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United States Patent
Tour et al.
(io) Patent No.: (45) Date of Patent:
US 7,176,146 B2 Feb.13, 2007
(54) METHOD OF MAKING A
(75) Inventors: James M. Tour, Bellaire, TX (US);
Michael P. Stewart, Houston, TX (US)
(73) Assignee: William Marsh Rice University,
Houston, TX (US)
( * ) Notice: Subject to any disclaimer, the term of this patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days.
(21) Appl. No.: 10/356,841
(22) Filed: Feb. 3, 2003
(65) Prior Publication Data
US 2004/0023479 Al Feb. 5, 2004
Related U.S. Application Data
(60) Provisional application No. 60/353,120, filed on Feb. 1, 2002.
(51) Int. CI.
H01L 21/31 (2006.01)
(52) U.S. CI 438/765; 438/767; 438/780;
(58) Field of Classification Search 438/765,
438/767, 769, 780, 99 See application file for complete search history.
(56) References Cited
U.S. PATENT DOCUMENTS
5,429,708 A * 7/1995 Linford et al 216/66
5,554,739 A 9/1996 Belmont 534/885
6,042,643 A 3/2000 Belmont et al 106/472
6,217,740 Bl 4/2001 Andrieux et al 205/413
6,284,317 Bl 9/2001 Laibinis et al 427/258
6,368,239 Bl 4/2002 Devonport et al 473/449.2
6,432,511 Bl 8/2002 Tour et al 702/19
2002/0063212 Al* 5/2002 Mirkin et al 250/306
2002/0105897 Al * 8/2002 McCreery 369/126
2003/0058697 Al 3/2003 Tour et al 365/200
FOREIGN PATENT DOCUMENTS
WO 02/060812 8/2002
WO 03/032330 4/2003
Villeneuve et al. "Electrochemical Formation of Close-packed Phenyl Layers on Si(lll)" J. Phys. Chem. B 1997, 101, pp. 2415-2420 *
Liu and McCreery, "Reactions of Organic Molecules on Carbon Surfaces" Journal of the American Chemical Society 1995, 117(45), pp. 11254-11259 *
Primary Examiner—Thanh Nguyen
(74) Attorney, Agent, or Firm—Robert
Winstead Sechrest & Minick PC.
Allongue et al. "Structural characterization of organic monolayers on Si<lll> from capacitance measurements" Electrochimica Acta, 45 (2000), pp. 3241-3248.*
Article entitled "Ideal Hydrogen Termination of the SI (111) Surface," Higashi et al., AT&T Bell Laboratories, Dec. 4, 1989, pp. 657-658.
Article entitled "Quantitative Determination of Molecular Structure in Multilayered Thin Films of Biaxial and Lower Symmetry From Photon Spectroscopies I. Relection Infrared vibrational Spectroscopy," Parikh et al., Department of Materials Cienc and Chemistry, Oct. 3, 1991, pp. 927-945.
Article entitled "Formation and Structure of Self-Assembled Monolayers," A. Ulman, Department of Chemical Engineering, Chemistry and Materials Science and the Herman P. Mark Polymer Research Institute, Polytechnic University, Apr. 18, 1996, pp. 15331554.
Article entitled "Electrochemical Formation of Close-Packed Phenyl Layers On Se(lll)," Villeneuve et al., /. Phys. Chem. B. vol. 101, No. 14, 1997, pp. 2415-2420.
Article entitled "Preparation of Pit-Free Hydrogen-Terminated Si(lll) in Deoxygenated Ammonium Fluoride," Wade et al., Materials.Research Society Symp. Proc. vol. 477, 1997, pp. 298-305.
Article entitled "Current and Future Applications of Nanoclusters," Schmid et al., Chem. Soc. Rev., 1999, vol. 28, pp. 179-185. Article entitled "Large On-Off Ratios and Negative Differential Resistance in a Molecular Electronic Device," Chen et al., Science vol. 386, Nov. 19, 1999, pp. 1550-1552.
Article entitled "Molecular Electronic. Synthesis and Testing of Components," J.M. Tour, American Chemical Society, Apr. 13, 2000, Page Est: 13.6, pp. A-N.
Article entitled "Molecular Random Access Memory Cell," Reed et al., Applied Physics Letters vol. 78 No. 3, Jun. 4, 2001, pp. 3735-3737.
Article entitled "Advanced Materials Progress Report on Molecules and Electronic Materials," Cahen et al., Adv. Mater, vol. 14 No. 11, Jun. 5, 2002, pp. 789-798.
Article entitled "X-ray Photoelectron Spectroscopy Evidence for the Covalent Bond Between an Iron Surface and Aryl Groups Attached by the Electrochemical Reduction of Diazonium Salts,"Boukerma et al., American Chemical Society, no page numbers given, May 16, 2003.
* cited by examiner
METHOD OF MAKING A
CROSS-REFERENCE TO RELATED
This non-provisional application claims the benefit of U.S. provisional application Ser. No. 60/353,120 entitled Self-Assembly of Covalently Bound Organic Layers On Semiconductor Surfaces, filed Feb. 1, 2002. 1°
STATEMENT REGARDING FEDERALLY
SPONSORED RESEARCH OR DEVELOPMENT
This work was supported by funding from the Department 15 of Defense Advanced Research Projects Agency (DARPA) administered by the Office of Naval Research (ONR) Grant Nos. N00014-01-1-0657 and N00014-99-1-0406.
FIELD OF THE INVENTION 20
This invention is generally related to a method of making a molecule-surface interface. The surface comprises at least one material and at least one organic group adjoined to the ^ surface. The method comprises contacting at least one organic group precursor with at least one surface wherein the organic group precursor is capable of reacting with the surface in a manner sufficient to adjoin the organic group and the surface. 3Q
BACKGROUND OF THE INVENTION
Modem solid-state electronic devices, such as transistors and other circuits and switches rely on high-quality, easily 35 manufactured electrical interconnects, where an interconnect comprises a point of contact between at least two different materials. Key to the proper function of such interconnect devices is the robustness of the interconnect and its ability to reliably conduct electronic signals such as 40 current and potential. Additionally, interconnect devices may also be required to conduct photons as for example to transmit light-based signals. Dependable techniques of manufacturing strive to consistently create high quality, defect-free interconnects. Such devices fail when contact 45 across the interconnect is impeded or prevented. For example, at small dimensions surface roughness at the contact boundary can make it difficult to achieve or maintain contact sufficient to ensure proper electrical conduction. At dimensions approaching the nanometer scale, normal sur- 50 face topology of metal surfaces ordinarily used in interconnects can prevent large portions of the corresponding surfaces from establishing contact. These gaps substantially increase the electrical resistance in the interconnect device and often result in an interconnect device that cannot 55 adequately conduct electrical current.
Recent advances in nanotechnology have made it possible to consider the smallest possible sizes for electronic devices. Namely, circuits and devices, including electrical interconnects, employing devices that comprise one or a small 60 collection of molecules are now within the realm of plausible device structures. Engineering good contacts at the molecular level poses a significant challenge. As the fabrication of coherent molecular electronic structures on various surfaces evolves, the detailed chemical nature of the con- 65 nection between the molecular and macro-scale worlds will become increasingly important. See, for example, Cahen,
D.; Hodes, G.Adv. Mater. 2002, 14, 789 and Yaliraki, S. N.; Ratner, M. A. Ann. N.Y. Acad. Sci. 2002, 960, 153.
Ideally, in the case of electronic devices employing conjugated organic molecules, a bond allowing strong electronic coupling between the energy bands of a bulk contact and the orbitals of a conjugated organic molecule would allow for a great deal of synthetic variation in device properties. Recent advances in surface chemistry offer an increasingly sophisticated range of techniques for orienting molecules on a wide variety of materials. See for example, Ullman, A. Chem. Rev. 1996, 96, 1533; Buriak, J. M. Chem. Rev. 2002, 102, 1271; and Seker, F.; Meeker, K.; Kuech, T. F.; Ellis, A. B. Chem. Rev. 2000, 100, 2505. These new techniques improve the prospects of future 'bottom-up' fabrication strategies in nanotechnology using chemical techniques and molecular components to augment traditional fabrication schemes. See, for example, Chen, J.; Reed, M. A.; Rawlett, A. M.; Tour, J. M. Science 1999, 286, 1550; Tour, J. M. Acc. Chem. Res. 2000, 33, 791; and Reed, M. A.; Chen, J.; Rawlett, A. M.; Price, D. W.; Tour, J. M. App. Phys. Lett. 2001, 78, 3735, all incorporated herein by reference.
Some have attempted to functionalize surfaces with organic molecules employing various combinations of conditions and/or reagents.
U.S. Pat. No. 5,429,708 to Linford et al. provides for a method for producing a molecular layer of a selected molecular moiety on a silicon surface in which a silicon surface is etched to form a hydrogenated silicon surface and combined with a free radical-producing compound, where the free radical produced by the free radical-producing compound corresponds to the selected molecular moiety. The combined silicon surface and free radical-producing compound is then heated to sufficient temperature to initiate reaction between the free radical-producing compound and the hydrogenated silicon surface.
U.S. Pat. No. 6,284,317 Bl to Laibinis et al. relates to methods of derivatizing semiconductor surfaces, particularly porous silicon surfaces with silicon-carbon units. The derivatization occurs through the direct addition of an organometallic reagent in the absence of an external energy source such as heat and photochemical or electrochemical energies. The method of the invention allows the formation of unique intermediates including silicon hydride units bonded to metal ions. Because of these unique intermediates, it is possible to form previously inaccessible siliconcarbon units, for example where the carbon atom is an unsaturated carbon atom. Such inaccessible silicon-carbon units also include silicon-polymer covalent bond formation, in particular where the polymer is a conducting polymer. Thus, the present invention also provides a novel semiconductor surface/polymer junction having improved interfacial interactions.
U.S. Pat. No. 6,217,740 Bl to Andrieux et al. concerns a process for electrochemically producing a carbonaceous material with its surface modified by organic groups, in particular functionalized organic groups. The process comprises providing a solution, in a protic or aprotic solvent, comprising a salt of a carboxylate of an organic residue capable of undergoing a Kolbe reaction. The solution is then put in contact with a carbonaceous material, wherein the carbonaceous material is positively polarized with respect to a cathode that is also in contact with the solution. The solution may optionally contain an electrolyte. The invention also concerns carbonaceous materials modified at the surface with arylmethyl groups and the use of these modified materials, for example, in the production of composite materials.