JP2007528796A - Micrometer direct writing method for patterning conductors and application to flat panel display repair - Google Patents

Abstract

A novel low temperature method for directly writing conductive metal traces having micron and submicron sized features. In this method, a trace of metal precursor ink is drawn on a substrate using a flat beam, which may or may not have a tip, such as an AFM cantilever. The size of the metal trace can be directly controlled by the shape of the cantilever, so that traces from 1 micron to over 100 microns wide can be controllably deposited by the microfabricated cantilever. Cantilevers with sharp tips can be used to further reduce the minimum feature size to submicron scale. The height of the feature can be increased by building a layer of similar or dissimilar materials. In order to obtain a robust pattern with high conductivity by this deposition method, two general ink formulations were designed. The main component of both ink systems is nanoparticles with a diameter of less than 100 nm. Nanoparticles typically have a significantly lower melting point than bulk materials, so that a collection of discrete particles can be melted, sintered, or agglomerated at very low temperatures (less than 300 ° C, or even about 120 ° C) for continuous (multiple ) It can be a crystalline film. In the first method, hydrocarbon-capped nanoparticles can be dispersed in a suitable solvent, deposited on the surface in the form of a pattern, and then the film can be annealed by heating to form a continuous metal pattern. . In the second method, the metal compound is carried to the surface in the presence of a reducing matrix and then formed in situ by heating, which subsequently aggregates to form a continuous metal pattern. In studies using platinum and gold inks, both nanoparticle-based methods formed micron-sized traces on glass and silicon oxide with low resistivity (4 microohms.cm) and excellent adhesion.

Description

FIELD OF THE INVENTION The present invention is generally referred to as (i) a micron-scale direct write patterning method using an ink-coated microfabricated (chipless) cantilever, which can be referred to as cantilever microdeposition, and (ii) flat It relates to panel display restoration, especially its application to TFT LCD (Thin Film Transistor Liquid Crystal Display) restoration.

This application claims the priority of US Provisional Application No. 60 / 547,091 (Attorney No. 083847-0234) filed February 25, 2004, which is incorporated by reference in its entirety. This application is also a partially pending application of US Patent Application No. 10 / 647,430 (Attorney No. 083847-0200) filed on August 26, 2003. Claim priority of 60 / 405,741 (Agent number 083847-0150).

BACKGROUND In many current developmental technical fields, there is a strong commercial need for direct write technology that can deposit materials, particularly metals and semiconductors, in patterns of micron and submicron sized features. Although most microelectronic devices are manufactured by photolithography technology, the need for direct writing technology is particularly significant in the areas of additive defect repair and circuit correction. For example, damaged or missing photomasks are discarded at a very high cost for the microelectronics industry due to the lack of tools suitable for additive repair of missing materials on nanoscale features. At the micron long scale, damage to thin film transistor (TFT) array metal parts in flat panel displays (FPDs) is difficult to repair due to the lack of a quick and inexpensive method for depositing micron sized conductive traces. Although photolithography can be performed to manufacture the device, it requires complex and expensive equipment use that makes the technology tremendously expensive for small quantities of high performance components or prototype applications. In such cases, other techniques, such as direct writing, can provide unique advantages and capabilities. As the most common direct writing technique, inkjet printing provides a simple and flexible method for printing on a range of materials, from biological molecules to microelectronic materials. However, the resolution of this technique is generally limited to 15-200 micron sized dots that are insufficient for many applications (see, eg, US Patent Application No. 2004/0261700 to Edwards et al.). Other direct writing tools such as laser assisted deposition, electron or ion beam lithography are subject to similar resolution limitations, are too expensive for many applications, or are active and passive microelectronic or optoelectronic components. Has serious material limitations that prevent direct manufacturing or repair applications. In particular, electron beam lithography, ion beam microfabrication, laser or electron beam assisted chemical vapor deposition requires a (partial) vacuum, which is the case for very large flat panels (eg wide TV or computer screens). It is expensive outside.

Overview The present invention is further described using a non-limiting overview. A novel contact method has been developed for writing conductive metal features that provides controllable feature sizes from 100 microns to sub-micron dimensions. In this method, (microfabricated) cantilevers can be loaded with, for example, molecular or nanoparticulate ink, which is dispensed in small amounts, for example in the form of lines or dot patterns, by contacting the surface. In this embodiment, cantilever loading and deposition can be performed passively. However, by increasing the complexity of microfabricated cantilevers, additional systems can incorporate active ink delivery. In addition, a number of metal precursor ink systems that are compatible with this method have been developed to allow patterning with a number of different metals and metal oxide materials. Importantly, the precursor ink can be patterned under ambient environmental conditions and converted to a metal film at a relatively low temperature, which allows substrates such as plastics that cannot withstand high temperature processing to be made. Can also be applied.

  In a preferred embodiment, the present invention is a method for writing to a conductive metal or metal precursor, for example, providing a cantilever having a cantilever end, which can be a tipless cantilever, disposed at the cantilever end. A method is provided that includes providing ink, providing a substrate surface, and moving the cantilever end or substrate surface such that ink is carried from the cantilever end to the substrate surface. The substrate surface can be moved to hold the cantilever in a fixed state, or the substrate surface can be moved to hold the cantilever in a fixed state. The movement that causes ink delivery can generally cause contact between the cantilever and the substrate surface, although there may possibly be ink between the cantilever and the surface.

  In another preferred embodiment, the present invention is a method for writing to a conductive metal or metal precursor, each of which has a cantilever end, can include a tip at the end, or is a tipless cantilever And providing two or more cantilevers with a gap between about 1 micron and about 20 microns, providing an ink disposed in the gap, providing a substrate surface, providing ink with a gap A method comprising contacting two or more cantilevers with the gap and the substrate surface to be carried from the substrate to the substrate surface.

  The present invention also provides an ink formulation for microlithography or nanolithography comprising one or more metal salts and one or more solvents, wherein the metal salt concentration is about 1 mg / 100 μL to about 500 mg / Provide an ink formulation that is 100 μL. The amount of metal salt can be adjusted to a height sufficient to provide a suitable dispersion and a suitable mass density and thickness for a given application.

  The present invention also provides a method of writing directly to a conductive metal, the step of providing a cantilever that is a tipless cantilever having a cantilever end, an ink comprising metal nanoparticles disposed at the cantilever end. There is provided a method comprising the steps of: providing a substrate surface; contacting the cantilever edge with the substrate surface such that ink is carried from the cantilever edge to the substrate surface.

  An important advantage of the present invention is in a variety of different sizes for a particular system, such as from about 1 micron to about 15 microns or lateral dimensions, such as from about 1 micron to about 10 microns (eg, single digit) for length and width. Including the ability to operate with excellent control. Problems with nozzle or pipette clogging can be avoided in many ways. Equipment use to implement this is relatively simple and does not require high vacuum, for example. Registration and flexibility are excellent. Mass production and disposable are possible.

In addition, a series of numbered embodiments are provided.
1. A method for depositing a conductive coating on a substrate in a desired pattern, the step of depositing the precursor on the substrate in a desired pattern using a chip coated with the precursor by nanolithography, a precursor Contacting the body with the ligand, applying sufficient energy to transfer electrons from the ligand to the precursor, thereby decomposing the precursor and forming a conductive precipitate in the desired pattern; Thereby forming a conductor pattern directly on the substrate.
2. The method according to 1, wherein the tip is a nanoscopic tip.
3. The method according to 1, wherein the tip is a scanning probe microscopic tip.
4. The method according to 1, wherein the tip is an atomic force microscope tip.
5. The method of 1, wherein the coating comprises at least about 80% pure metal.
6. The method of 1, wherein the coating comprises a metal having a thickness of less than about 10 angstroms.
7. The method of 1, wherein the coating comprises a metal that is at least about 100 angstroms thick.
8. The method according to 1, wherein the precursor comprises a salt selected from the group consisting of carboxylates, halides, pseudohalides and nitrates.
9. The method of 1, wherein the precursor comprises a carboxylate.
10. The method of 1, wherein the pattern comprises a circuit.
11. The method of 1, wherein the ligand comprises a material selected from the group consisting of amines, amides, phosphines, sulfides and esters.
12. The method of 1, wherein the ligand is selected from the group consisting of a nitrogen donor, a sulfur donor, and a phosphorus donor.
13. The method according to 1, wherein the precipitate comprises a metal.
14. The method of 1, wherein the precipitate is selected from the group consisting of copper, zinc, palladium, platinum, silver, gold, cadmium, titanium, cobalt, lead, tin, silicon and germanium.
15. The method of 1, wherein the precipitate comprises a conductor.
16. The method of 1, wherein the precipitate comprises a semiconductor.
17. The method of 1, wherein the substrate comprises a nonconductor.
18. The method of 1, wherein the substrate comprises at least one of a conductor and a semiconductor.
19. The method of 1, wherein the step of applying energy comprises applying heat.
20. The method of 1, wherein the step of applying energy comprises applying infrared or UV radiation.
21. The method according to 1, wherein the step of applying energy comprises applying vibrational energy.
22. The precursor comprises a salt selected from the group consisting of carboxylates, halides, pseudohalides, nitrates, and the ligand is selected from the group consisting of amines, amides, phosphines, sulfides and esters. 2. The method according to 1, comprising a substance.
23. The method according to 19, wherein the precipitate is selected from the group consisting of copper, zinc, palladium, platinum, silver, gold, cadmium, titanium, cobalt, lead, tin, silicon and germanium.
24. The method according to 19, wherein the step of applying energy comprises applying radiant heat.
25. A method of printing a conductive metal in a desired pattern on a substrate,
Nanolithography uses a precursor-coated tip to pull the metal precursor and ligand directly onto the substrate according to the desired pattern, and decompose the precursor by applying energy, Forming a conductive metal in a desired pattern without removing a substantial amount of precursor from the substrate and without removing a substantial amount of metal from the substrate.
26. The method according to 25, wherein the metal pattern comprises substantially pure metal having impurities less than about 20% by weight.
27. The method according to 25, wherein the decomposing step comprises thermal decomposition.
28. The method of 25, wherein the decomposing comprises pyrolyzing at a temperature of less than about 300 ° C.
29. The method according to 25, wherein the metal is selected from the group consisting of elemental metals, alloys, metal / metal composites, metal ceramic composites, and metal polymer composites.
30. A nanolithographic method comprising the steps of attaching a metal precursor from a chip to a substrate to form a nanostructure, and then converting the precursor nanostructure to a metal deposit.
31. The method according to 30, wherein the deposition and conversion is carried out without using an electrical bias between the chip and the substrate.
32. The method according to 30, wherein the attachment and conversion is carried out using a chemical agent in addition to the substrate.
33. The method according to 30, wherein the tip is a nanoscopic tip.
34. The method according to 30, wherein the tip is a scanning probe microscopic tip.
35. The method according to 30, wherein the tip is an AFM tip.
36. The method of 35, wherein the deposition and conversion is performed without using an electrical bias between the chip and the substrate.
37. The method according to 30, which is repeated to form a multilayer.
38. The method according to 30, wherein the tip is adapted not to react with the precursor.
39. The method according to 30, wherein the method is used to connect at least one nanowire with another structure.
40. The method according to 30, which is used for connecting at least two electrodes.
41. The method according to 30, which is used to prepare a sensor.
42. The method according to 30, which is used to produce a lithographic template.
43. The method according to 30, which is used to prepare a biosensor.
44. Consisting essentially of the steps of attaching an ink composition consisting essentially of a metal precursor from a nanoscopic chip to a substrate to form a nanostructure, and then converting the nanostructured metal precursor to a metallic form. Nanolithography method.
45. The method according to 44, wherein the conversion is a thermal conversion without using a chemical agent.
46. The method according to 44, wherein the conversion is a chemical conversion performed using a reducing agent.
47. The method according to 44, wherein the conversion is carried out using the reducing agent in the vapor state.
48. The method according to 44, wherein the tip is an AFM tip.
49. The method according to 44, wherein the tip comprises a surface that does not react with the precursor.
50. The method according to 44, wherein the method is repeated a plurality of times to form a multilayer structure.
51. A method of printing without using an electrochemical bias or reaction between an ink and a substrate, wherein a metal precursor ink composition is deposited from a chip in the form of a microstructure or nanostructure onto the substrate. Forming an array having discrete objects separated from each other by less than about 1 micron.
52. The method according to 51, further comprising forming a metal from the precursor.
53. The method according to 51, wherein the discrete objects are separated from each other by about 500 nm or less.
54. The method according to 51, wherein the discrete objects are separated from each other by about 100 nm or less.
55. Providing a cantilever having a cantilever end, which can include a tip at the end or can be a tipless cantilever,
Providing ink disposed at the end of the cantilever;
Providing a substrate surface;
Contacting the cantilever end with the substrate surface such that ink is carried from the cantilever end to the substrate surface.
56. The method according to 55, wherein the substrate surface is moved to fix the cantilever.
57. The method according to 55, wherein the substrate surface is fixed and the cantilever is moved.
58. The method according to 55, wherein the cantilever is a tipless cantilever.
59. The method according to 55, wherein the cantilever includes a tip at the end of the cantilever.
60. The method according to 55, wherein the ink comprises one or more metals.
61. The method according to 55, wherein the ink comprises one or more metal salts.
62. The method according to 55, wherein the ink comprises one or more metal nanoparticles.
63. The method according to 55, wherein the ink comprises one or more hydrophobic nanoparticles.
64. The method according to 55, wherein the ink comprises one or more hydrophilic nanoparticles.
65. The method according to 55, wherein the ink comprises one or more metal nanoparticles having an organic shell.
66. The method according to 55, wherein the ink comprises one or more metal nanoparticles having an insulating shell.
67. The method according to 55, wherein the ink is a hydrophobic ink.
68. The method according to 55, wherein the ink is a hydrophilic ink.
69. The method according to 55, wherein the ink is a hydrophobic ink and the substrate surface is a hydrophobic surface.
70. The method according to 55, wherein the ink is a hydrophilic ink and the substrate surface is a hydrophilic surface.
71. The method according to 55, wherein the ink comprises both a hydrophobic agent and a hydrophilic agent.
72. The method according to 55, wherein the ink comprises one or more metal nanoparticles having an average diameter of about 100 nm or less.
73. The method according to 55, wherein the ink comprises one or more biological molecules.
74. The method according to 55, wherein the ink comprises one or more peptides or proteins.
75. The method according to 55, wherein the ink comprises one or more nucleic acids.
76. The method according to 55, wherein the ink comprises one or more sol-gel materials.
77. The method according to 55, wherein the ink comprises one or more magnetic materials or precursors thereof.
78. The method according to 55, wherein the ink comprises one or more semiconductor materials or precursors thereof.
79. The method according to 55, wherein the ink comprises one or more optical materials or precursors thereof.
80. The method according to 55, wherein the ink comprises one or more solvents having a boiling point greater than 100 ° C.
81. The method according to 55, wherein the ink comprises one or more compounds that are chemisorbed or covalently bonded to the substrate surface.
82. The method according to 55, wherein the ink forms a feature on the substrate surface.
83. The method according to 55, wherein the ink forms a metal oxide on the surface.
84. The method according to 55, wherein the ink forms an alloy on the surface.
85. The method according to 55, wherein the ink forms a feature on the substrate surface having a dimension controlled by the shape of the cantilever.
86. The method according to 55, wherein the ink forms a feature on the substrate surface having a width of about 1 micron to about 100 microns.
87. The method according to 55, wherein the ink forms a feature on the surface of the substrate, and the feature is subjected to melting, sintering or agglomerating conditions.
88. The method according to 55, wherein the ink forms a feature on the surface of the substrate, and the feature is subjected to annealing.
89. The method according to 55, wherein the ink forms a feature on the surface of the substrate, and the feature is subjected to light.
90. The method according to 55, wherein the ink forms a feature on the substrate surface and the feature is subjected to a laser.
91. The method according to 55, wherein the ink forms a feature on the surface of the substrate and the feature is subjected to an electric current.
92. The method according to 55, wherein the ink forms a feature on the substrate surface that contacts one or more electrodes on the substrate surface.
93. The method according to 55, wherein the ink forms a feature on the substrate surface and is annealed at a temperature of about 300 ° C. or less.
94. The method according to 55, wherein the ink forms a shape on the surface of the substrate and is subjected to annealing at a temperature of about 100 ° C. to about 300 ° C.
95. The method according to 55, wherein the ink is subjected to a reduction reaction on the substrate surface.
96. The method according to 55, wherein the ink forms a continuous surface on the substrate surface after contact.
97. The method according to 55, wherein the ink forms a form on the substrate surface that is converted to a metallic state having a resistivity of about 10 microohm * cm or less.
98. The method according to 55, wherein the ink forms a feature on the substrate surface that is converted to a metallic state having a resistivity of about 1 micro ohm * cm to about 10 micro ohm * cm.
99. The method according to 55, wherein the ink forms a feature on the substrate surface having a width of about 5 nm to about 1 micron.
100. The method according to 55, wherein the method is repeated to form a layer of ink on the substrate surface.
101. The method according to 55, wherein the ink is the same material repeated to form a layer of ink on the substrate surface.
102. The method according to 55, wherein the ink is a different material repeated to form a layer of ink on the substrate surface.
103. The method according to 55, wherein the ink forms a feature on the substrate surface that is a line.
104. The method according to 55, wherein the ink forms a feature on the substrate surface that is a dot.
105. The method according to 55, wherein the cantilever is an AFM cantilever.
106. The method according to 55, wherein the substrate surface is glass.
107. The method according to 55, wherein the substrate surface is a thin film transistor array.
108. The method according to 55, used for repairing a flat panel display.
109. The method according to 55, wherein the cantilever is loaded with ink using a microfabricated ink well filled with ink.
110. The method according to 55, wherein the cantilever is contacted with the substrate surface at an angle of about 10 ° or less.
111. The method according to 55, wherein the cantilever is contacted with the substrate surface at an angle of about 5 ° or less.
112. The method according to 55, wherein the cantilever is bent by contact when viewed by optical microscopy.
113. The method according to 55, wherein the contact is performed by use of force feedback.
114. The method according to 55, wherein the contacting is performed by use of a piezoelectric scanning mechanism.
115. The method according to 55, wherein the cantilever has a width of about 1 micron to about 100 microns.
116. The method according to 55, wherein the cantilever has a width of about 5 microns to about 25 microns.
117. The method according to 55, wherein the cantilever is a linear beam cantilever.
118. The method according to 55, wherein the contact is performed by use of force feedback.
119. The method according to 55, wherein the cantilever has a spring constant of about 0.001 N / m to about 0.50 N / m.
120. The method according to 55, wherein the cantilever has a spring constant of about 0.004 N / m to about 0.20 N / m.
121. The method according to 55, wherein the cantilever has a length of about 100 microns to about 400 microns.
122. The method according to 55, wherein the cantilever has a length of about 150 microns to about 300 microns.
123. The method according to 55, wherein the cantilever is one of a plurality of cantilevers that deposit ink in parallel.
124. The method according to 55, wherein the ink is a polyol ink.
125. The method according to 55, wherein the ink comprises a metal salt with one or more alcohols or polyols.
126. The method according to 55, wherein the ink forms a feature on the substrate surface having a lateral dimension of about 1 micron to about 15 microns.
127. The method according to 55, wherein the ink forms a feature on the substrate surface having a lateral dimension of about 1 micron to about 10 microns.
128. The method according to 55, wherein the ink forms a feature on the substrate surface having a lateral dimension of about 1 micron to about 15 microns.
129. A substrate comprising a substrate surface and ink thereon prepared by the method of claim 55.
130. A method of writing to a conductive metal,
Providing two or more cantilevers, each having a cantilever end, which can include a tip at the end or can be a tipless cantilever, with a gap between about 1 micron and about 20 microns in between. Providing an ink disposed in the gap; providing a substrate surface; contacting two or more cantilevers with the gap and the substrate surface such that ink is carried from the gap to the substrate surface. .
131. The method according to 130, wherein the gap is from about 1 micron to about 5 microns.
132. The method according to 130, wherein the gap is from about 5 microns to about 10 microns.
133. The method according to 130, wherein the gap is from about 10 microns to about 20 microns.
134. An ink formulation for nanolithography comprising one or more metal salts and one or more solvents, wherein the metal salt concentration is about 1 mg / 100 μL to about 500 mg / 100 μL .
135. The ink formulation of 134, wherein the concentration of the metal salt is from about 1 mg / 100 μL to about 200 mg / 100 μL.
136. The ink formulation of 134, wherein the concentration of the metal salt is from about 5 mg / 100 μL to about 30 mg / 100 μL.
137. The ink formulation of 134, further comprising two or more oligomeric or polymeric additives having different average molecular weights.
138. The ink formulation of 134, further comprising at least one oligomer and at least one polymer.
139. The ink formulation of 100, comprising two or more metal salts.
140. The ink formulation according to 100, further comprising an epoxy.
141. A method of writing directly to a conductive metal, the cantilever having a cantilever end, including a tip at the end, or a tipless cantilever, disposed at the end of the cantilever A method comprising: providing an ink comprising metal nanoparticles; providing a substrate surface; contacting the cantilever end with the substrate surface such that the ink is carried from the cantilever end to the substrate surface.
142. The method according to 141, wherein the ink forms a feature on the surface of the substrate and the feature is subjected to post-treatment.
143. The method according to 141, wherein the ink forms a feature on the surface of the substrate and the feature is subjected to a heat treatment.
144. The method according to 141, wherein the ink forms a feature on the surface of the substrate, and the feature is subjected to light treatment.
145. The method according to 141, wherein the ink forms a feature on the substrate surface, and the feature is subjected to a heat treatment at less than about 300 ° C.

DETAILED DESCRIPTION The present invention, which can be conveniently referred to as “cantilever microdeposition (CMD)” in a preferred embodiment, can be implemented in a number of ways, including those described in the examples below.

Embodiment 1: Cantilever Microdeposition In a first embodiment, the present invention is a method for producing micrometer scale and submicrometer patterns using a cantilever or microbrush comprising: (1) a cantilever or microbrush; Providing, (2) providing an ink, i.e. a compound or mixture thereof, disposed on the cantilever or microbrush, (3) providing a substrate surface, and (4) the ink cantilever or microbrush. A method comprising contacting a microbrush with a substrate surface such that the microbrush is conveyed to the substrate surface. FIG. 36 illustrates the principle of this method.

  Preferably, the minimum lateral dimension of the resulting pattern (measured parallel to the substrate surface, eg line width) is in the range of 0.5 microns to 15 microns. Its maximum lateral dimension (eg line length) is greater than 100 microns, preferably greater than 200 microns, and its height (eg measured substantially perpendicular to the local plane) is between 1 nm and 2 microns It is a range.

  Preferably, the cantilever or microbrush is manufactured using standard microfabrication techniques including microfabricated equipment, i.e., photolithography, electron beam lithography, thin film deposition, etching, lift-off and focused ion beam micromachining. Microelectromechanical system (MEMS). The microbrush may have the shape of a cantilever having a free end and an end coupled to a macroscopic or mesoscopic body, or may be a device that includes multiple cantilevers. The cantilever may or may not have a tip protruding from the main plane of the cantilever. The meso / macroscopic body may be a diced (silicon or glass) wafer.

  Two or more adjacent cantilever bodies can form a constant or variable width gap or slit that can be used for ink storage or dispensing. A microfluidic circuit may be formed in the cantilever body and / or the mesoscopic or macroscopic body to which it is attached. The microfluidic circuit can include a reservoir, channel and bias for ink delivery. The channel and reservoir can be formed by two substantially parallel surfaces (eg, the wall of the slit) or more than two surfaces (eg, forming an open channel or a completely closed channel). In a preferred embodiment, a substantially flat tipless cantilever is used.

  A variety of inks including organic and inorganic compounds such as metal salts and complexes, sol-gel precursors, polymers, biomolecules such as nucleic acids (eg DNA), peptides and proteins, nanoparticles and solutions or mixtures thereof Can be made. Deposition can be performed before or after a number of processes including substrate cleaning, subsurface preparation, drilling, laser or ion beam micromachining, photolithography and curing by application of heat or light.

Literature useful for practicing the present invention Cantilevers, tips, inks, substrate surfaces and contact methods are known in the art, and those skilled in the art will include the preferred embodiments and examples described below. The following technical documents can be referred to when implementing in many aspects. In addition, a list of references is provided later in this specification, and all references herein are hereby incorporated by reference in their entirety and can generally be relied upon in the practice of the present invention. .

  Cantilever microdeposition is a technology developed commercially by NanoInk (Chicago, IL), typically (1) a sharp tip with a nanometer scale apex is coated with ink, and (2) the ink is a tip Is related to, but separate from, Dip Pen Nanolithography ™ (DPN ™), which flows through the meniscus to the substrate and spontaneously condenses at the contact joint. In contrast to DPN printing, the present invention does not require a sharp tip, but rather preferably uses a flat, spatula micrometer sized cantilever or cantilever as an ink application means. Cantilever microdeposition is optimally used to produce critical dimension patterns ranging from high sub-micrometer to 10 micron range, while DPN printing is optimal for ultra-high resolution (eg nanoscale) patterning.

  Cantilever microdeposition has a lower resolution, but in particular the higher speed (cantilever or microbrush speed relative to the surface) can be used, so its throughput (in units of square microns per second) is higher than the throughput of DPN printing. Is also expensive. In general, the cantilevers used in the present invention are not in direct contact with the surface of the substrate. Rather, a layer of ink is trapped between the surface and the microbrush or cantilever end. While not wishing to be bound by theory, it is believed that the interaction between hydrodynamics and capillary tension in the space between the cantilever and the surface controls ink deposition. For example, pattern height and overall quality (continuity) are sensitive to pressure applied to the cantilever, but this is generally not the case with DPN. Line width correlates strongly with cantilever width (see, eg, FIGS. 37 and 38) and is largely independent of patterning speed, but in contrast, DPN printing uses ink from a point source (tip-sample contact). Controlled by the diffusion rate and patterning rate.

  However, many technical developments related to dip pen nanolithography, including ink, ink delivery technology, cantilever / brush manufacturing method, cantilever position control technology and computer control design and manufacturing algorithm, are now available for cantilever microdeposition Strongly related.

  Variety related to DPN printing, including attachment equipment (eg NSCRIPTOR ™ platform), computer software, environmental chambers, pens, substrates, kits, inks, ink wells, calibration software, alignment software, accessories, etc. Products can be obtained from NanoInk. Single DPN printed probes, passive multi-probe arrays, A-frame cantilevers, diverging cantilevers and AC mode cantilevers can be obtained from NanoInk. Also available are sharpened and unsharpened tips. DIP PEN NANOLITHOGRAPHY ™ and DPN ™ are trademarks of NanoInk, Inc., Chicago, IL, and are used accordingly herein.

DPN printing and deposition methods are incorporated herein by reference in their entirety and are extensively described in the following patent applications and patent publications that assist in the disclosure of the present invention, particularly with respect to experimental parameters for performing deposition:
1. US Patent Provisional Application No. 60 / 115,133 ("Dip Pen Nanolithography") filed January 7, 1999.
2. US Patent Provisional Application No. 60 / 157,633 filed Oct. 4, 1999 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced Character").
3. US Patent Application No. 09 / 477,997 filed January 5, 2000 ("Methods Utilizing Scanning Probe Microscope Tips and Products There for or Produced Features"), US to Mirkin et al., Already filed October 21, 2003 Patent No. 6,635,311.
4. US Provisional Application No. 60 / 207,713 filed May 26, 2000 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced Character"). This application describes, for example, wet chemical etching, working examples, references and figures, and is incorporated by reference in its entirety).
5. US Provisional Application No. 60 / 207,711 filed May 26, 2000 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced Character").
6. US Patent Application No. 09 / 866,533, filed May 24, 2001 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced Character"). This application describes, for example, wet chemical etching, working examples (eg, Example 5), references and figures, and is incorporated by reference in its entirety).
7. US Patent Publication No. 2002/0063212 A1 published on May 30, 2002 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced Reactor").
8. US Patent Publication No. 2002/0122873 A1 ("Nanolithography Methods and Products Produced Therefor and Produced Characters") published September 5, 2002.
9. PCT Publication No. WO 00/41213 A1 published on 13 July 2000 based on PCT Publication No. PCT / US00 / 00319 filed 7 January 2000 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced accordingly ").
10. PCT Publication No. WO01 / 91855 A1 published on Dec. 6, 2001 based on PCT Publication No. PCT / USO1 / 17067 filed on May 25, 2001 ("Methods Utilizing Scanning Probe Microscope Tips and Products Therefor or Produced composition ").
11. US Provisional Application No. 60 / 326,767 filed October 2, 2001 ("Protein Arrays with Nanoscopic Features Generated by Dip-Pen Nanolithography"), 2003 to Mirkin et al., Published April 10, 2003 / 0068446.
12. US Provisional Patent Application No. 60 / 337,598 ("Patterning of Nucleic Acids by Dip-Pen Nanolithography") filed November 30, 2001 and US Patent General Application to Mirkin et al. Filed December 2, 2002 10 / 307,515.
13. US Provisional Patent Application No. 60 / 341,614 ("Patterning of Solid State Features by Dip-Pen Nanolithography") filed December 17, 2001, 2003/28 to Mirkin et al., Published April 28, 2003. 0162004. This application includes descriptions of metallic, metal oxides and inorganic solid state structures.
14. US Provisional Patent Application No. 60 / 367,514 ("Method and Apparatus for Aligning Patterns on a Substrate") filed March 27, 2002, and published 2003-0285967 to Eby et al.
15. US Provisional Patent Application No. 60 / 379,755 ("Nanolithographic Calibration Methods") filed May 14, 2002 and US Patent Application No. 10 / 375,060 to Cruchon-Dupeyrat et al. Filed February 28, 2003. .
16. In addition, US regular application No. 10 / 647,430 to Crocker et al. Filed Aug. 26, 2003 (published, 2004/0127025) ("Processes for fabrication g conductive patterns using nanolithography as a patterning tool") Describes a variety of metallic inks that can be patterned in accordance with the present invention, which is incorporated herein by reference in its entirety (to further enable those skilled in the art to practice the present invention, Many of which are provided below). Also, a US regular application to Crunchon-Dupeyrat et al. Published February 12, 2004 as 2004/0026681 ("Protosubstrates") printed on micro and nano structures that can be tested on a macro scale. Various aspects are described, and are incorporated herein by reference in their entirety. Also, US General Application ("Electrostatically Driven Nanolithography") publication number 2004/0008330 published on January 15, 2004 to Mirkin et al. Describes conductive polymer patterning and is generally referenced. Is incorporated herein by reference. No. 10 / 442,189 (“Peptide and Protein Nanoarrays and Direct-Write Nonolithographic Printing of Peptides and Proteins”) filed May 21, 2003 to Mirkin et al. A variety of peptides and proteins are described that can be incorporated into the book and patterned according to the present invention. US patent application Ser. No. 10 / 689,547 (“Nanometer Scale Engineering Structures ...”) to Van Crocker et al., Filed Oct. 21, 2003, is hereby incorporated by reference in its entirety. US patent application Ser. No. 10 / 705,776 (“Methods and Apparatus for Ink Delivery ...”) to Cruchun-Dupeyrat et al., Filed Nov. 12, 2003, is hereby incorporated by reference in its entirety.

  In general, current state-of-the-art DPN ™ printing and deposition related products, including hardware, software, and equipment, are also commercially available from NanoInk (Chicago, IL) to implement the present invention. These can be used. For example, NSCRIPTOR ™ equipment can be used for patterning. DPN printing is further described, for example, in Ginger, Zhang, and Mirkin, Angew. Chem. Int. Ed., 2004, 43 (1), 30-45.

  The parallel method of DPN printing can be performed as described, for example, in US Patent Application No. 6,642,129 filed Nov. 4, 2003 to Liu et al.

  In addition, the following documents describe wet chemical etching methods used with direct write nanolithography and are hereby incorporated by reference in their entirety, including drawings, references and 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; Zhang et al.," Fabrication of Sub-50 nm Solid-State Nanostructures on the Basis of Dip-Pen Nanolithography "; Nano Lett ., 2003, 3, 43-45. In addition, US patent application “Fabrication of Solid-State Nanostructures including sub-50 nm Solid-State Nanostructures Based on Nanolithography and Wet Chemical Etching” (No. 10 / 725,939, filed Dec. 3, 2003 to Mirkin et al. ) Also describe etching and single layer resists that can be used in the present invention and are incorporated herein by reference in their entirety.

Also available Fundamentals of Microfabrication, The Science of Minitaturization , 2 nd Ed., Marc J. Madou , the micro and nanotechnology including addition and subtraction, for example, lithography (Chapter), the pattern transfer by dry etching (Chapter) Additive pattern transfer (Chapter 3) and wet bulk micromachining (Chapter 4). Also, Direct-Write Technologies for Rapid Prototyping Applications: Sensors, Electronics, and Integrated Power Sources (Eds. A. Pique and DB Chrisey) describe micro and nanotechnology, including addition and subtraction. For example, bulk micromachining and etching are described on pages 617-619. DPN printing on a sub-100 nanometer long scale is described in Chapter 10.

Further Embodiment Embodiment 2: Cantilever Microdeposition and Curing for Manufacturing Conductive Metal and Other Patterns In a preferred embodiment, for example, the present invention is a method for writing to a conductive metal comprising: (1) a cantilever end A step of providing a cantilever that can include a tip at the end or can be a tipless cantilever, (2) a step of providing ink disposed at the end of the cantilever, (3) providing a substrate surface And (4) contacting the cantilever end with the substrate surface such that ink is carried from the cantilever end to the substrate surface. After deposition, a local heat curing step is preferably performed, for example by using an intermediate power laser or an infrared gun.

  In another preferred embodiment, the material is deposited using a stamp chip, further described below. The stamp chip is, for example, a provisional patent application to H. Zhang et al. Entitled “Direct-Write Nanolithography with Stamp Tip: Fabrication and Applications,” filed February 13, 2004, which is incorporated herein by reference in its entirety. No. 60 / 544,260 and US patent application Ser. No. 11 / 056,391 filed Feb. 14, 2005 (attorney number 083847-0264).

  Cantilevers are known in the art and are commercially available from, for example, MikroMasch USA (Portland, OR). The cantilever can be coated and functionalized as desired. Tipless cantilevers are also known in the art, as described, for example, in US Pat. No. 5,958,701 to Green et al., US Pat. No. 6,524,435 to Agarwal and US Pat. No. 6,573,369 to Henderson et al.

  An important feature of the present invention is that the shape size and shape of the cantilever can be used to control at least one dimension of the feature formed on the substrate surface from the ink.

  Although the ink is not particularly limited, the main aspect of the present invention is metal-based inks including metal precursor inks and metal nanoparticle inks that often use metal salts. Useful embodiments are further described in the above patent application number 16 (conductor pattern), and are described further below.

  In general, the three main ink components are: (1) the main material to be deposited, eg one or more metals or metal salts, (2) one or more solvents, and (3) one or more, as desired. Contains multiple additives. The components of the ink can be adjusted to work with the cantilever, tip (if any) and substrate.

  If desired, the ink can be completely or partially dried on the cantilever or cantilever tip prior to delivery to the substrate surface. After delivery, the ink can be completely or partially dried on the substrate surface.

  Although the nanoparticles of the ink are not particularly limited, the main aspect of the present invention is a metal-based ink. Inorganic compounds can also be used in the nanoparticles. The nanoparticles can be substantially homogeneous or heterogeneous. If desired, it may have a core-shell structure. If desired, it can also have an organic surface coating or shell. It can also be magnetic. It can be semiconducting, whether doped or undoped. The nanoparticles can be electrically insulating or can have an insulating shell. The nanoparticles can be hydrophilic or hydrophobic. Nanoparticles can also be precursors of other technically useful materials including conductors, magnetic materials including ferromagnetic materials, semiconductors and optical materials. Nanoparticles exhibit quantum confinement effects and can exhibit useful properties such as various colors of electroluminescence and photoluminescence. The nanoparticles can be functionalized to chemisorb or covalently bond to the surface.

  The solvent system is not particularly limited. Ink solvents having a high boiling point are generally preferred. For example, a solvent with a boiling point above about 100 ° C., in particular above about 150 ° C., can be used. For example, aromatic hydrocarbons are one type of high boiling point solvent.

  When transported to the substrate surface, the ink begins to dry as desired to form a feature that is preferably stable even after, for example, a month. Preferably, the form can be cured and stabilized against washing with aggressive solvents and solvents including etching systems. The feature can be subjected to annealing, light, laser, current and other stimuli.

  In many cases, it is desirable to form a continuous structural mass that provides, for example, high conductivity. In many cases, it is desirable to form a high quality contact between a feature and a surface or other feature on the surface, such as an electrode.

  The feature can be nanostructured or microstructured. Since the height can be increased by performing lamination, the height of the feature is not particularly limited. Since nanoscale and micron scale dimensions can be prepared using the methods described herein, lateral dimensions such as length and width are not particularly limited. For example, the dot diameter or line width can be, for example, from about 5 nm to about 1 micron. Alternatively, the dot diameter or line width can be, for example, from about 1 micron to about 100 microns or from about 5 microns to about 25 microns.

  Additional references for use in practicing the present invention are set forth in the remainder of the specification. We do not admit that any of these references is prior art. The invention is further illustrated by the following non-limiting examples.

Examples In the following examples, gold and platinum traces were written by this novel method to form low resistivity traces that adhere strongly to substrates such as glass. The examples are subdivided into (1) experimental part and (2) results and discussion.

Experimental Materials All metal salts were purchased with the highest purity commercially available from Aldrich (Milwaukee, Wis.). By standard microfabrication methods, silicon nitride cantilevers were prepared with various beam widths with and without tips. To further test the effect of cantilever width, some cantilevers were constricted using focused ion beam (FIB) technology.

Nanoparticle preparation Nanoparticles were prepared using the method described by Murray and coworkers in MJ Hostetler et. Al., Langmuir 14, 17 (1998).

Patterning
Micron-sized patterns were formed using a translation stage of a Thermomicroscopes CR Research instrument or an NSCRIPTOR (NanoInk, Chicago, IL) instrument. The cantilever was coated with various metal precursor inks by contacting the cantilever with a microfabricated ink well filled with ink using a z-step motor. The coated cantilever was then placed over the substrate using a z motor and xy translation stage, and the cantilever was in contact with the surface. The cantilever was contacted at a slight angle (several degrees) so that only the end of the cantilever was in contact with the surface. A slight bend in the flexible cantilever monitored by optical microscopy indicated that contact occurred. Note that when patterning microscale features, it was not necessary to use instrument force feedback and piezoelectric scanning / positioning mechanisms. However, in the case of nanoscale patterns, these fine positioning features provided control of feature size and alignment at the submicron and sometimes sub-100 nm scale.

Results and Discussion Ink deposition A new method of writing directly on the surface with ink has been developed that allows line and dot patterns with dimensions of only a few hundred microns or even submicrons. This ink delivery method included the following general steps.

Ink loading The flexible cantilever was loaded with ink. Depending on the application, the cantilever can have a sharp tip at the end or tipless and can have a variety of end shapes and widths from a few microns to a few hundred microns. . Ink loading can be carried out passively by bringing the cantilever into contact with an ink drop or reservoir and then removing it. The ink wets the lower surface of the cantilever and adheres by cohesive force. Passive ink loading and delivery was demonstrated in the examples. The method described by C. Bergaud et al. Can be used to actively wick liquid ink and control adhesion by electrowetting and dielectrophoresis.

Procedure The cantilever can be brought into contact with the surface to be patterned. In most cases, no laser force feedback mechanism is required and no piezoelectric scanning / positioning mechanism is required. A mechanical “Z” step motor can be used to contact the cantilever with the surface, and optical microscopy can be used to detect deflection of the cantilever as it contacts the surface.

Feature control A line pattern can be formed by pulling a cantilever along a surface. For the NSCRIPTOR and Thermomicroscopes CP Research platforms, “X” and “Y” step motors or fine-tuning manual positioning screws can be used to translate the lever along the surface into the desired pattern shape. A commercially available high-resolution piezoelectric stage (NPoint, Madison, WI) may be retrofitted to any device. For the NSCRIPTOR platform, custom pattern design software can be used to direct cantilever movement. Importantly, if the cantilever is translated along the surface in the direction of the longitudinal axis of the cantilever, the line width can be directly related to the width of the end of the cantilever, as shown in FIG. Therefore, the shape of the line, for example, the line width can be controlled by the size of the cantilever. Using standard microfabrication techniques, cantilevers with a width of about 1 micron to about 100 microns can be manufactured. Therefore, in this method, a line pattern having a width from less than 1 micron to over 100 microns can be formed. A large range of line widths that can be patterned using various cantilever structures is shown in FIGS. For example, FIG. 1 shows an optical image of lines 60 and 45 microns wide. FIG. 6 shows optical and AFM height images of lines 5 and 4 microns wide, and FIG. 7 shows lines 3 and 2 microns wide. Even at the narrowest line width, the line has sufficient continuity to produce a low resistivity of 4 microohms.cm.

  The best feature control was achieved using a linear beam cantilever, and the “V” or “A” cantilever did not form a controlled width line. Also, line shape control can be achieved with a wide variety of cantilever spring constants (i.e., stiffness of 0.004 N / m to 0.19 N / m) and length (150-300 microns). Also, the optimal length for a fixed width cantilever depends on the spring constant of the material. In fact, very good line control was achieved with a cantilever with a width of 15 microns, a length of 150 microns and a spring constant of 0.032 N / m, but a width of 15 microns, a length of 300 microns and a spring constant of 0.004 N / m The cantilever achieved only a moderate line control. Using advanced lithographic methods such as focused ion beams, the cantilever dimensions can be further reduced by milling. It will be appreciated that the process works equally well when the surface is translated under a stationary cantilever. Current equipment can produce lines with a width of less than 100 microns and a width of less than 1 micron with a single cantilever pass at a rate of 20 microns per second, but with a write speed of 10 microns per second, higher conductivity The trace is obtained.

Feature Height Control Line trace height can be varied by controlling several patterning variables. In general, the thickness of the line pattern formed by a single pass can be less than 1 nm to several hundred nanometers after curing (see section below). To ensure optimal control over the line shape, the cantilever is contacted with the surface at an angle greater than a few degrees rather than parallel to the surface. By controlling the distance between the cantilever and the surface, the force or bending of the cantilever and the translation speed of the tip, the height of the trace can be varied.

  Pressing the cantilever against the surface with high force reduces the height of the patterned trace. In order to achieve the maximum height per pass in the case of metallic inks, the distance between the cantilever and the surface can be maximized as long as contact is not lost. Therefore, higher inks with higher viscosities and higher metal concentrations allow higher patterns in this way. In preliminary experiments, the force was roughly controlled by changing the distance between the cantilever and the surface while monitoring the cantilever deflection. The height / force control can be further improved by embedding in the cantilever a piezoelectric material for sensing the force between the cantilever and the substrate when approaching the surface and patterning the surface. A qualitative observation is implied that another way to increase the height of the pattern is to reduce the translation speed of the cantilever during patterning. With low-speed chip translation, a 100 nm-high feature (after curing) can be formed in a single pass. In order to form a dot pattern, the cantilever is brought into contact with the surface, kept in contact for a certain time (usually several seconds), and then removed.

By changing the shape and size of the divided cantilevers and a large number of cantilevers, the maximum ink loading amount and thus the maximum line length can be increased. Using a single cantilever that is 50 microns to 200 microns in length can reproducibly produce lines of several hundred microns in a single loading step for two different chip shapes and sizes as shown in Figure 8. it can. Writing with adjacent cantilevers with very small gaps (microns) in between can greatly improve the total supply of ink (ie, the amount obtained from a single dipping). Increasing ink supply can result in higher patterns or longer line patterns. The slits or gaps between the cantilevers act as reservoirs for holding ink by capillary action. This method can also be used to increase the line width of the trace if the cantilevers are closely spaced (a few microns to 10 microns). Alternatively, if a large number of cantilevers are arranged farther apart, they can be used to form the same or different ink dots or line patterns in parallel. FIG. 9 is an optical image of a patterning line formed using a number of adjacent cantilevers. Note that the maximum line length (and hence ink loading) obtained increases with the number of cantilevers (1, 4, and 2 adjacent cantilevers) in the “pen”. Also note that the increase in line width increases with the number of cantilevers in the pen.

Layering The height of line and dot patterns can be increased by applying multiple layers. Usually, in the case of metal ink, each layer is first cured by heating and then a second layer of the same metal precursor ink is applied. A nanoscale bilayer palladium pattern is shown in the AFM image and line scan of FIG. Note the increase in height from 2 nm of the first layer to 10 nm of the second layer. The ink used in this experiment was a saturated solution of palladium acetate dissolved in 80% ethylene glycol: 20% water. For other applications, it may be necessary to build layered features of dissimilar materials such as metals, oxides and semiconductors. For these experiments, the substrate was removed from the patterning device and the layers were cured, but the improved device could also include an energy source that could anneal or sinter the ink while remaining attached to the surface. it can. The energy source may be a heated sample stage for thermal curing, a laser or other light source, or an electric current is applied to the substrate to the final metal or metal oxide form. It may be a method of inducing ink conversion.

General methods for patterning ink conductive features include selecting an appropriate precursor ink and dispersant, such as applying ink to a surface using the methods described in the previous section, and finally, for example, Processing the pattern by applying energy, such as heat, to convert the precursor material to the final desired material. This section describes two different nanoparticle ink methods that are compatible with this patterning method. For specific applications, it may be useful to use different ink modifications or combinations.

1. Single-layer protective nanoparticle inks Inorganic materials are generally undesirable for writing directly on a substrate due to their high melting point. However, many material nanoparticles (less than 100 nm in diameter) show extreme melting point reductions (as high as 1000 ° C.) compared to bulk materials. Thus, nanoparticles provide a route to obtain inks for direct write deposition of metals and metal oxides that can be converted to a continuous film at low temperatures. This principle has been applied by others in combination with, for example, inkjet technology. Jacobson et al. (US Pat. No. 6,294,401) formed II-VI semiconductor patterns starting from nanoparticle inks such as CdTe and CdSe (see also Ridley et al. Science 1999 286 746-749). The best nanoparticles for direct writing inks are easily dispersed in a carrier solvent or matrix, have good stability at ambient conditions, are inexpensive to prepare, and can be converted cleanly into a continuous film at low temperatures.

Ink preparation
Various alkanethiol capped gold nanoparticles were prepared according to the method described by Hostetler, Murray et al. This method has also been used to prepare other metal nanoparticles such as platinum, palladium and silver. In addition, there are many similar methods of preparing other metal stabilized nanoparticles that would be equally useful for this application. Such methods use various surfactants, lipids and polymers to prevent the particles from aggregating. However, this synthesis method is relatively simple, and the Hostetler and Murray methods were selected to produce stable particles that can be decomposed into metal films at low temperatures. Subramanian and co-workers say that the temperature at which the nanoparticles are converted to a continuous film is strongly related to the number of carbons in the stabilized surfactant and the diameter of the nanoparticles, with shorter chains and larger particles breaking down at lower temperatures. (Huang, J. Electrochem. Soc. 2003, 150, G412).

  In the case of hydrophobic particles, hexanethiol was selected, and in the case of hydrophilic particles, thioctic acid and mercaptosuccinic acid were selected. After synthesizing particles according to the technique described by Murray and co-workers, inks are prepared by dispersing the particles in high boiling solvents such as mesitylene, xylene and dimethylformamide to reduce ink evaporation. It was.

Nanoparticle ink deposition and conversion to metal In order to achieve an ink that is compatible with the substrate of interest, one generally chooses a thiol-capped surfactant and solvent that allows the ink to wet the surface. Is useful. For example, if the nanoparticles are prepared using hexanethiol as a surfactant, the nanoparticles become hydrophobic and disperse well in nonpolar solvents such as toluene, mesitylene and xylene. These inks were very useful for patterning hydrophobic or non-clean surfaces. On the other hand, nanoparticles prepared using thioctic acid or mercaptosuccinic acid are dispersed in relatively polar solvents, such as alcohols, so that parent materials such as clean glass, quartz, silicon oxide, silicon and silicon nitride can be used. Used to pattern the water surface. If the ink is incompatible with the surface, the ink does not form a continuous line, but dewets from the surface to form a drop. Some non-polar solvents such as mesitylene have been useful for both hydrophilic and hydrophobic glass surfaces. After depositing the ink on an appropriate substrate, the surface was heated with a hot air gun at 250 ° C. for several seconds to convert the nanoparticle pattern into a continuous metal film. In principle, as long as the temperature is sufficient to remove the insulating organic shell, the nanoparticles can be converted to bulk metal using a number of different energy sources including lasers or heating stages. In FIGS. 1-7, the optical images show gold traces written between two gold electrodes before and after curing, and AFM line scanning obtains an average height of about 12 nm to 90 nm with one ink layer Show that you can.

  Surprisingly, the addition of long chain carbon compounds such as C-5 to C-50, preferably C-10 to C-18, improved the results. Preferably, the long chain carbon has a boiling point of 200 ° C. or higher. Similar to the ink compositions of the examples shown in FIGS. 1 and 2, the inventors have added a high-boiling long chain carbon compound (preferably 10-18 carbons) to the ink formulation. For example, dodecane or pentadecane having boiling points of 215 ° C. and 270 ° C., respectively, can be used. In the example shown in FIGS. 3-7, the inventors attended 1-2 microliters of pentadecane to 4 microliters of a nanoparticle solution composed of (nanoparticles, mesitylene and thioctic acid). These long-chain carbons interact with the carbon chains on the nanoparticles and mesh with each other to form a three-dimensional structure, as shown in the optical images of FIGS. 3-7 in comparison with the optical images of FIGS. A continuous and homogeneous film is formed. By comparing the AFM image of FIG. 2D with FIGS. 3C, 4A & B, 5C, 6B & E, 7B & E, there are few cracks or holes in FIGS. 3-7 and hardening compared to FIG. 2D where holes and cracks are present Later, a relatively smooth surface is formed. The addition of long chain carbon reduces the evaporation rate on the surface or in the ink well from a few minutes for mesitylene to a few hours for pentadecane, as shown in the optical images of FIGS. Helped to form a homogeneous line.

Gold Trace Properties Surprisingly, gold films prepared from nanoparticle precursors attached very well to clean glass surfaces (see Figure 40), but the nature of the cap group plays an important role in adhesion. Can play. For example, nanoparticles prepared with acid-terminated thiol capping groups, such as thioctic acid, form a film on glass that withstands the Scotch tape test where strips of tape are placed on the pattern and then scraped off. It was a thing. However, these hydrophilic films on the glass were peeled off by washing with water. On the other hand, cured films made from hydrophobic gold nanoparticles (ie, capped with methyl-terminated alkanethiols such as hexanethiol) were peeled off by the Scotch tape test, but withstood the water washing treatment. The best overall adhesion and conductivity was obtained by combining hydrophilic and hydrophobic drugs with gold nanoparticles. Specifically, the organic soluble ink was prepared by dissolving nanoparticles prepared using hexanethiol in mesitylene and then adding 100 mg / ml thioctic acid. The single layer pattern of this hybrid ink remained intact after the Scotch tape adhesion test and withstood water. In fact, the ink had excellent writing properties, wetted the glass surface well during writing and cured cleanly at 250 ° C. Evidence of excellent resistance to scotch tape and cleaning tests is shown in FIGS. The obtained gold thin film is metallic yellow, has a thickness of about 50 to 100 nm as measured by AFM, and exhibits excellent conductivity as measured by a two-probe structure. For example, a trace as shown in FIG. 2 that is approximately 250 microns in length and approximately 15 microns in width has a measured resistance value of approximately 18 ohms. Therefore, a resistivity of 8 microhm.cm was calculated for this particular trace, and a resistivity as low as 4 microohm.cm was measured for the patterned trace. For reference, the bulk resistivity of gold is 2.44 microohms.cm. Similar results can be obtained by preparing inks from nanoparticles having a ratio of acid-terminated thiols to hydrophobic methyl-terminated thiols. Particles with different ratios of dissimilar thiol cap molecules can be prepared in situ or the place exchange reaction described by Hostetler and co-workers (MJ Hostetler, SJ Green, JJ Stokes, and RW Murray, J. Am. Chem. Soc. 1996, 118, 4212-4213). Although this example demonstrated gold particle inks, the patterning method is generally applicable to any nanoparticle material that can be prepared using a cap ligand. There are various reports in the literature on how to produce particles with particle sizes ranging from sub-nanometers to 100 nanometers from materials including Cu, Pd, Ag, Ru, Mo, CdSe, Ni, Co and others .

Nanoscale Patterns Using Nanoparticle Inks Nanoparticle-based ink formulations can be patterned using dip pen nanolithographic printing methods to produce submicron sized patterns. In one experiment, hexanethiol capped gold nanoparticles (saturated solution in mesitylene) were patterned on quartz using a silicon nitride cantilever / tip assembly. Specifically, the chip was coated with the nanoparticle ink by contacting the chip with a drop of nanoparticle ink in a silicon ink well for a few seconds. Lines and dot features were then formed on the quartz surface using the coated chips. For example, the dot pattern was formed by holding the chip in contact with the surface for 10 seconds as shown in FIG. By changing the applied force from 0.2 nN to 4 nN, the diameter and height of the dots were changed from 50 nm to 85 nm in width and from 2.5 nm to 7.5 nm in height. Lines were formed by translating the tip over the surface at a constant speed (approximately 0.15 microns / second). As shown in FIG. 12, the height and width of the line were changed by changing the applied force. The nanoscale particle pattern was cured by applying heat from a heat gun (250 ° C., 5 seconds) and again verified by imaging. FIG.

2. Polyol ink Another method for preparing nanoparticles is to chemically reduce the metal salt by heat in the presence of alcohol or polyol. This method has been reported by Figlarz et al. As a means of producing dispersed nanoparticles (US Pat. No. 4,539,041). The method was improved by Chow et al. Who reported a similar method for forming continuous films. This polyol method can be creatively and conveniently adapted to form nanoparticles for use as inks for nanoscale and microscale conductor patterns.

Ink Preparation A common formulation for metal precursor inks includes an alcohol containing a matrix and a metal salt. After patterning, when the salt is converted into nanoparticles in situ, the nanoparticles aggregate into a metal film due to increased heat. In preliminary experiments, this method has been demonstrated for metals such as Au, Pt, Pd and Ag, but many other metals and alloys (reviewed in US Pat. Nos. 5,759,230 and 4,539,041) are also included in this method. It can be adapted.

Example 1 of nanometer scale pattern with polyol ink
Platinum nanoscale features were written using a precursor ink consisting of 10 mg / 100 μL of hexachloroplatinum (IV) hydrogen hydrate (hydrate) dissolved in 20% Millipore water and 80% ethylene glycol. This ink can be written on clean glass or silicon oxide substrates using DPN printing technology. For micron-sized patterns, tipless cantilevers provide optimal control of pattern size and thickness, and for nanoscale patterns, have ultra-sharp tips (eg, silicon nitride) at the end of flexible cantilevers Cantilevers provide optimal resolution. After deposition, the precursor pattern is converted into a metal form by heating with a hot plate or hot air gun. This curing or conversion reaction occurs rapidly (in seconds) at temperatures around 250 ° C. The thickness of the pattern can be increased by adding a layer of ink between the curing steps. FIG. 10 shows a layered nanoscale pattern formed on silicon oxide using this ink. A similar method was used to draw micron-sized platinum traces between gold electrodes on silicon oxide. FIG. 14 shows a 110 micron long line drawn with platinum chloride ink by translating a cantilever coated with ink in a direction parallel to its minor axis. After curing, the single layer ink exhibited a high resistance, but subsequent layers could be added to increase the pattern height and thus the conductivity.

Example 2
In another example, platinum ink was used to form dot features between micron-sized gold electrodes. The dots are formed by bringing the coated tip / cantilever assembly into contact with the surface for a short time (several seconds) and then retracting the tip to leave a drop, as shown in the optical image of FIG. The size of the droplets depends on the wettability of the ink to the surface, chip loading and possibly chip-substrate retention time.

Example 3
Several different polymers were used as additives to change the viscosity and wettability of the metal salt precursor ink. For example, the properties of the ink were improved by using polyethylene glycol as the reducing agent instead of ethylene glycol. By using a mixture of two different molecular weight polyethylene glycols, a particularly useful platinum ink is obtained. To prepare this ink, 100 mg of hexachloroplatinic (IV) hydrogen hydrate (hydrate) was dissolved in 15 microliters of an aqueous solution containing 30 mg each of 300 and 10,000 polyethylene glycols. The ink sufficiently wets the glass surface, and after being cured by heat, forms a conductive platinum film. For example, FIG. 16 shows an example of a single layer platinum trace drawn between chrome electrodes. After curing, the 50 micron long trace had a resistance of 80 ohms and the trace adhered well to the surface during cleaning and scotch tape peel tests.

Example 4
Gold has a much lower bulk resistivity than platinum. Therefore, to improve the conductivity of metal traces for applications such as metal trace repair in thin film transistors, a similar metal ink precursor based on the gold salt tetrachlorogold (III) hydrogen (trihydrate) is used. Tested. A typical formulation contains 100 mg Au salt in 80% ethylene glycol / 20% water. The gold precursor ink was sufficiently wetted on the silicon oxide and glass surfaces during writing and cured on a hot plate at 200 ° C. for 5-10 seconds. The resulting film appeared black in the optical micrograph, and according to the AFM image, consisted of small separated particles. Single layer traces were usually non-conductive and adhered poorly to clean silicon oxide substrates. Subsequent layers (up to 5 layers) increased the height and diameter of individual particles to several hundred nanometers, but at high resistance (several hundred ohms across a 100 micron long electrode gap) Separation occurs. The AFM scan of FIG. 17 shows large gold particles formed after three layers of gold chloride ink deposited on the silicon oxide between the gold electrodes.

Example 5
Inks useful for forming conductive traces on silicon oxide would combine the properties of gold and platinum precursor inks. Therefore, in order to obtain high gold conductivity and excellent platinum adhesion and film adhesion, alloy-forming inks based on gold and platinum were developed. For example, one formulation that was very compatible with the patterning method consisted of 100 mg platinum salt and 50 mg gold salt simultaneously dissolved in 30 microliters of water containing 60 mg each of 300 and 10,000 MW polyethylene glycol. there were. The two layer pattern drawn across the 30 micron gap on silicon oxide, shown in FIG. 17A, showed a resistance of 90 ohms after curing. Six layers of the same alloy ink written between chrome electrodes using PDMS (polydimethylsiloxane) coated AFM tips showed a resistance of 32 ohms after curing and reached a height of 80 nm (FIG. 17B) . FIG. 17C shows uniform Au—Pt particles in a six-layer pattern measured by atomic force microscopy. In order to further increase the conductivity of the metal trace, the substrate was immersed in a silver enhancement solution for 1 hour. Optical and AFM images showed that the silver enhancement solution formed a silver coating only in areas that already contained gold. This experiment provides further evidence that the pattern contains gold metal in a fully reduced state. Current-voltage measurements show that the resistance dropped to 24Ω after silver was deposited.

Example 6
One way to improve the adhesion of polyol inks to glass surfaces (and many other surfaces) is to add a small amount of epoxy to the ink formulation. For one such ink, 85 mg of gold hydrogen tetrachloride was dissolved in 50 microliters of dimethylformamide. To 3 microliters of this salt solution, 1 microliter of ethylene glycol and 1 microliter of epoxy mixture were added. Two parts of epoxy purchased from Epotek (377 Epotek) were cured for 1 hour at 120 ° C in the absence of metal salt, and epoxy purchased from Aldrich (bisphenol F) was cured for 1 minute at 150 ° C, but the curing time was gold Increased in the presence of salt. The resulting ink mixture easily transferred to the surface in the standard deposition process, but did not wet the glass surface very well. After patterning, heat was used to convert the metal salt to nanoparticles and to crosslink the epoxy. The resulting film adhered very well to the glass surface and withstood all standard cleaning treatments (water washing and scotch tape peeling) and mechanical wear. As long as the metal content of the ink was sufficiently high, the metal trace formed between the gold electrodes had a sufficiently low resistance. FIG. 18 shows an optical micrograph of a large metal mold on glass prepared by curing for 2 hours at 150 ° C. using an epoxy enhanced ink. The resistance value of the film was 0.3 ohm.

Example 7
In all of the above examples, micron scale patterns were deposited using cantilevers as the ink source and main delivery tool. However, to form submicron-sized features using these metal precursor inks, it is useful to use a sharp tip at the end of the cantilever as a source and tool for ink delivery. . One metallic ink that works particularly well for micron and submicron scale patterning is a modification of the gold ink described above. To prepare the ink, gold chloride (85.5 mg) is dissolved in 50 μL of dimethylformamide. To this solution is added 1 μL of ethylene glycol and 0.1 mg of thioctic acid. This ink can be applied using a silicon nitride chip, but if a PDMS (polydimethylsiloxane) coated chip is used for writing, the patterning reliability is improved. When this ink is written on a quartz substrate, a 15 nm high feature is obtained, as demonstrated by the AFM image in FIG. The precursor ink pattern is cured in an oven at 120 ° C. for 5 minutes and then at 250 ° C. for 10 seconds. Importantly, the pattern shows excellent stability and withstands water washing and two piranha solution washings (3: 1, H ₂ SO ₄ / H ₂ O ₂ ) for 10 minutes each at 120 ° C.

All of the following references are incorporated herein by reference in their entirety.
Additional references related to ink and deposition technology

Further description from reference 16 ("Conductor pattern")
In order to further enable those skilled in the art to practice the present invention, the above reference 16, which is incorporated herein by reference in its entirety, is provided below (patent application “Processes for Fabricating Conductive Patterns Using Nanolithography as a Patterning Tool”). ").

  As further background information, many important applications in biotechnology, diagnostics, microelectronics and nanotechnology require metal nanostructures as one of the essential components. For example, better microelectronics are needed to provide smaller and faster computer chips and circuit boards, and metal can provide the conductivity necessary to complete the circuit. Metals can also be used as catalysts. However, metal processing is difficult and working at the nanoscale can make things more difficult. Many methods are limited to micron level manufacturing. Many methods are limited by the need for electrochemical bias or very high temperatures. Moreover, many methods are limited by the physical requirements of the deposition process, such as ink viscosity. In particular, there is a need for better methods for fabricating metal nanostructures that provide alignment, the ability to layer films and wires, high resolution and flexibility.

  In summary, the present invention includes a series of aspects outlined herein without limiting the scope of the invention. For example, the present invention is a method of depositing a conductive coating on a substrate in a desired pattern, (a) using a chip coated with the precursor by nanolithography, the precursor in a desired pattern (B) contacting the precursor with the ligand, (c) applying sufficient energy from a dispersive irradiation light source, optionally to move electrons from the ligand to the precursor, thereby Providing a method comprising the steps of decomposing the precursor to form a conductive deposit in the desired pattern and thus forming the conductor pattern directly on the substrate.

  The present invention is also a method of printing a conductive metal in a desired pattern on a substrate using (a) a chip coated with the precursor by nanolithography, using the metal precursor and ligand Drawing directly onto the substrate according to the desired pattern, and (b) decomposing the precursor, optionally by applying energy from a distributed illumination source, to remove a substantial amount of the precursor from the substrate. And a method comprising forming a conductive metal in a desired pattern without removing a substantial amount of metal from a substrate.

  The present invention also provides a nanolithographic method comprising attaching a metal precursor from a chip to a substrate to form a nanostructure, and then converting the precursor nanostructure to a metal deposit. The deposition can be performed without using an electrical bias between the chip and the substrate.

  The present invention also provides a nanolithographic method consisting essentially of attaching a metal precursor from a nanoscopic tip to a substrate to form a nanostructure and then converting the nanostructured metal precursor to a metal form. To do. Although the basic and novel aspects of the present invention are described throughout the specification, these aspects do not require stamps and resists, do not require electrochemical bias, are used in general laboratories and manufacturing. This means that there is no need for expensive equipment that is not easily available at the facility, and no reaction between the substrate and the ink is required. Thus, compositions and inks can be formulated and patterned without these limitations.

  The present invention is also a method for printing without using an electrochemical bias or reaction between an ink and a substrate, wherein the metal precursor ink composition is formed from a chip in the form of a microstructure or nanostructure. To form an array having discrete objects separated from each other by about 1 micron or less, about 500 nm or less, or about 100 nm or less.

  The present invention also provides a patterned array comprising a substrate and discrete nanoscopic and / or microscopic metal deposits thereon prepared by the method of the present invention. The metal deposit can be, for example, a rectangle, square, dot or line.

  The invention also provides methods of using these methods, including, for example, preparing sensors, biosensors and lithographic templates and other applications described herein.

  FIG. 1 of Reference 16 shows AFM data of the palladium structure in Example 1 of the present invention.

  FIG. 2 of Reference 16 shows AFM data of the palladium structure in Example 3 of the present invention.

  FIG. 3 of Reference 16 shows AFM data of the palladium structure in Example 4 of the present invention.

  FIG. 4 of Reference 16 shows AFM data of the palladium structure in Example 5 of the present invention.

  FIG. 5 of Reference 16 shows AFM data of the palladium structure in Example 5 of the present invention.

Detailed explanation in Reference 16 ("Conductor pattern")
Reference 16 is provisional application 60 / 405,741 to Crocker et al. Filed Aug. 26, 2002 and provisional application to Crocker et al. Filed Oct. 21, 2002, which is incorporated herein by reference in its entirety. Claims benefits for 60 / 419,781.

  As noted above, DPN ™ and DIP PEN NANOLITHOGRAPHY ™ are trademarks of NanoInk, Inc., and are used accordingly herein (eg, DPN printing or DIP PEN NANOLITHOGRAPHY printing). DPN methods and equipment are generally commercially available from NanoInk, Inc. (Chicago, IL), including NScriptor ™, which can be used to perform nanolithography according to the present invention.

  This written description provides guidance, including a reference to a technical document, for those skilled in the art to practice the invention, but this reference is not an admission that the technical document is prior art.

  Direct write technology can be implemented by the method described in, for example, Direct-Write Technologies for Rapid Prototyping Applications: Sensors, Electronics, and Integrated Power Sources, Ed. By A. Pique and DB Chrisey, Academic Press, 2002. . For example, Chapter 10 by Mirkin, Demers and Hong describes nanolithographic printing on a sub-100 nanometer length scale and is incorporated herein by reference (pages 303-312). Pages 311-312 provide further references on scanning probe lithography and direct writing methods using patterning compounds carried from a nanoscopic tip to a substrate that can guide one skilled in the practice of the present invention. . This text also describes conductor patterns.

  Nanolithography and nanofabrication are also described in Marc J. Madou's Fundamentals of Microfabrication, The Science of Miniaturization, 2nd Ed., Including metal deposition on pages 344-357.

This application discloses numerous embodiments for producing conductor patterns using dip pen nanolithography (DPN) printing as a patterning tool. For all aspects of the present disclosure, the following documents disclosing DPN printing methods are hereby incorporated by reference and form part of the present disclosure:
(1) Piner et al., Science, January 29, 1999, 283, 661-663 (2) US provisional application 60 / 115,133 to Mirkin et al. Filed January 7, 1999 (3) US Patent Provisional Application No. 60 / 207,713 filed October 4, 1999 to Mirkin et al. (4) US Patent Application No. 09 / 477,997 filed January 5, 2000 to Mirkin et al. (5) 2000 US Provisional Application No. 60 / 207,713 to Mirkin et al. Filed on May 26 (6) US Provisional Patent Application No. 60 / 207,711 to Mirkin et al. Filed May 26, 2000 (7) May 2001 U.S. Patent Application No. 09 / 866,533 to Mirkin et al. Filed 24 days (8) U.S. Patent Publication No. 2002/0063212 A1 to Mirkin et al.

  The present invention is not limited to the use of only one chip for printing, but many chips can be used. See, for example, US Patent Publication No. 2003/0022470 (“Parallel, Individually Addressable Probes for Nanolithography”) to Liu et al., Published January 30, 2003.

  In particular, prior application No. 09 / 866,533 filed May 24, 2001 (references 7 and 8 above, 2002/0063212 A1 published May 30, 2002), background and procedures for direct write nanolithography printing. Are described in detail, for example, background (pages 1 to 3), overview (pages 3 to 4), brief description of drawings (pages 4 to 10), use of scanning probe microscope tips (pages 10 to 12), Substrates (pages 12 to 13), patterning compounds (pages 13 to 17), implementation methods including chip coating (pages 18 to 20), devices including nanoplotters (pages 20 to 24), multilayer And the use of related printing and lithographic methods (pages 24-26), resolution (pages 26-27), arrays and combinatorial arrays (pages 27-30), software and calibration (pages 30-35, pages 68-70), Kits and other articles (pp. 35-37), including chips coated with hydrophobic compounds, examples (38 -67), corresponding claims and abstracts (pages 71-82) and a wide variety of embodiments, including Figures 1-28. This disclosure need not be repeated here, but is incorporated herein by reference in its entirety.

  Also, US Patent Publication No. 2002 0122873 A1 to Mirkin et al., Published September 5, 2002, need not be repeated here, but is incorporated herein by reference in its entirety. This published application includes, for example, the use of chips with external openings and internal cavities and the use of electrical, mechanical and chemical driving forces to carry ink (or deposited compounds) to the substrate. One method involves aperture pennography where the speed and range of movement of the attached compound through the aperture is controlled by the driving force. This published application also describes coated chips, patterns, substrates, inks, patterning compounds, adhesion compounds, multichip nanolithography, multiple adhesion compounds and arrays.

Nanolithography is also described in the following references.
(A) BW Maynor et al., Langmuir, 17, 2575-2578 ("Au'Ink'for AFM'Dip-Pen 'Nanolithography") describes the formation of gold nanostructures by surface-induced reduction of metal ions. Yes. However, this method limits the processing and involves careful selection of the appropriate gold precursor and the substrate surface that reacts with gold, which is not necessary in the present invention.
(B) Y. Li et al., J. Am. Chem. Soc., 2001, 123, 2105-2106 ("Electrochemical AFM 'Dip-Pen'Nanolithography") describes the deposition of platinum metal. However, this method limits the processing and involves the use of an external electrochemical bias between the chip and the substrate, which is not necessary with the present invention.

  In the DPN printing method, ink is transferred to a substrate. The substrate can be flat, rough, curved or have a surface feature. The substrate can also be pre-patterned. Immobilization of the ink to the substrate can be performed by chemisorption and / or covalent bonding. The transferred ink can be used directly as part of the manufacturing design, if desired, or indirectly as a template for further manufacturing. For example, the protein can be patterned directly onto the substrate by DPN printing, or the template compound used to bind to the protein can be patterned. The advantages and uses of DPN printing are numerous and are described in the above references. For example, complex structures with high resolution and good alignment can be achieved. Structures with line widths, cross sections and perimeters of less than 1 micron, in particular less than 100 nm, in particular less than 50 nm can be achieved. In short, DPN printing is a nanofabrication / nanolithography technology that allows fabrication and lithography to be performed at the nanometer level with outstanding control and flexibility. This type of nanofabrication and nanolithography is difficult to achieve with many technologies that are more suitable for micron-scale operations. DPN printing can also be used to produce micron scale structures if desired, but nanostructures are generally preferred.

  The chip can be a nanoscopic chip. This can be a scanning probe microscopic tip including an AFM tip. It can be hollow or non-hollow. The ink can pass through the center of the hollow tip and cover the end of the tip. The chip can also be modified to facilitate printing of the precursor ink. In general, it is preferable that the chip does not react with the ink and that the chip can be used for a long period of time.

  The pattern deposited by nanolithography is not particularly limited by the shape of the pattern. Common patterns include dots and lines and their arrays. The height of the pattern can be, for example, about 10 nm or less, and more preferably about 5 nm or less. If the line is patterned, the line can be, for example, about 1 micron or less in width, particularly about 500 nm or less, particularly about 100 nm or less in width. If the dots are patterned, the dots can be, for example, a width of about 1 micron or less in diameter, particularly a width of about 500 nm or less, particularly a width of about 100 nm or less.

  Nanolithography is preferably performed to form nanostructures, but micron scale structures can also be considered. For example, experiments used to pattern structures with an area of 1-10 square microns, such as rectangles, squares, dots or lines, are also useful for designing experiments for smaller nanostructures.

In another embodiment, the conductor pattern including the nanoscopic pattern is formed by the following steps:
1) using a coated chip to attach a precursor, for example a metal salt, to the substrate in the desired pattern;
2) applying a suitable ligand to the substrate, for example a ligand containing a donor atom such as nitrogen, phosphorus or sulfur;
3) Using DPN using a process that applies sufficient energy to transfer electrons from the ligand to the precursor, eg radiant heat, thereby decomposing the precursor to form a precipitate, eg metal It is formed.

  Metal patterning methods and chemistry are incorporated herein by reference (1) US Pat. No. 5,980,998 (issued Nov. 9, 1999) to Sharma et al., And incorporated herein by reference. U.S. Pat. No. 6,146,716 to Narang et al. (Issued 14 November 2000). However, these references do not disclose or suggest the use of other nanolithography for dip pen nanolithography printing or deposition, nor do they disclose or suggest the benefits resulting from DPN printing. If anything, it discloses the use of a conventional printing method using a dispenser that includes a reservoir and an applicator. In this specification, the chemistry and patterning disclosed in Sharma's 5,980,998 patent is generally modified in an unexpected way, resulting in unexpected results including DPN printing as a patterning method. Embodiments are disclosed that have been modified in other ways to produce unexpected results including the chemistry disclosed in Sharma's 5,980,998 patent.

  As used herein, an ink solution is generally considered to include a solvent and a solute. The solvent can be any substance that can solvate the solute, but is generally considered to include relatively inexpensive and readily available non-toxic substances such as water, various alcohols, and the like. Solutes are generally considered to include at least two components that chemically react with each other under the influence of an energy source so that a metal or other material precipitates out of solution. In a preferred embodiment, one component of the solute contains a salt and the other component of the solution contains a suitable ligand. As used herein, “salt” refers to a combination of an acid (A) and a base (B). Examples are metal salts such as copper formate, copper acetate, copper acrylate, copper thiocyanate and copper iodide. Other examples are non-metallic salts such as ammonium formate and ammonium acrylate.

  The various components of the solution can be attached to the substrate simultaneously or sequentially, or can be attached to the substrate in a combination of the two. Therefore, it is considered that the salt may be attached simultaneously with the ligand, or may be attached separately from the ligand. It is also believed that the solvent itself constitutes or contributes to one or more aspects of the salt or ligand.

  As used herein, “ligand” (L) is thermally activated to push one or more aspects of a salt through a redox reaction to AB + L <−> AL + B or AB + L <−> A + BL. Refers to any substance. In the methods contemplated herein, preferred ligands are amorphous, do not leave non-metallic residues, and are stable under normal ambient temperature conditions. Most preferred ligands can also participate in the redox reaction, in which case the particular salt is used at a reasonable temperature, generally considered to be less than about 300 ° C.

  A preferred class of ligands are nitrogen donors such as cyclohexylamine. However, many other nitrogen donors and mixtures thereof can also be used. Examples are 3-picoline, lutidine, quinoline and isoquinoline, cyclopentylamine, cyclohexylamine, cycloheptylamine, cyclooctylamine and the like. However, these are just a few examples and many other aliphatic primary, secondary and tertiary amines and / or aromatic nitrogen donors can be used.

  Possible solutions include other compounds besides salts and ligands. For example, a mixture of copper (II) formate in a nitrogen donor solvent with or without water and alcohol may be used to facilitate transport from chip to substrate. Small amounts of solvent-based polymers or surfactants are also useful additives to adjust the rheology of the precursor solution to facilitate chip-to-substrate transport and provide better film formation. Can be. On the other hand, higher amounts of high boiling solvents and / or additives, such as triethyl phosphate, Triton X100, glycerol, etc., are membranes produced due to incomplete pyrolysis on temperature sensitive substrates such as Kapton ™ or paper. It is preferable to avoid it. Furthermore, it may be worth treating the substrate with a coupling agent to improve the adhesion of the adhesive material to the substrate as a function of a coupling agent that changes the hydrophobicity or hydrophilicity of the substrate surface. unknown.

  If the salt contains a metal, all metals are contemplated. Preferred metals include conductive elements such as copper, silver and gold, but also semiconductors such as silicon and germanium. Depending on the purpose, it may be possible to use metals such as cadmium, chromium, cobalt, iron, lead, manganese, nickel, platinum, palladium, rhodium, silver, tin, titanium, zinc, etc., especially in the case of catalyst production. It is done. Also, as used herein, “metal” includes alloys, metal / metal composites, metal ceramic composites, metal polymer composites, and other metal composites.

  Substrates can include virtually any substance to which a compound can be attached. For example, possible substrates include metals and non-metals, conductors and non-conductors, flexible and non-flexible materials, absorbent and non-absorbent materials, flat and curved materials, textured and non-textured materials, There are solid and hollow materials and large and small objects. Particularly preferred substrates are circuit boards, paper, glass and metal objects. Viewed from another perspective, the width of the substrate considered provides an indication of the range of possible objects to which the present teachings can be advantageously applied. Accordingly, the methods and apparatus taught herein include multichip modules, PCMCIA cards, printed circuit boards, silicon wafers, security printing, decorative printing, catalysts, electrostatic shields, hydrogen transport films, functionally gradient materials, nanomaterials Can be used in a variety of applications including battery electrodes, fuel cell electrodes, actuators, electrical contacts, capacitors, and the like. The method and apparatus can be used as sensors and biosensors. The method and apparatus can be used to prepare templates for further lithography, for example imprinted nanolithography. It is of particular interest to connect nanowires and nanotubes using methods.

  Thus, the substrate is installed in electronic devices such as computers, disk drives or other data processing or storage devices, telephones or other communication devices and batteries, capacitors, chargers, control devices or other energy storage related devices. Or any part of the substrate, particularly any suitable substrate, including circuit boards.

  Suitable energy sources contemplated herein include any energy source that can cause a desired chemical reaction without causing undue damage to the substrate or coating. Thus, particularly preferred energy sources are radiant and convective heat sources, particularly including infrared lamps and hot air blowers. Other suitable energy sources include electron beams and non-IR wavelength emitters including X-rays, gamma rays and ultraviolet radiation. Yet another suitable energy source is a vibration source, such as a microwave transmitter. It should also be considered that various energy sources can be applied in a number of ways. In a preferred embodiment, the energy source is directed towards the precursor / ligand attached to the substrate. However, in an alternative embodiment, for example, the heated ligand may be applied to a room temperature precursor, or the heated precursor may be applied to a room temperature ligand.

  From the present invention, a number of advantages can be observed including, for example, smooth surfaces, good coating adhesion and coating thickness control. Yet another advantage of various aspects of the present teachings is that the coating can be deposited with a purity of at least 80% by weight. In a more preferred embodiment, the purity of the metal or other material intended to be included in the coating is at least 90% by weight, in a more preferred embodiment the purity is at least 95%, and in a most preferred embodiment the purity is at least 97%. It is.

  Yet another advantage of various aspects of the present teachings is that the coating can be applied with little waste. In preferred embodiments, at least 80% by weight of the material deposited on the substrate remains to form the desired pattern. For example, if copper formate (II) is used to produce a copper circuit, at least 80% of the copper deposited on the substrate can stay to form the desired pattern, with 20% or less of the copper being " It is removed as “waste”. In a more preferred embodiment, the waste is 10% or less, in a further preferred embodiment, the waste is 95% or less, and in a most preferred embodiment, the waste is 3% or less.

  Yet another advantage of various aspects of the present teachings is low temperature operation. The metal can be deposited in the desired pattern, for example at less than about 150 ° C., preferably less than about 100 ° C., more preferably less than about 75 ° C., and most preferably at normal room temperature (25-30 ° C.). Redox or “curing” processes can also be performed at relatively low temperatures of less than about 100 ° C., more preferably less than about 75 ° C., and even about 50 ° C. Lower temperatures are possible, but below about 50 ° C., redox reactions tend to be too slow for most applications. These ranges allow the precursor solution to be prepared at room temperature, allow the deposition to be performed at room temperature, and achieve decomposition in a room temperature environment using relatively low heat such as coming out of a heat gun. Make it possible.

  The prior art describes additional methods and compositions that can be used to practice the present invention. For example, US Pat. No. 5,894,038 (Apr. 13, 1999) to Sharma et al., Incorporated herein by reference in its entirety, (1) preparing a solution of a palladium precursor, (2) a palladium precursor. Direct deposition of palladium including a method of forming a layer of palladium on a substrate, including applying a body to the surface of the substrate, (3) decomposing the palladium precursor by subjecting the precursor to heat. Disclosure. This method can also be adapted to perform nanolithography according to the present invention.

  In addition, US Pat. No. 5,846,615 to Sharma et al. (December 8, 1998), incorporated herein by reference in its entirety, decomposes a gold precursor to form a gold layer on a substrate. Is disclosed. This method can also be adapted to perform nanolithography according to the present invention.

  U.S. Pat. No. 4,933,204 is hereby incorporated by reference in its entirety and discloses the decomposition of gold precursors to form a metal mold. This method can also be adapted to perform nanolithography according to the present invention.

  Further, US Pat. No. 6,548,122 to Sharma et al. (April 15, 2003) is also incorporated herein by reference in its entirety and discloses the use of copper (II) formate precursors and gold and silver precursors. is doing.

  Although the present invention is considered broad, the following inks or patterning compounds are particularly important to the present invention: copper formate or copper acetate; silver sulfate; silver nitrate; silver tetrafluoroborate; palladium chloride, acetate and acetyl Acetonate; hexachloroplatinum (IV) acid; ammonium iron citrate; zinc, nickel, cadmium, titanium, cobalt, lead, iron and tin carboxylates, (pseudo) halides, sulfates and nitrates; metal carbonyl complexes For example chromium hexacarbonyl; amine bases such as cyclohexylamine, 3-picoline, (iso) quinoline, cyclopentylamine, dimethyl sulfoxide, dimethylformamide, formamide, ethylenediamine; polymers such as poly (ethylene oxide), poly (methyl methacrylate) G), poly (vinylcarbozole) and poly (acrylamide).

  In preferred embodiments, for example, the deposition can be performed using an aqueous solution as the ink, in which case the solution comprises water, a metal salt and a water soluble polymer, such as a polyalkylene oxide polymer having a molecular weight of about 50,000 or less. Including. The aqueous solution is also useful as a carrier for the reducing agent. For example, deposition of disodium palladium chloride by DPN printing on aminosilanized glass in water containing 10% polyethylene oxide (MW 10,000) can be performed (Schott Glass company) followed by a reducing agent such as dimethylamine: borane Perform chemical reduction to palladium metal using 0.03M aqueous solution of the complex (DMAB). In order to determine the best conditions for the reduction, the concentration of the reducing agent can be varied. Atomic force micrographs of the pattern can be obtained before and after reduction. AFM imaging can be performed using the tip used to attach the structure or a different tip. If a different chip is used, the image can be better, especially if the chip is selected or adapted for imaging rather than for attachment. In general, polymers used industrially in printing inks can be used in the present invention.

  In another preferred embodiment, the nanolithographic deposition is from a palladium acetylacetonate (Pd (acac)) to a silicon oxide substrate, followed by DPN printing and then (1) a reducing agent, such as a liquid reducing agent such as formamide and ( 2) Can be carried out by reduction by application of heat to the patterned surface. Another system is palladium acetate in DMF solvent. Prior to patterning and reduction, Pd (acac) is dissolved in a halogenated solvent, for example an organic solvent such as chloroform, to form an ink that can be used to coat a solid chip or pass through a hollow chip can do. The heat treatment can be sufficient to effect the reduction, including, for example, a temperature of about 100 ° C. to about 300 ° C. or about 150 ° C. Heating time, temperature and atmospheric conditions can be adjusted to achieve the desired pattern. In general, a heating time of 1-5 minutes at 150 ° C. can achieve the desired result. The stability of the deposited pattern can be tested by solvent washing and the experimental conditions can be changed to improve stability. Nanolithographic experimental variables, including substrate and ink composition, can also be modified to provide higher resolution. AFM micrographs can be obtained, including the use of pattern height scanning analysis, before reduction and after application of heat. Imaging parameters can be changed to improve resolution.

  In some cases, a tip such as a gold-coated tip may catalyze the reduction of the metal salt directly on the cantilever. To prevent this, the chip composition can be changed. For example, an aluminum coated probe is useful to avoid this reduction on the tip. In general, the chip is preferably selected and adapted for long-term use, avoiding catalysis with the ink.

  The reduction of the nanolithographic patterned metal salt can also be carried out by gas phase reduction rather than liquid phase reduction, in which case the reducing agent is converted to a vapor form and onto the patterned substrate. Passed. In order to heat the reducing agent into a vapor state, a heater known in the art can be used as necessary. In some cases, this type of treatment can improve the preservation of the original pattern during reduction.

  In a preferred embodiment, the deposition is carried out on an aminosilanized glass substrate, in the case of a silver salt emulsion consisting of ferric ammonium chloride, tartaric acid, silver nitrate and water, by DPN printing followed by photoreduction development under a UV lamp. Can do. AFM imaging can be performed to show the pattern.

  In another preferred embodiment, the reduction step can be performed with sufficient heat and sufficient time to reduce the metal salt without the use of a chemical reducing agent. For example, temperatures below about 400 ° C. or temperatures below about 200 ° C. can be used. One skilled in the art can select temperatures and experiments accordingly based on a given ink system and pattern.

  The deposition method of the present invention can also use one or more pre-deposition steps, one or more probe cleaning or chemical modification steps to improve ink coverage, and dip pen nanolithography printing technology. Or it can include one or more post-attachment steps including multiple attachment steps, cleaning steps and inspection steps.

Although there exist the following as a base-material surface treatment process before adhesion, it is not limited to these (in particular there is no order).
(1) Plasma, UV or ozone cleaning, water cleaning, drying, blow drying,
(2) chemical cleaning, eg piranha cleaning, base etching (eg hydrogen peroxide and ammonium hydroxide),
(3) Chemical or physical modification or covalent modification to promote ink transport or adhesion (eg, base treatment to provide a charged surface to silicon oxide, amino or mercaptosilanizing agent, chemically reactive functionality) Silanization using a polymer having a group)
(4) protection against adverse effects of subsequent processes (eg coating with resist or thin film),
(5) Optical microscopy (eg AIMS), electron microscopy (eg CD SEM) or imaging (eg EDS, AES, XPS), ion imaging (eg TOF SSIMS) or scanning probe imaging (eg AFM, AC, AFM) , NSOM, EFM ...), inspection of substrates using any of the steps detailed below in the post-attachment section and combinations thereof.

Probe cleaning or modification steps include, but are not limited to, the following (in particular no order).
(A) Plasma cleaning, water washing, drying, blow drying,
(B) chemical cleaning, eg piranha cleaning, base etching (eg hydrogen peroxide and ammonium hydroxide),
(C) chemical or physical modification of the probe to promote or enhance ink coating, adhesion or transport (eg, base treatment to provide a charged surface of a silicon nitride chip, silane using an amino or mercaptosilanizing agent Such covalent modifications using small molecules or polymeric agents such as poly (ethylene glycol). Such modifications can increase the porosity or load the ink onto the chip by increasing the surface area available for ink delivery. Includes increasing amounts of modification.

Adhesion process The adhesion process includes, but is not limited to, adhesion of one or more inks by DPN ™ printing or adhesion using one or more probes. Possible inks include, but are not limited to, precursors, compounds that form the bulk of the final pattern, catalysts, solvents, small molecule or polymer carriers, host matrix materials or sacrificial reducing agents, and mixtures of the above materials. They can be deposited as thin films or as thick multilayers (formed by multiple deposition processes), with or without changing the chemical composition between the layers.

Although there exist the following as a post-attachment process, it is not limited to these (in particular there is no order).
(1) Heating of the substrate with, for example, a heat lamp, hot air blow or hot plate,
(2) Irradiation of the substrate with electromagnetic radiation (eg IR, visible light and UV light) or charged particles (eg ions derived from an electron, gun or plasma source). This treatment can be carried out in air, in vacuum or in solution, with or without a sensitizer.
(3) immersion of the patterned substrate in one or more solutions,
(4) Electrochemical reduction,
(5) chemical reduction,
(6) exposure of patterned substrate to vapor or gas,
(7) Sonication of the patterned substrate and, if applicable, all nanoscale local equivalent processing of the process outlined above. The source of energy and / or composition is provided by one or more probes that may or may not be the same as the DPN probe. Although there are the following, it is not limited to these.
(A) local heating of the adherent or surrounding substrate,
(B) Local irradiation of the adherent or surrounding substrate and all combinations thereof.

  The sequence of all or some steps can be repeated several times.

  The metal nanostructure can be in the form of a conductive nanoscopic grid that can include nanowires. For example, a crossbar structure can be formed. A metal layer can be formed on each. Structures for integrating nanoscopic conductor patterns with microscopic and macroscopic test methods can also be included. If desired, a circuit can be formed using resistors, capacitors, electrodes and inductors. Semiconductors and transistors can be used if desired. Multiple layers can be formed to increase the height of the structure. Different metals can be used in different layers of the multilayer. The method of the present invention can be used to electrically connect electrodes. In sensor applications, for example, metal deposits can have a resistivity that changes when an analyte binds to the structure. For example, in biosensor applications, antibody-antigen, DNA hybridization, protein absorption and other molecular recognition events can be used to induce a change in resistivity. The method of the present invention can also be used for barcode applications.

  For example, US Pat. No. 6,579,742 to Chen describes a nanolithographic structure formed by imprinting for nanocomputer and microelectronic applications. However, the imprinting may be adversely affected by the mold adherence effect. The nanocomputer applications and structures of US Pat. No. 6,579,742 can be implemented using the nanolithographic methods described herein, which is incorporated herein by reference in its entirety.

  The substrate can be, for example, the proto substrates described in US patent application Ser. No. 10 / 444,061 “Proto substrates” filed May 23, 2003 to Cruton-Dupeyrat et al. This makes it possible to test the conductivity of the printed structure by a macroscopic method.

  A non-limiting example of reference 16 is described below.

Reference 16 Example General Procedure This method provides for the direct deposition of metal nanopatterns. The oxidizing compound and the reducing compound can be mixed, applied to the chip, and deposited on the substrate at a selected location by DPN ™ printing or deposition. The ink mixture can then be heated (by heating the entire substrate or local probe-induced heating). Specifically, a cocktail of a metal salt and an organic ligand can be used. A typical ink formulation can include a metal salt (eg, carboxylate, nitrate or halide) with a suitable organic Lewis base or ligand (amine, phosphine). Also, additives that change the solubility, reactivity or rheological properties of the ink (small molecules such as ethylene glycol, polymers such as polyethylene oxide, PMMA, polyvinylcarbazole, etc.) may be used. After deposition of the ink mixture, gentle heating in the ambient or inert environment (eg, 40-200 ° C.) can help disproportionate the salt from forming metal deposits and volatile organics. This procedure allows the deposition of various metals or metal oxides including, for example, copper, under mild conditions and almost no organic contaminants (see, eg, Sharma et al. US Pat. No. 5,980,998). This complete disclosure is incorporated herein by reference, particularly with regard to the material to be deposited). If the ligand evaporates from the patterned substrate before the reaction takes place, potential pitfalls may occur. In this case, the salt-patterned substrate can be exposed to the ligand in a second step prior to heating.

  Attachment experiments and AFM imaging can be performed using CP Research AFM (Veeco Instruments, Santa Barabara, Calif.) Or NSCRIPTOR (NanoInk). For both attachment and imaging, contact modes including topography or lateral force modes can be used.

Example 1 of reference 16
One specific example of the use of this method is to oxidize palladium acetylacetonate (1 mg / microliter, generally a saturated ink solution is generally desirable) dissolved in chloroform using DPN ™ printing or deposition. Patterned on silicon, glass or aminosilanized glass. After dot patterning, 1 drop of formamide (1 microliter) was placed on a horizontal substrate and heated to 150 ° C. for 2 minutes. The resulting metal pattern was stable to solvent washing (water, alcohol and other nonpolar organic compounds), but the salt pattern prior to reduction was removed by solvent washing. FIG. 1 shows an AFM image and height scan of the pattern before (FIG. 1a) and after (FIG. 1b and 1c) before treatment with formamide and heat.

Example 2 of reference 16.
Palladium nanopatterns were deposited by DPN printing and metallized by gas phase reduction. DPN ink consisting of palladium acetate in dimethylformamide was patterned on silicon oxide using DPN technology. The DPN pen used was a silicon nitride probe with a gold coating. This method works well with DPN probes with an aluminum coating. The reason is that the Al coating does not catalyze the reduction of the metal salt directly on the cantilever, as does the gold coated probe. Prior to patterning, the silicon / silicon oxide wafer was cleaned by sonication in Millipore water for 5 minutes. The patterned substrate was placed vertically in a conical polyethylene tube and 10 microliters of formamide solution was placed at the bottom of the tube. The tube was placed on a heating block and heated at 80 ° C. for 30 minutes so that the vapor caused reduction of the metal precursor. This method is useful because it preserves the metal pattern on the substrate. The resulting metal structure was resistant to solvent washing and other common cleaning methods.

Example 3 of reference 16.
Palladium nanopatterns deposited by DPN and metallized by chemical reduction. DPN ink consisting of disodium palladium chloride in water containing 10% polyethylene oxide (MW 10,000) was patterned on aminosilanized glass (Schott Glass company) using DPN technology. The patterned substrate was exposed to a 0.03M aqueous solution of dimethylamine: borane complex (DMAB) to cause reduction of the metal precursor to a conductive metal. The resulting metal structure is resistant to solvent washing. FIG. 2 shows an AFM image and height scan of the pattern before (2a) and after (2b, 2c) before processing by DMAB.

Example 4 of reference 16.
Platinum nanopatterns deposited by DPN and metallized by chemical reduction. DPN ink consisting of platinum tetrachloride in water was patterned on aminosilanized glass (Schott Glass company) using DPN technology. The patterned substrate was exposed to a 0.03M aqueous solution of dimethylamine: borane complex (DMAB) to cause reduction of the metal precursor to a conductive metal. The reduction reaction takes place within a few seconds after immersion. The resulting metal structure is resistant to solvent washing. FIG. 3 shows an AFM height scan of platinum nanostructures deposited by DPN and reduced by DMAB.

Example 5 of reference 16.
Palladium pattern deposited by DPN. DPN ink consisting of palladium acetate in dimethylformamide was patterned on silicon oxide using DPN technology. Prior to patterning, the substrate was cleaned in piranha solution at 80 ° C. for 15 minutes. After patterning, the substrate was heated in air for at least 1 minute using a hot plate. After heating, the pattern was imaged by AFM. The resulting metal structure exhibits a high topography and is resistant to solvent washing and other common cleaning methods. 4 and 5 show the desired structural design (left figure) and actual pattern before reduction (middle figure) and after thermal reduction (right figure). The imaging of these patterns, especially already reduced patterns, can be improved, for example, by using a clean tip that was not used for deposition.

  In general, in reference 16, nanolithographic deposition of metal nanostructures is provided using a coated chip for use in microelectronics, catalysis and diagnostics. The AFM tip can be coated with a metal precursor and the precursor can be patterned on the substrate. The patterned precursor can be converted to the metallic state by the application of heat. This concludes the section “Further Description from Reference 16 (“ Conductor Pattern ”)”.

Further Examples The following describes further examples that make the present invention more illustrative and feasible, particularly with respect to alternative ink formulations, alternative substrates that can be patterned. We also demonstrated multi-layer patterning, ink delivery to a cantilever using microfluidic reservoirs, and actual TFT substrate repair.

Example 8: Ink Formulations Various ink compositions can be written directly by contact with a cantilever. In addition to the polyol and gold nanoparticle / mesitylene ink described above, the following ink formulations adhered well by CMD.

Ink composition # 1: Gold nanoparticles in mesitylene / decanol mixture The gold nanoparticle ink described in the above example was modified by the addition of an alcohol, such as decanol CH ₃ (CH 2) ₉ OH. The addition of decanol improves the wetting of the hydrophilic substrate, in particular beading, where the deposited ink will drop on the hydrophilic substrate, resulting in discontinuous (non-conductive) lines. To prevent. This ink composition was usually prepared by dissolving 1 mg of gold nanoparticles capped with hexanethiol in 1.5 μL of thioctic acid (1 mg / ml) and 0.3 μL of decanol dissolved in mesitylene. The ink was converted to a low resistivity metal form by curing at 250-300 ° C for 7 minutes at high temperature and then at 120 ° C for 60 minutes at a lower temperature.

Ink composition # 2: gold nanoparticles in 1,3,5-triethylbenzene In place of mesitylene and decanol, 1,3,5-triethylbenzene (1,3,5-5- The above gold nanoparticle ink was further improved by using TEB). Solvent replacement increases the life of the ink (because of reduced drying) over the decanol-based ink, and ultimately results in a decanol-rich phase that will result in nanoparticle precipitation and loss of useful metal content. Avoid phase separation between mesitylene-rich phases.

Ink composition # 3: Commercial silver nanoparticle ink Commercial silver paste (Nanopaste NPS-J from Harima Chemicals, Japan, http://www.harima.co.jp) for flat panel display restoration Used as ink. The silver paste contains monodisperse nanoparticles formed by gas evaporation and protected by a dispersant. The average nanoparticle diameter is about 7 nm. Because each nanoparticle is covered with a dispersant, this ink acts almost like a liquid even at high metal contents. It may therefore be necessary to concentrate this ink (by solvent evaporation in air) to reach an optimum viscosity. Circuit formation by printing, dispensing and impregnation using this ink is known in the art. Its sintering temperature is less than 200 ° C. Similar commercial inks containing silver, gold (Harima NPG-J) or other types of nanoparticles can also be used.

Example 9: Various ink depositions on various substrates FIGS. 20, 21, 22 and 39 show the good deposition of the ink disclosed in Example 8 on various substrates. For example, FIG. 20 shows direct writing of a silver line to a silicon nitride substrate by using Harima silver nanoparticle ink (Composition # 3). The observed line width and quality variations are a result of the ink viscosity increase (density increase) over time. Over time, the ink became too viscous to form an unbroken line. All lines were drawn at the same cantilever speed for the substrate. The perceived striation is an artifact of the intermittent motion of the precision stage used in this experiment. FIG. 21 shows the same ink deposition on a glass substrate. FIG. 22 shows the deposition and low temperature curing of a commercial silver nanoparticle ink on a glass substrate coated with a chromium thin film. Grooves were formed in the chrome film using laser ablation to expose the underlying glass substrate (image center). Then, using a chipless cantilever, two lines were drawn on the chromium film on each side of the laser ablation gap and across the gap. Adhesion to the chrome film itself was successful, but not at the gap. The reason is that in this case the glass substrate remaining after laser ablation was particularly rough (> 1 micron higher than the deposited film). FIG. 39 shows the deposition of ink composition # 1 on chromium and glass, and FIG. 30 (described in further detail below) shows the deposition of gold nanoparticles / 1,3,5-TEB ink.

Example 10: Fabrication of multilayer pattern Figure 23 shows the fabrication of multilayer lines (up to 3 layers) using tipless cantilevers coated with gold nanoparticles / mesitylene ink as described above. The first layer was attached to the substrate. After reloading the ink, the cantilever was repositioned at the start of the first layer line and used to draw the second layer line directly above the first layer line. Due to the small amount of deposited material, the solvent in the first layer dries fast enough to allow writing of the second layer without the need for an intermediate thermosetting step. The third layer was deposited by repeating the same process to form a third layer line. This method allows the production of thick lines with higher conductivity and improves line continuity. In addition, widening of the line was recognized. However, part of the line broadening is thought to result from the limitations of the existing XY stage. If you switch to a stage with higher repeatability, you should get a thinner line.

Example 11 Ink Delivery to Cantilever FIG. 24 shows the coating of a chipless cantilever (with or without slits) with ink by immersion in a microfabricated reservoir. In this experiment, a microfabricated cantilever was attached to an NSCRIPTOR instrument (NanoInk, Inc. Chicago, IL) scan head and above a silicon micromachined ink well tip with the help of a planar image microscope and XY motor stage built into the instrument. Arranged. The manufacture of this ink well tip, which is typically used to deliver ink to the tip in the case of dip pen nanolithographic printing, is described in US patent application Ser. No. 10 / 705,776 to Cruchun-Dupeyrat et al. . The ink well includes a microfluidic millimeter scale reservoir to which ink can be deposited using a pipette. The cantilever was immersed in one pool of ink in the reservoir (bottom of the image). Note the meniscus around the cantilever in image B. This method is easily automated using an appropriate (Z-axis) positioning device and software.

Example 12: Repair of an actual TFT liquid crystal display (LCD) sample FIG. 25 shows the repair of a thin film transistor (TFT) flat panel display. Laser ablation was used to drill holes in the insulating (silicon nitride) layer that protected on each side the defects in the conductive traces that form the electronic circuit on the flat panel display. A line was drawn with gold nanoparticle ink between these holes. The line was then cured to form an electrical bridge between the left and right portions of the trace to repair the defect.

Example 13: Attachment using cantilevers with integrated slits or microfluidic channels FIG. 26 is a schematic illustration of a chipless cantilever with ink storage slits or channels. This cantilever can store a larger amount of ink per dipping, which on the other hand writes better uniformity, increased line height, better conductivity and higher steps over the entire length of the line Give better performance for. FIG. 27 shows four additional designs of tipless cantilevers that can be triangular or rectangular and can include an enlarged portion that serves as a reservoir for fluid storage. Manufacturing techniques can be adapted from methods for manufacturing AFM cantilevers known in the art. Briefly, a silicon nitride film is deposited by CVD on a sacrificial silicon substrate. A portion of the silicon nitride is then patterned and then etched to form cantilevers and slits. The underlying silicon may be partially anisotropically etched to release the cantilever. Alternatively, the silicon nitride layer may be bonded to a Pyrex glass wafer and the silicon substrate may be etched entirely. Then, the wafer is diced to obtain a chip having a chipless slit cantilever at the end. The cantilever may optionally be coated with a thin reflective metal layer. The metal coating must be carefully selected so that it does not react with the ink or otherwise affect the ink. FIGS. 28 and 29 are slit silicon nitride cantilevers of ink composition # 3 (silver nanoparticles) straddling the gap between a glass substrate and a gold electrode patterned on the glass substrate (blueprint in FIG. 26). Shows the actual adhesion using The resistance between the two gold electrodes in image B was about 100 ohms after heat curing. Note that after heat gun cure, you cannot see ink deposited directly on the gold electrode, possibly as a result of alloying or dewetting during cure. FIG. 30 demonstrates the adhesion of gold nanoparticles / 1,3,5-TEB ink composition # 2 when using the same type of cantilever.

Further Embodiments Hereinafter, further embodiments will be described, particularly with respect to equipment and methods for flat panel display repair.

Embodiment 3: Apparatus and Method for Flat Panel Display Repair Using Cantilever Microdeposition and Laser Curing The present invention is further an apparatus for repairing gaps in open traces on flat panel display substrates and similar devices. (1) a cantilever (or microbrush) adapted to receive ink, (2) contacting the cantilever to pattern the ink in the form of a repair patch on the substrate, A cantilever holding and positioning means adapted to translate the cantilever on the surface of the flat panel display substrate, (3) an ink supply mechanism for supplying the ink to the cantilever, and (4) in some cases attached Adapted to convert material to a low resistivity form adapted to conductivity Providing a device comprising a cured system. The curing system can include a laser and its focusing optics. The cantilever positioning means includes: (1) a nanometer resolution stage that controls movement of the microbrush along the X, Y, and Z axes; and (2) coarse motion adapted to contact the microbrush with the substrate. A wide-range Z stage, (3) a rotary stage that can position the microbrush at an arbitrary angle around the Z axis, and (4) a cantilever contact detection means in some cases.

  If the cantilever or the cantilever device has at least partly a reflective coating, the contact detection and cantilever deflection measuring means are: (1) light reflected by the video camera, its corresponding optical element, light source and at least part of the cantilever A computing means adapted to measure the brightness of the light source; (2) a laser reflection sensor; and (3) a confocal distance measurement system.

In a preferred embodiment, the present invention provides equipment adapted for the repair of flat panel displays and other substantially flat circuits, such as printed circuit boards. The instrument can include some or all of the following:
(1) (Sub) micrometer width cantilever,
(2) a micro / nanometer scale XYZ stage that provides cantilever tremors, and (3) a laser to cure the deposited material ("ink"),
(4) Ink supply mechanism that supplies material (“ink”) to the microcantilever before touching the surface,
(5) Large range of motion Z stage motion that can supply gloss Z motion for ink supply,
(6) A rotary stage that can position the cantilever at an arbitrary angle around the Z axis.

  FIG. 31 shows a first design of this instrument that monitors the brightness of the cantilever by video imaging to detect the cantilever contact to the surface. In this embodiment, the task of detecting the exact height at which the microbrush or cantilever is in contact with the substrate is the computer image of the video image corresponding to the cantilever with respect to the change in brightness when the nanometer scale XYZ stage moves the cantilever down. Achieved by monitoring at. When touched under appropriate lighting, a dramatic change in brightness occurs with sufficient sensitivity to allow detection of touch (due to cantilever bending). After contact, the nanometer scale XYZ stage can move the cantilever in the XYZ direction to deposit ink on 2D and 3D surface structures. The 360 ° motorized rotary stage allows the cantilever to be pulled rather than always pushed (ie, from its free end to its constraining end in a direction parallel to its length, see examples below). This prevents cantilever folds and other problems that lead to poor patterning results.

  To apply ink to the cantilever, the cantilever is moved up by a coarse motor Z stage until it is above the level of the ink well rotation stage. Then, the ink well rotation stage rotates the ink well to a position just below the cantilever. When the cantilever is lowered into the ink well, the ink covers the cantilever. The cantilever is then moved up again and the ink well is rotated out of the cantilever area. The cantilever is now ready to attach the ink to the substrate.

  After the ink deposition is complete in a given area, the curing laser is activated. Laser light is directed toward the area where the ink is deposited through a mirror and beam splitter (or other device that selectively reflects light from the laser toward the substrate). Curing can be considered to occur as it passes through the beam splitter and reaches the camera and microscope assembly. The entire assembly can be moved over a large distance (in meters) to place the assembly over an area of the substrate that requires repair. The required flat panel display support frame and extensive positioning system are not shown but are known in the art. Or use the gantry XY movement, which can move the entire assembly over a large distance (in meters) and place a cantilever or curing laser over the repair area, directing the laser light down or diagonally without a mirror Can do. Note that the use of direct laser illumination may interfere with the microscopic examination of the curing process.

  In another embodiment (FIG. 32), the task of detecting the exact height at which the microbrush or cantilever is in contact with the substrate is the computer of the output of the Z-axis laser reflection sensor (Keyence Corp., Japan) focused on the cantilever. Achieved by monitoring. Upon contact, a dramatic change in sensor output occurs with sensitivity that allows detection of contact. After contact, the nanometer scale XYZ stage can move the cantilever in the XYZ direction to deposit ink on 2D and 3D surface structures. In yet another embodiment (Figure 33), the task of detecting the exact height at which the cantilever contacts the substrate is performed by computer monitoring of the output of a confocal distance sensor (also commercially available from Keyence Corp.) that targets the cantilever. Achieved by: Because the confocal sensor can incorporate a built-in CCD array, laser curing can be viewed as it occurs.

The invention further provides a method of additive repair of gaps in open traces on flat panel display substrates by locally depositing a precursor ink and then curing the ink to a conductive form, comprising:
Providing a cantilever (or microbrush);
Providing a precursor ink;
Placing the ink on the cantilever;
Providing a substrate surface;
Contacting the cantilever with the substrate surface such that ink is carried from the cantilever to the substrate surface;
A method is provided that includes curing the deposited ink.

Example 14: Bidirectional writing and cantilever rotation In FIG. 34, a gold trace was deposited across a dielectric gap of a conductive ITO (indium tin oxide) electrode from a 5 μm tipless cantilever loaded with gold nanoparticle ink. When this experiment was repeated many times, it was found that these gold traces were often interrupted and had a small gap adjacent to only one of the ITO steps. FIG. 35 illustrates how a gap is formed near the topography step when drawing a line using a tipless cantilever. In this figure, a cantilever draws a line with ink from right to left on two ITO islands separated by a groove (see FIG. 34) on a non-conductive glass substrate. The end of the cantilever faithfully adheres ink on the right edge, but if the cantilever body hits the left edge, there is a risk of lifting from the bottom of the groove. This may cause non-conductive lines after the ink is cured. A simple solution to this problem consists of (i) writing a first layer of ink, for example from right to left, and (ii) writing a second layer from left to right on the first layer ( Also called “bidirectional writing”). Since the best patterning result (the narrowest line) was obtained when the cantilever was moved parallel to its length from its free end to its constrained end, the cantilever was preferably 180 ° before writing the second layer. Rotate. Otherwise, the cantilever may bend or fold and release ink to unwanted areas. This is best achieved by incorporating a cantilever rotary stage in the patterning device.

  Those skilled in the art will recognize that there are numerous alternative aspects and applications of the present invention. These alternative embodiments are considered to be within the scope of the present invention. In particular, this includes (iii) the production of a network of conductive traces on a flat panel display, (ii) elements of the flat panel display other than metal conductive traces, eg semiconductive (polysilicon) layers, transparent conductive oxidation Repair or manufacture of material layers (eg ITO), (iii) Repair of color filters, especially for flat panel displays, (iv) Repair or manufacture of other types of flat or flexible displays, eg (v) Organic light emitting diodes (OLED) ) Repair of displays, (vi) manufacture or repair of masks used in semiconductor chip manufacturing, including photomasks used in UV photolithography, (vii) manufacture or repair of micro- or nanostructured stamps or molds, (Vii) thin film resistors or other thick or thin film passive components (Viii) use of the cantilever for other micron-scale precision deposition applications. The cantilevers used in CMD can also be modified for better ink retention or adhesion capability. For example, the entire cantilever may be coated with a layer of polymer, such as PDMS (polydimethylsiloxane). Patterning may be more controlled using integrated actuators, such as cantilevers with integrated heaters and thermally driven bimorph elements. Cantilevers adapted for CMD may be combined with other devices on the same chip, for example, an atomic force microscopy cantilever integrated with a chip for high resolution imaging or ink after the cantilever is attached Some are integrated with a heating tip for curing.

The following are typical specifications for open line repair.

  This patent or application file contains at least one drawing made in color. Copies of this patent or patent application publication with color drawing / drawings attached will be provided by the Office upon request and payment of the necessary fee.

Au nanoparticles adhered between gold electrodes. (A) and (D) Optical images of two lines of approximately 60 and 45 μm, formed by drawing an inked cantilever along the surface. The cantilever width was 60 and 45 μm, respectively. (B) and (E) Same pattern as (A) and (D) after reduction. In the case of these patterns, the resistance values measured across the gap are 32 and 18 ohms. As shown in (C) and (F), the electrodes peeled off, but the pattern did not peel off. Au nanoparticles adhered between gold electrodes. (A) and (B) Optical images before and after curing of a line formed by pulling a 15 μm inked cantilever between two electrodes. In the case of this pattern, the resistance measured across the gap is 18 ohms. As shown in (C), the electrode peeled off, but the line pattern did not peel off. (D) Topographic AFM image of a line with a width of 14.5 μm and a height of 90 nm. (E) Corresponds to the position display distribution of manufactured lines. Au nanoparticles adhered between gold electrodes. (A) and (B) Optical images before and after curing of a line formed by pulling a 15 μm inked cantilever between two electrodes. In the case of this pattern, the resistance measured across the gap is 19 ohms. (C) Topographic AFM image of a 15.8 μm wide and 38 nm high line in the red box area of (B). (D) Corresponds to the position display distribution of manufactured lines. Au nanoparticles adhered between gold electrodes. (A) and (D) Optical images before and after curing of a line formed by pulling a 10 μm inked cantilever (stenosis using FIB; the cantilever is shown by a yellow box) across the two electrodes . In the case of this pattern, the resistance measured across the gap is 9 ohms. Topographic AFM images of 15.5 μm wide, 95 nm high, and 11.5 μm lines for FIB chips in the red and blue box areas of (B) and (E) and (D), respectively. (C) and (F) correspond to the position distribution of manufactured lines. Au nanoparticles adhered between gold electrodes. (A) and (B) Optical images before and after curing of a line formed by pulling a 10 μm wide FIB cantilever across two electrodes. In this pattern, the resistance measured across the gap is 22 ohms. (C) Topographic AFM image of a 11.5 μm wide and 80 nm high line in the red box area of (B). (D) Corresponds to the position display distribution of manufactured lines. Au nanoparticles adhered between gold electrodes. (A) and (D) Optical image of a gold line formed over two electrodes. In the case of the line pattern (A), the resistance measured across the gap is 190 ohms. (B) and (E) (A) and (D) Topographic AFM images of lines 5 and 4 μm wide and 12 nm high in the respective red and blue box areas. (C) and (F) correspond to the position distribution of manufactured lines. Au nanoparticles adhered between gold electrodes. (A) and (D) Optical image of a gold line formed between two electrodes. (B) and (E) (A) and (D) Topographic AFM images of lines 3 and 2 μm wide and 8 nm high in the respective red and blue box areas. (C) and (F) correspond to the position distribution of manufactured lines. Platinum / gold alloy ink deposited between gold electrodes on silicon oxide using a cantilever. Each line was formed by immersing the cantilever in an ink well filled with ink and then drawing the line until the ink disappeared from the cantilever. Note the similarity in line shape and length. Platinum / gold alloy ink deposited between gold electrodes on silicon oxide using adjacent cantilevers. Each of the three lines was manufactured using one cantilever loaded with ink or an adjacent cantilever. The line on the left was formed by drawing a single cantilever 31 microns wide on the surface until no ink was left. The widest central line was formed by four adjacent cantilevers with a width of 31 microns, and the right line was formed by two adjacent cantilevers with a width of 31 microns. Note that the maximum length of the line increases with the number of writing cantilevers. AFM height image of nanoscale palladium pattern on silicon oxide. PDMS coated silicon nitride AFM tips were used to pattern palladium acetate dissolved in 80% ethylene glycol to saturation. A line scan of the cured pattern reveals a 2-10 nm height increase between the first layer and the second layer. AFM height image of nanoscale gold pattern on quartz. Gold nanoparticle ink was patterned by holding a conventional silicon nitride AFM cantilever / tip coated with ink in contact with the surface with constant force for 10 seconds. The rightmost dot (diameter 50nm, height 3.5nm) is formed with a force of 0.2nN, and the middle dot (diameter 65nm, height 6nm) is formed with a force of 1.5nN. The dots in this row (diameter 85 nm, height 7.5 nm) were formed with a force of 4 nN. The pattern was imaged immediately after patterning with the coated chip. AFM height image of nanoscale gold pattern on quartz. Gold nanoparticles ("ink") dissolved in mesitylene were patterned by translating a conventional silicon nitride AFM tip coated with ink over the surface at a rate of 0.15 microns / second. The line trace shows that the line height and width increase with the applied force. AFM height image of nanoscale gold pattern on quartz. Gold nanoparticles ("ink") dissolved in mesitylene were patterned by holding a conventional silicon nitride AFM chip coated with ink for 10 seconds in contact with the surface. The obtained pattern was cured with a heat gun at 250 ° C. for 10 seconds, and then imaged. After curing, the particle pattern height decreased from about 30 nm to about 15 nm. Optical image of a micron-scale platinum line drawn with a silicon nitride cantilever between gold electrodes on a silicon oxide wafer. The platinum ink contained platinum chloride (100 mg in 15 microliters) dissolved in 80% ethylene glycol. The precursor ink was converted to metal by heating at 200 ° C. for 20 seconds on a hot plate. The line width after curing was about 5 microns. Optical image of a hardened micron-scale platinum line drawn with a silicon nitride cantilever between chrome electrodes on a glass wafer. The platinum ink contained 100 mg platinum chloride dissolved in 15 microliters of an aqueous solution containing 30 mg each of 300 and 10,000 polyethylene glycols of molecular weight. The precursor ink was converted to metallic platinum by heating at 250 ° C. for 10 seconds using a heat gun. AFM height image of nanoscale molds drawn between gold electrodes on silicon oxide. The gold precursor ink solution contains 100 mg of gold tetrachloride salt dissolved in 80% ethylene glycol / 20% water. The large particles are the result of three layers of ink each cured by heating at 200 ° C. for 10 seconds on a hot plate. This trace was not conductive. An image of a platinum-gold alloy pattern formed using an AFM cantilever. The alloy precursor ink contained 100 mg platinum salt and 50 mg gold salt simultaneously dissolved in 30 microliters of water containing 60 mg each of 300 and 10,000 MW polyethylene glycol. The trace was cured by heating at 250 ° C. for 10 seconds using a heat gun. (A) A two-layer pattern drawn across a 30 micron gap between gold electrodes on a silicon oxide wafer. The resistance value of the trace was 90 ohms. (B) A 6-layer pattern drawn between chrome electrodes on a glass wafer. The resistance value of the trace was 32 ohms. FIG. 17 (B) was performed using a PDMS DPN stamp chip. (C) AFM image showing large granular microstructure of platinum gold alloy film. The particle size was about 150 nm. Optical micrograph of a large metal mold on glass prepared by dropping an epoxy / gold precursor onto a slide and then curing at 150 ° C. for 2 hours. The gold precursor ink was prepared by dissolving 85 mg of gold hydrogen tetrachloride in 50 microliters of dimethylformamide and then adding 1 microliter of ethylene glycol and 1 microliter of the epoxy mixture to 3 microliters of this salt solution. The resistance value of the film was 0.3 ohm. AFM height image of a gold pattern formed by depositing gold precursor ink on quartz using a PDMS coated silicon nitride AFM tip. The gold precursor ink was prepared by dissolving 85.5 mg of gold tetrachloride (85.5 mg) in 50 μL of dimethylformamide. To this solution, 1 μL of ethylene glycol and 0.1 mg of thioctic acid were added. A square pattern of 4.5 × 4.5 microns was cured by heating at 250 ° C. for 10 seconds using a hot air gun. This single layer pattern was 15 nm high after curing (see line trace). Direct writing of silver lines to silicon nitride substrates using commercially available silver nanoparticle inks. (A) Optical image of a 200um long silver ink line after direct writing. (B) Silver microstructure obtained after low temperature curing. (C) Topographic atomic force microscope image of a small portion of the line corresponding to the average height distribution. Clarify that the line is 117.9 nm thick. Optical images showing cantilever microdeposition of commercially available silver nanoparticle ink on a glass substrate before and after curing. Adhesion and low temperature curing of commercially available silver nanoparticle inks on a glass substrate coated with a chromium thin film. Laser ablation was used to form a gap in the chrome film to expose the underlying glass substrate (center of image). Then, using a chipless cantilever, two lines were drawn on the chromium film on each side of the laser-ablated gap and across the gap. An optical image showing the production of a multilayer line by repeated drawing. (1L) 1 layer line with 6μm width and 30nm thickness, (2L) 2 layer line with 8.6μm width and 41nm thickness, (3L) 3 layer line with 8μm width and 70nm thickness Covering tipless cantilevers with ink by immersing them in a microfabricated reservoir. (A) A 1 mm wide circular reservoir ink pool (manufactured by deep reactive ion etching of a silicon wafer; bottom of image) or (B) Planar optical image of a cantilever immersed in that pool . Note the meniscus around the cantilever in image B. Optical image showing the repair of a thin film transistor (TFT) flat panel display. Schematic of a tipless cantilever with an ink storage slit. The figure which shows the alternative design of a chipless slit cantilever. The optical image which shows adhesion of the commercially available silver ink on the glass base material using a slit cantilever. Two examples of using a slit cantilever to attach and cure a line made of silver nanoparticle ink across the gap between gold electrodes on a glass substrate. Line writing using a slit cantilever loaded with gold nanoparticles / 1,3,5-TEB ink. FIG. 2 shows an apparatus for flat panel display and similar object repair. A cantilever coated with a metal precursor ink or a microbrush with a cantilever is used to repair the gap in the conductive trace. The XYZ stage controls the high-resolution movement of the cantilever. An ink supply mechanism including an ink well and its protective cover supplies material to the cantilever prior to touching operation. A coarse Z motion stage is provided to supply ink to the cantilever and contact the surface, while the rotary stage can position it at any angle about the Z axis. Monitoring cantilever brightness (which changes with bending) by video imaging using the included camera system and appropriate image processing software detects the cantilever's tangent to the surface when the cantilever first contacts the surface . A laser system is provided for (thermal) curing the microdeposited material. Schematic diagram showing a second device for flat panel repair. In this design, when the laser refraction sensor measures the Z position of the cantilever, its output is monitored to detect the contact surface of the cantilever with the substrate surface. Similar to the above design, a few nanometer resolution XYZ stage provides cantilever movement and a laser (not shown) cures the deposited material ("ink"). An ink supply mechanism supplies material (“ink”) to the cantilever prior to the contact operation. The large range of motion Z stage provides gloss Z motion for ink supply, while the rotating stage can position the cantilever at any angle about the Z axis. An alternative design for FPD restoration equipment where the confocal distance measuring device detects the contact surface of the cantilever with the substrate surface. Adhesion of conductive Au traces deposited across various gaps (10, 20, 40 μm) of insulation gap between 5μm tipless cantilever loaded with gold nanoparticle ink and conductive ITO (indium tin oxide) electrode An optical image showing. FIG. 6 shows a method of forming a gap near a topography step when drawing a line using a tipless cantilever. FIG. 4 shows loading and manufacturing of micron-scale (conductive) lines by direct writing using a chipless cantilever coated with ink and then curing. Experimental cure conditions suitable for low temperature cure inks such as gold nanoparticle inks are shown. The figure which shows the method by which a line width is controlled by a cantilever width (proportional to a cantilever width). Experimental results showing how the line width is controlled by the cantilever width (proportional to the cantilever width). (A) A 10 micron wide cantilever is shown writing a line of the same width. (B) A 2 micron cantilever is shown writing a 2 micron line. Both images are at the same scale to facilitate line width comparison. Optical and AFM images (A and B, respectively) of conductive gold traces deposited across a 200 μm gap between chrome electrodes. In this experiment, a gold nanoparticle / mesitylene / decanol mixture (described in further examples) was used. The ink was converted to a low resistivity metal form by curing for 7 minutes at a high temperature of 250-300 ° C. and then for 60 minutes at a lower temperature of 120 ° C. Adhesion test. Single adhesion gold lines were adhered to the glass with three adhesion test samples and cured at 150 ° C. for about 10 seconds. The tape peel test showed no loss of adhesion to the substrate and the line withstood chemical cleaning.

Claims (50)

Providing a cantilever that is a tipless cantilever having a cantilever end;
Providing ink disposed at the end of the cantilever;
Providing a substrate surface;
Moving the cantilever edge or substrate surface such that ink is carried from the cantilever edge to the substrate surface;
Including methods.   The method of claim 1, wherein the substrate surface is moved to secure the cantilever.   The method according to claim 1, wherein the substrate surface is fixed and the cantilever is moved.   2. The method of claim 1, wherein the substrate is a flat panel display substrate.   2. The method of claim 1, wherein the ink comprises one or more metals, metal salts or metal nanoparticles.   The method of claim 1, wherein the ink comprises one or more solvents having a boiling point greater than 100 ° C.   The method of claim 1, wherein the ink forms a feature on the substrate surface having dimensions controlled by the shape of the cantilever.   The method of claim 1, wherein the ink forms a feature on the substrate surface having a width of about 1 micron to about 100 microns.   The method of claim 1, wherein the ink forms a feature on the surface of the substrate, and the feature is subjected to melting, sintering, or agglomerating conditions.   The method of claim 1, wherein the ink forms a feature on the substrate surface and the feature is subjected to annealing.   The method of claim 1, wherein the ink forms a feature on the substrate surface and the feature is subjected to light.   The method of claim 1, wherein the ink forms a feature on the substrate surface and the feature is subjected to laser curing.   The method of claim 1, wherein the ink forms a continuous surface on the substrate surface after contact.   The method of claim 1, wherein the ink forms a shape on the substrate surface that is converted to a metallic state having a resistivity of about 10 microohms.cm or less.   The method of claim 1, wherein the ink forms a feature on the substrate surface having a width of about 5 nm to about 1 micron.   The method of claim 1, wherein the method is repeated to form a layer of ink on the substrate surface.   The method of claim 1, wherein the cantilever comprises an ink storage slit or channel.   The method of claim 1, wherein the cantilever has a width of about 1 micron to about 100 microns and a length of about 100 microns to about 400 microns.   The method of claim 1, wherein the cantilever has a width of about 5 microns to about 25 microns.   The method of claim 1, wherein the cantilever is a straight beam cantilever and is pulled rather than pushed.   2. The method of claim 1 used for thin film transistor repair.   The method of claim 1, wherein the cantilever is one of a plurality of cantilevers that deposit ink in parallel.   2. The method according to claim 1, wherein the ink is a polyol ink.   The method of claim 1, wherein the ink comprises a metal salt with one or more alcohols or polyols.   The method of claim 1, wherein the ink forms a feature on the substrate surface having a lateral dimension of about 1 micron to about 15 microns.   The method of claim 1, wherein the ink forms a feature on the substrate surface having a lateral dimension of about 1 micron to about 10 microns.   The method of claim 1, wherein the ink forms a feature on the substrate surface having a lateral dimension of about 1 micron to about 15 microns. Providing two or more cantilevers, each having a cantilever end, can include a tip at the end, or can be a tipless cantilever, with a gap between about 1 micron and about 20 microns in between Process,
Providing ink disposed in the gap;
Providing a substrate surface; and contacting two or more cantilevers with the substrate surface with the ink disposed in the gap such that the ink is carried from the gap to the substrate surface;
A method of writing to a conductive metal, comprising:   30. The method of claim 28, wherein the gap is from about 1 micron to about 5 microns.   30. The method of claim 28, wherein the gap is from about 5 microns to about 10 microns.   30. The method of claim 28, wherein the gap is from about 10 microns to about 20 microns.   An ink formulation for nanolithography or microlithography comprising one or more metal salts and one or more solvents, wherein the metal salt concentration is from about 1 mg / 100 μL to about 500 mg / 100 μL.   36. The ink formulation of claim 32, wherein the concentration of metal salt is from about 1 mg / 100 [mu] L to about 200 mg / 100 [mu] L.   35. The ink formulation of claim 32, wherein the metal salt concentration is from about 5 mg / 100 [mu] L to about 30 mg / 100 [mu] L.   35. The ink formulation of claim 32, further comprising two or more oligomeric or polymeric additives having different average molecular weights.   35. The ink formulation of claim 32, further comprising at least one oligomer and at least one polymer.   40. The ink formulation of claim 32, comprising two or more metal salts.   35. The ink formulation of claim 32, further comprising an epoxy. Providing a tipless cantilever having a cantilever end;
Providing an ink comprising one or more metals, one or more metal nanoparticles or one or more metal salts disposed at the end of the cantilever;
Providing a substrate surface; and contacting the cantilever end with the substrate surface such that ink is carried from the cantilever end to the substrate surface;
A method of writing directly to a conductive metal or metal precursor.   40. The method of claim 39, wherein the cantilever is pulled rather than pushed.   40. The method of claim 39, wherein the tipless cantilever is part of an array of cantilevers.   40. The method of claim 39, wherein the ink comprises metal nanoparticles.   40. The method of claim 39, wherein the ink is cured after being delivered to the substrate surface.   40. The method of claim 39, wherein the ink is cured at a temperature of about 300 ° C. or less after being delivered to the substrate surface.   Depositing a metal trace from a tipless cantilever loaded with nanoparticle ink across an insulating gap between conductors. Providing a cantilever,
Providing a precursor ink;
Placing the ink on the cantilever;
Providing a substrate surface;
Contacting the cantilever with the substrate surface such that the ink is transported from the cantilever to the substrate surface; and curing the adhered ink to a conductive form;
A method of additive repair of gaps in open traces on flat panel display substrates by locally depositing a precursor ink and then curing the ink to a conductive form. (1) Micrometer-wide cantilever for attaching ink to the substrate,
(2) Micro / nanometer scale XYZ stage that provides cantilever tremors,
(3) A laser to cure the ink attached to the substrate,
(4) Ink supply mechanism or device that supplies ink to the cantilever before adhesion,
(5) Large range of motion Z stage mover for supplying gloss Z movement for ink supply, and (6) Rotary stage that can position the cantilever at any angle around the Z axis,
Including flat panel displays and other equipment that is adapted for the repair of substantially flat circuits:   48. The apparatus of claim 47, further comprising a device for detecting bending of the cantilever when ink is applied. (1) cantilever adapted to receive ink,
(2) A cantilever holding adapted to contact the cantilever to pattern the ink in the form of a repair patch on the substrate and to translate the cantilever on the surface of the flat panel display substrate And positioning device,
(3) an ink supply device for supplying the ink to the cantilever, and (4) a curing system, optionally adapted to convert the deposited material to a low resistivity form adapted to electrical conductivity,
A device for repairing gaps in open traces on flat panel display substrates and similar devices.   A curing system exists, the curing system includes a laser and its focusing optics, and a cantilever positioning device (1) a nanometer resolution stage that controls the movement of the cantilever along the X, Y, and Z axes; (2) the Coarse-motion wide-range Z stage adapted to bring the cantilever into contact with the substrate, (3) Rotary stage that can position the cantilever at any angle around the Z axis, (4) Optionally, cantilever contact detection 50. The device of claim 49, comprising an apparatus.

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