phthalocyaninatometal Langmuir-Blodgett films

ELSEVIER

Synthetic hletals 86 (1997) 2281-2282

Fabrication and fullerene/phthalocyaninatometal IZI.Rikukawa.

electrical

S. Furumi.

properties of Langmuir-Blodgett

K. Sanui. and iv. Ogata

Sophra LJni~~ersr I!. 7-l Kioi-Cho,

Ileparrmenr of Chemislry.

films

Chryodo-Ku,

Tokyo 102, Japan

depositedas

I.-type

Abstract The mised fullereneiphthalocyaninatometal method

\\lth

multila!er

films

films

onto

ratio solid

were ~nllucnced

response

of about

Fullerenes,

monolayers unity.

although

ion species

by the irradiation

Phthalocyanine,

were successfully

the lc11lercne monolayers

The molecular

substrates.

by center-metal

time \vas observed

KeywordsI.

a transrer

orpani/.ations

or II-\‘is

technique,

method

(II)

chloride Other

Throyh

the me oU our mixed

conventional

fabricate

ultra thin

with

It IS possible

the nano-scale

photocurrent

to

(CoPcTH)

were also

chloride)

the presence of ammonium chemicals

of the

ml ‘) onto

their must

purtl‘ication

on the \trwture

molecule be) ny manipulated and ~hc nature of Intermolecular interactions ,&I el‘fecl~\‘e cics~gn strateg> be armed at using

the molecular

\~th the I.13 manipulation structure

and

molecular

eng~neerinp.

Fullerene attention Modgett stable

molecular

and

formation

2.

films

prcat deal 01 recent

thin

charge

such

as

transfer

with

con&wed

nieas uremcn t s

lansmtor-

speed

to Fabricate ml~tures

1n addition. Interaction

and

ot the

were

purified

of

lifting f,l.

top position

t \()I hcrrn

at 10 Y’ \\itIt Multila>cr

\\erc hult

onto

h! drophobic

diffractIon.

and

were cfippcd fi‘ilm \~‘:Is dned \Vailing

and 38 set at the bottom

with Iv

a dippIn

1 h after

times or IX min at the posltlon

\\cre used tjr

dips

I,13

Experimental

from

Iron

pentacarbonyl

ethylcnegl!cof \vas carrlcd ethylacetate palladium

and

at 200 “C. out

by

column

(40: I)]. (II) (PdPcTR)

( .\lPcTB )

(II) (Fef’cTB)

l’etra-

was synthesized

-I-rr,~-hld?lphthalonltrile

The purification chromatograph)

in

of crude prodwts [:ilO,-bcnzene-

Tetra-/en-butylphthaloc>aninaloandTetra-rm-butylphthaloc>aninatv-

0379-6779197/$17.00 0 1997 Elsevier Science S.A. At1 rights reserved PII SO379-6779(96)04836-9

Scheme

I Schematic

structure of fullerene

metal complexes.

li)r

conductlvlt)

2.1 Matrrrrils frr?-butylphthalocyaninatoiron

’

flas

I.3,3,_7-he~ameth~-Icds~lazane

The

up

at IO ‘(1 and 20 mS m

were also investigated.

‘l‘etra-rrr7-but\i~hthalocsaninatometal(lI)

RII \\cre

;I c(,mpression

films

’

mln

rn~

;I ‘I‘Oli \\.I’[

pressure-area

method

S-ray

the second lajer.

all subsequent

\\II~

The substrates

5 mm

depositing

’ mln ‘.

mi~turcs

and

for the fullerene.phthafoc\,aninatometal

1~1

0.0.~

elcctrlcaf

condwtivit>

111

T

(concentration

were transferred

absorption.

stable

I~ifms from

electrical

treated

o[Illcal

I,). the

\ve attempted

at 2 IO

purified

a I;tuda I’iIm balance

5 .A molecule

The multilayer

to make

stw.

and multilayer

photoconductlv~ty

rnca~uredon speedof

these

fullerene

pallacfiunm

phthaloc)aninatc~mctal

solutions The

given

phthalocyaninatometals

01’ the

properties

of

In this

monolaxers

I’ullerene

films

it is difficult

s> slcni.

\ ertical

b!

I’rom

Iphthalonltrile

chemicals

subphase

I~! the ~)pical

have attracteda

and multilayers

a \\atcr

1a!r1

are

synthesl/ed

molybdate

01. l‘ulferene

the \\elf-&Pined

organization

films

Ho\\ever, technlqw

\lonofa)ers

slides

ultra thin

monola]ers

sel f-orpan~~at ion prc>pert IC\

because both

photo

2.2 .\!anrprrltrrroti of /nrt?gr?lrrrr-Hlod~~rrr J~/m.s

and superlattlcc

optical

depend

a shoti

prior to use.

\\c’rc spread Krom bcn/.cnc

ultimately

in the I.13

\\lth

and I-/en-but!

Other

methods

The I’inal nanostruclure from fullerene compolmds and molecular orpanlzation and hence thclr clectncaf and struclures

propertIe‘;

liliinp

homoycneou%

films

(or cobalt

been frequently used to create the nanostructure and molecular 0rganlzation of functional orpanic materials have

films

fhph

Semiconducting cobalt

andselfassembl>,

LB system.

to transfer

lipht to these I-I!, films.

Lansmuir-Rlcdpett

(LB) technique

films by the \.ertical

stiff

and f’hthaloc)anlnatometals

or fullerene

of I~l~thaloc\anInatometals.

Introduction Ianpmur-MlodFett

were too

l)hthaloc!aninato-

hf. Rib-uhmva et al. /SjwtheticMetuls

86 (1997,2281-2282

atlri buIcdtu molecular agprc+lon and edyxm of phthalocyanine rings on the air-\vater presswe-area macroc~clcs

The isotherms of mixtures indicated that the .\~Il’cTB were oriented nearly perpendicular to the surface

The

multilayer

rabricated

onto

films

solid

of

IilXiny method absorption

\vith a transfer

spcclra

The electrical 01 l,,,“, ana .\It’c I u, ._.__

m

500

FcPcTR

2.00

svste_nL

were also

found to be frcquentl~

and photocurrent

Col’c’l‘li

ol’ these

LB

photocurrent and ._ ^ LU tllms Gth 20

svstem

/

<

E

t; 40.0 E 2 u

CI

1.00

5 k (3

20.0

0.50

0.00

0

1000

500

Voltage

/

0

500 Voltage

mV

l:~p, 2 Photocurrent

and darkcurrent

1000 I mV

Ia)ers.

Kcithley 220 current source and a Takeda Riken TR8652. 3. Results and Discussion Xlonolayers were spread from benzene solutions of these mixtures. Figure I sho\vs the pressure-area isotherms of These \ll’cTB (bL=l’d and (To), (:60, and these misturcs. mixtures

formed stable condensed monolayers on The limiting arcas of mixtures were surface almost intermediate areas between C,, and MPcTB. These Also, it areas are dependent on the center-metal ion species.

the al r-!\ater

the isotherms

exhibit

by the (XX model.

0

500 Voltage

1000 I mV

versus 1oltnpc l’or (‘,,,, .\LPc’l‘l3 1.H films with 20 layers

The I .I3films wcrc chcmlcally dqed by csposins them into were I: gas for IO min at 20 Y:. 11 C. in-plane condwtivities measured by the standard row-probe technique at room \\ith 21 temperature utilizing a \'a11 dcr Pauw configuration

areas estimated

unity.

1.50

5.

is notedthat

ratio of about

Light 60.0

WVTB’C,,,

the mixed

of these LB films were measured,

conductivity

so.0 svstcm

Pd PcTU

were

as I’-type films by the

films were measured I:ipure 2 shows _ ~.___ darkcurrent versus voltape ol C,,.‘MPcTB

at IO ‘(1

mixtures

Co0 monolayers

multilayers,

were s~~cessfull~~ deposited

and multilayer thin films deposited upto -50 layers

lsotnerms

Although

monola)xrs I A’-\is

then mixtures

X1PcTB

CyhO.

substrates.

were too stiff to IransTir homogeneous vertical

I up I >urtace pressure-area

confipuration ~nterllce.

smaller limiting areas than This type of behavior is

The photwurrcnt

than the dark current,

ol’ (IhO PdPcTB I,13 film was higher \vhile (‘,,‘FePcTB and C,,‘CoPcTB LB

films eshibited no photosensitivity. condwtivity of these I.13 lilms \vas estimated

The electrical as IO’ S cm for

(‘ti,,, Pdl’cTH IS fi Ims. IO ” S cm for C,, FePcTH I,13 films.

and

IO’S cm for C,,,‘CoI’cTl~ L13 films without chemical doping. ‘l’hesc results sqpcst that (Yhnand AlPcTB ma)’ form weak CT coniple\tcs 4.

Acknowledgments

The authors are g-ateful [or financial support Prom Granl-in.\id [or Scientific Kescarch on Priority Arcas (50.262) from The \linlstr~ References

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