Chemical functionalization nanolithography

Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Making electrical device

Reexamination Certificate

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C430S296000, C430S322000, C430S394000, C427S402000

Reexamination Certificate

active

06835534

ABSTRACT:

FIELD OF INVENTION
This invention relates generally to the field of nanofabrication. More specifically, the invention relates to methods of fabricating and modifying nanostructures by patterning the chemical functionality of molecules that overlay a substrate. The invention provides for chemical and spatial complexity and precision such that even nanostructures are scaled down using molecular science. The invention is suited for use in fabricating devices such as sensors, in directional growth or placement of cells, and in self assembly of components into devices.
BACKGROUND OF THE INVENTION
The ability to construct increasingly small and complex structures is of great importance in the fabrication of advanced electronic, optical, photonic, and sensing devices, as well as in other applications. There continues to be increased interest in creating smaller and more precise patterns. Of particular interest is creating patterns on the mesoscale or even the nanoscale. Some of the methods and attempts relating to creating smaller patterns relate to molecular science.
Conventionally, electron, photon, or ion exposure has been used to induce massive changes and bond breakages in polymer resists located on surfaces. Either the exposed or unexposed portions of polymer resists are then removed to leave a pattern. These and other lithographic approaches have been used to pattern surfaces. Lithography techniques involve printing on a surface in either an additive or subtractive process. In an additive process, the pattern that is printed onto a surface creates a new structure or modification to a structure. In a subtractive process, the pattern serves an intermediary role, protecting a portion of the surface while other portions are removed. Such common methods include electron beam lithography. See P. Rai-Choudhury, Ed.
SPIE handbook of Microlithography, Micromachining and Microfabrication
(SPIE, 1997) vol. 1. Other techniques utilize a scanning probe microscope (SPM). See H. Sugimura, N. Nakagiri,
J. Am. Chem. Soc.
119, 9226 (1997); M. A. Reed, J. Chen, C. L. Asplund, A. M. Cassell, M. L. Myrick, A. M. Rawlett, J. M. Tour, P. G. Van Patten,
Appl. Phys. Lett.
75, 624 (1999); S. Hong, J. Zhu, C. A. Mirkin,
Science
286, 523 (1999).
Despite all these different possible methods of creating nanostructures, significant problems and limitations remain. One problem has been that the chemistry used has been imprecise. Typically, polymer molecules are destroyed by irradiation with electrons, ion, and/or photons. These induced reactions are not well-defined and are imprecise. There have been few exceptions to the general problems of poorly defined resists and poorly defined products of induced reactions. One attempt to address one aspect of these problems has been by using monolayers as resists to replace more typical polymer resists in which molecules are randomly oriented, overlay one another in random orientations, and the thickness of the film varies. See R. C. Tiberio, H. G. Craighead, M. Lercel, T. Lau, C. W. Sheen, D. L. Allara,
Appl. Phys. Lett.
62, 476-478 (1993). In this case, the reaction products and resulting structures remain ill-defined.
One attempt at patterning surfaces is based on selective attachment of monolayers and multi-layers. See A. Hatzor and P. S. Weiss,
Science
291, 1019 (2001). This method is useful in creating further patterns.
Non-lithographic methods of patterning have been used to pattern surfaces. These methods have been referred to as soft lithography. See R. S. Kane, S. Takayama, E. Ostuni, D. E. Ingber, G. M. Whitesides,
Biomaterials
20, 2363 (1999). These techniques include microcontact printing, patterning using microfludic channels, and laminar flow patterning. These patterned surfaces have been further used to pattern proteins and cells.
Microcontact printing relies upon the molecular self assembly of self-assembled monolayers (SAMs) to provide for surface patterning. In microcontact printing, a molecular stamp is inked and then applied to a surface. The molecular stamp is then removed, leaving the ink on the surface. Typically, the surface is then immersed in a solution that promotes formation of the self-assembled monolayers on that portion of the surface that was not inked thereby creating a pattern.
Microcontact printing has been combined with chemical reaction. See L. Yan, C. Marzolin, A. Terfort, G. M. Whitesides,
Langmuir
13, 6704-6712 (1997); L. Yan, X. M. Zhao, G. M. Whitesides,
J. Am. Chem. Soc.
120, 6179-6180 (1998). A reactive SAM is placed on a substrate, and this reactive substrate is stamped. The mixed SAM can then be reacted further. One advantage of reactive SAM microcontact printing is that more types of functional groups are available than would be using other chemical methods.
Yet problems remain. The precision available using microcontact printing techniques is limited. Further, a number of steps may be required to create complex patterning.
Another attempt at patterning surfaces involves dip-pen lithography. Dip-pen lithography combines atomic force microscopy (AFM) and SAMs technology to provide for direct writing of a pattern on a surface. SAMs are transferred down the tip of the pen to the substrate. Dip-pen lithography provides a direct method of patterning, but is problematic in at least several respects. For example, the process is a very slow serial process. Although it is possible to use tips in parallel, only limited increases in speed are achievable and the resolution is limited.
Generally, in soft lithography, resolution and accessible patterns, and chemical functionality are all limited. One partial exception has been nanoscale patterning of hydrogen terminated silicon surfaces. See J. W. Lyding, T. C. Shen, J. S. Hubacek, J. R. Tucker, G. C. Abeln,
Appl. Phys. Lett.
64, 2962 (1994). Patterning occurs when electrons field emitted from the probe of a scanning tunneling microscope locally desorb hydrogen, converting the surface into clean silicon. The limitation of this method is that the hydrogen monolayer may not be chemically modified to tailor surface properties further; silicon can be, but has very limited accessible chemistry.
As can be seen from the foregoing discussion, creating devices with nanoscale structures or chemical patterns remains a considerable problem. Thus, a need exists in the art for a method of creating spatially and chemically precise nanostructures or chemically patterned materials or substrates. Such materials would be useful in electronic component fabrication, sensor construction, component assembly, and other applications.
It is therefore an object of the present invention to provide a method for creating such structures that greatly improves the state of the art.
It is another object of the present invention to provide a method of creating nanoscale structures that results in structures that are chemically precise, spatially precise, and simultaneously both chemically and spatially precise.
It is a further object of the present invention to provide a method for creating nanoscale structures that can be chemically modified.
It is a further object of the present invention to provide a method for creating stable nanostructures that can be chemically modified.
It is a further object of the present invention to provide a method for making nanoscale structures that permits complex patterns to be made.
It is a further object of the present invention to provide a method for making nanoscale structures that permit a variety of structures to be created or modified.
It is a further object of the present invention to provide a method of creating nanostructures that allows a number of different nanostructures to be constructed in a single fabrication process or in a series of simple steps.
Yet another object of the present invention is to provide a method of creating patterns through chemical functionalization.
A further object of the present invention is to provide a method of creating patterns that is chemically flexible.
A still further object of the present invention is to provide a me

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