Supramolecular 3,4:9,10-perylenetetracarboxylic diimide triads containing moieties of sumanene polyphenol derivative: Synthesis and photochemical transformations

Article abstract of DOI:10.1134/S0012500816080036

A polyphenol derivative of the sumanene-containing triad with a central perylenetetracarboxylic diimide moiety was synthesized via several consecutive chemical transformations of N,N'-bis(3',5'-dimethoxybenzyl)-1,7-bis[4''-(N,N'-disumanenyl)aminophenyl]perylene-3,4:9,10-tetracarboxylic diimide. The phenolic hydroxyl groups of the resulting derivative were partly protected by introduction of two different protective groups, pentaspiran and tert-butyl butyrate ones. It was shown that this modified derivative can be used to obtain a promising positive-tone photoresists with high parameters for extreme ultraviolet nanolithography on exposure to light at 13.5 nm for the manufacture of 20 to 16 nanometer chips.

Full text of DOI:10.1134/S0012500816080036

ISSN 0012-5008, Doklady Chemistry, 2016, Vol. 469, Part 2, pp. 233–237. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.Ya. Vainer, K.M. Dymaev, A.M. Kovalenko, T.D. Belskii, S.A. Krichevskaya, L.I. Martova, 2016, published in Doklady Akademii Nauk, 2016, Vol. 469,
No. 5, pp. 577–581.
CHEMISTRY
Supramolecular 3,4:9,10-Perylenetetracarboxylic Diimide Triads
Containing Moieties of Sumanene Polyphenol Derivative:
Synthesis and Photochemical Transformations
A. Ya. Vainer*, Corresponding Member of the RAS K. M. Dymaev, A. M. Kovalenko,
T. D. Belskii, S. A. Krichevskaya, and L. I. Martova
Received March 9, 2016
Abstract—A polyphenol derivative of the sumanene-containing triad with a central perylenetetracarboxylic
diimide moiety was synthesized via several consecutive chemical transformations of N,N'-bis(3',5'-dime-
thoxybenzyl)-1,7-bis[4''-(N,N'-disumanenyl)aminophenyl]perylene-3,4:9,10-tetracarboxylic diimide. The
phenolic hydroxyl groups of the resulting derivative were partly protected by introduction of two different pro-
tective groups, pentaspiran and tert-butyl butyrate ones. It was shown that this modified derivative can be
used to obtain a promising positive-tone photoresists with high parameters for extreme ultraviolet nanoli-
thography on exposure to light at 13.5 nm for the manufacture of 20 to 16 nanometer chips.
DOI: 10.1134/S0012500816080036
In recent years, the world microelectronics has
mastered the manufacture of microcircuit chips with
the 45, 32, and 22 nm geometry and closely
approached the sub-20 nm technology level [1]. The
smaller the minimum characteristic size of the elec-
tronic chips, the greater the attention drawn by
extreme ultraviolet (EUV) nanolithography using the
radiation wavelength of 13.5 nm [1].
Among rather few studies on the design of photore-
sists that meet the requirements of EUV lithography
needed to move toward the level of 16 nm and smaller
chips, note several papers dealing with the chemically
amplified resists based on fullerene derivatives with
enhanced plasma resistance. In particular, it was
shown [4] that systems of this type developed initially
for electron-beam lithography are also of certain
interest for EUV lithography.
The international roadmap for the development of
semiconductor technology [2] is targeting towards
this, most promising lithography; the main hopes for
fabrication of chips of 11 nm and sub-11 nm geometry
are attached to this technology. However, successful
implementation of EUV nanolithography on an
industrial scale requires development of photoresists
adequately meeting the exceptionally stringent
demands on parameters such as light sensitivity, reso-
lution, line edge roughness, and plasma resistance.
The key problem faced by design of these resists is that
these parameters are balanced with one another, and
improvement of one parameter results in impairment
of some other [2, 3]. Thus, for solving this difficult
task, of high priority is the search for novel non-trivial
engineering solutions that would enable advancement
towards 16–11 nm and less geometry.
Unfortunately, the fullerene-containing negative-
tone photoresists [4], although have a resolution at a
22 nm level, still do not comply with the roadmap
requirements [2] in the edge roughness and light sen-
sitivity.
Among polyphenols, the polynuclear hydrocarbon
sumanene, C21H12, is most promising for the develop-
ment of new effective photoresists for EUV lithogra-
phy. The non-planar molecules of this compound are
considered as bowl-like fullerene fragments [5].
Sumanene has unique physical and chemical proper-
ties. Its functionalization can give rise to novel com-
pounds with a set of valuable properties for the devel-
opment of innovative products [5], in particular, for
the manufacture of various electronic materials and in
the synthesis of intermediates for fullerenes.
Here we propose a new strategy for the synthesis
of polyphenol derivatives of sumanene-containing
perylenetetracarboxylic diimide triads as the base of
positive-tone photoresists for EUV lithography,
which would allow the manufacture of chips with
minimum 22–16 nm geometry. We synthesized new
polyphenols of this chemical triad via consecutive
All-Russia Institute of Medicinal and Aromatic Plants,
Russian Academy of Agricultural Sciences,
ul. Grina 7, Moscow, 113628 Russia
*e-mail: nvbarannik@mail.ru
233

234
VAINER et al.
Unless otherwise specified, commercial Aldrich
Molecular masses of the synthesized products
chemicals were used. The consecutive chemical trans-
formations for the synthesis of polyphenol derivative
of the sumanene triad are shown in Scheme 1. N,N'-
Bis(3',5'-dimethoxybenzyl)-1,7-dibromoperylene-
3,4:9,10-tetracarboxylic diimide (I) was prepared by
known procedures. The initial perylene-3,4:9,10-tet-
racarboxylic acid dianhydride was brominated in the
presence of catalytic amount of iodine [6]. Then imi-
dation of the resulting mixture of brominated perylene
dianhydride derivatives was performed in an argon
atmosphere by the reaction with 3,5-dimethoxyben-
zylamine according to a reported procedure [7]. The
target compound I was isolated from the reaction mix-
ture by three recrystallizations from a CH2Cl2–
CH3OH mixture (1 : 1 vol/vol) as described in [6].
Molecular mass, g/mol
Com-
pound
Gross
formula
found*
calculated
848.5092
942.6395
696.6517
848.5181
942.6447
696.6581
1922.1973
5526.4907
4797.0820
I
C42H28Br2N2O8
C54H52B2N2O12
C48H26BrN
II
III
IV
V
C138H80N4O8
C354H320N4O56
C302H216N4O56
1922.1941
5526.4882
4797.0815
VI
* From MALDI–TOF MS data.
chemical transformations of previously unknown
N,N'-bis(3',5'-dimethoxybenzyl)-1,7-bis[4''-(N,N'-
disumanenyl)aminophenyl]perylene-3,4:9,10-tetra-
carboxylic diimide.
The Suzuki–Miyaura reaction of diimide I with
bis(pinacolato)diboron afforded N,N'-bis(3',5'-dime-
thoxybenzyl)-1,7-bis(4'',4'',5'',5''-tetramethyl-
1'',3'',2''-dioxaborolan-2''-yl)perylene-3,4:9,10-tetra-
carboxylic diimide (II). Compound II was synthesized
[8] in DMSO with dichloro[1,1-bis(diphenylphos-
phino)ferrocene]palladium([(dppf)Fe]PdCl2) (Strem
Chemical Co., USA) as the catalyst.
Further, the phenolic hydroxyls in the prepared
supramolecular sumanene-based triad derivatives
were partly protected by introducing two acid-labile
protective groups, pentaspiran and tert-butyl butyrate
ones. The lithographic parameters of the positive-tone
EUV resists based on these modified sumanene deriv-
atives were evaluated in the formation of patterns with
a characteristic size of 22–16 nm.
Sumanene, which was prepared by procedure [9],
was iodinated with N-iodosuccinimide in the presence
of gold trichloride as the catalyst by procedure [10].
Iodosumanene reacted with 4-bromoaniline to give
H3CO
OCH3
H3CO
OCH3
CH2
N
CH2
N
O
O
O
O
O
O
O
3
4
5
2
6
1
Br
B
pin-
Br
B-pin
a, b
c
7
8
12
11
10
9
O
N
CH2
O
O
N
CH2
O
O
O
O
II
OCH3
H3CO
OCH3
H3CO
B-pin
I
O
B
O
Scheme 1. Reagents and conditions: (a) Br , I , 98% H SO , 85°C, 11 h, 87%; (b) imidazole, 3,5-dimethoxybenzylamine, 140°C,
2
2
2
4
4 h, 25%; (c) bis(pinacolato)diboron, KOAc, DMSO, [(dppfFe]PdCl , 80°C, 4 h, 58%.
2
DOKLADY CHEMISTRY
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SUPRAMOLECULAR 3,4:9,10-PERYLENETETRACARBOXYLIC
Br
235
N
а
H3CO
O
OCH3
O
III
b
8
7
6
10
9
21
19
11
12
13
CH2
N
1
20
2
Ar =
5
3
4
18
R
R
17
14
N(Ar)2
15
16
Ar' =
(Ar)2N
R'
R'
R
R
IV
R
R
Ar'' =
O
N
CH2
O
OCH3
R'
R'
H2
R'
C
R'
R =
H3CO
OCH3
OCH3
OH
c
H2
C
R' =
HO
OH
O
H3CO
O
OCH3
OH
CH2
N
CH2
N
O
O
N(Ar'')2
N(Ar')2
d
(Ar'')2N
(Ar')2N
V
VI
O
N
O
O
N
O
CH2
CH2
HO
OH
H3CO
OCH3
Scheme 2. Reagents and conditions: (a) iodosumanene, 4-bromoaniline, CuCl, 1,10-phenanthroline, KOH, toluene, 125°C, 12 h,
69%; (b) IV, V, [(dppf)Fe]PdCl , KOAc, DMSO, 80°C, 6 h, 68%; (c) 3,5-dimethoxybenzyl bromide, triethylbenzylammonium
2
chloride, 50% aq. NaOH, DMSO, 22°C, 6 h, 67%; (d) BBr , CH Cl , 22°C, 3 h, 94%.
3
2
2
DOKLADY CHEMISTRY Vol. 469 Part 2 2016

236
VAINER et al.
N,N'-bis(sumanenyl)-4-bromoaniline
(III)
as protective groups — pentaspiran and tert-butyl butyr-
described in [11]. The sumanene-containing triad IV ate ones (to give compound VII). The degrees of pro-
was synthesized by the Suzuki–Miyaura reaction tection of phenolic hydroxyls by these groups in com-
during the condensation of compounds II and III pound V are 12 and 26 mol %, respectively; the desired
according to procedure [8] (Scheme 2).
degree of protection was achieved by varying the
amounts of chloromethyl ether of pen-
taspiro[3.0.2.0.3.0.2.0.3.1]nonadecan-19-ol [13] and
tert-butyl 2-bromobutyrate (Alfa Aesar, China) added
to the reaction mixture. The starting pentaspiran
derivative was prepared by procedure [14]. The degree
of substitution of phenolic hydroxyls in VII was deter-
mined from the intensity change of the 1H NMR sig-
nals of these groups at δ = 10.24 ppm.
The positive-tone photoresist film based on modi-
fied product VII and triphenylsulfonium perfluorobu-
tanesulfonate as the acid photogenerator (5% relative
to the weight of VII) formed on a silicon substrate
from a solution in 1-methoxy-2-propanol was exposed
to EUV light at 13.5 nm wavelength. The irradiation
was performed on a small exposure field pilot setup
(Canon, USA) with a numerical aperture of 0.3. The
resist film was dried at 130°C for 90 s, and the post-
exposure drying was performed at 110°C (also for 90 s).
The resist was developed by a standard 2.38% aqueous
solution of tetramethylamminium hydroxide (NMD-3
developer manufactured by Tokyo Ohka Co., Japan).
This resist has an extremely high resolution: pat-
terns with line and gap widths of 22 nm were formed in
a 50-nm thick resist film. The line edge roughness was
2.9 nm, which is quite acceptable for the fabrication of
some chips with 20 nm geometry. Note rather high
light sensitivity of this resist, which is 7.8 mJ/cm2. The
sumanene-containing photoresist possesses a plasma
resistance adequate to the modern nanolithography
and comparable with that attained in the plasma etch-
ing of industrial positive-tone novolac-based photore-
sists such as SAL 600 (manufactured by Rohm and
Haas, USA).
Preliminary testing that we carried out at an exper-
imental interference type EUV lithography setup
manufactured as indicated in [15] showed that pat-
terns with 16 nm units can be formed in a 25-nm thick
film, the line edge roughness being 2.8 nm.
The benzylation of triad IV with 3,5-dibromoben-
zyl bromide (Tokyo Kasei Kogyo Co., Japan) accord-
ing to a described procedure [12] furnished triad (V)
containing four 8,8',13,13',18,18'-hexa(3'',5''-dime-
thoxybenzyl)sumanenyl moieties. Finally, the target
triad (VI) was prepared by exhaustive demethylation of
compound V according to procedure [12].
The newly synthesized compounds I–VI were
purified by preparative high performance liquid chro-
matography (HPLC). The product structures were
established by MALDI–TOF mass spectrometry and
1H and 13C NMR and IR spectroscopy, and confirmed
by analytical HPLC and elemental analysis data. The
molecular weights of the products are summarized in
the table.
The analytical data were considered in more detail
in relation to the polyphenol derivative of sumanene-
containing triad VI. We marked only those absorption
bands and signals that are significant for structural
diagnosis. For example, the IR spectrum of this com-
pound exhibits absorption bands characteristic of five-
membered imide rings (1707, 1668, 1356, and 730 cm–1).
1
The H NMR spectrum of triad VI exhibits the
proton signal for phenolic hydroxyls at 10.24 ppm,
whereas the singlet at 3.89 ppm corresponding to the
methoxy group protons is absent. Note also signals at
δ = 8.18 and 8.05–8.03 ppm due to perylene cage pro-
tons and a broad signal at 4.20–4.15 ppm (N–CH2).
The 13C NMR spectrum of the synthesized triad VI
shows signals for imide carbonyl carbons at 163.05 and
162.9 ppm and signals for perylene cage carbons at
134.9, 129.4, 127.5, 123.5, and 123.2 ppm. The signals
at δ = 148.78, 148.60, and 123.15 ppm can be assigned
to carbon atoms of the sumanenyl moieties of triad VI.
Alkali developable chemically amplified positive-
tone photoresists, which are normally used in EUV
lithography, are based on compounds with acid-labile
protective groups. On thermal activation, these groups
are eliminated on treatment with photogenerated acid.
The advancement to the 22 and sub-22 nm resolution
level sharply complicates the requirements to the pro-
tective groups, which are expected to contribute to
balancing of the photoresist characteristics, which are
in some cases mutually exclusive, such as light sensi-
tivity, line edge roughness, plasma resistance, adhe-
sion to the substrate, and the amount of volatile prod-
ucts during exposure and the subsequent heat treat-
ment.
Thus, we synthesized for the first time a polyphe-
nol derivative of the sumanene-containing triad with a
central perylenetetracarboxylic diimide moiety via
several consecutive chemical transformations of the
initial triad IV. The phenolic hydroxyls in the resulting
derivative were partly protected by introducing two
different types of protective groups, pentaspiran and
tert-butyl butyrate ones. The degrees of protection of
the phenolic hydroxyls in the sumanene-containing
triad by these groups were 12 and 26 mol %, respec-
tively. The modified compound VII was shown to be
Considering the development of positive-tone suitable for the design of promising positive-tone pho-
EUV resists based on the polyphenol derivative of toresists exhibiting high characteristics for EUV nano-
sumanene-containing triad VI, we partly protected the lithography on exposure to light at 13.5 nm in the
phenolic hydroxyls by successive introduction of two manufacture of 20–16 nanometer chips.
DOKLADY CHEMISTRY
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DOKLADY CHEMISTRY Vol. 469 Part 2 2016