alues o e e ence linea e polyme an-L.
Publica ions and manusc ip s
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Publica ions and manusc ip s
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Publica ion lis
137
5 Publica ion lis
Publica ions and manusc ip s o his hesis
1. F. Wiebe ge , T. Kolb, C. Neube , C. K. Obe , and H.-W. Schmid
“Combina o ial echniques o e icien ly in es iga e and op imize hin ilm
nanopa e ning”
Submi ed o Molecules
2. F. Wiebe ge , D. C. Fo man, C. Neube , A. H. G öschel, M. Böhm, A. H. E. Mülle ,
H.-W. Schmid and C. K. Obe
“Tailo ed S a -Shaped S a is ical Te oligome s ia ATRP o Li hog aphic Applica ions“
Jou nal o Ma e ials Chemis y 2012, 22, 73-79
3. F. Wiebe ge , C. Neube , C. K. Obe , and H.-W Schmid
“Tailo ed S a Block Copolyme A chi ec u e o High Pe o mance Chemically
Ampli ied Resis s“
Ad anced Ma e ials 2012, 24, 5939-5944.
Addi ional publica ions
1. F. Schache , T. Rudolph, F. Wiebe ge , M. Ulb ich , and A. H. E. Mülle
“Double S imuli-Responsi e Ul a il a ion Memb anes om Polys y ene-block-
poly(N,N-dime hylaminoe hyl me hac yla e) Diblock Copolyme s”
ACS Applied Ma e ials & In e aces 2009, 1(7), 1492-1503
2. F. Wiebe ge , D. C. Fo man, M. Ska ba, C. Schneide , C. K. Obe , M. Ballau ,
A. H. E. Mülle , and H.-W. Schmid
“Repo on S a Resis s in Solu ion and on Su aces“
Semiconduc o Resea ch Co po a ion Deli e able Repo 2009, P051494
