U.S. patent application number 13/919185 was filed with the patent office on 2013-10-24 for templated monolayer polymerization and replication.
This patent application is currently assigned to MASSACHUSETTS INSTITUTE OF TECHNOLOGY. The applicant listed for this patent is Joseph M. Jacobson, David W. Mosley. Invention is credited to Joseph M. Jacobson, David W. Mosley.
Application Number | 20130280920 13/919185 |
Document ID | / |
Family ID | 32095955 |
Filed Date | 2013-10-24 |
United States Patent
Application |
20130280920 |
Kind Code |
A1 |
Jacobson; Joseph M. ; et
al. |
October 24, 2013 |
Templated Monolayer Polymerization and Replication
Abstract
A self-replicating monolayer system employing polymerization of
monomers or nanoparticle ensembles on a defined template provides
synthesis of two-dimensional single molecule polymers. Systems of
self-replicating monolayers are used as templates for growth of
inorganic colloids. A preferred embodiment employs SAM-based
replication, wherein an initial monolayer is patterned and used as
a template for self-assembly of a second monolayer by molecular
recognition. The second monolayer is polymerized in place and the
monolayers are separated to form a replicate. Both may then
function as templates for monolayer assemblies. A generic
self-replicating monomer unit comprises a polymerizable moiety
attached by methylene repeats to a recognition element and an
ending unit that will not interfere with the chosen recognition
chemistry. The recognition element is self-complementary, unless
two replicating monomers with compatible cross-linking chemistry
are employed. After replication, selective mineralization and/or
electroless plating may produce a two-dimensional inorganic sheet
having patterned domains within it.
Inventors: |
Jacobson; Joseph M.;
(Newton, MA) ; Mosley; David W.; (Cambridge,
MA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Jacobson; Joseph M.
Mosley; David W. |
Newton
Cambridge |
MA
MA |
US
US |
|
|
Assignee: |
MASSACHUSETTS INSTITUTE OF
TECHNOLOGY
Cambridge
MA
|
Family ID: |
32095955 |
Appl. No.: |
13/919185 |
Filed: |
June 17, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13556148 |
Jul 23, 2012 |
8465803 |
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13919185 |
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12505508 |
Jul 19, 2009 |
8227035 |
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13556148 |
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11963970 |
Dec 24, 2007 |
7563482 |
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12505508 |
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10621897 |
Jul 17, 2003 |
7311943 |
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11963970 |
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60396486 |
Jul 17, 2002 |
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Current U.S.
Class: |
438/780 ;
264/293; 427/383.1; 427/58 |
Current CPC
Class: |
Y10S 977/882 20130101;
B82Y 40/00 20130101; G03F 7/165 20130101; H01L 21/283 20130101;
Y10S 977/883 20130101; H01L 21/02112 20130101; G01N 31/22 20130101;
B82Y 30/00 20130101; B05D 1/185 20130101 |
Class at
Publication: |
438/780 ;
264/293; 427/383.1; 427/58 |
International
Class: |
H01L 21/02 20060101
H01L021/02; H01L 21/283 20060101 H01L021/283 |
Claims
1. A method for replicating a two-dimensional patterned structure
comprising the steps of: binding a plurality of monomer units
having crosslinker arms to a template of the two-dimensional
patterned structure; reacting the crosslinker arms to bind the
monomer units to each other to form a replicated two-dimensional
patterned structure; and disassociating the replicated
two-dimensional patterned structure from the template.
2. The method of claim 1, further including the step of selective
mineralization of the replicated two-dimensional patterned
structure.
3. The method of claim 1, further including the step of electroless
plating of the replicated two-dimensional patterned structure.
4. The method of claim 1, further including the steps of
nanoparticle adhesion to, and sintering of, the replicated
two-dimensional patterned structure.
5. The method of claim 1, further including the step of growing an
inorganic structure upon the replicated two-dimensional patterned
structure.
6. The method of claim 5, wherein the inorganic structure is a
semiconductor.
7. The method of claim 1, further including the step of binding a
plurality of inorganic materials to the replicated two-dimensional
patterned structure.
8. The method of claim 7, wherein at least one of the inorganic
materials is metallic.
9. The method of claim 1, wherein the monomers are nucleotides,
oligonucleotides, or amino acids.
10. The method of claim 1, wherein the monomers are nanoparticle
ensembles.
11. The method of claim 1, wherein the monomers are selected from
the group consisting of Hentriaconta-11,13,20,22-tetraynoic acid,
Hentriaconta-11,13,20,22-tetraynoic acid amide,
Triaconta-10,12,19,21-tetraynoic acid amide, and
Triaconta-10,12,19,21-tetraynoic acid.
Description
RELATED APPLICATIONS
[0001] This application is a divisional application of co-pending
U.S. patent application Ser. No. 13/556,148, filed Jul. 23, 2012,
now U.S. Pat. No. 8,465,803, issued Jun, 18, 2013, which is a
divisional application of co-pending U.S. patent application Ser.
No. 12/505,508, filed Jul. 19, 2009, now U.S. Pat. No. 8,227,035,
issued Jul. 24, 2012, which is a continuation application of
co-pending U.S. patent application Ser. No. 11/963,970, filed Dec.
24, 2007, now U.S. Pat. No. 7,563,482, issued Jul. 21, 2009, which
is a divisional application of U.S. patent application Ser. No.
10/621,897, filed Jul. 17, 2003, now U.S. Pat. No. 7,311,943,
issued Dec, 25, 2007, which claims the benefit of U.S. Provisional
Application Ser. No. 60/396,486, filed Jul. 17, 2002. The entire
disclosures of each of the aforementioned applications are
incorporated by reference herein in their entirety.
FIELD OF THE INVENTION
[0002] This invention relates to monolayer polymerization and, in
particular, to self-replicating systems of monolayers and methods
for polymerizing organic thin film monolayer assemblies.
BACKGROUND
[0003] As nanotechnology pushes forward, the need increases for
reliable methods of producing discrete nanostructures, either
organic or inorganic, of specific shape and size, particularly in
the 2-1000 nm regime. Two general approaches exist for making
nanostructures: from the bottom up through chemical synthesis and
from the top down through lithographic methodology. Techniques that
target the region between the current capabilities of these two
technologies, i.e., from about 2 nm to about 1000 nm, are currently
highly sought after.
[0004] Prior art nanostructure synthesis methods that have been
developed include focused-ion beam milling, scanning probe
techniques, and x-ray lithography. While advanced mask-based
lithography techniques are capable of producing large quantities of
structures of small size, they are typically very expensive.
Although milling techniques and scanning probe techniques are
somewhat more affordable, they are primarily useful for the
production of very small numbers of nanostructures. Further, all
these available techniques are generally deployed to produce
structures that are directly attached to surfaces or are integral
parts of a surface. There are no general methods to produce mole
quantity (6.times.10.sup.23) amounts of nanostructures that are
lithographically defined. Such large quantities of nanostructures
are almost by necessity solution based, since they would otherwise
occupy a very large amount of surface area.
[0005] Biological systems utilize templated replication to produce
large quantities of nanostructures such as nucleotide chains and
peptide chains. Nucleotide synthesis is based upon hydrogen bond
templating, followed by polymerization. Attempts have therefore
been made to mimic the efficiency of oligonucleotide synthesis for
various kinds of polymers, typically via hydrogen-bonded assembly
or electrostatic assembly.
[0006] In general, polymerization of monolayers has been
extensively studied. Many different routes to achieve non-patterned
polymerization of a single monolayer have been investigated. Of
particular relevance are polymerization systems that are
topochemical in nature. A topochemical polymerization typically
results in very little rearrangement of the monolayer once
polymerization has occurred.
[0007] The poly(diacetylene)s (PDAs) exemplify such a system. PDA
polymerization in both a self-assembled monolayer and in a
Langmuir-Blodgett (LB) monolayer on gold has been achieved. FIG. 1
depicts a prior art scheme of diacetylene polymerization on a gold
substrate by attachment of functionalized alkyl thiols. Attempts
have been made to use hydrogen bonding to control polymerization in
Langmuir-Blodgett monolayers. Since PDAs are polymerized by UV
light, extensions to lithographic production of monolayers are
relatively straightforward.
[0008] PDAs have also been polymerized in covalently bonded
multilayers of monolayers. A multilayer film can be produced by
covalent linkages, with the number of layers being controlled by a
sequence of steps. Multilayer films have also been generated using
hydrogen bonding and coordination bonding. FIG. 2 depicts a prior
art approach to synthesis of a multilayer film, wherein a second
monolayer is grown on a gold-alkyl thiol self-assembled monolayer
(SAM) via hydrogen bonding (amide recognition).
[0009] Replication of siloxane monolayers through several
generations on a substrate has also been reported. The monolayers
replicate through what is understood to be an acetone-assisted
process, involving hydrogen bonding and solvent intercalation for
separating the replicate from the template. The replication process
is not a one-pot process, nor are the monolayers specifically
cross-linked or patterned. The monolayers are attached to the
surface of a silicon substrate, and replication stalls after 4-5
generations. A method of replicating monolayers that is highly
controlled and can be used to replicate patterns over many
generations would be highly desirable and has never been
reported.
[0010] Large scale two-dimensional polymers have often been
produced by Langmuir-Blodgett techniques (Palacin et al., Thin
Films 20:69-82 (1995)). One instance of patterned polymer
multilayers that are free of a surface has been reported (Stroock
et al., Langmuir 19(6): 2466-2472 (2003)), however, synthesis of
two-dimensional lithographically defined single molecule polymers
that can be readily suspended in a solvent has not.
[0011] Electroless plating of metals onto organic molecules is a
common technique in biology, often used for histology staining
Electroless plating onto nanostructures has also been reported
recently, using an amide template to coordinate metal ions as the
electroless plating seeds (Matsui et al., J. Phys. Chem. B 104:
9576-79 (2000)). In addition, mineralization of organic structures
is also a burgeoning field, and techniques for mineralizing
CaCO.sub.3 and SiO.sub.2 are being developed and explored.
Templating of semiconductor crystals has also been reported (Whaley
S. R. et al., Nature 405: 665-668 (2000)).
[0012] Polymerization of nanoparticles has been reported in many
ways. Typically, nanoparticles have been polymerized by using a
polymerizable moiety in the ligand sphere of the nanoparticle (Boal
et al., Adv. Functional Mat. 11(6): 461-465 (2001)), or by
decorating a pre-existing polymer chain with nanoparticles (Walker
et al., J. Amer. Chem. Soc. 123: 3846-3847 (2001)). Polymerization
in films has been reported using dithiol chemistry (Musick et al.,
Chem. Mater. 12: 2869-2881 (2000)). Further, melting or
agglomeration of nanoparticles into films is well known (U.S. Pat.
No. 6,294,401, Ridley et al. (2001)). However, polymerization of a
nanoparticle ensemble using a lithographically defined template has
not been reported.
[0013] What has been needed, therefore, are techniques for making
large quantities of nanostructures that target the region between
the capabilities of current technology, i.e., from about 2 nm to
about 1000 nm. In particular, what is needed is a method for
synthesis of two-dimensional lithographically-defined single
molecule polymers that can be readily suspended in a solvent, and
may be further used to generate inorganic structures. What is
further particularly needed is a method of replicating monolayers
that is highly controlled and can be used to replicate patterns
over many generations, preferably as a "one-pot" process producing
monolayers that are specifically cross-linked or patterned.
SUMMARY
[0014] These and other objectives are met by the present invention,
which combines monolayer replication, hydrogen-bonding, and
topochemical polymerization in order to achieve a self-replicating
monolayer system. The present invention features techniques that
are particularly useful for the synthesis of nanostructures sized
from about 2 nm to about 1000 nm. The method of the present
invention is highly controllable, can be used to replicate patterns
over many generations, and is a "one-pot" process producing
monolayers that are specifically cross-linked or patterned. In one
aspect, the apparatus and method of the present invention provide a
self-replicating monolayer system through polymerization of a
nanoparticle ensemble using a lithographically-defined template.
The present invention further provides a method for synthesis of
two-dimensional lithographically-defined single molecule polymers
that can be readily suspended in a solvent.
[0015] The self-replicating system of the present invention may be
implemented using lithography or other techniques known in the art.
Once created, the monolayers are used as templates for the growth
of inorganic colloids, such as colloids of metals, semiconductors,
and insulators. In one aspect, the invention features systems of
self-replicating monolayers. The systems include a group of
components, each of which may be varied, with the combination of
the components providing the self-replicating system.
[0016] A preferred embodiment of the present invention is a
self-assembling monolayer (SAM)-based replication scheme. An
initial monolayer is patterned and then used as a template for the
self-assembly of a second monolayer by molecular recognition. The
initial monolayer may optionally be polymerized, in order to
provide better lattice matching and structural rigidity of the
desired pattern. Once the second monolayer has formed through
self-assembly, it is polymerized in place. The two monolayers are
then separated through any suitable mechanism, forming a replicate
of the original monolayer. Both the replicate and the original
monolayer may now function as templates for monolayer assemblies,
and the process can be repeated, forming an exponential replication
system.
[0017] In a generic self-replicating monomer unit according to one
embodiment of the present invention, an ending unit that will not
interfere with the chosen recognition chemistry is attached by
methylene repeats to a polymerizable moiety. The polymerizable
moiety may be a single polymerizable unit, but preferably contains
two polymerizable units separated by some number of methylenes. The
polymerizable moiety is then attached by further methylene repeats
to recognition chemistry based on any suitable chemistry. Whatever
the choice for recognition chemistry, the template must display a
complementary recognition element.
[0018] The recognition element must be self-complementary, unless
there is a set of two replicating monomers. In an exemplary
two-component replication system utilizing two different kinds of
recognition chemistries, the initial template undergoes replication
cycles, while maintaining the two-dimensional segregation of the
two types of replicating monomers having compatible cross-linking
chemistry. During subsequent replications, the component domains
experience little or no mixing, allowing the two-component,
patterned assembly to be exponentially replicated. After
replication, selective mineralization and/or electroless plating
may produce a two-dimensional inorganic sheet having patterned
domains within it. In general, inorganic colloid growth may be
achieved through appropriate reduction chemistry of the desired
metal salts and the use of seed or template-mediated
nucleation.
[0019] More than two chemically compatible molecules may be used in
monolayer synthesis. Patterning of the initial template is
accomplished according to the defined regions of the two or more
molecules composing the monolayer. After replication is complete,
the two component replicates may then be mineralized or electroless
plated in a way that maintains the pattern of the replicants,
creating opportunities for making two-component inorganic colloids
that are patterned.
BRIEF DESCRIPTION OF THE DRAWINGS
[0020] FIG. 1 depicts prior art diacetylene polymerization on a
gold substrate by attachment of functionalized alkyl thiols;
[0021] FIG. 2 depicts a prior art approach to synthesis of a
multilayer film, wherein a second monolayer is grown on a
gold-alkyl thiol self-assembled monolayer via hydrogen bonding;
[0022] FIG. 3A illustrates the first part of a self-assembling
monolayer (SAM)-based replication scheme according to an embodiment
of the present invention;
[0023] FIG. 3B illustrates the second part of a self-assembling
monolayer (SAM)-based replication scheme according to an embodiment
of the present invention;
[0024] FIG. 4 depicts exemplary molecules that can be used in a
SAM-based system according to an embodiment of the present
invention;
[0025] FIG. 5A depicts a generic self-replicating monomer unit
utilized in an embodiment of the present invention;
[0026] FIG. 5B illustrates a two-component replication system
according to an embodiment of the present invention;
[0027] FIGS. 6A-B depict generalized replicating monomer units
assembling on a template according to an embodiment of the present
invention;
[0028] FIGS. 7A-B illustrate two-component nanoparticle
cross-linking and replication according to an embodiment of the
present invention;
[0029] FIG. 8 illustrates surface pattern recognition with
nanoparticles according to an embodiment of the present invention;
and
[0030] FIG. 9 depicts synthesis of a BisDA replicating monomer
according to an embodiment of the present invention.
DETAILED DESCRIPTION
[0031] The present invention combines monolayer replication,
hydrogen bonding, and topochemical polymerization in order to
achieve a self-replicating monolayer system. The self-replicating
system can be implemented using lithography or any other suitable
technique known in the art. Once created, the monolayers are used
as templates for the growth of inorganic colloids, such as colloids
of metals, semiconductors, and insulators. In one aspect, the
invention features systems of self-replicating monolayers. The
systems include a group of components, each of which may be varied.
The combination of the components provides the self-replicating
system.
[0032] Polymerization. In accordance with the present invention,
polymerization techniques are utilized to effect polymer formation
in the monolayer. A topochemical polymerization is typically
preferred, although a non-topochemical polymerization may also be
advantageously employed. A topochemical polymerization is
preferable because it will generally cause the least perturbation
of the monolayer conformation, either on a surface or in a
solution. Also, a topochemical polymerization generally does not
result in polymer formation by solution species, which can be
important when a system is to be replicated many times.
[0033] Polymerizations by externally controllable means relative to
the reaction mixture are preferred. Preferably, no additional
reagents are used to cause polymerization. Particularly suitable
polymerization methods include, but are not limited to,
`reagentless` polymerizations, such as where a polymerization
reaction is catalyzed by heat, by electromagnetic radiation, or by
particle radiation.
[0034] A two-dimensional, cross-linked polymer network is generally
preferred, and can be produced from monomers with two or more
reactive sites. Such cross-linked monolayers have been made using
Langmuir-Blodgett (LB) monolayer techniques (Ahmed et al., Thin
Solid Films 187: 141-153 (1990)). A cross-linked monolayer is
typically more structurally robust.
[0035] The polymerization reactions and replication steps are
typically carried out in a solvent. The solvent used to carry out
replication is generally selected for its ability to solubilize the
monolayer assemblies and the monomer feedstock.
[0036] Monomers and Monolayer. The "monolayer basis" is the base
monolayer system used to form patterns and serves as the initial
template for replication. Monolayers can be formed as
self-assembled monolayers (SAMs) on substrates (e.g., ultraflat
surfaces), or as LB monolayers at, for example, the air-water
interface.
[0037] Preferably, the monolayer template is created with as few
defects as possible, making it as close to atomically smooth as
possible. The monolayer basis should be patternable by one of the
methods known in the art for two-dimensional patterning. Both SAMs
and LB monolayers can be used. LB monolayers are readily prepared
in atomically flat form, and maintain high ordering even during
transfer to a substrate. SAM systems on gold typically exhibit a
measurable roughness, even on ultraflat gold substrates, which may
be due to the act of SAM creation itself in the gold/alkyl thiol
system. However, small step heights on a surface often do not
affect the chosen polymerization technique. Siloxane monolayers can
also be prepared on ultraflat surfaces such as glass and
silicon.
[0038] The monolayer basis, if it has an underlying set of lattice
constants, should match the lattice constants and geometries
required for the monolayer templating chemistry and the
polymerization chemistry. In addition, the polymerization employed
should result in a polymer with the requisite lattice constants and
angles needed for formation of another monolayer after
polymerization. For example, in a PDA system, the lattice spacing
between monomers is about 4.9 angstroms in order for polymerization
to occur. This lattice spacing should coincide with the lattice
spacing necessary for monolayer packing on a SAM or in a LB film,
as well as with the molecular recognition chemistry needed to
assemble a multilayer film. In order for the system of the
invention to successfully function as a self-replicating monolayer
system, all these factors must be considered during selection of
the ensemble of components.
[0039] The monomers used to form the replicating monolayers
normally incorporate all the structural moieties necessary to
effect the desired polymerization technique and/or monolayer
formation technique, as well as to influence such properties as
overall solubilities, dissociation methods, and lithographic
methods. Many monomers can be designed for use in templated
monolayer replication systems. The monomers typically contain at
least one, and preferably two, reactive functional groups. The
monomers also may contain a terminus bearing one or more molecular
recognition elements, such as, but not limited to, carbonyl
functionalities, heterocycles, and charged moieties. This terminus
is used to guide assembly of the second monolayer prior to
replication by polymerization. The monomers can also be designed to
enhance colloidal solubility of the resulting monolayers.
[0040] The molecules used to form organic monolayers generally
include various organic functional groups interspersed with chains
of methylene groups. The molecules are typically long chain carbon
structures containing methylene chains to facilitate packing The
packing between methylene groups allows weak Van der Waals bonding
to occur, enhancing the stability of the films produced and
counteracting the entropic penalties associated with forming an
ordered phase. In addition, hydrogen-bonding moieties may be
present at one terminus of the molecules, in order to allow
templating of an adjacent monolayer, in which case the
polymerizable chemical moieties are then placed in the middle of
the chain or at the opposite terminus.
[0041] As shown in FIGS. 3A and 3B, if a SAM-based system is used,
an additional molecule is generally utilized to form the initial
template. This additional molecule has appropriate functionality at
one of its termini in order to form a SAM. For example, on a gold
surface, a terminal thiol can be included. There are a wide variety
of organic molecules that may be employed to effect replication.
Topochemically polymerizable moieties, such as dienes and
diacetylenes, are particularly desirable as the polymerizing
components. These can be interspersed with variable lengths of
methylene linkers. Exemplary target molecules that can be used in a
SAM-based system are shown in FIG. 4. FIG. 5A depicts a generic
organic monolayer replicating monomer.
[0042] For an LB monolayer system, only one monomer molecule is
needed because the molecular recognition moiety can also serve as
the polar functional group for LB formation purposes. Lithography
can be carried out on a LB monolayer transferred to a substrate, or
directly in the trough. For example, an LB monolayer of diacetylene
monomers can be patterned by UV exposure through a mask or by
electron beam patterning.
[0043] Monolayer formation can be facilitated by utilizing
molecules that undergo a topochemical polymerization in the
monolayer phase, but not in the solution or gas phase. By exposing
the assembling film to a polymerization catalyst, the film can be
grown in situ, and changed from a dynamic molecular assembly to a
more robust polymerized assembly.
[0044] Since polymerization only occurs in the monolayer, monolayer
formation can be promoted by exposure to UV light or polymerization
catalysts. The inherent stresses and surface tensions of thin (1-10
m) two-dimensional polymer or inorganic films can be used to create
three-dimensional folded structures. "Molecular origami" can then
be practiced in solution.
[0045] Molecular Recognition. Any suitable molecular recognition
chemistry can be used in forming the assembly. Multilayers have
been successfully assembled based on electrostatic interaction, Van
der Waals interaction, metal chelation, coordination bonding (i.e.,
Lewis acid/base interactions), ionic bonding, covalent bonding, and
hydrogen bonding. The molecular recognition chemistry used
preferably will have spatial requirements compatible with the
polymerization technique employed. The strength of the interactions
used to assemble the replicate molecules onto the template
monolayer is preferably tuned both for optimal assembly (i.e., low
defect density) and for convenient release of the replicate from
the template.
[0046] Hydrogen bonding offers a straightforward approach. No
discrete bond forming steps are needed, and dissociation of
hydrogen-bonded networks may be caused by thermally heating them to
disrupt the hydrogen bonds. Multilayer film assembly in accordance
herewith may use hydrogen bonding of amides, carboxylic acids, and
amines. Conveniently, the lattice constants of amide-containing
films overlap with the lattice constants needed for diacetylene
polymerization. Readily reversible covalent/coordination bonds,
such as disulfides or metal chelated ensembles, may alternatively
be used, with reversibility being effected by oxidation/reduction
chemistry. Electrostatic/ionic bonding can also be reversibly
controlled by protonation-deprotonation reactions. Multilayer films
can advantageously be built up by carboxylate-amine
chemistries.
[0047] Dissociation. A variety of techniques may be employed to
effect the dissociation of the replicate monolayer from the
template monolayer. Controllable dissociation of the replicated
monolayer from the template monolayer is preferred. Suitable
dissociation mechanisms include, but are not limited to, heat
(e.g., similar to DNA denaturation), sonication, irradiation,
oxidation/reduction (e.g., electrochemical and reagent
chemistries), pH modification, solvent exchanges (e.g., solvent
polarity modification), and/or physical separation methods.
[0048] In addition, a mild "one-pot" procedure is preferred,
particularly a one-pot reaction that allows the entire replicating
system to be replicated many times. Controls that do not require
solvent removal or reaction work-up are also preferred, such as,
but not limited to, lightwave irradiation, heating, sonication,
electrochemical oxidation/reduction, addition of monomer feedstock
for the replication, and addition of acids or bases. Preferably,
these controls are arranged so that the system can perform many
replications.
[0049] As an example, a method of assembling multilayer films in
one pot using hydrogen bonded assembly chemistry is simple, cost
effective, and allows for the control of overall film thickness and
robustness by altering the hydrogen-bonding moieties, alkyl chain
lengths, and solution concentrations during the film formation
step. Preferred methods for separating the replicate from the
template in a hydrogen-bonded system include, but are not limited
to, the use of heat, sonication, radiation, and/or solvent
exchange. For example, a change in solvent polarity can be used to
disrupt hydrogen bonds.
[0050] Other suitable methods of separating the replicate from the
template, albeit typically less desirable, include physical
stripping from a surface-fixed template. In systems involving
covalent bonding between replicate and template (e.g., via
disulfides or metal coordination bonds), oxidation-reduction
chemistry can be used, either in an electrochemical fashion or by
direct chemical oxidants/reductants. In systems involving
ionic/electrostatic bonding, pH can be used as a control for
splitting the replicate and template. Other methods that are used
for microstructure manipulations, such as the placement of release
holes within the two-dimensional structure, may also be used to
facilitate the dissociation of the template from the replicate. In
particular, release holes allow solvent to access interior
locations within the structure, thereby increasing the likelihood
of splitting two flat sheets.
[0051] Monolayer Patterning. Any of the techniques known in the art
for monolayer patterning may be used for patterning of the initial
monolayer. Techniques useful in patterning a monolayer include, but
are not limited to, photolithography, e-beam techniques, focused
ion-beam techniques, and soft lithography. Various protection
schemes such as photoresist can be used for a SAM-based system.
Likewise, block copolymer patterns can be formed on gold and
selectively etched to form patterns. For a two-component system,
patterning can also be achieved with readily available
techniques.
[0052] Soft lithography techniques are especially convenient.
Ultraviolet light and a mask can be used for patterning the
monomers in place, after their assembly into a monolayer. For
instance, an unpatterned base monolayer may be used as a platform
for assembly of the UV/particle beam reactive monomer monolayer.
The monomer monolayer may then be patterned by UV photolithography,
e-beam lithography, or ion beam lithography, even though the base
SAM is not patterned.
[0053] Inorganics. The present invention also allows templating of
inorganic structures using replicated monolayers. Growth of
inorganic colloids can be achieved by various growth mechanisms
available for templated formation of inorganics on organic
surfaces, such as through appropriate reduction chemistry of the
desired metal salts and the use of seed or template-mediated
nucleation. Using the recognition elements that provide for
assembly of a second monolayer on the first, inorganic growth can
be catalyzed at this interface by a variety of methods. Colloidally
soluble inorganic structures can also be produced. Insulators,
semiconductors, and metals, are templatable using either
electroless plating techniques or mineralization.
[0054] Once the patterned monolayers have been made and replicated
as many times as desired, the monolayers can be used as templates
for the growth of inorganic compounds in the form of colloids
bearing the shape of the patterned organic monolayer. Insulators
can be patterned by carbonyl functionalities; it is well known that
calcium carbonate and silica are templated by various carbonyl
functionalities such as carboxylic acids and amides. By controlling
the crystal growth conditions, it is possible to control the
thickness and crystal morphology of the mineral growth. Titanium
dioxide can also be templated.
[0055] Templated electroless plating techniques can be used to
synthesize metals using existing organic functional groups. In
particular, by chelating metal atoms to the carbonyl moieties of
the organic replicates, electroless metal deposition can be
catalyzed on these organic replicates, forming patterned metallic
colloids. For instance, Cu, Au, Ni, Ag, Pd, Pt and many other
metals plateable by electroless plating conditions may be used to
form two-dimensional metal colloids in the shape of the organic
monolayer that has been replicated. By controlling the electroless
plating conditions, it is possible to control the thickness of the
plated metal layer. If nanoparticles are attached to the
hydrogen-bonding surface, such as, for example, covalently by
chemical modification, an inorganic solid can be formed by melting
the nanoparticles together. By controlling the size and thickness
of the nanoparticle layer, the thickness of the sintered metal
layer can be controlled. Likewise, by attaching seed nanoparticles
to the organic template by hydrogen bonding, these seeds can be
used as catalysts for electroless plating onto the organic
template.
[0056] Carbonyl moieties may be used for templating of
semiconducting materials as well, forming semiconducting colloids
based on the shape of the organic replicant monolayers.
Semiconductors of the II-VI type (CdSe, ZnO, and the rest of the
analogs) have been reported (Saito et al., Adv. Mater. 14(6):
418-421 (2002)), and III-V semiconductors are also feasible, using
mineralization, electroless plating, or seed mediated growth.
[0057] One major benefit of the method of the present invention is
that the replicated monolayers are used as templates for inorganic
structures. Additionally, by using two compatible recognition
chemistries within the same monolayer, such as an amide and a
carboxylic acid moiety, the growth of separate inorganic compounds
and structures can be templated in whatever pattern was defined on
the starting template.
[0058] Assaying a replicating organic monolayer system is a
difficult task. Techniques that are suitable for assaying small
quantities of shapes include AFM or cryo-TEM techniques. Growth of
inorganic colloids using the organic monolayers as templates can
also be a useful assay technique, allowing for a relatively
straightforward examination of small evaporated aliquots of
solution by, for instance, SEM, relying on a metal colloid to show
up clearly by SEM. Metal colloids grown on organic monolayers also
provide a better spectroscopic handle at the very low
concentrations that are likely to be encountered during the early
replication cycles.
[0059] Indeed, specific shapes of replicating organic monolayers,
when `developed` with a metal, can be expected to have distinct
spectroscopic signatures in the UV-vis or infrared regions due to
plasmon bands. For instance, colloidal silver triangles have
different spectra depending on their size and quality. Such
distinctive spectroscopic signatures can be used to ascertain the
quality and fidelity of the replicating monolayer system, thus
allowing for process optimization during replication.
[0060] In addition to replication of monolayers in solution,
replication of patterned monolayers may also be conducted on a
surface. Multilayer films involving insulating or semiconducting
layers can be produced. Particularly, the assembly of multilayer
hydrogen-bonded films of a controllable thickness can be achieved
in a one-step process. By controlling the concentration of a
difunctional long-chain alkyl molecule with termini that include
hydrogen-bonding groups, multilayer films can be produced, the
thickness of which depend on the concentration of the solution. If
this approach is combined with a remotely polymerizable (UV
initiated for instance) moiety in the component molecules, the
resulting film so produced will generally be more robust than
previous one-step methods (Miura et al., Thin Solid Films 393:
59-65 (2001); Viana et al., Phys. Chem. Chem. Phys. 3: 3411-3419
(2001)). In addition, a greater range of thicknesses (number of
multilayers) should be possible.
[0061] Additionally, topochemical polymerization can aid in the
monolayer assembly process itself. Since polymerization only occurs
in the monolayer, monolayer formation can be triggered and promoted
by exposure to UV light or polymerization catalysts. Hence, the
process of monolayer formation may be kinetically speeded up since
the reverse reaction (dissociation of monomer from the monolayer)
is not possible once the monomer molecule has been added to a
growing polymer chain. By this method, the formation of thick
multilayers through hydrogen bonding interactions is made
possible.
[0062] An example of the system of the present invention is
illustrated in FIGS. 3A and 3B, which depict the parts of a
SAM-based replication scheme. As shown in FIG. 3A, an initial
monolayer 302, is patterned by a chosen technique. In the example
of FIG. 3A, a thiol chain is patterned 304 on patterned gold film
304 to form a SAM 302 with amide caps 308. Initial monolayer 302 is
then used as a template for the self-assembly 309 of a second
monolayer 310 on top of it by molecular recognition. The initial
monolayer 302 may itself be optionally polymerized 312, in order to
provide better lattice matching and structural rigidity of the
desired pattern. In the example shown, self-assembly step 309 is
initiated by addition of a PDA precursor chain with amide cap.
[0063] Once the second monolayer 310 has formed through
self-assembly, it is polymerized 316 in place. The two monolayers
are then separated 318 through any suitable mechanism, such as
solvent exchange or heat, to form replicate 320 of the original
monolayer 302. Both replicate 320 and the original monolayer 302
can now function as templates for monolayer assemblies 330, 332. As
depicted in FIG. 3B, the process can be repeated many times,
forming an exponential replication system.
[0064] A preferred embodiment of the example system illustrated in
FIGS. 3A and 3B utilizes diacetylene polymerization. The lattice
constants appropriate for the polymerization, the amide hydrogen
bonding space requirements, and the thiol-gold contact spacing all
fall within essentially the same range, which is preferred. Thus,
the spatial requirements of the polymerization reaction and
molecular interactions (e.g., hydrogen bonding, electrostatic or
covalent interactions) overlap. For a Langmuir-Blodgett-based
system, there is no issue with the underlying substrate, which also
needs to be lattice matched.
[0065] FIG. 4 depicts exemplary target molecules (in this case, for
C9 chains) designed for use in the system illustrated in FIGS. 3A
and 3B. In general, the number of methylene linker carbons 402 used
as spacers between the polymerizable moieties 410 and the
recognition elements 420 can be quite varied, being typically in
(but not limited to) a range of 1 to 20. Thus, in the exemplary
molecules of FIG. 4, any entity labeled "C" followed by a number
(referring to the number of methylene units) may be varied in order
to construct different target molecules suitable for use in the
present invention.
[0066] Molecules 401, 441, 451, 461 are intended to be used for the
formation of a patterned template SAM on a gold surface, and allow
for the use of either amide or carboxylate hydrogen bonding as the
organizing principle for templated replication. In particular,
molecules 401, 441 incorporate a polymerizable diacetylene unit,
which may be beneficial in locking in the desired lattice constants
and ordering within the base SAM template. However, molecules 451,
461 may work just as well for the formation of a base SAM patterned
template, and polymerization is not required. Ending unit 430 will
be bound to the gold surface in a SAM, and will not interfere with
the monolayer templating effect.
[0067] Molecules 411, 421, 431 are potential replicating monomers.
Molecules 421, 431 have two polymerizable units 410 in the chain,
allowing for thorough cross-linking of the monolayer. The family of
replicating monomers exemplified by molecule 431
(Hentriaconta-11,13,20,22-tetraynoic acid) and by molecule 421
(Hentriaconta- 11,13,20,22-tetraynoic acid amide) is particularly
desirable for this invention. Also useful are
Triaconta-10,12,19,21-tetraynoic acid amide and
Triaconta-10,12,19,21-tetraynoic acid. A family of molecules which
are especially useful for the invention is therefore defined as
molecules of the type of molecule 431
(Hentriaconta-11,13,20,22-tetraynoic acid) or molecule 421
(Hentriaconta-11,13,20,22-tetraynoic acid amide), which have two
diacetylene units linked by a methylene chain of from 1 to 20
carbons to form a bis(diacetylene) unit, and which have an alkyl
chain of from 1 to 20 carbons terminating in an inert functionality
such as a methyl on one end of the bis(diacetylene) unit, and which
have an alkyl chain of from 1 to 20 carbons terminating in an amide
or carboxylic acid at the other end of the bis(diacetylene)
unit.
[0068] While in the embodiment shown molecular recognition between
monolayers is achieved by the bonding between amide functionalities
or the bonding between carboxylic acid functionalities, many other
functionalities may be advantageously utilized in the present
invention. Certain other suitable functionalities may require
additional components and/or additional steps in the replication
process that are apparent to one of skill in the art.
[0069] FIG. 5A depicts a generic self-replicating monomer unit, of
which the molecules in FIG. 4 are specific examples. In FIG. 5A,
ending unit Z 502 for the monomer chain may be--methyl, a
functionality designed to affect the solubility of the monomer or
resulting colloidal shape (such as, for example, --CH.sub.2OH),
--CH.sub.2OBn, --NMe.sub.2, or any other group that will not
interfere with the recognition chemistry. Ending unit Z 502 is
attached by methylene repeats m 504 to polymerizable moiety Polym
510. Polymerizable moiety Polym 510 may be a single polymerizable
unit, but preferably contains two polymerizable units separated by
some number of methylenes. Polymerizable units such as
diacetylenes, olefins, or dienes are particularly suitable.
[0070] Polymerizable moiety Polym 510 is further attached by
methylene repeats n 514 to recognition chemistry Recog 520.
Methylene repeats m 504, n 514 are used for increasing order and
van der Waals interactions in a SAM. Recognition chemistry Recog
520 may be based on any suitable chemistry, including, but not
limited to, hydrogen bonding, such as amide-amide bonding, or more
complex hydrogen-bonding patterns, such as barbituric acid or
diaminotriazine. Whatever the choice for recognition chemistry
Recog 520, the template must display a complementary recognition
element. The recognition element must be self-complementary unless
there is a set of two replicating monomers.
[0071] FIG. 5B depicts an exemplary two-component replication
system utilizing two different kinds of recognition chemistries
(i.e., the monolayer is composed of two chemically compatible
molecules). In FIG. 5B, initial template monolayer 550 containing
component A, which contains a pattern of component B 551 within it,
undergoes replication cycles 555, maintaining the two-dimensional
segregation of replicating monomers 560, 561 (for two different
types of replicating monomer units with compatible cross-linking
chemistry). After replication, selective mineralization and/or
electroless plating 565 produces a two-dimensional inorganic sheet
570 with patterned domains 575 within it.
[0072] One suitable system utilizes two different recognition
chemistries in the diacetylene system, amide-based and carboxylic
acid-based. Since these systems have very similar lattice
constants, they can form the basis of a self-replicating system
composed of two components. During subsequent replications, the
carboxylic acid domains and the amide domains experience little or
no mixing, allowing the two-component, patterned assembly to be
exponentially replicated. Use of a metal ion to chelate to the
carboxylate moiety may be useful in keeping the two components well
segregated during replication cycles, maintaining the pattern
integrity within the assembly.
[0073] More than two chemically compatible molecules may be used in
monolayer synthesis. Patterning of the initial template can occur
according to the defined regions of the two or more molecules
composing the monolayer. After replication is complete, the two
component replicates can then be mineralized or electroless plated
in a way that maintains the pattern of the replicants, creating
opportunities for making two component inorganic colloids that are
patterned.
[0074] An alternate embodiment of the present invention provides a
replicating system wherein the replicating monomer is not
necessarily self-complementary. In this case, there is no pattern
in the monolayer to be replicated, but there are two types of
monolayers in the system, each of which are composed of different
monomers. In an example implementation, a monomer with Adenine as
the recognition element forming the basis of a monolayer template
(to use DNA as a simple example) is paired with another monomer
terminating in Thymine (the H Bond partner of Adenine in DNA) in
order to replicate this monolayer. This provides one template
terminating in Adenines, and another one terminating in Thymines
after disassociation. The system of this embodiment is therefore
capable of self-replication, but requires two separate monomers
present at once (typically in equal amounts).
[0075] Replication system based on nanoparticles. The present
invention may be extended to replication of two-dimensional
assemblies of nanoparticles, an example that is also instructive as
to the requirements for replication of monolayers according to the
present invention. The basic requirements of a replication system
based on nanoparticles are depicted in FIGS. 6A-B. The key
component of the replicating system is generalized replicating
monomer unit 610. Choices regarding patterning to form the initial
template, as well as the replication cycle, are determined at least
in part by the make-up of replicating monomer unit 610.
[0076] As shown in FIGS. 6A-B, monomer unit 610 is built on
inorganic or organic nanoparticle 612 to which multiple
Crosslinkers 615 are attached. The number of Crosslinkers 615
attached to nanoparticle 612 may vary, but monomer unit 610 should
have the ability to cross-link with more than 2 adjoining monomer
units in the two-dimensional matrix. In addition, monomer unit 610
must incorporate Recognition Element 620 capable of binding to
template 640 reversibly (yet strongly enough to form a complete
monolayer on the template), in order that a replication cycle can
be performed. As multiple replicating monomer units 610 assemble on
template 640 in the xy plane, it is important that they be able to
crosslink 615 in multiple directions and not just form chains. This
allows formation of a robust sheet that replicates the pattern.
[0077] An additional desirable property of the monomer unit, though
not strictly necessary for replication, is that polymerization of
the monomer takes place predominantly when it is bound to the
template. In other words, unproductive polymerization of the
replicating monomer unit, such as that which takes place in
solution away from the 2-D template, is desirably minimized,
preferably having a very low rate relative to the rate of the
desired polymerization reaction that occurs when the monomer is
bound to the template. This eases purification of the replicated
structures, and makes for more efficient use of the replicating
monomer. Minimization of unwanted polymerization helps to make the
system of the present invention a practical replication system.
[0078] Topochemical polymerization is a very useful reaction in
this context, because it helps ensure that polymerization occurs
exclusively on the surface where the monomers can form an organized
array resembling the solid state. Groups that perform topochemical
polymerization, such as diacetylenes or butadienes, can thus be
used as linkers. However, polymerizations that can be speeded up by
many orders of magnitude due to proximity effects on the template
are also useful. These may involve a two-member set of replicating
monomer units.
[0079] For example, one of the monomers (A) may possess epoxides or
other relatively electrophilic moieties within the ligand shell of
a nanoparticle, as seen in FIGS. 7A-B. The other monomer unit (B)
then should possess nucleophilic moieties within its ligand shell
that are expected to react with monomer (A) upon close proximity.
However, such reaction is normally slow when the two monomers are
simply dissolved in the same solution. Only when they enter a phase
involving intimate contact and close packing (such as occurs within
a monolayer) do these groups react. There is some precedent for
this application within the realm of nanoparticle chemistry, as it
is often the case that nanoparticles are stable in solution but
irreversibly agglomerate in the solid phase (Leff et al., Langmuir
12: 4723-4730 (1996)). Both monomers (A) and (B) contain the same
recognition chemistry, and distribute evenly across a template
surface, giving on average an ensemble mixture of (A) and (B) which
may form a cross-linked sheet.
[0080] FIGS. 7A-B depict an especially robust four-hydrogen bond
self-complementary recognition motif that is useful for large
replicating monomers. In FIG. 7A, methylene chains 710 shield
electrophilic amines 720 from epoxide units 730 while in the
solution phase. As seen in FIG. 7B, once on template 750 with
exposed quadruple hydrogen-bonding groups 760, methylene chains 710
intercalate, and amines 720 and epoxides 730 react to create a
crosslinked sheet.
[0081] Nanoparticles that are monofunctionalized regarding the
recognition element are important for this type of a
self-replicating monolayer system. If the replicating monomer
nanoparticles are not monofunctionalized with regards to the
recognition element, forming multilayers and/or polymeric chains of
the replicating monomers will become problematic due to unwanted
cross-linking The patent family of Hainfeld et al (U.S. Pat. No.
5,521,289, Hainfeld et al. (1996); U.S. Pat. No. 6,121,425,
Hainfeld et al. (2000)) discloses methods for making
monofunctionalized nanoparticles that involve HPLC purification and
various precipitations. Various statistical methods can also be
envisioned for obtaining monofunctionalized nanoparticles (which
can otherwise be fully functionalized with the cross-linking
ligands). Other suitable methods for making monofunctionalized
nanoparticles are described in co-pending U.S. patent application
Ser. No. 10/621,790, ("Nanoparticle chains and preparation
thereof", Jacobson et al., Jul. 17, 2003).
[0082] FIG. 8 depicts an exemplary embodiment of the method of the
present invention, achieving replication of a structure patterned
on gold. The method of FIG. 8 includes forming gold patterns 805 on
a surface 810 by patterning with, for example, photoresist and then
exposing the underlying gold surface. Boundaries 812 formed by
photoresist define the shape to be replicated. Thereafter,
nanoparticles 815 (formed from Au, Ag, or other elements) are
anchored to the patterned gold surface via thiol linkages 820 or
some other recognition element. Upon heat curing, the nanoparticles
can be melted or sintered together 830, forming a solid sheet
replicate 840 of the patterned gold, having a thickness
approximately half the diameter of starting nanoparticles 815.
[0083] Alternatively, solution stable nanoparticles that
agglomerate in the solid phase can be used, so long as they are
monofunctionalized with a recognition moiety having reversible
binding. This provides a relatively simple replicating unit. After
sintering or agglomeration on the 2-D template, the replicate is
then separated from the surface by thermal energy or mechanical
energy, for instance by heating in a solvent or mechanical
stripping. The replicant may then itself be used as a template for
further replication.
[0084] Sintering of nanoparticles is one technique known for
producing patterns on a surface (Fullam et al., Adv. Mater. 12:
1430-1432 (2000); U.S. Pat. No. 6,294,401, Ridley et al. (2001);
Wuelfing et al., Chem. Mater. 13: 87-95 (2001)). A variety of
capping groups and elemental compositions can be used to help
determine the sintering conditions needed. Nanoparticles also
spontaneously "melt" when the capping groups are removed, so more
labile capping groups such as amines on gold may be used to
facilitate formation of gold films. A replication system based on
nanoparticle sintering or melting can thus be designed to allow
exponential replication.
[0085] Further specific examples, embodiments and synthesis
methods. The synthesis of the BisDA replicating monomer 980 was
carried out using Cadiot-Chodkiewics coupling chemistry, as is
shown in FIG. 9. The Cadiot-Chodkiewics couplings using amines as
solvents were found to be far more effective for these compounds
than the traditional reagent set. (Alami et al., Tet. Lett. 37(16):
2763-5 (1996)) Molecule 910 1,8-Nonadiyne is commercially
available. Molecule 920 1-iodo-1-decyne(Narayana, Rao et al. 1995)
has been previously synthesized. Using cuprous iodide and
pyrollidine as solvent, these were coupled to produce molecule 940.
Molecule 940 was then lithiated to produce molecule 960. Molecule
960 may then be coupled using cuprous iodide and pyrollidine with
10-undecynoic acid amide to yield molecule 980. 10-Undecynoic acid
amide (Crisp et al., Tetrahedron 53(4): 1505-1522 (1997)) has been
previously synthesized as well. The bis(diacetylene) 980 is quite
labile to heat and light in the solid state or on silica gel, so it
is stored in a methylene chloride solution at liquid nitrogen
temperatures. Full synthetic details follow. Included is a
synthesis of 11-dodecynoic acid amide, which can be substituted in
step 970 of FIG. 9 to result in the bis(diacetylene) replicating
monomer 421 shown in FIG. 4.
[0086] Synthesis of molecule 16-mercaptohexadecanamide, similar in
function in the context of the present invention as molecule 461 of
FIG. 4, was achieved by the method reported by Nuzzo and coworkers
(Nuzzo et al., J. Am. Chem. Soc. 112: 558-569 (1990)). This
molecule was used to create a base SAM template for replication of
monomer 980.
[0087] 11-dodecynoic acid amide (an alternate chain for building
the BisDA replicating monomer) 421. 11-Dodecyne nitrile (3.936 g,
22.2 mmol) and potassium carbonate (0.441 g, 3.19 mmol) were added
to a flask and inerted with nitrogen, followed by the addition of
6.7 mL of DMSO. The flask was cooled in an ice bath and 2.7 mL of
30% H.sub.2O.sub.2 was added slowly via syringe. The reaction was
allowed to warm to room temperature and stirred overnight.
Additional hydrogen peroxide can be added if the reaction shows
remaining starting material. The reaction was diluted with 100 mL
of diethyl ether and worked up by extraction with 1 M HCl
(3.times.80 mL), and with water (3.times.80 mL). The organic phase
was dried over MgSO.sub.4 and concentrated in vacuo to yield 2.352
g of pure A. 54% yield; .sup.1H NMR (CDCl.sub.3) .delta. 5.55 (s,
2H, NH.sub.2), 2.18 (m, 4H, CH.sub.2-C.ident.C & CH.sub.2-CO),
1.92 (t, J=2.4 Hz, 1H, H-C.ident.C), 1.61 (m, 2H, CH.sub.2-C-CO),
1.49 (m, 2H, CH.sub.2-C-C.ident.C), 1.26 (m, 10H, CH.sub.2 chains);
MS (ESI) [M+Na].sup.+ calc. 218.1515 found 218.1516. Elemental
analysis calc. for C.sub.12H.sub.21NO: C, 73.80; H, 10.84; N, 7.17.
Found: C, 74.14; H, 10.99; N, 7.54.
[0088] Nonadeca-1,8,10-triyne (940). Pyrollidine (20 mL) and CuI
(0.65 g, 3.42 mmol) were added to a nitrogen flushed reaction
vessel. Nona-1,8-diyne (1.58 g, 13.17 mmol) was added via syringe.
1-Iodo-1decyne (2.26 g, 8.53 mmol) was added via syringe dropwise
to the solution over ten minutes. The reaction was stirred under
nitrogen for 24 h. The reaction mix was then quenched with ammonium
chloride (10 mL), separated with diethyl ether, and dried with
anhydrous magnesium sulfate. Nonadeca-1,8,10-triyne was then
isolated using silica column chromatography with a 1% ether/hexane
eluting solution obtaining 1.06 g of an oil. 50% yield; .sup.1H NMR
(CDCl.sub.3) .delta. 2.29 (m, 4H, CH.sub.2-C.ident.C), 2.22 (dt,
2H, CH.sub.2-C.ident.C, J=7, 2.7 Hz), 1.97 (t, 1H, H-C.ident.C,
J=2.7 Hz), 1.54 (m, 6H, CH.sub.2-C-C.ident.C), 1.33-1.40
(sextuplet, 2H, CH.sub.2-CH.sub.2-CH.sub.3), 1.27 (m, 10H,
C-CH.sub.2-C), 0.88 (t, 3H, CH.sub.3); .sup.13C NMR (CDCl.sub.3)
.delta.: 84.62, 77.99, 77.36, 68.63, 65.76, 65.45, 32.21, 29.54,
29.46, 29.25, 28.72, 28.34, 28.31, 28.23, 23.06, 19.61, 19.52,
14.53; MS (ESI) [M+Na].sup.+ calc. 279.2083 found 279.1723 (very
unstable to any MS technique). Elemental analysis calc. for
C.sub.19H.sub.28: C, 88.99; H, 11.01. Found: C, 88.80; H,
10.96.
[0089] 1-Iodo-nonadeca-1,8,10-triyne (960). Nonadeca-1,8,10-triyne
(0.802 g, 3.133 mmol) and anhydrous THF (96 mL) was cooled to
-78.degree. C. in a dry flask under nitrogen.
LiN[Si(CH.sub.3)].sub.2 (LHMDS) in THF (3.76 mmol) was added to the
reaction mix slowly via dry syringe. In a separate flask I.sub.2
(9.55 g, 3.76 mmol) was dissolved in dry THF (20 mL). The iodine
solution was added dropwise to the nonadeca-1,8,10-triyne solution
until reaction completion (notably becoming orange-red). The
reaction was stirred for 30 min, and slowly warmed to room
temperature. The reaction was extracted with diethyl ether and 1M
K.sub.2S.sub.2O.sub.3. The organic phase was dried over anhydrous
MgSO.sub.4, and concentrated by evaporation to yield
1-iodo-nonadeca-1,8,10-triyne (0.93 g, 2.45 mmol). GC/MS showed no
starting material remaining 79% yield; .sup.1H NMR (CDCl.sub.3)
.delta. 2.15-2.33 (m, 6H, CH.sub.2-C.ident.C), 1.48 (m, 6H,
CH.sub.2-C-C.ident.C), 1.33-1.39 (m, 2H,
CH.sub.2-CH.sub.2-CH.sub.3), 1.28 (m, 10H, C-CH.sub.2-C), 0.85 (t,
3H, CH.sub.3).
[0090] Triaconta-10,12,19,21-tetraynoic acid amide (BisDA) (980).
CuI (0.126 g, 0.66 mmol) and 10-undecynoic acid amide (0.29 g, 1.59
mmol) were added to a flask and inerted with nitrogen. Pyrollidine
(5 mL) was then added. In a separate flask
1-Iodo-nonadeca-1,8,10-triyne (0.5 g, 1.3 mmol) was mixed with
pyrollidine (5 mL) and subsequently added slowly to the amide
solution. The reaction mix was left in darkness under nitrogen for
48 hours, then quenched with aqueous 1M NH.sub.4Cl (10 mL), and
worked up with CH.sub.2Cl.sub.2 and 1 M HCl. The organic was dried
over anhydrous MgSO.sub.4. Organic products were concentrated by
rotary evaporation, although polymer formed, decreasing yield.
Hexanes trituration removed unreacted
1-Iodo-nonadeca-1,8,10-triyne. Desired product was obtained by
several crystallizations from hexanes/ethyl acetate, again under
dark conditions. All handling of the solid was done under red
light. Final product triaconta-10,12,19,21-tetraynoic acid amide
was made up of white crystals (0.377 g, 0.86 mmol) and was stored
frozen (liquid nitrogen) in methylene chloride. 65% yield; .sup.1H
NMR (CDCl.sub.3) .delta.: 5.31 (s, 2H, NH.sub.2), 2.22-2.26 (m,
10H, CH.sub.2-C.ident.C & CH.sub.2-CO), 1.58-1.66 (quin, 2H,
J=7, CH.sub.2-C-CO), 1.45-1.56 (m, 8H, CH.sub.2-C-C.ident.C),
1.28-1.4 (m, 20H, C-CH.sub.2-C), 0.86-0.91 (t, 3H, CH.sub.3);
.sup.13C NMR (CDCl.sub.3) .delta. 175.69, 77.98, 77.84, 77.34,
65.69, 69.45, 65.37, 57.68, 53.63, 38.37, 38.35, 33.80, 32.97,
32.92, 32.03, 29.34, 29.27, 29.07, 28.94, 28.55, 28.47, 28.26,
28.26, 28.06, 27.17, 25.67, 22.86, 19.39, 19.32 14.30. MS (ESI)
[M+H].sup.+ calc. 436.3574 found 436.3560.
[0091] Formation of a patterned monolayer template utilizing amide
hydrogen bonding, followed by formation of the first replicate.
Patterning and formation of an initial template for replication
using the replicating monomer triaconta-10,12,19,21-tetraynoic acid
amide (BisDA 980) can be performed as follows. An ultraflat gold
substrate is prepared by a template stripping technique. The
substrate is immediately stamped with a patterned
poly(dimethylsiloxane) stamp which has been wet-inked or
contact-inked with octadecanethiol (Libioulle et al., Langmuir 15:
300-304 (1999)). After stamping, the substrate is immersed into a
solution of 0.1 mM 16-mercaptohexadecanamide in ethanol for 4
hours. The substrate is then transferred to a solution of 0.25 mM
BisDA (in decalin, under low light conditions).
[0092] The substrate is soaked in the solution of BisDA in darkness
for 12-16 hours. Upon removal of the substrate, it is blown dry
with nitrogen, but not rinsed. Areas of the substrate exclusively
covered with a bis(diacetylene) adlayer dewetted. The substrate is
then polymerized in a nitrogen atmosphere for 2 minutes using a UV
pen lamp at 254 nm, forming a cross-linked replicate of the
template pattern. The amount of UV exposure is important for proper
cross-linking of the replicate structure. Two minutes is at the
lower end of the preferred exposure time, while 60 minutes is at
the upper end. In addition, the degree of order in the patterned
template monolayer is critical. The higher the degree of order, the
better the replicate monolayer forms and is polymerized. The degree
of order for both the template monolayer and the replicate
monolayer can be judged by contact angle, ellipsometry, and grazing
angle FTIR among the typical techniques.
[0093] The solvent used for formation of the pre-polymerized
replicate/template structure (often called an adlayer structure in
the literature) is important. Non-hydrogen bonding solvents are
preferred when using the BisDA system. Solvents such as decalin
(decahydronapthalene) form the pre-polymerized adlayer structure
quite well. Other similar solvents, such as hexadecane and dodecane
will also be expected to perform similarly. In addition, comixtures
of decalin and toluene with ratios up to 1:3 decalin:toluene have
been found to produce polymerizable adlayer structures. Other
mixtures of solvents that allow for the desired hydrogen bonding
interaction in the case of the BisDA molecule and similar molecules
are included as possible solvents for use during replication
cycles.
[0094] Using soft lithography, templates with features of many
microns down to 100 nm are accessible. For very small templated
shapes and features, an alternate fabrication technique may be
needed due to difficulties with alkyl thiol ink diffusion. Also,
alkyl thiol ink diffusion may create some disorder at the edges of
a given pattern, decreasing the resolution of a replicate
monolayer. An approach based on an inorganic e-beam resist, such as
HSQ, should make it possible to directly fabricate thiol patterns
with very small features on ultraflat gold.
[0095] Liftoff or `melting` of the first replicate. The patterned
replicate monolayers are themselves soluble and can be used to
begin replication cycles in solution, away from the patterned
surface. For instance, the shapes can be lifted off from the
substrate in polar solvents that are capable of solubilizing the
replicate monolayers, which have alkyl groups on one side and amide
groups on the other side. The monolayer sheets in the case of BisDA
are approximately 2.5 nm thick, as judged by ellipsometry
measurements on a surface. These monolayer sheets may or may not
remain flat when they are solubilized, and their degree of
curvature and aggregation will be dictated by the solubility
parameters of the solvent in which they are dissolved. Appropriate
solvents for the shapes include warm chloroform and
N-methyl-pyrrolidinone. Further solvents with similar solubility
characteristics are also appropriate for solvation, such as, but
not limited to, dichloroethane and other halogenated solvents, and
the large family of dipolar aprotic solvents which are well known
to disrupt hydrogen bonding (for example dimethylsulfate,
hexamethylphosphoramide, dimethylformamide, N,N-dimethyl
acetamide). Solvation of replicated monolayer structures will also
depend in large part on the size and shape of the pattern. Larger
micron and higher-sized patterns may be more prone to aggregation
that will inhibit further replication cycles. Smaller patterns
below 1 micron in size will be more soluble and easier to
replicate.
[0096] Solution replication of monolayer patterned shapes.
Replication chemistry is preferably conducted in fluorinated
labware to prevent loss of replicated monolayers due to surface
adhesion. In general, the replication system is kept in darkened
conditions to ensure that unnecessary degradation of the
replicating monomers or monolayers does not occur. A solvent such
as decalin is used for chelation of the replicating monomers to the
template monolayers. The solution is exposed to UV light, 254 nm.
In order to separate the replicated monolayer from the template
monolayer, several options exist depending on the size of the
replicated shape/pattern. Heating of the decalin solution may
suffice. Addition of more replicating monomer, so that it breaks
apart the two monolayer sheets, may also be useful. Solvent
addition in the form of a volatile chlorinated solvent, such as
chloroform or methylene chloride, combined with heating, may
further be a useful technique. Or a combination of these options
may be necessary, again depending on the size of the replicated
pattern. Upon starting the next replication cycle, removal of any
added chlorinated solvent can be accomplished by vacuum
evaporation, since decalin has a much lower volatility than a
solvent such as chloroform.
[0097] Monitoring of replication cycle progress can be assayed in
many ways. Since the BisDA monomer forms a polymer sheet with a
high absorption coefficient in the visible light region, simple
UV-vis monitoring may be useful. In addition, assays based on
taking aliquots can be used. An aliquot may be analyzed by AFM
(contact, non-contact, tapping, either after drying the aliquot or
in the solution phase). Alternatively, cryo-TEM techniques based on
a flash freeze and metal evaporation at liquid nitrogen
temperatures or mass spectrometry techniques can be used. A
technique based on electroless plating or immunogold-silver plating
can be used for either TEM or SEM evaluation.
[0098] Preparation of ultraflat gold substrates. Ultraflat template
stripped gold substrates are fabricated using mica from SPI (grade
V-4 muscovite) as follows. 150 nm of gold is e-beam evaporated at 2
A.degree. /sec onto freshly cleaved mica, followed by 50 nm of
titanium at 2-3 A.degree. /sec, as monitored by QCM. The e-beam
chamber is typically at 3*10.sup.-6 torr, with no temperature
control on the substrates. These gold substrates are then coated
with a layer of spin-on-glass to prevent alloying of indium with
the titanium and gold. Filmtronics SOG 20B is applied by static
dispensing, followed by spinning at 2000 rpm for 30 seconds. The
substrates are soft-baked at 80, 150, and 250.degree. C. for one
minute each. The substrates are then immediately placed upside down
onto a glass slide covered with molten indium at 250.degree. C. on
a hot plate. For 1.4 cm.sup.2 mica substrates, a 1 cm.sup.2 piece
of 10 mil thick indium foil is more than adequate. The mica is
pressed firmly down with a hot weight to form an indium/gold/mica
sandwich. After 1-2 min, the substrates are set aside to cool, and
can be stored until needed. The sandwich can be cleaved by placing
it in hot DI water (80-100 C) for about 10 minutes. Trimming a side
of the mica aids this process, thus ensuring that one edge is not
`sealed` by indium or spin-on-glass. The gold surfaces thus
produced have RMS roughness values of 0.35-0.45 nm as measured by
AFM.
[0099] The apparatus and method of the present invention,
therefore, provide a self-replicating monolayer system. The present
invention features techniques that may be advantageously employed
for making nanostructures of sizes from about 2 nm to about 1000
nm. The method of the present invention is highly controllable, can
be used to replicate patterns over many generations, and is
preferably, though not required to be, a "one-pot" process
producing monolayers that are specifically cross-linked or
patterned. In one particular embodiment, the system of the
invention utilizes polymerization of a nanoparticle ensemble using
a lithographically-defined template. Another particular embodiment
of the present invention provides a method for synthesis of
two-dimensional lithographically defined single molecule polymers
that can be readily suspended in a solvent. Each of the various
embodiments described above may be combined with other described
embodiments in order to provide multiple features. Furthermore,
while the foregoing describes a number of separate embodiments of
the apparatus and method of the present invention, what has been
described herein is merely illustrative of the application of the
principles of the present invention. Other arrangements, methods,
modifications and substitutions by one of ordinary skill in the art
are therefore also considered to be within the scope of the present
invention, which is not to be limited except by the claims that
follow.
* * * * *