FunGren

12

Prof. Dr. Brig

Tel. 0351 4658

voit@ipfdd.de

Prof. Dr. Manf

Tel. 0351 4658

stamm@ipfdd

ktionnzflä

itte Voit

8-590

fred Stamm

8-225

d.de

nale nächen

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Synthesis omobility pol Anton Kiriy,Doris Pospi -conjugateare an impovarious optofabrication olight-emittinhigh molecuto achieve smorphologiFor example10 cm2/V−1 s−

molecular wCP whereasmolecular wCPs are usupolymerizatcatalyzed Stso-called AAmolecular wthe preparawith these tbalance of Aloading of etimes and hformation odrawback in Chain-growpolycondenspreparationwith controldispersity awe have foupolycondensfluorenic mligated by brapidly undecatalyst loaand leads tomolecular w1) [2]. Such for the prepmaterials frUnpreceden(above 7000of up to 280highest valufor transitio

ktionnzflä

of semiconduclymers

Roman Tkacech, Brigitte V

ed (semiconduortant class ofoelectronic apof efficient phng diodes andular weight posuperior chargcal, and film-e, a remarkab−1 was recentlweight diketops the performaweight polymeually synthesiztions, most ofttille polycondA/BB approacweight polymeation of high mechniques req

A- and B-funcxpensive cataigh reaction tf toxic byprod

nherent to Stil

wth catalyst-trsation proved

n of CPs and blled moleculand specific en

und that Negissation of a Znonomer catalulky electron-er mild conditdings (down to high molecuweights of up tlow catalyst lo

paration of eleree from metantedly high tur00) and turnov s-1 were obse

ues reported son-metal cata

nale nächen

cting, high car

hov, Tim ErdmVoit, Manfred

ucting) polymef materials enpplications. Footovoltaic dev

d thin-film traolymers are dge transport, forming prope

ble hole mobily reported for

pyrrolopyrroleance of lower ers was reduczed by step-grten by using Pensations usi

ch. While achiers is typically

molecular weigquires judiciotional groups

alysts, long reemperatures

ducts is anothelle polyconden

ansfer an alternativlock copolymer weight, low

nd functions. Rshi chain-grow–organic AB-tyzed by Pd co-rich PtBu3 octions at extremo ppm concen

ular weight PFto 120 kg/mol oadings are at

ectronic-gradeal impurities. rnover numbe

ver frequencieerved, which aso far in the lilyzed cross-c

nanon und

rrier

mann, Stamm

ers (CPs) nabling or the vices, nsistors, esirable

erties. lity up to r a high e-based

ced. rowth Pd-ng the eving low y simple, ght CPs us , high action . The er nsation.

e tool for ers [1]

Recently, wth type mplexes curs mely low ntrations) F2/6 with (Figure ttractive e

ers (TON) es (TOF) re the terature oupling

pcotTwwplitmtp

Tpb

strukd Poly

polycondensacorrespondingof functional Atwo orders of TOFs. Similar well as AA+BBwas determinpolymerizatiolifetime are duintramoleculatransfer procemechanism. Tthe design of tpolycondensa

The Pd/PtBu3 cpolymerize nabased anion-r

R R

Br

R R

ClZn

+

R R

Br

kturiymer

tions. In contrg step-growthAA/BB-type mmagnitude lotrends were

B-Suzuki polyed in this worn rate and lonue to a faster ar (vs. intermoess underlyingThese findingsthe next genetion catalysts

catalyst was aaphthalene diiradical monom

Br

ZnCl

1000 ppm of P

23°C, 32

TON = 2

TOF < 1.6

AA/BB-ty

ZnCl10 ppm of Pd

23°C, 1 h

TON = 1

TOF up t

AB-typ

ierte rsyst

rast, the h polycondens

monomers prower TONs andobserved in A

ycondensationrk, the much hnger catalyst and safer

olecular) catag the chain-grs are importanration of

s.

also applied toimide-dithiophmers (Figure 2

R

Pd(PtBu3)

h

600

6 s-1

ype

R

d(PtBu3)

h

00 000

to 280s-1

pe

eme

sation vided d

AB- as s. As it

higher

lyst-rowth nt for

o hene 2).

s

t

s

f

a

t

a

Rn

Rn

Keywords

semiconductive

organic electron

printed devices

high electron m

transistors

Fig. 1:

Chain-growth (to

step-growth

polycondensation

fluorene-based m

in the presence o

catalyst: much hi

efficiency of the f

approach is due t

intramolecular c

transfer mechan

inherent to the C

growth polycond

Fig. 2:

Chain-growth pre

of high molecula

n-type PNDIT2 (to

exhibits electron

up to 1 cm2/V s (o

characteristics o

representative P

based OFET fabri

glass with Au ele

are shown in the

plot).

13

polymers

nics

mobility

op) versus

ns of

monomers

of Pd/PtBu3

igher

former

to the

atalyst-

ism

hain-

ensation.

eparation

r weight

op) which

n mobilities

output

f the

PNDIT2-

icated on

ectrodes

bottom

FunGren

14

Fig. 3:

(a) Representa

image of high m

weight PNDIT2

the ability of P

form large are

which favor eff

charge transpo

PNDIT2 deposi

diluted solutio

resolved as ind

chains and few

aggregates du

extremely high

weight (and lar

length).

ktionnzflä

ative AFM

molecular

2 highlights

NDIT2 to

ea networks

ficient

ort; (b)

ited from

n can be

dividual

w-molecule

e to its

h molecular

rge contour

nale nächen

With this mesemiconductmolecular w(Figure 3) catemperatureconcentratio

In general, mpolymers caconditions (ereaction timetechnologicamild conditiobased monomused Stille prevealed thaunusual comstep-growth thus-prepareelectron mobmeasured in(FETs) on glsource/draindemonstrateremarkably eanion-radicahomopolyme Very recentlyand Brinkmawith narrow broadly distrPreliminary growth-derivcontrol. An cmobility, thinweight distriscale alignmwas achievedsubsequent highly orientanisotropic iwith top-gate

nanon und

ethod, the corrting polymer,

weight larger tn be obtained

e and at ratherons [3].

molecular wein be regulate

e.g., catalyst ce). This polymal advantages ons and does nmers (usual dolycondensatt the polymer

mbination of chmechanisms

ed PNDIT2 exbilities of up t top-gate fieldass substrate

n electrodes. Ped that the Pd/efficient in po

al monomers iers [4] and blo

y, the groups ann studied thdispersity in c

ributed commtests demonsved CPs allowcorrelation ben-film morphobution was es

ment and imprd by high tempost-rubbing ed morphologn-plane charge transistors p

strukd Poly

responding PNDIT2 with han 1000 kg/m

d quickly at ror low catalyst

ghts of the red by reaction

concentration merization has

as it proceednot involve tox

drawback of wion). Detailed

rization involvehain-growth a. It was foundhibits field-efo ∼1 cm2/V s ad-effect transes with Au Preliminary st/PtBu3 catalyslymerizing othinto correspoock copolymer

of Ludwigs, Nhe PNDIT2 sacomparison toercial N2200

strated that thwed better mor

tween chargeology and molstablished. Laoved moleculperature rubbannealing. Th

gies allowed ge transport pparallel and

kturiymer

a mol om

sulting

and several s fast at xic tin-

widely studies

es an and that fect as sistors

tudies st is her nding rs [5].

Neher mples o [6]. e chain-rphology

e carrier lecular rge-ar order

bing and hese

probed

pMtohc FpoloacomfaddinFspliecPtrspteOthinBwnwe(PPfupapli>tyatheethsc

ierte rsyst

erpendicular Mobility up to 0o the polymerigher than thahain.

Furthermore, aolymeric devin semiconducow-cost technrea arrays, foircuits for actf such FETs o

manufacturingabrication usieposition andifferent (mass

nkjet, gravureFurthermore, cemiconductinlastic substraghtweight, strlectronic deviollaboration w

Print Technoloransistors witource/drain elastic foils by echnologies in

One of the moshis work is thenstead of trad

Because PEDOwork function t

-type PNDIT2work, surface t

lectrodes withPEIE) which re

PEDOT:PSS waunction from -rovided reducchieved high eolymeric PNDnear and satu

>0.1 cm2/V s. Hype, plastic OFmbient laborahose achievedxpensive techlectrodes andhermal anneauch, this is a sommercializa

eme

to the polyme0.1 cm2/V s war chain, which at perpendicu

a step forwardces was achiecting polymernology for appr example, baive matrix disriginate from

g costs thanksng common s patterning tes) printing tec, flexo- and ofcircuits based

ng polymers aates so that coructurally robces can be m

with the Instituogy Chemnitz (h polymeric P

electrodes wermeans of ma

n a roll-to-rolst innovative ae use of polymitionally used

OT:PSS possesto efficiently i

2 semiconducttreatment of th ethoxylated educes the woas performed -5.4 down to -ction of threshelectron mob

DIT2 OFETs acuration FET mHence, the perFET devices patory conditiod by more sophnologies, utild time/energy aling and lithosubstantial st

ation of fully p

er chain directas observed pa

is up to 10 timlar to the poly

d to fully printeved. FETs bars are potentialications in la

ackplane/drivesplays. Advant the potential

s to device olution-based

echniques succhnologies likeffset printing.

d on re compatible

ompact, bust and flexibanufactured. ute of Media a(TU Chemnitz

PEDOT:PSS re fabricated ss printing l printing pres

achievements meric electrod

gold electrodsses a too hignject electrontor used in thithe printed polyethylenim

ork function oto lower the w

-4. 5 eV. This hold voltage aility. Thus, ful

chieved averagmobilities of rformance of nrepared undens approachehisticated andizing gold consuming graphic stepsep toward lastic transist

tion. arallel

mes ymer

ted sed

ally rge-er tages

lower

d ch as e

e with

ble In a

and ),

on

ss [7]. of

des des. h

ns into s

mine f work

nd lly ge

n-er es d

s. As

tors.

Funktionale nanostrukturierte Grenzflächen und Polymersysteme

15

Acknowledgement: We gratefully acknowledge support from the German Excellence Initiative in the Cluster of Excellence EXC 1056 “Center for Advancing Electronics Dresden" (cfAED) and DFG (SPP 1355 “Elementary Processes of Organic Photovoltaics”, grant KI-1094/4). Co-operation: Prof. A. Facchetti, Polyera Corporation, USA. Prof. A. C. Hübler, Dr. G. C. Schmidt, Institute for Print and Media Technology, Chemnitz University of Technology, Chemnitz, Germany Prof. Dieter Neher, University Potsdam. Prof. Sabine Ludwigs, University Stuttgart. [1] T. Erdmann, R. Tkachov, A. Kiriy, J. Back,

S. Ludwigs, B. Voit, Polym. Chem. 2014, 5, 5383-5390.

[2] Tkachov, R.; Senkovskyy, V.; Beryozkina, T.; Boyko, K.; Bakulev, V.; Lederer, A.; Sahre, K.; Voit, B.; Kiriy, A. Angew. Chem. Int. Ed. 2014, 53, 2402 – 2407.

[3] Tkachov, R.; Karpov, Y.; Senkovskyy, V.; Raguzin, I.; Zessin, J.; Lederer, A.; Stamm, M.; Voit, B.; Beryozkina, T.; Bakulev, V.; Zhao, W.; Facchetti, A.; Kiriy, A. Macromolecules 2014, 47, 3845 - 3851.

[4] Liu, W.; Tkachov, R.; Komber, H.; Senkovskyy, V.; Schubert, M.; Neher, D.; Zhao, W.; Facchetti, A.; Kiriy, A. Polym. Chem. 2014, 5, 3404-3411.

[5] Tkachov, R.; Komber, H.; Rauch, S.; Lederer, A.; Oertel, U.; Häußler, L.;, Voit, B.; Kiriy, A. A Macromolecules 2014, 47, 4994 – 5001.

[6] Tremel, K.; Fischer, F.S.U.; Kayunkid, N.; Di Pietro, R.; Tkachov, R.; Kiriy, A.; Neher, D.; Ludwigs, S.; Brinkmann, M., Adv. Energy Mater. 2014, 4, ID 1301659.

[7] Schmidt, G. C.; Höft, D.; Haase, K.; Hübler, A. C.; Karpov, E.; Tkachov, R.; Stamm, M.; Kiriy, A.; Haidu, F.; Zahn, D.; Yane, H.; Facchetti, A. J. Mater. Chem. C, 2014, 2, 5149 – 5154.

Development of new polymers as dielectrics in organic thin-film transistors Andreas Berndt, Doris Pospiech, Robert Pötzsch, Qiang Wei, Brigitte Voit Zur Weiterentwicklung und Optimierung von organischen Feldeffekttransistoren (OFETs) - grundlegende Bauelementen für die organi-sche Elektronik - wird am IPF Dresden ein ganzheitlicher polymerchemischer Ansatz verfolgt. Neben halbleitenden (konjugierten) Polymeren tragen vor allem auch die Dielektrika zur Effizienz von Transistoren bei. Im Rahmen des Center for Advancing Electro-nics Dresden (cfaed) werden hierzu am IPF zwei verschiedene Strategien bearbeitet, zum einen basierend auf Polyphenylenen, zum anderen auf Basis von Methacrylat-Copolymeren. Hochverzweigte Polyphenylene für den Einsatz als Gate-Dielektrika [1] weisen gute Film-bildungs- sowie dielektrische Eigenschaften auf. Vernetzte Polymerfilme zeigen Durch-bruchfeldstärken von bis zu 5.8 MV/cm sowie konstante Kapazitäten über einen breiten Frequenz- und Spannungsbereich. Die Charakteristika von Transistoren, basierend auf vernetzbaren Polyphenylenen als Dielektrikum, Pentacen als Halbleiter und Goldelektroden sind mit Literaturwerten organischer Feldeffekttransistoren vergleich-bar. Die Ladungsträgermobilitäten liegen im Bereich von ca. 0.09 bis 0.26 cm²/Vs, Schwell-spannungen im Bereich von -12 bis -14 V und Ion/Ioff-Verhältnisse im Bereich von 230 bis 420. Aktuell werden diese sowie strukturell vergleichbare hochverzweigte Polymere (Abb. 1, links) für optoelektronische Anwendungen entwickelt [2,3]. Dabei liegt der Fokus auf Transparenz und einem hohen Brechungsindex. Erste Erfolge zeigen thermisch stabile Polymere, welche sich zu homogenen transparenten dünnen Filmen verarbeiten lassen und Brechungsindizes von bis zu 1,7839 aufweisen. Für dielektrische Anwendungszwecke werden derzeit Methacrylat-Copolymere mit maßge-schneiderten Eigenschaften synthetisiert und charakterisiert (Abb. 1, rechts) [4].

Keywords

dielectrics

polyphenylene

methacrylate copolymers

liquid crystalline side

chains

breakdown field strength

relative permittivity

refractive index

FunGren

16

Abb. 1:

Chemische Str

verzweigter Po

OLED-Anwend

(links) sowie ch

Struktur der al

elektrika entw

Methacrylat-Co

mit verschiede

netzungsstrate

und flüssigkris

Comonomeren

(rechts).

Abb. 2:

Durchbruchfel

(unter Verwen

gedruckter

Silberelektrod

(grün), UV-ver

PMMA (blau), t

vernetztes PM

PMMA mit 1,6-

Bis(trichlorsily

externer Verne

(orange).

ktionnzflä

ruktur hoch-

olymere für

ungen

hemische

ls Di-

wickelten

opolymere

enen Ver-

egien (blau)

stallinen

n (rotbraun)

ldstärke

dung

den): PMMA

netztes

thermisch

MA (rot),

yl)hexan als

etzer

nale nächen

Da zur HerstLösungsverfPrinting zumVernetzungshohe DurchbAuch mit diebereits sehr realisiert weunvernetztemsowohl das Dverwendetenabgeschiede

Eine weiterewickelten porelative Permunter anderezum Einsatz tisiert und obHerstellung Filme ist aufPartikel mit zu achten, umeinen entschfläche zwisch

nanon und

tellung der Deahren wie Spi

m Einsatz komsmethoden erfbruchfeldstärksem Polymergute Werte vo

erden, im Vergm PMMA mit 0Dielektrikum an Elektroden aen wurden (Ab

Anforderungolymeren Dielemittivitäten (hem high-k BaTkommen. Die

berflächenmodünner Polym

f eine homogemöglichst germ glatte Filmheidenden Einhen Halbleite

strukd Poly

evices insbesoincoating und men, sind effiforderlich, umke zu gewährlrsystem konnton bis zu 4.0 Mgleich zu 0.3 MV/cm, woals auch die aus Lösung bb. 2).

an die neu enektrika sind high-k). HierzuTiO3-Nanoparese wurden syodifiziert. Bei dmer-Nanocomene Verteilungringer Agglome zu erhalten,fluss auf die Gr und Dielektr

kturiymer

ondere Inkjet

iziente m eine leisten. ten MV/cm

obei

nt-hohe u sollen tikel

ynthe-der

mposit-g der meration , da dies Grenz-rikum

hCgoSSsdZdDemmHre

FDDfo

KPKMDPKfüU

[1

[2

[3

[4

ierte rsyst

at. Des Weiteomonomere iriert, um diesptimieren. Dutrukturen in dtruktur, Morpchaften des Hie Effizienz deukünftig solleerten Kompon

Dielektrikum einander abges

mit der Arbeitsmit der EntwicHalbleiterpolymealisiert werd

Förderer: Deutsche ForsDeutsche Exzeor Advancing

KooperationenProf. Dr. W.-J. Kumar, InstituMikrosystemteDresden, DresProf. Dr. K. LeoKasemann, M. ür Angewandt

Universität Dre

1] R. PötzschUniversitäDeutschla

2] R. PötzschHawker, B5, 2911-292

3] Q. Wei, R. Pospiech, 5607.

4] A. Berndt,Häußler, BPlötner, AAppl. Mate10.1021/am

eme

ren werden flin die Polymese Grenzflächeurch Ausbilduder dielektriscphologie und fHalbleiters verer OFETs gesten so OFETs mnenten wie Ha

entwickelt werstimmt sind. Isgruppe von Dklung und Opmere beschäf

den.

schungsgesellellenzinitiativeElectronics D

n: Fischer, Dr. Mt für Halbleite

echnik, Technden. o, Prof. Dr. S. Sawatski, A. A

te Photophysikesden, Dresde

h; Dissertationät Dresden, Drnd, 2014.

h, B. Stahl, H. B. Voit; Polyme21. Pötzsch, H. KB. Voit; Polym

D. Pospiech, B. Voit, M. Al-H

A. Kumar, W.-Jer. Interfaces

m5069479.

lüssigkristallirstruktur intee weiter zu ng geordnetechen Schicht sfolglich die Eigrbessert und steigert werdenmit maßgeschalbleiter und rden, die auf-In Zusammen

Dr. Kiriy, die stimierung neu

ftigt, soll diese

lschaft (DFG), e EXC 1056 „Ceresden“ (cfae

M. Plötner, A. er- und ische Univers

Mannsfeld, DA. Günther, Ink , Technischeen.

n, Technischeresden,

Komber, C. Jer Chemistry

Komber, D. mer 2014, 55, 5

D. JehnichenHussein, M. J. Fischer; AC2014, DOI:

ne e-

r sollen gen-somit n. nei-

narbeit ich uer es Ziel

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. 2014,

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FunGren

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rich, Mikhail Mhhorn, Brigitte

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ronic packaginolyimide pre-c

m solution (1). Sby photolithogr film is converocess (3). In ring the proce

nale nächen

netics of es in solid stations

Malanin, Klaue Voit

of microelecthe field of 3D-d Wafer-Level

with a complexs and substratin this technospecific temp

sirable to redupolymer pass

. Polyimides (nt classes of hn this area of ut require curnd higher, whrature ranges pplications. Reolyimide formbine a low-h the excellen Using imidizarature for thed to less than es it is desirabization reactioocess in solid tive in this worn kinetics in-santitatively. Thking on the kilt a cure modbe the imidiza

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r was studied process used

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– (3) are

Tttcmaddcarr(c

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strukd Poly

The imidizatiotemperature rtransmission coated films omental data wand conversiodiffusion moddetail in [1-3]. change of the and degree ofrate constant.results for an (exposure dosconditions).

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kturiymer

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Keywords

imidization

polyimide

kinetics

Fig. 1:

Photosensitive es

polyimide chemis

Fig. 2:

Regression resul

exposed PI precu

(exposure dose

200mJ/cm2)

17

ster-type

stry

lts for

ursor layer

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Keywords

microswimme

hydrogel

actuator

Fig. 3:

Eyring plot of k

dependence on

energy

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kchem in

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photo-crosslthe reacting PI pre-cursoimidization rregion (kchem) This is causequantified usactivated comwhich can beentropy and in the chemi

The main outhigh imide cominimum recontrolled rerequires a ceresults showcan be achie230°C for undegree, caushigh a furthenecessary to>99% polyimoverall decrecompensated Sponsor: Bundesminis Cooperation:Fraunhofer IIntegration D [1] F. Windr

(2013) [2] F. Windr

Voit, K. D1692, do

[3] J. D. RusCompos

nanon und

linking the mopoly(amic est

or is further rerate in the che

compared to ed by an entrosing Eyring’s emplex loses de detected in afinally in a lowcally-controll

tcome of the contents at lowmaining prop

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w that >99% deved with a curexposed films

sed by high exer increase in o ensure enoumide. At lower ease of reactiod by an increa

sterium für Bi

: ZM, Center „A

Dresden – ASS

rich, Master T

rich, M. MalanD. Lang, MRS i:10.1557/opl.2ssel, J. L. Kar

sites, 18, pp. 64

strukd Poly

olecular mobiter) groups wieduced and limemically-contr

non-exposedopic effect andequation. The egrees of freea reduced actwer imidizatioled region (see

cure model isw process timeortion of chem

s necessary, wrature. The FTegree of imidiring process fs. If the crosslxposure doses

cure temperagh energy to yexposure dos

on rate may base in reaction

ildung und Fo

All Silicon SysSID“

Thesis TU Dres

nin, K. J. EichhProceedings,

2014.520, (2014rdos, Polymer4-78, (1997)

kturiymer

lity of thin the

mits the rolled films.

d was

edom, ivation

on rate e Fig. 3)

that for es a mically-which T-IR ization for 3h at linking s, is too ature is yield ses the be n time.

orschung

stem

sden

horn, B. , Vol. 4) r

Sre

G

BoflpmppsfotocpbasmgfumababHthmfiisbte(Pdsacthstrapmasnm

ierte rsyst

Stimuli-responeconfigurable

Georgi Stoyche

Biological micrr sperm cellslexible or movropulsion of t

movement of brovided by oscowered by enome of them corces are geno respond to ghemical, pH, lropelled micry multiple merchitectures spherical parti

more. Those areat possibilitundamental m

micro- and nannd environmeiological swimre commonly ased on inorg

Here, we presehermo-respon

micro-swimmelms consistin

sopropylacrylaelow 32°C andemperature, hPCL) and thin ecompositionelf-propelled nd unfold in ahanges in temhey are immetart and stop adius of curvaroperty, adde

makes this typttractive for such as the effucleation and

microjets.

eme

nsive microjee shape

ev, Leonid Ion

ro-swimmers are generally

ving parts, whhe micro-org

biological swimcillation of a fergy rich chemcontain smallerated. In add

gradients of telight and othero-nanomotorethods leadingsuch as, nanocles, helical sutonomous mties for resear

mechanisms onoscale to potental applicatimmers, artific

formed by rigganic materialent the fabricansive polymerers are formeg of thermoreamide) (PNIPAd shrinks abovhydrophobic player of Pt, w of hydrogen microjets can

an accurate mmperature of t

rsed. This effemultiple time

ature of the md to its semi-e of microjet tudying funda

fect of curvatud its correlatio

ets with

ov

s such as bacty composed oich thrust theanism. The mmers is ofteflexible tail mical reactionl nozzles wherdition, they areemperature, ers. Artificial srs are engineeg to a rich varwires, microt

structures, anmicromotors o

rch from of motion at thtential bio-meions. In contraial micromoto

gid structuresls. ation of flexibr microjets. Oued by self-foldesponsive polyAM), which swve this

polycaprolactohich catalyzesperoxide. Then reversibly fo

manner by apphe solution wect allows the

es by controllinicrotube. Thistransparencyespecially

amental questure on the bubon with the sp

eria f

e

en

ns and re jet e able

self-ered iety of ubes,

nd ffer

he edical ast to ors s

le ur ing y(N-

wells

one s

ese old lying

where em to ng the s ,

tions bble eed of

FunGren

Fig. 1.

Scheme of stim

reconfigurable

of movement o

Co-operatioProf. O. SchIFW Dresde [1] Magdan

SancheInt. Ed.

[2] ZakharG.; Stam(2010), 2

ktionnzflä

muli-responsive m

e shape (left) and

on temperature (r

on: hmidt, Dr. S. Sen

nz, V.; Stoycheez, S.; Schmid 126 (2014), 27

rchenko, S.; Pmm, M.; Ionov2633-2636.

nale nächen

microjets with

dependence of th

right).

Sanchez, V. Ma

ey, G.; Ionov, Lt, O. Angew. C

711. uretskiy, S.; Sv, L. Soft Matt

nanon und

heir speed

agdanz,

L.; Chem.

Stoychev, er 12

Ha

A

SplmpaobcnsVtoJtsmmptficTsapwaptm

W2fdc

strukd Poly

Hairy Janus pand assembly

Alla Synytska,

Self-assemblyparticularly falocated at themacro-worldsparticles one assembly on tof macroscopbuilding blockcompositions,now available superstructurVery interestintheoretical poof asymmetricJanus particlethe two-facedsignificant attmultifunctionamolecular amphospholipidstheir unique afound their apincluding stabcatalysis, drugTheir controllswitchable prassembly towparticular chawork we synthamphiphilic hpolymers are the core) and mechanisms (

We found that2 left) and PDform chain-likdispersions, wcharacter of t

kturiymer

particles: Mary

, Alina Kirillov

y of colloidal pascinating top border betwes. With the hecan transfer rthe nanoscaleic structures.

ks of different , patterns andfor the creati

res. ng from exper

oints of view isc colloidal pares. Janus part Roman god) ention due to ality and rese

mphiphiles sucs, and block coanisotropy, Japplications in dbilization of emg delivery, dised synthesis woperties and c

wards new matallenging taskhesized differeairy Janus pagrafted onto thave studied (Fig. 2).

t amphiphilic MAEMA/PLMAke aggregateswhich is becauhe particles.

ierte rsyst

rriage of oppo

va, Georgi Sto

particles is a ic because theen nano- andlp of colloidalrules of self-e level for the A variety of nshapes,

d functionalitieion of new

rimental and s the self-asserticles such asticles (named have attractetheir mblance to th

ch as surfactaopolymers. Dunus particles different fieldmulsions, chesplay technolowith even control over terials is a

k. Therefore inent kinds of rticles (Fig. 1, the opposite stheir self-ass

PEG/PLMA-JPA-JP (Fig. 2 ris in water use of the Jan

eme

osites

ychev

ey are d

design new

es is

embly s after d

he nts, ue to have s, mical

ogy.

n this

two sides of sembly

P (Fig. ight)

us

J

s

s

Keywords

Janus particles

self-assembly

stimuli-respons

multifunctional

Fig. 1.:

Representative S

PDMAEMA side –

PLMA side – oran

cryo-TEM (right,

is hairy side) ima

PDMAEMA/PLMA

particles

19

sive

SEM (left,

– green,

nge) and

PDMAEMA

ages of

A Janus

FunGren

20

Fig. 2.:

Proposed struc

chain-like stru

formed by PEG

(left) and

PDMAEMA/PLM

(right) Janus p

water: Fluores

microscopy im

representative

Scale bars: 5 μ

ktionnzflä

cture of the

uctures

G/PLMA-JP

MA-JP

articles in DI

scence

ages and

e cartoons.

μm

nale nächen

In fact, PEG/JP Janus parwhich is swoside. As resueach other bin order to mbetween PLMformation of character of however, on PEG/PLMA-J(Fig. 2 left).

PDMAEMA/Pstructures (Fhighly swolleto come too PLMA sides. contact betwthat leads toleft). In the cmore compleobserved dueswollen in wparticles tensides; howevto have morelarge size of of ‘stickier’ P(Fig. 2 right).of the PDMAincreasing thlinear structmechanism wGranick et aleffects to constructures frhowever, witThese studiegeneral knowof building bfunctional mby which theobtained kno

nanon und

/PLMA-JP andrticle have on

ollen in water,ult these partiy their hydrop

minimize unfavMA and waterlinear chain-these agglomthe kind of Ja

JP form thin o

PLMA-JP formFig. 2 right). Wen and doesn’close to each As result the

ween hydropho formation of

case of PDMAEex aggregatioe to the fact thater and is pod to touch by

ver, there are e neighboring the polymer p

PLMA larger s. When the eleEMA sides is

he ionic strengures are formwas observedl., where they nstruct linearrom amphiphithout hairy moes are expectewledge about locks for the faterials as wey interact with

owledge will o

strukd Poly

d PDMAEMA/Pe hydrophilic and one hydrcles tend to s

phobic sides invorable contac. This leads tolike structure

merates depenanus particlesone-particle c

m linear 3D heWe believe tha

t allow the paother with the area of possi

obic sides is rlinear chains

EMA/PLMA-Jn behavior is hat PDMAEMAositively chargtheir hydrophpossibilities fparticles due

patches. In thstructures areectrostatic rephindered by gth, even larg

med. A similar d in the work o

used the samr 3D helical lic particles,

orphologies. ed to broaden the design prfabrication of ell as the prinh each other.

open new hori

kturiymer

PLMA-side,

rophobic tick to n water cts o es. The nds, s. hains

elical t PEG is

articles eir ible educed (Fig. 2

P a

A is ged. The hobic for them e to the e case

e formed pulsion

er

of me

the rinciples

ciples The zons in

dwfl

SD(P

CP

[1

[2

[3

ierte rsyst

esign of advawith an essentlexibility to res

ponsor: Deutsche ForsProject SY 125

o-operation: Prof. L. Isa, ET

1] A. KirillovaSynytska, Colloidal PArchitectuLangmuir (among thin Novemb

2] A. Synytskand ContaJanus Par79, 656-66

3] A. SynytskJanus parSystems C922-930

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nced reconfigial feature: frshape.

schungsgemei5/4-1)

TH Zürich

a, G. StoychevSelf-Assembl

Particles with ures: Mixed ve

2014, 30 (43), e most read p

ber 2014) ka, A. Kirillovact-Angle Mea

rticles CHEMP61 ka, L. Ionov, Stticles, Particl

Characterizati

urable matereedom and

inschaft DFG

v, L. Ionov andly Behavior ofDifferent

ersus Janus. pp 12765–127

papers in Lang

a, L. Isa, Synthsurements of

PLUSCHEM 20

timuli-Respone & Particle on 2013, 30 (11

rials

d A. f Hairy

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Helical packcylindrical dassembled Andriy HoreStamm Theoretical self-assembparticles maconfined in structures mzigzag partiwide spectrachiral partsuperstructobserved foin hollow cypatterned sare of particnanoparticlwhose uniquare superimtheir packinAn applicatipatterning oplacement osize, shape matrix has amany reseaof diverse mnanostructuparticle locaestablishedmost of the the structurthemselvesparticle arraself-assembTheoretical NP/BCP sysspherical naattraction toself-assembgenerate a vmorphologiassemblies unstable anrange, thus In the presefirst time thnanoparticlassembled

ktionnzflä

king of nanop domains of a block copolym

echyy, Petr Fo

models predibled superstray result whea 1D space [1]may include scle arrangem

rum of more cicle assembli

tures has beer hard spheri

ylindrical chanubstrates. Thcular interest es (NP), like pue, often size-

mposed with thng geometry. ion of block coof nanomateriof nanoparticland compositattracted signrch groups. T

methods to geures and contration within th and widely deliterature rep

res formed by, revealing in angements wbled BCP matmodeling and

stems predict anoparticles wo the one of thble within thevariety of ordees. However, were predicte

nd occur in vernever observ

ent work we dhat the polymees (AgNP) concylindrical do

nale nächen

particles confi self- mer structure

rmanek, Man

ict that a varieuctures of sphn particles ar. Such super-imple chain-l

ments, as well omplex chiraes. Formationn experimentacal particles c

nnels or in groese superstruwhen formed

plasmonics or-dependent phose originati

opolymers (BCials, such as oles (NP) of vartion into polymnificant interesThus, a large nnerate NP/BCrol over the nahe BCP matrixescribed. Howports do not dy the nanopartmost cases raithin host dom

trix. d simulations that uniform

with preferenthe blocks can host domain ered structurethese nanopaed as metastary narrow parved before [2].emonstrate fo

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nanon und

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e

fred

ety of herical

re -ike or as a l and n of such ally confined ooves on uctures d by the r QDs, roperties ng from

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main of

of

tial also and es and articles able or ameter or the er

self-ock

cwF

Mbnb

TdreNActntTtncs

strukd Poly

copolymer sewith densely nFig. 1 [3].

Moreover, thebe isolated in nanofibers (Nbeing preserv

The exact natudimensional nresolved usingelectron tomoNF loaded witAgNP packingcentral chain the NF surrounanoparticlestwisted 36° wiThis twist of ato a spiral or hnanoparticleschain is surrosuch chain is

kturiymer

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ved inside the

ure of the ordnanoparticle sg TEM imaginography technth AgNP. The 3g inside the naof AgNPs alon

unded by a sta, whereby adjith respect to

adjacent partichelical arrang, where the ceunded by five highlighted in

ierte rsyst

nto a superstrpacking as sho

cles assemblidual polymer

P close packinnanofiber (Fig

ered three-structure was g combined w

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n red in Fig. 3)

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Fig. 3). es rise

article s (one .

s

T

a

f

a

T

A

f

Keywords

block copolyme

helical packing;

nanoobjects;

nanoparticles;

self-assembly

Fig. 1:

TEM images of se

assembled morp

formed in an AgN

P4VP sample loa

10 wt.% AgNPs: (

along the plane o

cylinder axis, (b)

normal to the pla

PS cylinder axis.

bars of the inset

correspond to 50

Fig. 2:

TEM image of a s

isolated from the

AgNP/PS-b-P4VP

composite with c

packed ordered s

formed by AgNP.

21

rs;

;

elf-

phologies

NP/PS-b-

aded with

a) view

of the PS

view

ane of the

Scale

images

0 nm.

single NF

e

P

losely

structure

.

FunGren

22

Keywords

fullerenes

dyad

computer sim

self-assembly

hydrophobic i

electrostatic i

Fig. 3.

3D reconstruct

by the tomogra

packing inside

formed by the

block copolym

volume render

the entire stru

which the reco

density is color

according to th

where the AgN

red (high dens

BCP appears b

density). From

tomogram som

AgNPs are seg

visualize their

arrangement.

show sections

center of the 3

the three direc

space.

ktionnzflä

mulation

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interaction

tion obtained

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er. The 3D

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cture, in

onstructed

r coded

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NPs appear

ity) and the

lue (low

m the

me of the

gmented to

spiral

The slices

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nale nächen

Obtained resfor further fudirection anddiscovery of in NP/BCP synanoparticleinteresting inproperties, litransfer, andapplication-omaterials. Financial supForschungsg324/51-1 Co-operationProf. B. NandDr. D. Wolf, TDresden, Ge [1] Chan, H

Mughal,[2] Huh, J.;

Macrom[3] Sanwari

C.-Y.; ChM.; SrivaChem. In

[4] Pal, J.; SNandanChen, H25102-25

nanon und

sults provide uundamental red open up the novel hierarcystems. More

e arrangemenn terms of theike optical bed provide new oriented resea

pport providedgemeinschaft

n: dan, IIT Delhi,Triebenberg Lrmany

. K.; Weaire, D A.: Phys. RevGinzburg, V. V

molecules 2000ia, S.; Horechyhen, H.-L.; Foastava, R.; Nant. Ed. 2014, 5Sanwaria, S.; , B.; Horechyy. L.: J. Mater. 5107.

strukd Poly

unique possibesearch in thinew ways forhical superstr

eover, such cots are very

eir structure-rhavior or eneropportunities

arch of such

d by Deutsche, Project No. S

, India Laboratory, TU

D.; Hutzler, S.v. E 2012, 85.V.; Balazs, A. 0, 33, 8085-80yy, A.; Wolf, Drmanek, P.; S

andan, B.: Ang53, 9090-9093.Srivastava, R.y, A.; Stamm, Chem. 2012, 2

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60-dyad aggretructures in a

Olga Guskova, Uwe Sommer

he study of agullerenes (Figroblem deser

nterest.

ig. 1:

he objects of the

61-butyric acid me

roup (b), charged

ulleropyrrolidines

yrrolidin-1-ylethy

methyl-pyrrolidin-

hloride, iodide or

ot shown). Grey,

arbon, oxygen, hy

espectively.

he C60-solventolubility is a papid advancem

material scienullerenes are romising comabrication of polloidal suspeelds.

But the key to making miniatomponents. Ittructures to bn polar solvenullerenes are ifferent in che

nto contact wiemonstrate tholloidal nm-smnifarious shesicles, needlbers. The hyd

earing carbon

eme

egates: Self-o aqueous solut

Srinivasa Rao

ggregate prop.1 a) in a liquid

rving increasin

study: a bare C60

ethyl ester (PCBM

d fulleropyrrolidin

s the “attached”

ylammonium, mo

-1-yl)-ethylammo

r perchlorate anio

red, white, blue c

ydrogen and nitro

t interactions primary factorment of fullerce applicationconsidered as

mponents for bphotonic mateensions for va

nanotechnoloure structuret may be forci

build themselvnts, including w

virtually insoemical sense th each otherheir phobia ofized clusters

hapes and geoles, rods, tubudrophilic deco cage via atta

organized tions

o Varanasi, Je

perties of pristd environmenng theoretical

fullerene (a), phe

M) with polar –C(O

ne derivatives (c,

organic moieties

onocation (b), 2-(1

onium, dication (d

ons are counterio

cylinders represe

ogen atoms/bond

and fullerener contributing ene chemistry

ns, where s extremely bottom-up erials and as rious medical

ogy is not only s out of indiving those ves. For examwater, the luble. When ssubstances co

r, buckyballs f water formin(“nano-C60” [1

ometries – sphules, disks, staration of a waching a wide r

ens-

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are 2-

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of well-hydrroute to proaggregativesequence, stwo levers, wunusual physimultaneou(Fig.1 b-d) ainto molecuSince the quintermolecuagglomeratto consider for the dyadglass” of thedynamic simIn our case contain 32 fseveral thou

Fig. 2:

An initial point

pyrrolidine cat

molecules ran

Grey, red, whit

oxygen, hydrog

respectively. T

[4].

In focus areshape of theA gentle inttension/elecfullerene dymicelles in

ktionnzflä

rated groups iomote and moe behaviour [2synthesized dywhich supply ysico-chemicausly hydrophond open scien

ular manipulatuestion about ular interactioion is still puzthe interactio

d self-assembe modern scie

mulation with simulated maullerene dyadusand water m

for molecular dy

tions, 32 chloride

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te, blue, green sp

gen, nitrogen and

The details of the

e the phenomee final ensemberplay of actinctrostatics) guyads to organiaqueous solu

nale nächen

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al properties oobic and hydrontists a new avtion of fullerepredominant

on in the fullerzzling, it is imon types respobly with a “magence – a moleatomistic res

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ynamics – 32 fulle

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d chlorine atoms/

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ena that deterble in water [4ng forces (suruides moleculize themselvetions (Fig.3).

nanon und

a popular

s at least its of being ophilic venue nes. rene portant

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ero-

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AsFeapabatshBcfwdsc

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A different typseen for neutrFullerene withester-side groaggregates inparticles (Fig.assemble in tbecause of theand counteriotemplate themstructures withydrophilic exBy changing tchloride over find a thickenwhich can be densation of lscreening of tcluster surfac

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kturiymer

pe of clusterinral and chargeh hydrophilic oup preferent water simila3a). Fulleropyurn into elonge presence of

ons that help mmselves into nth hydrophobixterior (Fig.3bhe size of the iodide to percing of the cyliexplained by sarger ions anhe charge rep

ce.

r the size depndensation is

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meters [4] canstimation of th

ierte rsyst

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molecules to non-spherical c core and , c). counterions f

chlorate (Fig. 4nder structurstronger con-d thus partial pulsion on the

pendence of s the formation

case of smallfrom the fullethe presence troduces the ng (cylindricabilayers) whi

way for fuller-aggregate (Figecular geometvaluation of crn be used for heir microstru

eme

on is ives. hort pherical

C60 lf-res ups

from 4) we

res -

e

n of a l ions rene of more l ch

g.3c). try of ritical

ucture.

S

a

f

f

f

s

S

f

w

a

s

s

s

s

f

s

a

S

Fig. 3:

Snapshots of sim

aggregates of (a)

fulleropyrrolidin

monocation, (c)

fulleropyrrolidin

forming in aqueo

solution; water m

(a-c) and chloride

(b, c) are omitted

clarity.

Fig. 4:

Snapshots of

fulleropyrrolidin

monocation aggr

with different cou

(a) chloride anion

CPK spheres, (b)

anions, purple CP

spheres and (c)

perchlorate anio

red tetrahedrons

molecules are om

clarity. Here sma

charge-dense Cl-

having large and

structured hydra

do not approach t

surface of the so

short distances; t

repelled from the

hydrophobic regi

fulleropyrollidine

molecules, formi

diffuse layer arou

cluster. In turn, t

significant numb

charge-diffuse pe

anions is present

micelle surface f

Stern layer of ads

ions.

23

mulated

) PCBM, (b)

ne

ne dication

ous

molecules

e ions

d for

ne

regates

unterions:

ns, green

iodide

PK

ns, green-

s; water

mitted for

all, - ions

ation shells

the

lute at

they are

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ions of the

e

ing a

und the

the

er of

erchlorate

t at the

forming a

sorbed

Funktionale nanostrukturierte Grenzflächen und Polymersysteme

24

Thereby, our work opens up the possibility of preparing increasingly complex molecular C60 arrangements, whose organization can be controlled. Further simulations will be focused on the phenomenon of hydrophobic hydration and such factors of self-assembly as the length of the hydrophilic addend, the bis-substitution of the C60-cage, as well as the theoretical investigation of nanoscale amphiphilic polymer/fullerene co-assemblies. The latter case is essential for developing smart nanostructured materials for the technological applications in the field of organic electronics, because the localization of molecular components (polymer donor and fullerene acceptor) having similar polarity in water offers a powerful, non-directional driving force for the self-assembly and folding in amphiphilic systems. Co-operation: Center for Information Services and High Performance Computing (ZIH) of the Technische Universität Dresden [1] J. D. Fortner, D. Y. Lyon, C. M. Sayes, A. M.

Boyd, J. C. Falkner, E. M. Hotze, L. B. Alemany, Y. J. Tao, W. Guo, K. D. Ausman, V. L. Colvin, J. B. Hughes: Environ. Sci. Technol. 39, 4307-4316, 2005.

[2] M. Prato, D. M. Guldi, M. Melle-Franco, F. Zerbetto: Proc. Nat. Acad. Sci. 99, 5075-5080, 2002.

[3] M. Prato, M. Maggini: Acc. Chem. Res. 31, 519-526, 1998.

[4] O. Guskova, S. R. Varanasi, J.-U. Sommer: J. Chem. Phys. 141, 144303 (1-11), 2014.

Polymere Druckfarbensammler im Deinkingprozess Simona Schwarz, Gudrun Petzold, Uwe Geißler Im Jahr 2010 lag der Einsatz von Altpapier, bezogen auf die Papierproduktion, in Deutsch-land bei 70 %. Altpapier stellt schon seit langem die wichtigste Rohstoffbasis der deutschen Papierindustrie dar. Typischerweise muss das Altpapier nach seiner Sammlung und Lagerung zunächst von Verunreinigungen wie Metall, Sand, Glas und Kunststoffen befreit werden, bevor es in den Auflöseaggregaten unter der Wirkung von Wasser und einem kleinen Teil chemischer Hilfsstoffe wie z.B. Tenside zerfasert wird. Um ein helles Papier auf der Basis von Altpapier zu erzeugen, müssen die Rohstoffe von den an ihren Oberflächen haftenden Druckfarbenresten befreit werden. Ziel ist es hierbei, eine möglichst vollständige Ablösung der Farbe von der Faser und deren anschlie-ßenden Austrag zu erreichen. Dieser als De-Inking bezeichnete Prozessschritt wird traditionell mit Hilfe der Flotation, also durch das Anlagern der Druckfarbenteilchen an Luft-blasen, durchgeführt. Der Prozess ist durch einen hohen Verbrauch an Wasser und Energie gekennzeichnet. An der Professur für Papiertechnik an der TU Dresden konnte kürzlich nachgewiesen werden, dass sich die von den Fasern abge-lösten Druckfarbenteilchen nicht nur – wie bei der Flotation - an Luftblasen, sondern auch an die Oberflächen synthetischer Polymerpartikel wie PA oder PP anlagern und mit diesen aus der Suspension ausgetragen werden können. Diese Anlagerung (Adsorption) kann bei wesentlich höheren Stoffdichten erfolgen als die Druckfarbenentfernung mittels Flotation und somit Wasser und Energie einsparen. Ziel eines gemeinsamen Projektes war es - die Mechanismen des Adsorptions-

deinkings zu untersuchen und damit zur Optimierung der Polymerteilchen bezüglich ihrer Oberflächenchemie beizutragen sowie

- eine Möglichkeit zur Entfernung der Druck-farben und somit zur Regenerierung der Teilchen zu finden.

Keywords

recycling

paper

polymer

surface tension

Funktionale nanostrukturierte Grenzflächen und Polymersysteme

25

0,1 1 1025

30

35

40

45

50

55

60

65

70

Sur

face

tens

ion

[mN

/m]

Time/Bubble age [s]

Surfactant mixture

Magazin paper

Newspaper

Abb. 1:

Dynamische Oberflächenspannung der Deinking-Lösung

im Vergleich zu den Stoffsuspensionen; während die

Tensidmischung in Wasser die Oberflächenspannung

bereits nach 1 s auf ca. 30mN/m erniedrigt wird das Tensid

in Anwesenheit der Papiere adsorbiert, was die

Oberflächenspannung erhöht

Im IPF erfolgten vor allem Untersuchungen zur Charakterisierung der Polymere, der Druckfarben und Papiere sowie der Wechsel-wirkungen in den tensidhaltigen Stoff-suspensionen. Wie in Abb. 1 dargestellt wird sind Oberflächenspannung (und Ladung) sowie Partikelgröße (Abb. 2) geeignete Parameter, um die Stoffsuspensionen zu beschreiben. Diese Parameter verändern sich in Abhängig-keit von Papierart und Druckfarbe. So steigt die Oberflächenspannung der tensidhaltigen Lösung durch Zusatz von Zeitungspapier (Newspaper; NP) stark an, da die Tenside an der Druckfarbe adsorbiert werden. Die Suspension „verarmt“ an Tensid und die Oberflächenspannung nähert sich dem Wasserwert. Jedoch zeigen Magazinpapiere (Light weight coated; LWC) ein völlig anderes Verhalten, das durch den Einfluss der Coating-schicht zu erklären ist, die zersetzt wird und die ebenfalls oberflächenaktive Substanzen freisetzt. Das konnte auch anhand von Partikelgrößenmessungen bestätigt werden (Abb. 2). Während Ruß als Hauptkomponente der Druckfarben eine mittlere Partikelgröße von etwa 10 μm besitzt fällt bei den LWC-Proben ein sehr hoher Feinanteil, der unabhängig von der verwendeten Druckfarbe ist, auf. Es handelt sich um anorganische Partikel, die aus dem Coating freigesetzt werden. Dagegen haben Zeitungsdruckpapiere (NP) den höchsten Anteil größerer Partikel, die

Druckfarbe enthalten. Somit wird die Partikelgröße in Suspension und damit die Effektivität des Deinkingprozesses weitgehend von der Art des Papiers, und weniger von der Druckfarbe bestimmt.

1 10 100

0

20

40

60

80

100

120

140

Partikelgröße x / µm

Vol

umen

vert

eilu

ngsd

icht

e q3

lg /

% Ruß - RAVEN 500 HS-NP CS-SC TD-SC CS-LWC HS-LWC TD-LWC

In weiteren Untersuchungen gelang es durch eine Kombination von Tensidlösung und Ultra-schall, die beladenen Polymerteilchen zu regenerieren, so dass sie dem Prozess wieder zugeführt werden können [3]. Von den geteste-ten Polymeren erwies sich Polypropylen als am besten geeignet. Somit konnten die Voraussetzungen für eine technische Nutzung des Adsorptionsdeinkings einschließlich des Granulatrecyclings geschaffen werden. Sponsor: Das IGF-Vorhaben (Nr. 17561) der Forschungsvereinigung DECHEMA wurde über die AiF im Rahmen des Programms der industriellen Gemeinschaftsforschung (IGF) vom Bundesministerium für Wirtschaft und Energie aufgrund eines Beschlusses des Deutschen Bundestages gefördert. Kooperation: Prof. H. Grossmann, Professur für Papiertechnik, TU Dresden [1] S. Schwarz, K. Wustrack, G. Petzold: GIT

11(2013), 2-4 [2] G. Petzold, S. Schwarz, V. Dutschk: Colloid

Polymer Sci. 292 (2014), 2197–2205 [3] S. Schwarz, G. Petzold, M. Oelmann: DE 10

2012 208 219.0, DE 10 2013 217 872 und EP 14183185.9-1308 „Verfahren zur Reinigung von Partikeln aus einem Altpapier-reinigungsprozess“

Abb. 2:

Partikelgrößenverteilung

in der Stoffsuspension;

verschiedene Papierarten

(NP, SC und LWC) und

Druckfarben (Cold-Set,

Heat-Set und Tiefdruck) im

Vergleich