U.S. patent application number 13/473536 was filed with the patent office on 2012-09-06 for etching and hole arrays.
This patent application is currently assigned to Northwestern University. Invention is credited to Chad A. Mirkin, Khalid Salaita.
Application Number | 20120225251 13/473536 |
Document ID | / |
Family ID | 39644987 |
Filed Date | 2012-09-06 |
United States Patent
Application |
20120225251 |
Kind Code |
A1 |
Mirkin; Chad A. ; et
al. |
September 6, 2012 |
ETCHING AND HOLE ARRAYS
Abstract
Lithographic and nanolithographic methods that involve
patterning a first compound on a substrate surface, exposing
non-patterned areas of the substrate surface to a second compound
and removing the first compound while leaving the second compound
intact. The resulting hole patterns can be used as templates for
either chemical etching of the patterned area of the substrate or
metal deposition on the patterned area of the substrate.
Inventors: |
Mirkin; Chad A.; (Wilmette,
IL) ; Salaita; Khalid; (Berkeley, CA) |
Assignee: |
Northwestern University
|
Family ID: |
39644987 |
Appl. No.: |
13/473536 |
Filed: |
May 16, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11770477 |
Jun 28, 2007 |
8192795 |
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13473536 |
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60816948 |
Jun 28, 2006 |
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Current U.S.
Class: |
428/156 ;
205/135; 257/E21.09; 257/E21.211; 427/256; 427/287; 427/58;
428/195.1; 438/478; 438/761; 977/700; 977/890 |
Current CPC
Class: |
Y10S 977/857 20130101;
B82Y 40/00 20130101; Y10T 428/24479 20150115; Y10S 977/888
20130101; B82Y 10/00 20130101; G03F 7/0002 20130101; Y10S 977/856
20130101; Y10T 428/24802 20150115; Y10S 977/849 20130101; Y10S
977/855 20130101 |
Class at
Publication: |
428/156 ;
427/256; 427/287; 427/58; 438/761; 438/478; 205/135; 428/195.1;
257/E21.211; 257/E21.09; 977/890; 977/700 |
International
Class: |
B32B 3/10 20060101
B32B003/10; B05D 7/14 20060101 B05D007/14; B05D 5/12 20060101
B05D005/12; H01L 21/20 20060101 H01L021/20; C25D 5/02 20060101
C25D005/02; B32B 3/30 20060101 B32B003/30; B05D 5/00 20060101
B05D005/00; H01L 21/30 20060101 H01L021/30 |
Goverment Interests
STATEMENT ON FEDERAL FUNDING
[0002] The presently claimed inventions were developed with use of
federal funding from NSF-NSEC, Grant No. EEC 011-8025, DARPA-ARD,
Grant No. DAAD 19-03-1-0065 and AFOSR/MURI Grant No.
F49-620-00-1-0283. The federal government may have certain rights
in the inventions.
Claims
1-24. (canceled)
25. A method comprising providing a tip and a substrate; applying a
first compound from the tip to a surface of the substrate to
produce a patterned area; depositing a second compound on a
non-patterned area of the surface by exposing the substrate to the
second compound; selectively removing the first compound from the
patterned area of the surface so that the second compound on the
non-patterned area of the surface remains deposited on the
non-patterned area; and depositing a material on the patterned area
of the surface.
26. The method of claim 25, wherein the surface of the substrate is
a metal surface.
27. The method of claim 25, wherein the substrate comprises a
semiconductor.
28. The method of claim 25, wherein the tip is a scanning probe
microscope tip.
29. The method of claim 25, wherein the tip is an atomic force
microscope tip.
30. The method of claim 25, wherein the tip is a hollow tip.
31. The method of claim 25, wherein the tip is a non-hollow
tip.
32. The method of claim 25, wherein the first compound is
chemisorbed on the surface.
33. The method of claim 25, wherein the first compound is a
sulfur-containing compound.
34. The method of claim 25, wherein the first compound forms a
self-assembled monolayer on the patterned area of the surface.
35. The method of claim 25, wherein the second compound is
chemisorbed on the surface.
36. The method of claim 25, wherein the second compound is a
sulfur-containing compound.
37. The method of claim 25, wherein the depositing the second
compound results in forming of a self-assembled monolayer.
38. The method of claim 25, wherein the depositing the second
compound comprises immersing the substrate in a solution comprising
the second compound.
39. The method of claim 25, wherein a desorption potential of the
second compound is higher than a desorption potential of the first
compound.
40. The method of claim 25, wherein the removing comprises
desorbing the first compound from the patterned area of the
surface.
41. The method of claim 40, wherein said desorbing is performed
electrochemically.
42. The method of claim 25, wherein the first compound is
16-mercaptohexadecanoic acid (MHA) and the second compound
1-octadecanethiol.
43. The method of claim 25, wherein depositing the material results
in forming a positive pattern comprising the material on the
patterned area of the surface.
44. The method of claim 43, wherein the positive pattern is an
array.
45. The method of claim 43, wherein the positive pattern comprises
lines or dots.
46. The method of claim 43, wherein the positive pattern is
characterized by features with lateral dimensions of about 500 nm
or less.
47. The method of claim 43, wherein the positive pattern is
characterized by features with lateral dimensions of about 200 nm
or less.
48. The method of claim 43, wherein the positive pattern is
characterized by features with lateral dimensions of about 100 nm
or less.
49. The method of claim 43, further comprising disposing on the
positive pattern a mixture comprising an elastomer precursor,
curing the precursor to form an elastomer, wherein said disposing
and curing results in forming a stamp comprising the elastomer,
said stamp having a negative pattern defined by the positive
pattern.
50. The method of claim 43, further comprising using the positive
pattern as a master in replication of a soft material stamp.
51. The method of claim 25, wherein the material is a metal, and
depositing the metal material comprises exposing the substrate to a
precursor comprising the metal.
52. The method of claim 51, wherein the precursor is a salt of the
metal.
53. The method of claim 25, wherein the material is a metal, and
the depositing the metal is performed electrochemically.
54. The method of claim 25, wherein the material is a metal, and
the depositing the metal is performed electrolessly.
55. (canceled)
56. A pattern formed by the method of claim 25.
57. A stamp formed by a method of claim 49.
58. A method comprising providing a nanoscopic tip and a substrate;
applying a first compound from the tip to a surface of the
substrate to produce a patterned area; depositing a second compound
on a non-patterned area of the surface by exposing the substrate to
the second compound; selectively removing the first compound from
the patterned area of the surface so that the second compound on
the non-patterned area of the surface remains deposited on the
non-patterned area; and depositing a material on the patterned area
of the surface.
59. The method according to claim 58, wherein the material can be
conductive or made to be conductive.
60. The method of claim 58, wherein the material comprises a
conjugated polymer.
61. The method of claim 58, wherein the material comprises a
semiconductor.
62. The method of claim 58, wherein the material comprises a
metal.
63. (canceled)
Description
RELATED APPLICATIONS
[0001] This application claims priority to U.S. provisional
application No. 60/816,948 filed Jun. 28, 2006, which is
incorporated herein by reference in its entirety.
BACKGROUND
[0003] Nanostructured metal surfaces currently play an important
role in electronics, optics, biodiagnostics and catalysis (1-3--see
reference listing hereinafter). Similar to a photoresist in
conventional photolithography, self-assembled monolayers (SAMs) of
alkanethiols have been utilized as masks to direct the patterning
of underlying thin metal films. Such a patterning has relied on at
least two approaches. A first approach is an indirect approach, in
which a focused ion (4) or electron beam (5-8), photoradiation
(9-10) or a scanning probe microscope tip (11) locally excites or
degrades an adsorbed monolayer. In most cases, the monolayer is
damaged or destroyed (12-13), but in some cases, the monolayer's
cross-linking is effected (14). SAMs patterned using the indirect
approach have been utilized as masks to control the
electrodeposition of metal salts or substrate etching at the
exposed regions of thin metal films (5, 7, 15-17). Still, the
indirect patterning of alkanethiols is a low-throughput process
that typically requires serial scanning with an exception of
photolithographic methods with limited patterning resolution.
[0004] A second approach of alkanethiol patterning uses direct
deposition tools, such as micro-contact printing (.mu.CP) (18) or
dip-pen nanolithography (DPN) printing (19, 20) to directly deposit
alkanethiols onto a thin metal film. .mu.CP and its variants allow
for massively parallel printing organic compounds on surfaces while
controlling feature size typically down to about 200 nm. .mu.CP
generated patterns of hexadecanethiol (CH.sub.3(CH.sub.2).sub.15SH)
have been used as a mask for the electroless deposition of Ni on Au
(3). .mu.CP patterned alkanethiols of various lengths can be used
to direct the electrodeposition of Ag and Au salts depending on the
applied potential (21).
[0005] DPN printing is a direct-write tool for tailoring the
chemical composition of surfaces on the sub-50 nm to many
micrometer length scale(19, 20). Small organic molecules (20,
22-24), oligonucleotides (25), proteins (26), conducting polymers
(27) and sol gels (28) have been patterned on inorganic substrates,
such as Au, Ag, and SiO.sub.x, using DPN printing. DPN-patterned
alkanethiols can be used as negative chemical etch resists for
generating a variety of inorganic nanostructures. For example,
16-mercaptohexadecanoic acid (MHA) and 1-octadecanethiol (ODT) were
each used as chemical etch resists to generate 12 nm gaps and
sub-50 nm metal disks comprising Au, Ag, or Pt on a silicon
substrate (29-33).
[0006] Approaches using alkanethiols as a positive etch resist have
been proposed and demonstrated for .mu.CP using bulky or poorly
ordered adsorbates that provide high adsorbate solution exchange
resistance, but are poor etch resists (34, 35).
SUMMARY
[0007] One embodiment provides, for example, a method comprising:
providing a tip and a substrate; applying a first compound from the
tip to a surface of the substrate to produce a patterned area;
depositing a second compound on a non-patterned area of the surface
by exposing the substrate to the second compound; selectively
removing the first compound from the patterned area of the surface
so that the second compound on the non-patterned area of the
surface remains deposited on the non-patterned area; and then
etching the patterned area of the surface.
[0008] Another embodiment provides a method comprising: providing a
tip and a substrate; applying a first compound from the tip to a
surface of the substrate to produce a patterned area; depositing a
second compound on a non-patterned area of the surface by exposing
the substrate to the second compound; selectively removing the
first compound from the patterned area of the surface so that the
second compound on the non-patterned area of the surface remains
deposited on the non-patterned area; and depositing a material on
the patterned area of the surface. The material can be, for
example, a conductive material or semiconductive material such as a
metal or conducting polymer or conjugated polymer.
[0009] Another embodiment provides a method comprising: providing a
nanoscopic tip and a solid substrate; disposing a composition
comprising a first compound on the tip; depositing the first
compound from the tip to a surface of the substrate to produce a
patterned area, wherein the first compound forms a self-assembled
monolayer on the surface; depositing a second compound on a
non-patterned area of the surface by exposing the substrate to the
second compound, wherein the second compound forms a self-assembled
monolayer on the surface; selectively electrochemically removing
the first compound from the patterned area of the surface so that
the second compound on the non-patterned area of the surface
remains deposited on the non-patterned area; and etching the
patterned area of the surface.
[0010] Advantages of one or more embodiments include ability to
selectively desorb similar molecules from a surface; use of
electrochemical approaches to desorption; good throughput; high
resolution; and combination of good throughput and high resolution,
among other things. For example, resolution can be micro to sub-100
nm lateral resolution and can be controlled as needed for an
application.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a diagram illustrating making hole arrays using
DPN and subsequent generation arrays of solid state features.
[0012] FIGS. 2 (A)-(D) present AFM data related to DPN generated
hole arrays and arrays of solid state features. (A) is an lateral
force microscopy (LFM) image of part of an array of 30.times.30 MHA
structures that includes rows of dots (4, 2, and 1 sec hold time)
with 430, 310, and 210 nm average dot diameters (.+-.20 nm)
generated using DPN on a 40 nm thick Au film evaporated on a
SiO.sub.x substrate. (B) is non-contact mode AFM (NCAFM) image of
an array of holes (380, 270, and 190 (.+-.20) nm diameter)
fabricated in a 40 nm Au film. (C) is NCAFM image of the entire 900
hole array (30.times.30). (D) Depth profile of two rows of holes as
indicated in (B). Note that wider templates generate deeper holes.
Z scale is 60 nm for (B) and (C).
[0013] FIG. 3 presents chemical structures of MHA and ODT and
cyclic voltammograms for bulk reductive desorption of ODT and MHA
monolayers on Au in 0.5 M KOH at a scan rate of 100 mV s.sup.-1.
The vertical lines indicate the boundaries of electrochemical
desorption for MHA and ODT, and the highlighted region (-800
mV>E.sub.des>-850 mV) indicates the potential, where MHA is
selectively desorbed, whereas ODT remains intact.
[0014] FIGS. 4 (A) and (B) present AFM data for a hole etched in a
60 nm polycrystalline gold film. (A) is NCAFM of the etched hole.
The faceted hole shape, which reflects the predominant Au(111)
character of the evaporated film. (B) is a depth profile of
highlighted region in the NCAFM image. The hole was etched down to
the Ti/SiO.sub.x substrate base, which explains why the base of the
hole is smoother than the polycrystalline top of the Au film.
[0015] FIGS. 5 (A)-(C) present AFM data related to a DPN generated
array of triangular holes and array of triangular solid structures.
(A) is an LFM image of part of an array of triangular MHA
structures written using a 1 .mu.m/s tip speed. The edge length is
740 nm and the line width is 190 nm (.+-.20 nm). (B) is an NCAFM
image of the same substrate as in (A) after selective desorption
(-800 mV, 5 min) of MHA, and subsequent etching at open circuit
potential (10 min). (C) is a depth profile of highlighted region in
(B). The average peak depth of all the structures is 34.+-.3
nm.
[0016] FIGS. 6 (A)-(C) relate to an array of Ag structures created
using a DPN generated hole array as a template. (A) is a dark field
microscopy image of an array of 15.times.15 Ag structures generated
on a polycrystalline Au substrate. Ag structures were electroplated
onto MHA defined dot templates with alternating diameters. The
inset is an AFM image of a part of the array. (B) is a height
profile of the array of (A). (C) schematically illustrates
generation of an array of Ag structures from a hole array
(template).
[0017] FIGS. 7 (A)-(E) relate to a PDMS array created using a array
of Ag structures as a template. (A) is an AFM image of
electrodeposited Ag "master" on DPN-defined templates. (B) is an
optical micrograph of a PDMS "replica" faithfully reproducing the
master from A. (C) is an optical micrograph of an array of Ag
"masters". The inset shows a representative AFM image of part of
the array. (D) is an AFM image a of PDMS mold replicated from the
Ag master shown in C. (E) is a schematic representation of the
process of molding PDMS "replicas" from DPN-defined "masters".
[0018] FIGS. 8 (A)-(C) present EDS analysis of DPN-templated hole
structures in Au film. A) FESEM image of DPN-templated holes. B)
and C) EDS analysis of highlighted regions "+" in SEM image, where
spectrum 1 corresponds to hole structure and spectrum 2 corresponds
to ODT passivated Au. Spectrum 2 exclusively shows the elemental
peaks associated with SiO.sub.x, and spectrum 1 exhibits the
elemental peaks associated with both Au and SiO.sub.x.
[0019] FIGS. 9 (A)-(C) present EDS analysis of DPN-templated Ag
structures electrodeposited on Au film. A) FESEM image of
DPN-defined Ag dot shaped structures. B) and C) EDS analysis of
highlighted regions "+" in SEM, where spectrum 1 corresponds to an
Ag structure and spectrum 2 corresponds to an ODT passivated Au
region. Spectrum 1 exhibits the characteristic elemental signatures
for both Au and Ag, while spectrum 2 exhibits the characteristic
elemental signatures for Au exclusively.
[0020] FIG. 10 presents non contact AFM (NCAFM) and phase images of
a 3H3 MHA dot array, where the background Au surface was passivated
with ODT and a potential of -750 mV was applied for 5 min. The
sample was then exposed to 1 mM KCN for 20 min. The MHA structures
remain intact and the Au substrate is not etched. Z scale is 20
nm.
[0021] FIG. 11 presents NCAFM image of a hole array generated by
applying a potential of -850 mV for 5 min, and subsequently
exposing the substrate to an alkaline CN.sup.- containing solution
at OCP. Note the presence of small pits in the ODT passivating
layer. Z scale is 60 nm.
[0022] FIGS. 12 (A)-(C) present NCAFM images of 3H3 hole arrays
generated by applying a selective desorption potential of -800 mV
for 5, 8, and 0 min, which correspond to A, B and C, respectively.
Z scale is 80 nm for A and B, 10 nm for C.
[0023] FIGS. 13 (A)-(D) demonstrate measuring the optical
properties of nanostructured Au films supported on a quartz
substrate (scheme right). Optical micrographs of triangular hole
array in A) darkfield reflection mode, B) brightfield reflection
mode, D) brightfield transmission mode. C) NCAFM image of a
representative triangular structure etched in a Au film.
DETAILED DESCRIPTION
Introduction
[0024] References will be made in detail to the preferred
embodiments, examples of which are illustrated in the accompanying
drawings. While the many facets of the inventions described will be
described in conjunction with the preferred embodiments, it will be
understood that they are not intended to limit the inventions to
those embodiments. On the contrary, the inventions are intended to
cover alternatives, modifications and equivalents, which may be
included within the spirit and scope of the inventions as defined
by the appended claims.
[0025] Nanolithography instruments and accessories for direct-write
printing can be obtained from NanoInk, Inc., Chicago, Ill. Dip Pen
Nanolithography.TM. and DPN.TM. are NanoInk, Inc. trademarks.
[0026] The following patents and co-pending applications related to
direct-write printing with use of cantilevers, tips, and patterning
compounds are hereby incorporated by reference in their
entirety:
[0027] U.S. Pat. No. 6,635,311 issued Oct. 21, 2003 ("Methods
Utilizing Scanning Probe Microscope Tips and Products Therefor or
Produced Thereby") to Mirkin et al., which describes fundamental
aspects of DPN printing including inks, tips, substrates, and other
instrumentation parameters and patterning methods;
[0028] U.S. Pat. No. 6,827,979 issued Dec. 7, 2004 ("Methods
Utilizing Scanning Probe Microscope Tips and Products Therefor or
Produced Thereby") to Mirkin et al., which further describes
fundamental aspects of DPN printing including software control,
etching procedures, nanoplotters, and arrays formation.
[0029] U.S. patent publication number 2002/0122873 A1 published
Sep. 5, 2002 ("Nanolithography Methods and Products Produced
Therefor and Produced Thereby"), which describes aperture
embodiments and driving force embodiments of DPN printing.
[0030] U.S. patent publication 2003/0185967 to Eby et al.,
published Oct. 2, 2003 ("Methods and Apparatus for Aligning
Patterns on a Substrate"), which describes alignment methods for
DPN printing.
[0031] U.S. Pat. No. 7,060,977 to Dupeyrat et al., issued Jun. 13,
2006 ("Nanolithographic Calibration Methods"), which describes
calibration methods for DPN printing.
[0032] U.S. Patent Publication 2003/0068446, published Apr. 10,
2003 to Mirkin et al. ("Protein and Peptide Nanoarrays"), which
describes nanoarrays of proteins and peptides;
[0033] U.S. patent application Ser. No. 10/307,515 filed Dec. 2,
2002 to Mirkin et al. ("Direct-Write Nanolithographic Deposition of
Nucleic Acids from Nanoscopic Tips"), which describes nucleic acid
patterning.
[0034] U.S. Patent Publication 2003/0162004 to Mirkin et al.
published Aug. 28, 2003 ("Patterning of Solid State Features by
Direct-Write Nanolithographic Printing"), which describes reactive
patterning and sol gel inks.
[0035] U.S. Pat. No. 6,642,129, issued Nov. 4, 2003, to Liu et al.
("Parallel, Individually Addressible Probes for
Nanolithography").
[0036] U.S. Pat. No. 6,737,646, issued May 18, 2004, to Schwartz
("Enhanced Scanning Probe Microscope and Nanolithographic Methods
Using Same").
[0037] U.S. Pat. No. 6,674,074 issued Jan. 6, 2004, to Schwartz
("Enhanced Scanning Probe Microscope").
[0038] U.S. Pat. No. 7,098,058 issued Aug. 29, 2006.
[0039] U.S. Patent publication 2004/0026681 published Feb. 12,
2004.
[0040] U.S. Pat. No. 7,005,378 issued Feb. 28, 2006.
[0041] U.S. Patent Publication 2004/0175631 published Sep. 9,
2004.
[0042] U.S. Pat. No. 7,034,854 issued Apr. 25, 2006.
[0043] U.S. Patent Publication 2005/0009206 published Jan. 13,
2005.
[0044] U.S. Patent Publication 2005/0272885 published Dec. 8,
2005.
[0045] U.S. Patent Publication 2005/0255237 published Nov. 17,
2005.
[0046] U.S. Patent Publication 2005/0235869 published Oct. 27,
2005.
[0047] In some embodiments, the direct-write nanolithography
methods described herein can be particularly of interest for use in
preparing bioarrays, nanoarrays, and microarrays based on peptides,
proteins, nucleic acids, DNA, RNA, viruses, and the like. See, for
example, U.S. Pat. Nos. 6,787,313 for mass fabrication of chips and
libraries; 5,443,791 for automated molecular biology laboratory
with pipette tips; 5,981,733 for apparatus for the automated
synthesis of molecular arrays in pharmaceutical applications;
[0048] Direct write methods, including DPN printing, are described
in for example Direct-Write Technologies, Sensors, Electronics, and
Integrated Power Sources, Pique and Chrisey (Eds), 2002.
[0049] Scanning probe microscopy is reviewed in Bottomley, Anal.
Chem., 1998, 70, 425R-475R.
[0050] Scanning probe microscopes are known in the art including
probe exchange mechanisms as described in U.S. Pat. No. 5,705,814
(Digital Instruments).
[0051] In addition, the following papers describes wet chemical
etching procedures used in conjunction with direct-write
nanolithography, and is hereby incorporated by reference in its
entirety including figures, references, and working examples: Zhang
et al., "Dip-Pen Nanolithography-Based Methodology for Preparing
Arrays of Nanostructures Functionalized with Oligonucleotides";
Adv. Mat., 2002, 14, No. 20, October 16, pages 1472-1474; Zhang et
al., "Biofunctionalized Nanoarrays of Inorganic Structures Prepared
by Dip-Pen Nanolithography"; Nanotechnology, 2003, 14,
1113-1117.
[0052] The text Fundamentals of Micro fabrication, The Science of
Minitaturization, 2.sup.nd Ed., Marc J. Madou, describes micro and
nanotechnologies including additive and substractive methods, for
example, lithography (Chapter 1), pattern transfer with dry etching
methods (Chapter 2), pattern transfer with additive methods
(Chapter 3), and wet bulk micromachining (Chapter 4).
[0053] Also, the text Direct-Write Technologies for Rapid
Prototyping Applications: Sensors, Electronics, and Integrated
Power Sources (Eds. A. Pique and D. B. Chrisey), describes micro
and nanotechnologies including additive and substractive methods.
For example, bulk micromachining and etching are described on pages
617-619. DPN printing on the Sub-100 nanometer length scale is
described in Chapter 10.
[0054] Self-assembled monolayers, etching, and microfabrication are
further described in, for example, U.S. Pat. Nos. 5,618,760 to Soh
et al; 5,620,850 to Bamdad et al.; and 5,512,131 to Kumar et
al.
[0055] US patent publication No. US 2006/018479 to Mirkin et al.
published Apr. 20, 2006, discloses methods of electrochemical
miniaturization of organic micro and nanostructures.
[0056] In addition, U.S. Pat. Nos. 5,827,417 and 5,635,047 relate
to electrochemical methods of controlling thiolate coverage on a
conductive substrate such as gold.
[0057] Provided herein is a method that includes patterning a first
compound on a surface of a substrate, passivating a non-patterned
area of the surface with a second compound and then removing the
first compound from the patterned area, while leaving the second
compound intact. The hole pattern formed after the removal of the
first compound can be used as a template that can either guide
etching of the patterned area of the surface or direct metal
deposition to the patterned area of the surface.
[0058] The method has at least three advantages. First, the method
is a maskless technique that does not require expensive
high-quality masters. As a result, rapid prototyping of patterns
having a variety of feature sizes and spacings can be performed a
greater ease. Second, the method does not require the use of a
clean room and can rely instead on wet chemical approaches. The wet
chemical based approaches can allow for precise immobilization of
reagents site-specifically to the generated patterns. Finally, the
method can be amenable to massive parallelization.
Tip
[0059] The tip embodiment will be further described. Tips known in
art of DPN printing can be used. Sharp tips can be used which are
characterized by a sharp, pointed end. The tip can be for example a
nanoscopic tip. The tip can be for example a scanning probe
microscope tip or an atomic force microscope tip. Tips can be
engineered to be useful for scanning probe or AFM measurements if
suitably adapted with cantilever and feedback mechanism. The tip
can be a hollow tip or a solid tip. The tip can comprise a channel
for delivery of a patterning compound. Tips including solid and
hollow tips are further described in for example U.S. Pat. Nos.
6,635,311 and 6,827,979, as well as 2002/0122873, which are herein
incorporated by reference in their entirety. WO 2005/115630 to
Henderson et al, published Dec. 8, 2005, also describes an
elongated beam with elongated aperture for deposition on surfaces.
See also US Patent Publication 2006/0096078 to Bergaud et al. for
deposition based on slit or groove technology; see also, Espinosa
et al., Small, 1, No. 6, 632-635, 2005 for nanofountain probe
writing; Lewis et al., Appl. Phys. Lett., 1999, 75, 2689-2691; Taha
et al., Appl. Phys. Lett., 2003, 83, 1041-1043; Hong et al, Appl.
Phys. Lett., 2000, 77, 2604-2606; Meister et al., Microelectron.
Eng., 2003, 67-68, 644-650; Deladi et al., Appl. Phys. Lett., 85,
5361-5363.
[0060] Tips can comprise hard inorganic, ceramic materials, or
softer organic materials. Semiconductor materials can be used.
Insulative and conductive materials can be used. Tips known in the
art of AFM imaging, for example, can be used including silicon or
silicon nitride. For example, polymer or polymer-coated tips can be
used. See, for example, US Patent Publication No. 2005/0255237 to
Zhang et al, which is herein incorporated by reference in its
entirety. Polymer tips and cantilevers are described in, for
example, Mirkin and Liu, US Patent Publication No. 2004/0228962,
related to scanning probe contact printing.
[0061] The tip disposed on the cantilever can be part of a larger
structure comprising a plurality of tips disposed on a plurality of
cantilevers. These can be called multipen structures or parallel
pen structures. For example, the multipen structure can have over
20, or over 100, or over 1,000, or over 10,000, or over 100,000, or
over 1,000,000 individual tips. The cantilevers and tips can be
adapted for individual actuation, wherein one tip can be raised or
lowered independently of another tip. Individual actuation is
described in for example U.S. Pat. Nos. 6,867,443 and 6,642,129 to
Liu et al, which are hereby incorporated by reference in their
entirety. Electrostatic or thermal actuation can be used.
[0062] Tips can be thermally heated and activated for temperature
control.
Substrate
[0063] The substrate surface can be a surface of a variety of
substrates particularly solid substrates. Smother substrates are
generally preferred for providing pattern's higher resolution. The
substrate can comprise, for example, a metal, a semiconductor, an
insulator, a magnetic material, a polymer material, a ceramic
material or a superconducting material. For example, the substrate
can comprise silica, silicon oxide SiO.sub.x, GaAs, InP, InAs or
glass. In some embodiments, a surface of the substrate can be a
metal surface comprising, for example, gold, silver, platinum or
palladium.
Patterning
[0064] The first compound can be transported to the substrate's
surface from a tip to form a pattern in several different ways and
is not particularly limited. Applying the first compound to the
surface results in formation of a patterned area of the surface,
i.e. the area of the surface, where the first compound was applied
to, and a non-patterned area of the surface, i.e. the area of the
surface, wherein the first compound was not applied. Known methods
in DPN printing can be used for patterning the first compound. For
instance, in scanning probe and AFM-related technology, different
modes can be used to have tips interact with surfaces, which
include contact mode, non-contact mode and intermittent contact
mode or tapping mode. Cantilevers can be oscillated. Known feedback
methods can be used for positioning and alignment the X, Y and Z
directions.
[0065] The transporting of the first compound from the tip to the
surface can be carried out by moving the tip only in the Z
direction up and down with respect to the XY plane of the substrate
surface. The delivery can be performed without translating the tip
over the substrate surface, moving in the XY plane. Alternatively,
the tip can be translated over the surface, moving in the XY
plane.
[0066] The transporting can be carried out under conditions such as
humidity, temperature, and gaseous atmosphere which provide for a
water meniscus between the tip and surface. For example, humidity
can be at least about 25%, or at least about 40%, or at least bout
50%. Conditions can be controlled with use of environmental
chambers. The gaseous atmosphere can be air, an inert atmosphere,
an atmosphere with controlled humidity, or with the presence of
other volatile or gaseous compounds such as vapors of organic
compounds or volatile solvents such as alcohols like methanol or
ethanol. Conditions can be selected to not favor a water meniscus
including, for example, anhydrous conditions or conditions wherein
all reagents and surfaces are selected to be free of water.
[0067] The transporting can be done manually or by instrument with
computer control. Software can be used which can facilitate pattern
design, calibration, leveling, and alignment. Calibration methods
are described in for example U.S. Pat. No. 7,060,977 to
Cruchon-Dupeyrat et al., which is hereby incorporated by reference.
Alignments methods are describe in for example 2003/0185967 to Eby
et al., which is hereby incorporated by reference.
[0068] The transporting can be done more than once, repetitively,
in either the same spot or at different locations.
Patterning Composition and Compound
[0069] The first compound can be a compound that can chemisorb or
covalently bind to the surface. When the surface comprises metal
such as gold, silver, palladium or platinum, the first compound can
be an organic compound containing sulfur, selenium or tellurium
atom. For instance, the first compound can be an organic compound
containing a thiol, disulfide, sulfide, selenol, selenide,
diselenide, tellurol, telluride or ditelluride group. Preferably,
the first compound is a organic compound capable of forming a
self-assembled monolayer, preferably an ordered self-assembled
monolayer, on the surface of the substrate. Compounds capable of
forming ordered self-assembled monolayers are known to those of
ordinary skill in the art, see e.g. A. Ulman, An Introduction to
Ultrathin Organic Films: From Langmuir--Blodgett to Self-Assembly,
Academic Press, San Diego, 1991. Compounds capable of forming
ordered self-assembled monolayers include compounds that contain
long chain alkane group, i.e. alkane group containing more than 8
or more than 10 or more than 12 carbon atoms. Examples of compounds
capable of forming ordered self-assembled include but not limited
to long chain alkane thiols, such as 16-mercaptohexadecanoic acid,
and 1-octadecanethiol and long chain alkane selenols, such as
octadecaneselenol.
[0070] Upon patterning the first compound, a plurality of dots or a
plurality of lines can be formed on the surface of the substrate.
The plurality of dots can be a lattice of dots including hexagonal
or square lattices as known in the art. The plurality of lines can
form a grid, including perpendicular and parallel arrangements of
the lines. Individual lines of the plurality can be straight or
non-straight lines. For example, the non-straight lines can form
individual patterns of various polygon shapes such as triangle,
square, rhomb, rectangle etc.
[0071] The lateral dimensions of the individual patterns including
dot diameters and the line widths can be, for example, about 2,000
or less, about 1,000 nm or less, about 500 nm or less, about 200 nm
or less, and more particularly about 100 nm or less. The range in
dimension can be, for example, about 1 nm to about 750 nm, about 10
nm to about 2,000 nm, about 10 nm to about 500 nm, and more
particularly about 100 nm to about 350 nm.
[0072] The number of patterns in the plurality of patterns is not
particularly limited. It can be, for example, at least 10, at least
100, at least 1,000, at least 10,000, even at least 100,000. Square
arrangements are possible such as, for example, a 10.times.10
array. High density arrays can be preferred.
[0073] The distance between the individual patterns on the
nanoarray can vary and is not particularly limited. For example,
the patterns can be separated by distances of less than one micron
or more than one micron. The distance can be, for example, about
300 to about 1,500 microns, or about 500 microns to about 1,000
microns. Distance between separated patterns can be measured from
the center of the pattern such as the center of a dot or the middle
of a line.
[0074] The method can be also applied for forming patterns of
larger scales such as micron scale, millimeter scale or centimeter
scale. Such larger patterns can be prepared, for example, utilizing
microcontact printing.
Second Compound
[0075] Like the first compound, the second compound can be a
compound that can chemisorb or covalently bind to the surface of
the substrate. Preferably, the second compound has a more negative
of threshold desorption potential than the first compound. For
example, for a substrate comprising Au, if the first compound is
16-mercaptohexadecanoic acid (threshold desorption potential -750
mV vs Ag/AgCl in 0.5 M KOH aqueous solution), the second compound
can be any compound having a desorption potential more negative
than -750 mV vs Ag/AgCl in 0.5 M KOH solution, such as octadecane
thiol (threshold desorption potential -850 mV vs Ag/AgCl).
[0076] An area of the substrate not patterned by the first compound
can be exposed to the second compound so that the second compound
is retained on the non-patterned area of the substrate's surface.
Such exposing can be performed using any applicable method. For
example, the second compound can be disposed on the non-patterned
part of the surface using any of the described patterning
technique. Still, it is more preferable to expose the area of the
substrate not patterned by the first compound using a
non-patterning technique, i.e. the whole surface of the substrate
can be exposed to a medium containing the second compound so that
the second compound chemisorbs or binds to the non-patterned part
of the substrate surface. Such non-patterning deposition can be
performed by immersing the surface of the substrate in a solution
containing the second compound or by exposing the surface of the
substrate to a vapor containing the second compound.
Removing First Compound
[0077] Removing the first compound, while keeping the second
compound intact can be performed using a variety of methods. A
preferable method is selective electrochemical desorption, which
can be performed by applying to the substrate a potential more
negative than a threshold desorption potential of the first
compound but still less negative than a threshold desorption
potential of the second compound. Particular conditions, such as
desorption time and desorption potential used for removing the
first compound can depend, for example, on a particular type of the
substrate, on a particular type of solution used for removing and
on particular first and second compounds used. The removing
conditions can be optimized as described in the working example
below.
[0078] Preferably, removing the first compound results in removing
all or the majority of the molecules of the first compound from the
substrate.
[0079] Electrochemical desorption of thiols is disclosed, for
example, in U.S. Pat. Nos. 5,827,417 and 5,635,047.
[0080] Selective electrochemical desorption is disclosed, for
example, in US patent publication No. 2006/0081479.
Hole Patterns
[0081] Removing of the first compound exposes a surface of the
substrate formerly covered by the first compound and thus forms a
hole or a negative pattern surrounded by the second compound.
Lateral dimensions of the hole are substantially defined by the
lateral dimensions of the initial pattern formed by the first
compound. The lateral dimensions of the hole can be equal to the
lateral dimensions of the initial pattern formed by the first
compound. The lateral dimensions of the hole can be also slightly
smaller than the lateral dimensions of the initial pattern formed
by the first compound, for example, due to the exchange between the
first compound and the second compound. As the initial patterns
formed by the first compound, the hole patterns can form a
plurality of dots or lines. As the lateral dimensions, the spacing
between the individual holes is defined by the original pattern
formed by the first compound.
Etching
[0082] In some embodiments, upon removing the first compound,
etching (wet or dry) can be applied to the substrate surface. In
such a case, the second compound left intact can act as an etch
resist and thus the etching can be limited only to the patterned
area of the surface. Although, in general, wet (chemical) etching
techniques are preferred, other types of etching can be used as
well. The wet etching procedures and materials used in them are
standard and well known in the art. See, e.g., Xia et al., Angew.
Chem. Int. Ed., 37 550 (1998); Xia et al., Chem. Mater., 7, 2332
(1995); Kumar et al., J. Am. Chem. Soc., 114, 9188-9189 (1992);
Seidel et al., J. Electrochem. Soc., 137, 3612 (1990). Wet etching
procedures are used for, e.g., the preparation of three-dimensional
architectures on or in substrates (e.g., Si wafers) of interest.
See, e.g., Xia et al., Angew. Chem. Int. Ed., 37, 550 (1998); Xia
et al., Chem. Mater., 7, 2332 (1995). After etching, the second
compound may be retained on the substrate or removed from it.
Methods of removing the compounds from the substrates are well
known in the art. For example, electrochemical desorption can be
used for removing the second compound from the unpatterned area of
the substrate after etching.
[0083] Upon etching, the pattern initially formed by the first
compound is transferred into a gap pattern. Lateral dimensions of
individual gap features and spacing between the individual gap
features are both defined by the initial pattern formed by the
first compound.
Metal Deposition
[0084] In some embodiments, upon removing the first compound, metal
can be deposited on the patterned area of the substrate. Metal
deposition can be performed by any appropriate method.
[0085] In some embodiments, the metal deposition can be electroless
deposition, i.e. deposition performed without applying an external
current to the surface. For electroless deposition, the substrate
can be exposed to a solution containing ions of the metal to be
deposited and a reductant, such as dimethylamine borane (DMAB),
hypophosphite ion, formaldehyde or hydrazine. The metal is
deposited on the patterned area of the surface, while the metal
deposition on the non-patterned area is prevented by the second
compound, which acts as a metal deposition resist. Electroless
metal deposition is known in the art, see e.g. Kumar, A.; Biebuyck,
H. A.; Whitesides, G. M. Langmuir 1994, 10, 1498-1511; Nakahara,
S.; Okinaka, Y. Annu. Rev. Mater. Sci. 1991, 21, 93-129; Kamrava,
S. J.; Soederholm, S. J. Mater. Sci 1990, 5, 1697-1702; Ohno, Izumi
Mater. Sci. Eng., A 1991, A146, 33-49.
[0086] In some embodiments, the metal deposition can be
electrochemical metal deposition. The electrochemical metal
deposition is performed by exposing the substrate to a solution
that containing ions of the metal to be deposited such as a
solution of the metal's salt and applying a negative potential to
the substrate. Similarly to the electroless deposition, the metal
is deposited on the patterned area of the surface, while the metal
deposition on the non-patterned area is prevented by the second
compound, which acts as a metal deposition resist.
[0087] The electrochemical metal deposition, also known as
electroplating, is known in the art, see e.g. Pesika, N. S.; Fan,
F. Q.; Searson, P. C.; Stebe, K. J. J Am Chem Soc 2005, 127,
11960-11962 and also working example of this application.
[0088] Metal deposition can result in formation a template (a
positive pattern) of solid state structures comprising the metal in
the patterned area of the substrate. Lateral dimensions of the
individual solid structures and spacings between them are defined
by the original pattern formed by the first compound. A height of
the structures can be controlled by varying deposition time. In
case of the electrochemical deposition, the height of the
structures can be controlled by adjusting the total number of
coulombs, i.e. a charge, passed through solution during the
deposition.
[0089] Another embodiment comprises the step of depositing a
material on the patterned area of the surface, wherein for example
the material can be conductive or made to be conductive or
semiconductive. For example, the conductive material can comprise a
conjugated polymer such as polyaniline or polythiophene. A
semiconductive material can be for example CdS or CdSe.
Stamp Fabrication
[0090] A pattern of solid structures fabricated via metal
deposition as discussed can be used as a master, from which a large
number duplicate structures could be fabricated. Such duplicates
can fabricated by disposing a deformable material such as elastomer
or one or more precursors of the deformable material on the solid
structure pattern. One example of the elastomer can be a silicone
elastomer or an elastomer with hydrophobic properties such as for
example polydimethyl siloxane (PDMS). For forming PDMS duplicate,
PDMS monomer and initiator can be disposed on the solid structure
pattern and cured under elevated temperature. The formed duplicate
has features that replicate the solid state structure pattern of
the master. The formed duplicate can be used a stamp to generate
features over large areas.
[0091] Embodiments described herein are further illustrated by,
though in no way limited to, the following working examples.
WORKING EXAMPLE
Experimental Section
[0092] Chemicals.
[0093] 1-octadecanethiol (ODT) (98%), 16-mercaptohexadecanoic acid
(MHA) (90%), KCN (97%), KOH (semiconductor-grade) were purchased
from Aldrich Chemical Co. Ethanol (ACS/USP grade) was purchased
from Pharmcoproducts Inc. Acetonitrile (reagent grade) and
methylene chloride (99.9%) were purchased from Fisher Scientific.
All chemicals were used as received.
[0094] Substrates, Patterning, and Imaging.
[0095] In a typical experiment, Au-coated (20-60 nm), Ti-coated (5
nm) silicon oxide (Au/Ti/SiO.sub.x/Si) prepared as detailed in (53)
was patterned via DPN with MHA using an Atomic Force Microscope
(AFM, CP, Veeco/ThermoMicroscopes, Sunnyvale, Calif.) equipped with
a 100-.mu.m scanner with closed-loop scan control, or an
Nscriptor.TM. (Nanoink Inc., Chicago, Ill.) equipped with a
100-.mu.m scanner and closed-loop scan control and commercial
lithography software (DPNWrite.TM., DPN System-1, Nanoink Inc.,
Chicago, Ill.). Gold-coated Si.sub.3N.sub.4 AFM cantilevers
(Microlever, Veeco/ThermoMicroscopes, Sunnyvale, Calif.) with a
spring constant of 0.05 N/m and commercially available gold-coated
Si.sub.3N.sub.4 multi-cantilever A-26 arrays with a spring constant
of 0.097 N/m (NanoInk, Chicago, Ill.) were used for patterning.
MHA-coated tips were prepared by immersing the cantilevers in
acetonitrile solution saturated with MHA for a few seconds. The
tips were then washed with a neat ethanol solution and subsequently
blown dry under a stream of N.sub.2.
[0096] Imaging of DPN-generated patterns was performed using a
clean AFM tip under conditions identical to those used for
patterning in contact mode. Patterned structures, post etching,
were characterized by scanning electron microscope, SEM (Leo Gemini
1525) and dark field microscopy (Zeiss Axiovert 100A inverted
microscope, Thornwood, N.Y.). The dark filed microscope was
equipped with a Penguin 600CL digital camera and StreamPix
software. Tapping mode AFM images were collected with a Nanoman AFM
equipped with a Nanoscope IV.
[0097] Etching.
[0098] CN.sup.--induced etching of substrates under potential
control was performed in an electrochemical cell as described
above, where the electrolyte was an alkaline solution containing
KCN (54). The open-circuit potential (OCP) of an ODT-passivated Au
substrate was about -520 mV (vs Ag/AgCl). The OCP was sufficiently
positive to initiate dissolution of unprotected Au, and patterned
substrates were immersed in the etching solution without stirring
or mixing, and subsequently washed with Nanopure.TM. water and
ethanol.
[0099] Electroplating.
[0100] Silver cyanide/potassium cyanide plating solution (Technic
Silver 1025) and potassium gold cyanide plating solution (Orotemp
24 plating solution) were purchased from Technic Inc., Cranston,
R.I. Prior to use, solutions were passed through a syringe filter
with a pore size of 0.2 .mu.m. Deposition was performed at ambient
conditions under potentiostatic control (typically -800 mV vs
Ag/AgCl) while stirring mildly (.about.100 rpm). Substrates were
washed with Nanopure.TM. water and ethanol respectively after
deposition.
[0101] PDMS Replica.
[0102] Stamps were fabricated by placing a DPN-prepared master (by
using the procedure describe above) in a glass Petra dish, followed
by pouring over the master a mixture of polydimethlysiloxane (PDMS,
Sylgard 184, Dow Corning, Midland, Mich.) in the ratio of 10:1
(v:v) monomer to initiator. After one hour degassing the elastomer
was cured for 2 h at 60.degree. C., and then gently peeled from the
master and inspected by optical microscopy.
Hole Array of Dots
[0103] FIG. 2A shows an array of 30.times.30 MHA structures of rows
of dots (4, 2, and 1 sec hold time) with 430, 310, and 210 nm
average dot diameters (.+-.20 nm) generated using DPN on a 40 nm
thick Au film evaporated on a SiO.sub.x substrate. The Au substrate
was then passivated in a 5 mM ODT solution for 15 min, and
subsequently rinsed with ethanol and Nanopure.TM. water. To effect
selective desorption of the MHA template, a potential of -800 mV
(vs Ag/AgCl, 3M NaCl) was applied to the substrate for 5 min. The
exposed Au template was etched by holding the sample at open
circuit potential (OCP) for 20 min in an alkaline 1 mM KCN solution
(the OCP of the ODT protected Au was about -520 mV). Non-contact
AFM images (NCAFM) in FIG. 2B-D indicate that the resulting hole
structures are very uniform, as defined by the hole diameter and
depth profile, and are consistent with the lateral dimensions and
lattice spacings of the DPN-generated MHA template. Interestingly,
the hole structures have a lateral diameter about .about.10%
smaller than that of the original DPN-defined MHA patterns and the
average dot diameters were 400 (.+-.21 nm), 270 (.+-.21 nm), and
190 (.+-.27 nm) for the dots prepared with 4, 2, and 1 sec holding
times, respectively (n=14). Although the embodiments described
herein are not limited by theory of operation, the difference
between MHA feature size and hole size may be the result of the
exchange of adsorbed MHA with the ODT in solution at the periphery
of the MHA features, which has previously been investigated in the
context of DPN deposited structures (43).
[0104] The depth of the holes is proportional to the diameter of
the MHA-defined templates. For example, the 430 nm diameter
templates yielded holes with an average depth of 40.+-.3 nm,
whereas the 310 nm diameter templates had an average depth of
37.+-.4 nm, and the 210 nm diameter templates had an average depth
of 30.+-.3 nm, see FIG. 2D. Gold remains at the bottom of each hole
in all cases.
[0105] Crooks and coworkers examined the corrosion of Au
<111> under potential control in CN.sup.- solution and found
that the etching rate of bare Au is considerably faster than that
of 1-hexadecanethiol monolayer passivated Au (44, 45). Exclusive
etching of the Au surface at the areas defined by the template
created by MHA desorption indicates that the majority of MHA
molecules are indeed reductively removed at the applied potential
of -800 mV. This process is highly sensitive to the applied
potential. For example, if the applied potential is -850 mV, ODT
desorption starts to occur, and as a result randomly dispersed pits
across the Au samples can be observed, see "Dependence on the
Applied Potential" below. Alternatively, holding an MHA patterned
Au substrate at -750 mV for 5 min, and exposing it to a CN.sup.-
etch solution for 20 min does not result in etching of the MHA
defined regions, see "Dependence on the Applied Potential" below.
Although MHA desorption is induced at all potentials more negative
than -800 mV, only within a relatively small window (-800
mV>E.sub.des>-850 mV) does selective desorption for MHA over
ODT occur, see shaded area, FIG. 3.
[0106] When the hole arrays are exposed to CN.sup.- solution for
extended periods of time (e.g., 30 min), some of the fabricated
holes reveal a highly faceted structure with three-fold symmetry,
see FIG. 4. Although the embodiments described herein are not
limited by theory of operation, this three-fold symmetry may
reflect the predominant Au<111> character of the evaporated
Au films on Ti coated silicon oxide and glass substrates (46).
These results are in agreement with STM observations by Bard and
McCarley of triangular etch pits formed during etching of single
crystal Au <111> in aqueous CN.sup.- solutions (47).
[0107] Another feature of these etch pits is that once all of the
Au is etched, the base of each hole is extremely flat because the
grain size of Ti/SiO.sub.x (-5-10 nm) is smaller than that of Au
(.about.30-50 nm) (compare FIGS. 4A and 4B). The chemical
composition of the substrate underneath the DPN-templated nanoholes
was confirmed by using energy-dispersive X-ray spectroscopy (EDS)
experiments, see FIG. 8. The EDS analysis indicates that the
nanoholes exclusively exhibit the characteristic elemental
signatures for SiO.sub.x, whereas ODT passivated Au exhibits the
elemental signatures of both Au and SiO.sub.x. In principle,
selective immobilization of reagents to the sidewall or the base of
the holes is possible, since they present different surfaces with
varying reactivity toward thiol and silane groups,
respectively.
Desorption Dependence on Applied Potential and Desorption Time
[0108] Dependence on the Applied Potential.
[0109] Desorption potential of ODT and MHA SAMs differ by
.about.100 mV in 0.5 M KOH solution, see FIG. 3. The onset of
electrochemical desorption for MHA perimeter sites was at -750 mV
(vs Ag/AgCl in 0.5 M KOH), whereas the onset of electrochemical
desorption for ODT perimeter sites was at -850 mV (vs Ag/AgCl in
0.5 M KOH) (1,2). However, once the periphery of the MHA dots are
blocked with ODT, electrochemical whittling no longer proceeds at
-750 mV, see FIG. 10. Therefore, selective desorption of MHA over
ODT does not proceed at potentials equal to or lower than -750 mV.
Conversely, if an overpotential of -850 mV is applied for 5 min,
desorption of the passivating ODT monolayer start to occur randomly
across the substrate, see FIG. 11.
[0110] Dependence on the Desorption Time.
[0111] Another important parameter that controls the formation of
holes is the duration of applied desorption potential. FIG. 12
demonstrates this dependence by showing three different MHA
patterned Au substrates, where all the conditions were maintained
(E.sub.des=-800 mV) except for the length of time that the
desorption potential was applied. When the desorption pulse is
applied for longer periods of time (t=8 min), some desorption of
the passivating ODT monolayer occurs, and subsequently the Au
surface is pitted, see FIG. 12B. If a desorption pulse is not
applied (t=0 min), then both the MHA and ODT structures remain
intact, and consequently the Au film is protected, see FIG. 12C.
This indicates that in order to minimize damage to the passivating
ODT layer, it is important to minimize the length of time that the
desorption potential is applied.
Arrays of Triangular Holes
[0112] To demonstrate that this method can be used to generate
nanoholes of almost any shape, DPN was used to pattern triangular
MHA frames with an edge length of 740.+-.30 nm and a line width of
190.+-.20 nm (FIG. 5A). This was achieved by using a relatively
fast tip writing speed (1 .mu.m/s) to avoid filling in the centers
of the triangular structures (33). The substrate was then
passivated with ODT, and then a potential of -800 mV (vs Ag/AgCl,
3M NaCl) was applied for 5 min. After exposure to the CN.sup.- etch
solution, the substrate was imaged by NCAFM (FIG. 5B). The
resulting triangular frame shaped holes have an edge length of
730.+-.30 nm, and a line width of 170 nm.+-.25 nm (FIG. 5C). Both
the edge length and the line width of the resulting triangle-shaped
holes are smaller than the original MHA-defined templates, which is
consistent with the dot-shaped structures described above, and
again is most likely a result of MHA exchange with the ODT in
solution. The average peak depth of the pits was 34 nm.+-.3 nm.
Hole Arrays on Transparent Substrates
[0113] In order to measure the transmission spectra of the
DPN-generated hole arrays, it is necessary to use a transparent
substrate. Therefore, the selective etching of MHA patterned
templates was performed on Au films supported on quartz substrates
in place of silicon substrates. The quality of hole arrays
generated on quartz was comparable to those on native-oxide coated
silicon, see FIG. 13, although the silicon substrates contained a
smaller density of dust and defects. The transmission mode
micrograph of the triangular hole arrays appeared to have a slight
bluish-green color, which indicated that the nanostructured Au film
interacts with transmitted light.
Selective Electrodeposition of Metal Salts
[0114] Bare Au templates also can be used to direct the selective
electrodeposition of metal salts, see FIG. 1. To demonstrate this
capability, an array of 15.times.15 MHA dots with alternating
diameters of 1 .mu.m and 400 nm was generated on a polycrystalline
Au substrate. The substrate was then passivated with ODT by
immersing it in a 5 mM ODT solution for 15 min. After rinsing with
ethanol and water, the MHA portion of the patterned substrate was
then selectively desorbed at a potential of -800 mV (vs Ag/AgCl, 3M
NaCl) for 5 min. Ag structures were then electrodeposited from a
commercial Ag plating bath (Tetronics 1025 Ag plating solution,
containing KAg(CN).sub.2) by applying a potential of -800 mV for
another 5 min. The resulting Ag structures had a hemispherical
shape and were characterized using darkfield microscopy and AFM
imaging (FIG. 6). The height of the Ag features can be controlled
by adjusting the total number of coulombs passed in the experiment,
and the lateral dimension of the Ag structures is defined by the
original MHA patterns.
[0115] 400 nm diameter dots resulted in Ag structures with a
diameter of 550.+-.70 nm and a height of 150.+-.20 nm, whereas the
1 .mu.m diameter features yielded 1.27.+-.0.15 .mu.m diameter Ag
structures with a height of 380.+-.20 nm. It is important to note
that the resulting Ag structures have a hemispherical shape since
it is equally likely that Ag deposits will grow from all directions
after the Ag grows beyond the height of the ODT barrier layer (2.2
nm). The rate of growth shows similar behavior to that observed
with the nanohole arrays, see FIG. 2, where larger diameter
templates generated deeper holes, see FIG. 6C. Although the reason
for this is unclear, this phenomena is likely not the result of
diffusion controlled Ag particle growth since that would result in
smaller templates growing faster than larger ones (49). The
chemical composition of DPN-templated nanoscale Ag structures was
confirmed by using EDS experiments, see FIG. 9. The EDS analysis of
Ag electrodeposited structures exhibits the characteristic
elemental signatures for both Au and Ag, whereas the background Au
surface exhibits elemental signatures for Au exclusively.
Making PDMS Stamps
[0116] Polydimethylsiloxane (PDMS) stamping is widely used as an
inexpensive high-throughput technique to generate .mu.m scale
features over large areas (18). However, expensive and precise
photolithographic masks are typically used to make the
micropatterned PDMS, and each pattern modification, such as shape,
size or spacing, requires designing a new mask. One application of
DPN templated solid features can be a master, from which a large
number of duplicate structures could be generated. Due to its
widespread applicability, PDMS was chosen to replicate DPN
templated features.
[0117] The PDMS monomer and initiator were poured over an array of
Ag structures, as shown in FIG. 7, and the PDMS was allowed to cure
overnight at 60.degree. C. The PDMS was then peeled, removed and
imaged using optical microscopy, and dot-shaped pits with identical
geometry and dimensions as the original Ag master were faithfully
replicated, see FIG. 7B. For example, 350 nm wide Ag dots with
alternating 1 and 2 .mu.m spacings in an array were generated on
Au, see FIG. 7C. AFM images of the PDMS replica indicate that the
features were accurately reproduced, and 350 nm recessions were
generated on the PDMS surface, see FIG. 7D. Although it may be
possible to replicate sub-50 features using this approach,
conventional PDMS stamping usually fails when the feature size is
below 500 nm (50).
[0118] The combination of high-resolution alkanethiol patterning
with selective electrochemical control provides a simple and
flexible approach for using alkanethiol as positive etch resists on
Au. Both the magnitude and the duration of the applied potential
play a significant role in controlling the selective desorption of
the alkanethiol adsorbates. The technique demonstrates that
DPN-templates can be used effectively to direct the selective
etching of Au and the selective electrodeposition of Ag to
nanopatterned regions of the substrates. Electrochemical control of
patterned adsorbates can be applied to generate structures over
large areas at the nanometer length scale.
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[0170] Although the foregoing refers to particular preferred
embodiments, it will be understood that the presently described
inventions are not so limited. It will occur to those of ordinary
skill in the art that various modifications may be made to the
disclosed embodiments and that such modifications are intended to
be within the scope of the presently claimed inventions.
[0171] All of the publications, patent applications and patents
cited in this specification are incorporated herein by reference in
their entirety.
* * * * *