CA2569438C

CA2569438C - Applicator liquid for use in electronic fabrication processes

Info

Publication number: CA2569438C
Application number: CA2569438A
Authority: CA
Inventors: Rahul Sen; Ramesh Sivarajan; Thomas Rueckes; Brent M. Segal
Original assignee: Nantero Inc
Current assignee: Nantero Inc
Priority date: 2004-06-03
Filing date: 2005-05-26
Publication date: 2012-02-21
Anticipated expiration: 2025-05-26
Also published as: WO2006078297A2; WO2006078297A3; US7504051B2; EP1751778A2; EP1751778A4; JP5781718B2; CA2569438A1; JP2008504198A; CN101015025A; CN101015025B; EP1751778B1; US20050269553A1; TWI317952B; TW200614272A

Abstract

Certain spin-coatable liquids and application techniques are described, which can be used to form nanotube films or fabrics of controlled properties. A spin-coatable liquid containing nanotubes for use in an electronics fabrication process includes a solvent containing a plurality of nanotubes. The nanotubes are at a concentration of greater than 1 mg/L. The nanotubes are pretreated to reduce the level of metallic and particulate impurities to a preselected level, and the preselected metal and particulate impurities levels are selected to be compatible with an electronics manufacturing process. The solvent also is selected for compatibility with an electronics manufacturing process.

Description

APPLICATOR LIQUID FOR USE IN
ELECTRONIC FABRICATION PROCESSES
Cross-Reference to Related Applications [0001] This application is related to the following applications, all of which are assigned to the assignee of this application: Nanotube Films and Articles (U.S. Patent No. 6706402) filed April 23, 2002; Methods ofNanotube Films and Articles (U.S.
Patent No. 6835591) filed April 23, 2002; and Patterning of Nanoscopic Articles (U.S.
Patent Publication Nos. 2005/0058590, 2005/0058797, and 2005/0128788).

Background 1. Technical Field [0002] This invention describes spin-coatable liquids (also referred to as applicator liquids throughout this specification) for use in the preparation of nanotube films. Such liquids are used in creating films and fabrics of nanotubes or mixtures of nanotubes and other materials on a variety of substrates including silicon, plastics, paper and other materials. In particular, the invention describes spin-coatable liquids containing nanotubes for use in electronics fabrication processes. Furthermore, the spin-eoatable liquids meet pr exceed specifications for a. semiconductor fabrication facility, including a class l environment.

2. Discussion of Related Art [0003] Nanotubes are useful for many applications; due to their electrical properties nanotubes may be used as conducting and semi-conducting elements in numerous electronic elements. Single walled carbon nanotubes (SWNTs) have emerged in the last decade as advanced materials exhibiting interesting electrical, mechanical and optical properties.
However, the inclusion or incorporation of the SWNT as part of standard microelectronic fabrication process has faced challenges due to a lack of a readily available application method compatible with existing semiconductor equipment and tools and meeting the stringent materials standards required in the electronic fabrication process.
Standards for such a method include, but are not limited to, non-toxicity, non-flammability, ready availability in CMOS or electronics grades, substantially free from suspended particles (including but not limited to submicro- and nano-scale particles and aggregates), and compatible with spin coating tracks and other tools currently used by the semiconductor industry.

[0004] Individual nanotubes may be used as conducting elements, e.g. as a channel in a transistor, however the placement of millions of catalyst particles and the growth of millions of properly aligned nanotubes of specific length presents serious challenges.
United States Patent Nos. 6,643,165 and 6,574,130 describe electromechanical switches using flexible nanotube-based fabrics (nanofabrics) derived from solution-phase coatings of nanotubes in which the nanotubes first are grown, then brought into solution, and applied to substrates at ambient temperatures. Nanotubes may be derivatized in order to facilitate bringing the tubes into solution, however in uses where pristine nanotubes are necessary, it is often difficult to remove the derivatizing agent. Even when removal of the derivatizing agent is not difficult, such removal is an added, time-consuming step.

[0005] There have been few attempts to disperse SWNTs in aqueous and non-aqueous solvents. Chen et al. first reported solubilization of shortened, end-functionalized SWNTs in solvents such as chloroform, dichloromethane, orthodichlorobenzene (ODCB), CS2, dimethyl formamide (DMF) and tetrahydrofuran (THF). See, "Solution Properties of Single-Walled Nanotubes", Science 1998, 282, 95-98. Ausman et al. reported the use of SWNTs solutions using sonication. The solvents used were N-methylpyrrolidone (NMP), DMF, hexamethylphosphoramide, cyclopentanone, tetramethylene sulfoxide and a-caprolactone (listed in decreasing order of carbon nanotube solvation). Ausman at el.
generally conclude that solvents with good Lewis basicity (i.e., availability of a free electron pair without hydrogen donors) are good solvents for SWNTs. See, "Organic Solvent Dispersions of Single-Walled Carbon Nanotubes: Toward Solutions of Pristine Nanotubes", J.
Phys. Chem.

B 2000, 104, 8911. Other early approaches involved the fluorination or sidewall covalent derivatization of SWNTs with aliphatic and aromatic moieties to improve nanotube solubility. See, e.g., E. T. Mickelson et al., "Solvation of Fluorinated Single-Wall Carbon Nanotubes in Alcohol Solvents", J. Phys. Chem. B 1999, 103, 4318-4322.

[0006] Full-length soluble SWNTs can be prepared by ionic functionalization of the SWNT ends dissolved in THE and DMF. See, Chen et al., "Dissolution of Full-Length Single-Walled Carbon Nanotubes", J. Phys. Chem. B 2001, 105, 2525-2528 and J.
L. Bahr et al Chem. Comm. 2001, 193-194. Chen et al. used HiPCOTM as-prepared (AP)-SWNTs and studied a wide range of solvents. (HiPCOTM is a trademark of Rice University for SWNTs prepared under high pressure carbon monoxide decomposition). The solutions were made using sonication.

[0007] Bahr et al. ("Dissolution Of Small Diameter Single-Wall Carbon Nanotubes In Organic Solvents?", Chem. Commun., 2001, 193-194) reported the most favorable solvation results using ODCB, followed by chloroform, methylnaphthalene, bromomethylnaphthalene, NMP and DMF as solvents. Subsequent work has shown that good solubility of AP-SWNT
in ODCB is due to sonication induced polymerization of ODCB, which then wraps around SWNTs, essentially producing soluble polymer wrapped (PW)-SWNTs. See Niyogi et al., "Ultrasonic Dispersions of Single-Walled Carbon Nanotubes", J. Phys. Chem. B
2003, 107, 8799-8804. Polymer wrapping usually affects sheet resistance of the SWNT
network and may not be appropriate for electronic applications where low sheet resistance is desired. See, e.g., A. Star et al., "Preparation and Properties of Polymer-Wrapped Single-Walled Carbon Nanotubes", Angew. Chem. Int. Ed. 2001, 40, 1721-1725 and M. J. O'Connell et al., "Reversible Water-Solubilization Of Single-Walled Carbon Nanotubes By Polymer Wrapping", Chem. Phys. Lett. 2001, 342, 265-271.

[0008] While these approaches were successful in solubilizing the SWNTs in a variety of organic solvents to practically relevant levels, all such attempts resulted in the depletion of the it electrons that are essential to retain interesting electrical and optical properties of nanotubes. Other earlier attempts involve the use of cationic, anionic or non-ionic surfactants to disperse the SWNT in aqueous and non aqueous systems. See, Matarredona et al., "Dispersion of Single-Walled Carbon Nanotubes in Aqueous Solutions of the Anionic Surfactant", J. Phys. Chem. B 2003, 107, 13357-13367. While this type of approach has helped to retain the electrical conductivity and optical properties of the SWNTs, most such methods leave halogens or alkali metals or polymeric residues, which tend to severely hamper any meaningful use in microelectronic fabrication facilities.

[0009] There is a need for a method of solvating or dispensing nanotubes in solvents for use in electronics applications. There remains a further need for methods that meet the criteria outlined above for low toxicity, purity, cleanliness, ease of handling and scalability.

Summary of the Invention [0010] One aspect of the present invention is directed to spin-coatable liquids for formation of high purity nanotube films.

[0011] According to one aspect of the present invention, a composition of nanotubes for use in an electronics fabrication process includes a liquid medium containing a plurality of nanotubes pretreated to reduce the level of metal and particulate impurities to a preselected level. The solvents are present at commercially meaningful levels, e.g., the nanotubes are at a concentration of greater than 1 mg/L. The nanotubes are homogeneously distributed in the liquid medium without substantial precipitation or flocculation.

[00-12] In one aspect of the present invention, a nanotube composition includes a stable distribution of nanotubes in a liquid medium and is substantially free of particulate and metallic impurities. The level of particulate and metallic impurities is commensurate with preselected fabrication requirements.

[0013] In one aspect of the invention, a spin-coatable liquid for formation of a nanotube film is provided including a liquid medium containing a controlled concentration of purified nanotubes, wherein the controlled concentration is sufficient to form a nanotube fabric or film of preselected density and uniformity, and wherein the spin-coatable liquid comprises less than 1 x 1018 atoms/cm3 of metallic impurities.

[0014] In one aspect of the invention, a spin-coatable liquid containing nanotubes for use in an electronics fabrication process includes a solvent containing a plurality of nanotubes, wherein the nanotubes are pretreated to reduce the level of metal and particulate impurities to a preselected level, wherein the nanotubes are substantially separated from one another and are distributed in the solvent without precipitation or flocculation, and wherein the solvent is selected for compatibility with an electronics manufacturing process.

[0015] In another aspect of the invention, a spin-coatable liquid containing nanotubes for use in an electronics fabrication process includes a solvent containing a plurality of nanotubes wherein the nanotubes are at a concentration of greater than 1 mg/L, wherein the nanotubes are pretreated to reduce the level of metallic and particulate impurities to a preselected level, and wherein the preselected metal and particulate impurities levels are selected to satisfy a criteria of an electronics manufacturing process.

[0016] According to one aspect of the present invention, methods and compositions for creating nanotube compositions for use in fabrication facilities having high standards of non-toxicity and purity are provided. Such processes include semiconductor fabrication processes, for example, CMOS and advanced logic and memory fabrications. Such fabrication processes may produce devices having fine features, e.g., <_250 nm.

[0017] According to other aspects of the present invention, the nanotube compositions are of a purity that is suitable for use in electronics fabrication facilities having less stringent standards for chemical composition and purity.
Such processes include, for example, interconnect fabrication and fabrication of chemical and biological sensors.

In more particular embodiments, there is provided:

(a) an applicator liquid for preparation of a nanotube film or fabric, comprising a controlled concentration of nanotubes dispersed in ethyl lactate, wherein the controlled concentration is sufficient to form a nanotube fabric or film of preselected density and uniformity and the applicator liquid is free of polymer and particle impurities having a diameter of greater than about 500 nm, and the applicator liquid comprises less than 1 x 1018 atoms/cm3 of metal impurities;

(b) an applicator liquid for preparation of a nanotube film, comprising a distribution of nanotubes in ethyl lactate, wherein the nanotubes remain separate from one another without precipitation or flocculation for a time sufficient to apply the applicator liquid to a surface and the applicator liquid is free of polymer and particle impurities having a diameter greater than about 500 nm, and the applicator liquid comprises less than 1 x 1018 atoms/cm3 of metal impurities;

(c) a nanotube composition comprising a plurality of nanotubes in ethyl lactate medium, wherein the nanotubes are separate from one another and homogeneously distributed throughout the ethyl lactate medium and the applicator liquid is free of polymer and particle impurities having a diameter greater than about 500 nm, and the nanotube composition comprises less than 1 x 1018 atoms/cm3 of metal impurities;

(d) a fullerene composition, comprising: a liquid medium containing a distribution of fullerenes, wherein the fullerenes remain separate from one another without precipitation or flocculation for a time sufficient to apply the fullerene composition to a surface, and wherein the composition comprises less than 1 x 1018 atoms/cm3 of metallic impurities;

(e) an applicator liquid comprising: a liquid medium containing a controlled concentration of purified nanotubes, wherein the controlled concentration is sufficient to form a nanotube fabric or film of preselected density and uniformity, wherein the purified nanotubes are substantially free of functionalization that deplete it electrons so that desired electrical properties of the nanotubes are maintained, wherein the applicator liquid is substantially free of surfactants and polymers, and wherein the applicator liquid comprises less than I x 1018 atoms/cm3 of metallic impurities;

(f) an applicator liquid comprising: a liquid medium containing a distribution of purified nanotubes, wherein the purified nanotubes remain separate from one another without precipitation or flocculation for a time sufficient to apply the applicator liquid to a surface, wherein the purified nanotubes are substantially free of functionalization that deplete it electrons so that desired electrical properties of the nanotubes are maintained, wherein the applicator liquid is substantially free of surfactants and polymers, and wherein the wherein the purified nanotubes are substantially free of functionalization that deplete 7r electrons so that desired electrical properties of the nanotubes are maintained, wherein the applicator liquid is substantially free of surfactants and polymers, 6a liquid is substantially free of particle impurities having a diameter of greater than about 500 nm;

(g) an applicator liquid for use in an electronics manufacturing process, comprising: an electronics-grade solvent and a plurality of nanotubes, wherein the applicator liquid is free of polymers and is free of surfactant, wherein the nanotubes are at a concentration of greater than or equal to 10 mg/L, wherein the nanotubes are separated from one another and are distributed in the solvent without precipitation or flocculation and can remain separated for about at least one week; wherein the nanotubes are pretreated to reduce a level of metal impurities to less than about 1 x 1018 atoms/cm3, and wherein said applicator liquid is free of particulates having a diameter greater than about 500 nm;

(h) a nanotube film comprising: a solution-deposited network of connected and purified nanotubes on a substrate, wherein the nanotubes form a film of substantially uniform porosity, the film is free of amorphous carbon, the film is free of polymer and surfactants, the film comprises less than about 1 x atoms/cm2 of metallic impurities, and the film is free of particle impurities having a diameter of greater than about 500 nm;

(i) an assembly comprising a substrate and a conductive element disposed on the substrate, wherein the conductive element comprises a solution-deposited network of purified nanotubes having a substantially uniform porosity contacting other purified nanotubes to define a plurality of conductive pathways along the conductive element, the conductive element is free of amorphous carbon, the conductive element is free of polymer and surfactants, the conductive element comprises less than 1 x 1018 atoms/cm2 of metal impurities and the conductive element is free of particle impurities greater than about 500 nm;
and (j) a method of making an applicator liquid containing nanotubes of high purity while achieving a stable distribution of nanotubes in the liquid for use in an electronics fabrication process, comprising: dispersing nanotubes into a solvent at a concentration of at least one milligram of nanotubes per liter solvent without addition of surfactants or polymers to form the applicator liquid; wherein the applicator liquid is substantially free of particulates having a diameter greater than 6b about 500 nm; wherein the applicator liquid has a level of metal impurities that is less than about I x 1018 atoms/cm3; and wherein the nanotubes are distributed in the solvent without substantial precipitation or flocculation.

Brief Description of the Drawing [0018] The invention is described with reference to the Drawing, which is presented for the purpose of illustration only and which is not intended to be limiting of the invention.

[0019] Figure 1 illustrates a typical scanning electron micrograph (SEM) of an unpurified nanotube fabric; and [0020] Figure 2 illustrates a typical SEM image of a purified nanotube fabric.
6c Detailed Description of the Invention [0021] Nanotubes have been the focus of intense research efforts into the development of applications that take advantage of their electronic, biological, and/or material properties. In one or more embodiments, a spin-coatable liquid containing a controlled concentration of purified nanotubes is prepared in a liquid medium. The spin-coatable liquid may be used to create nanotube films and fabrics of substantially uniform porosity. Certain embodiments provide spin-coatable liquids having a purity level that is commensurate with the intended application. Other applications provide spin-coatable liquids meeting or exceeding specifications for class 1 semiconductor fabrication.

[0022] In one or more embodiments, a nanotube composition includes a liquid medium containing a mixture of single-walled or multi-walled nanotubes that is stable enough for certain intended applications, such as spin coating in a class 1 production facility. The nanotubes in the nanotube composition remain suspended, dispersed, solvated or mixed in a liquid medium without substantial precipitation, flocculation or any other macroscopic interaction that would interfere with the ability to apply the nanotube solution to a substrate and form a uniform porosity. If there were significant precipitation or aggregation of the nanotubes, the nanotubes would clump together and form non-uniform films, which would be undesirable. The nature by which the nanotubes interact with the solvent to form a stable composition is not limited. Thus, for example, the nanotubes may be suspended or dispersed in the solvent or they may be solvated or solubilized in the solvent. The stable nanotube composition typically forms a homogeneous distribution of nanotubes in the solvent.

[0023] At the present time, it is desirable that the nanotubes remain distributed in the solvent medium without substantial precipitation, flocculation or other macroscopic interaction, for at least one hour, or for at least 24 hours, or even for at least one week.
Substantial precipitation and flocculation and the like can be detected by a variety of methods. Precipitates and aggregates can be detected by visual inspection.
Alternatively, precipitation or flocculation can be detected by analytical techniques, such light scattering or absorbance, or by observation of nanotubes once they are deposited on a substrate from the nanotube solution. A stable nanotube composition can exhibit prolonged suspension (typically several weeks to few months) of the SWNT in the medium with little or no detectable change in the scattered light intensity, or absorbance at a given wavelength, or viscosity.

[0024] Light scattering is measured using a monochromatic beam of light traveling through the solution. A change of light scattering intensity over time is recorded usually by a detector placed normal to the beam direction or from multiple detectors placed at various angles including the right angle. Another indicator especially at low concentrations of SWNT is the fall in absorbance (at a given wavelength) as function of time.
For higher concentrations of the solution, between the semidilute and nematic regimes, precipitation of individually suspended tubes leads to a noticeable fall in the viscosity of the suspension.
Other methods of determining the stability of a nanotube composition for its intended purpose will be apparent to those of skill in the art.

[0025] The nanotubes used in one or more embodiments of the present invention may be single walled nanotubes or multi-walled nanotubes and may be of varying lengths. The nanotubes may be conductive, semiconductive or combinations thereof.
Conductive SWNTs are useful in the manufacture of nanotube films, articles and devices and can be used in the nanotube solutions according to one or more embodiments of the invention.
Thus, the nanotube composition is integratable into current electronic fabrication processes including, by way of example, CMOS, bipolar-transistor, advanced memory and logic device, interconnect device, and chemical and biological sensor fabrications.

[0026] In selecting a solvent for the nanotube composition, the intended application for the nanotube composition is considered. The solvent meets or exceeds purity specifications required in the fabrication of intended application. The semiconductor manufacturing industry demands adherence to the specific standards set within the semiconductor manufacturing industry for ultra-clean, static-safe, controlled humidity storage and processing environments. Many of the common nanotube handling and processing procedures are simply incompatible with the industry standards. Furthermore, process engineers resist trying unfamiliar technologies. According to one aspect of the present invention, a solvent for use in a nanotube composition is selected based upon its compatibility or compliance with the electronics and/or semiconductor manufacturing industry standards.

[0027] Exemplary solvents that are compatible with many semiconducting fabrication processes, including but not limited to CMOS, bipolar, biCMOS, and MOSFET, include ethyl lactate, dimethyl sulfoxide (DMSO), monomethyl ether, 4-methyl -2 pentanone, N-methylpyrrolidone (NMP), t-butyl alcohol, methoxy propanol, propylene glycol, ethylene glycol, gamma butyrolactone, benzyl benzoate, salicyladehyde, tetramethyl ammonium hydroxide and esters of alpha-hydroxy carboxylic acids. In one or more embodiments, the solvent is a non-halogen solvent, or it is a non-aqueous solvent, both of which are desired in certain electronic fabrication processes. In one or more embodiments, the solvent disperses the nanotubes to form a stable composition without the addition of surfactants or other surface-active agents.

[0028] In one aspect of the invention, nanotube compositions include a plurality of single-walled or multi-walled nanotubes in ethyl lactate as the solvent. Ethyl lactate is one among the common solvent systems used by the electronics and electronic packaging industry and is an industry-accepted solvent that meets the industry standards for safety and purity. Ethyl lactate is available as a high purity solvent, or it can be purified to acceptable purity levels. Ethyl lactate has surprisingly been shown to exhibit excellent solubilizing capabilities for nanotubes. Furthermore, ethyl lactate can form stable nanotube compositions even in the presence of significant levels of impurities, thereby providing a versatile solution for application for formation of nanotube films and fabrics in a variety of applications. In one or more embodiments of the present invention, a nanotube solution of SWNT
in ethyl lactate is provided. Purified SWNTs can be solubilized in ethyl lactate at high concentrations, e.g., 100 mg/L, or even higher. Nanotube compositions include nanotubes homogeneously distributed in ethyl lactate without significant precipitation or flocculation.
[0029] Typical nanotube concentrations range from about 1 mg/L to 100 g/L, or from about 1 mg/L to 1g/L, or about 10 mg/L, or about 100 mg/L, or even about 1000 mg/L with a common concentration used for memory and logic applications of 100 mg/L. Such a concentration is exemplary various useful concentrations ranges depend upon the application.
For example in the case where a monolayer fabrics is desired one could use a less concentrated composition with a single or a few applications of the nanotube composition, e.g., by spin coating, to the substrate. In the event that a thick multilayer fabric is desired, a spraying technique could be employed with a nearly saturated nanotube composition. The concentration is, of course, dependent upon the specific solvent choice, method of nanotube dispersion and type of nanotube used, e.g., single-walled or multiwalled.

[0030] Nanotubes may be prepared using methods that are well known in the art, such as for example, chemical vapor deposition (CVD) or other vapor phase growth techniques (electric-arc discharge, laser ablation, etc.). Nanotubes of varying purity may also be purchased from several vendors, such as Carbon Nanotubes, Inc., Carbolex, Southwest Nanotechnologies, EliCarb, Nanocyl, Nanolabs, and BuckyUSA (a more complete list of carbon nanotube suppliers is found at http://www.cus.cam.ac.uk/-cs266/list.html). Vapor-phase catalysts are typically used to synthesize nanotubes and, as a result, the nanotubes are contaminated with metallic impurities. Furthermore, formation of nanotubes may also be accompanied by the formation of other carbonaceous materials, which are also a source of impurities in the nanotubes.

[0031] In one or more embodiments of the present invention, metallic particles and amorphous carbon particles are separated from nanotubes. The purification process reduces alkali metal ions, halogen ions, oligomers or polymers as active or inactive chemical components as part of the SWNT solution. The nanotube solutions according to certain embodiments of the present invention are substantially free of high levels of these particulate and/or insoluble materials (as well as other soluble materials that are incompatible with the semiconducting fabrication process). The nanotube solutions are thus purified for use in CMOS processing or other semiconducting fabrication process.

[0032] Appropriate purification techniques desirably remove impurities without affecting the nanotube chemical structure or electronic properties. Impurities may be removed for example, by dispersing the nanotubes in dilute acid solution to dissolve metal impurities, followed by separation of the nanotubes from the metallic solution. A mild acid treatment with nitric acid or hydrochloric acid may be used. Other suitable methods for metal removal include magnetic purification. Amorphous carbon may be removed, for example, by a combination of high speed centrifugation using an ultracentrifuge and filtration techniques for example but not limited to gravity filtration, cross flow filtration, vacuum filtration and others. Other suitable purification techniques include the preferential oxidation of non-fullerenic carbonaceous materials. Multiple purification steps may be desired in order to obtain nanotubes of a purity for use in a CMOS-grade nanotube solution. See, for example, Chiang, et al., J. Phys.ChemB 105, 1157 (2001); and Haddon, et al., MRS
Bulletin, April 2004) [0033] In one or more embodiments, nanotubes are pretreated to reduce the metallic impurity levels to preselected levels.

[0034] In one or more embodiments, the nanotubes composition contains less than about 1018 atoms/cm3 of metal impurities, or less than about 1016 atoms/cm3 of metal impurities, or less than about 1014 atoms/cm3 of metal impurities, or less than about 1012 atoms/cm3 of metal impurities, or less than about 1010 atoms/cm3 of metal impurities.
Compositions having lower levels of metallic impurities, e.g. ca. 1010 - 1012 atoms/cm3, may be used in the manufacture of advanced devices having fine features, for example, devices having features of less than or equal to 250 nm.

[0035] Heavy metals, for examples metals having a specific gravity of 5 glml, are generally toxic in relatively low concentrations to plant and animal life and tend to accumulate in the food chain. Examples include lead, mercury, cadmium, chromium, and arsenic. Such compounds are carefully regulated in the semiconductor fabrication industry and are desirably maintained at minimum levels. In one or more embodiments, the nanotube composition includes less than about 1018 atoms/cm3 of heavy metal impurities, or less than about 1016 atoms/cm3 of heavy metal impurities, or less than about 1014 atoms/cm3 of heavy metal impurities, or less than about 1012 atoms/cm3 of heavy metal impurities or even less than about 15 x 1010 atoms/cm3 of heavy metal impurities.

[0036] Similarly, the concentration of group I and group II elements is regulated due to the deleterious effect of elements such as sodium, potassium, magnesium and calcium, and the like, on the performance characteristics of the electronic device. In one or more embodiments, the nanotube composition includes less than about 1018 atoms/cm3 of group I
and group II element impurities, or less than about 1016 atoms/cm3 of group I
and group II
element impurities, or less than about 1014 atoms/cm3 of group I and group II
element impurities, or less than about 1012 atoms/cm3 of group I and group II element impurities or even less than about 15 x 1010 atoms/cm3 of group I and group II element impurities.
[0037] Lastly, transition metals are also avoided due to their ready migration and the deleterious effect of such migration to the device performance. See, Mayer, et al. Electronic Materials Science: For Integrated Circuits in Si and GaAs, 2nd Ed, Macmilliam, New York, 1988. As is the case for heavy metals and group I and group II metals, it is desired to maintain the impurity level of transition metals, such as copper, iron, cobalt, molybdenum, titanium and nickel, to less than preselected values. In one or more embodiments of the present invention, the nanotube composition includes less than about 1018 atoms/cm3 of transition metal impurities, or less than about 1016 atoms/cm3 of transition metal impurities, or less than about 1014 atoms/cm3 of transition metal impurities, or less than about 1012 atoms/cm3 of transition metal impurities or even less than about 15 x 1010 atoms/cm3 of transition metal impurities.

[0038] The impurity content of the nanotubes can be monitored using conventional methods, such as transmission electron microscopy (TEM) and scanning electron microscopy (SEM) and using analytical techniques such as x-ray microanalysis (EDAX), or Vapor Phase Decomposition and Inductively-Coupled Plasma Mass Spectrometry (VPD, ICP/MS).

[0039] Metallic impurity levels may be measured using conventional methods such as EDAX and VPD, ]PC/MS. If large quantities of solution (e.g., > about 1000 mL), are available for testing, direct volumetric concentration measurements (atoms/cm) can be determined. Alternatively, a known volume of the composition may be deposited over a known surface area and the surface impurity concentration (atoms/cm) can be determined.
[0040] In other embodiments of the present invention, nanotubes are pretreated to reduce the particulate impurities levels to a preselected level. The semiconductor industry has established standardized particulate impurity levels for particular processes, and the nanotubes may be pretreated to reduce the nanotube particulate levels to below the accepted levels. In one or more embodiments, the composition is substantially free of particle impurities having a diameter of greater than about 5 micron ( m), or about 1 m, or about 3 m, or about 500 nm, or 300 nm, or 100 nm, or even 45 nm.

[0041] Guidelines for particulate and metal impurity levels are found in the International Technology Roadmad for Semiconductors (ITRS Roadmap). For example, the ITRS
Roadmap states that at the 65 nm DRAM 1/a pitch, the critical particle size is 33 nm and only 1 particle/m3 is allowed over the critical size. From the ITRS 2002 update, at the 90 nm DRAM 1/2 pitch node, the critical particle size is 45 nm with only 2 particles/m3 allowed above the critical particle dimension. The ITRS Roadmap for 90nm DRAM V2 pitch mode allows for <15 x1010 atoms/cm3 of metal contamination during fabrication.
Liquid chemicals utilized for wafer fabrication may contribute <10 particles/mL of surface contamination.
Other fabrication specifications may be identified by the ITRS.

[0042] The semiconductor industry has well-established testing protocols for monitoring the particulate levels at, for example, 5 m, 3 m, 1 m, 500 nm, 300 nm and 100 nm. The metrology employed for detecting the particulate contaminate will have a resolution of 0.2 nm. Typical equipment include KLA Tencor surfscanTM and the like. Such testing methods and equipment may be readily adapted for use in evaluating the particulate levels of nanotube compositions.

[0043] In one or more embodiments of the present invention, the nanotube composition is a homogeneous mixture of purified single walled carbon nanotubes in ethyl lactate at concentrations high enough to be useful in practical applications in the electronics industry, e.g., > 10 mg/L. The nanotube composition can be electronics-grade purity. In some embodiments, nanotubes purified to an impurity content of less than 0.2 wt%, or less than 0.1 wt% free metal are solubilized in electronics-grade ethyl lactate or other suitable solvent.

[0044] It has been surprisingly discovered that nanotubes that have been pretreated to reduce the metallic and particulate impurity levels to below preselected levels, such as described herein, can form stable nanotube dispersions in a variety of solvents. Nanotubes, by way of example, SWNTs, and further by way of example purified SWNT, may be solubilized by dispersion in the appropriate solvent. One or more steps of grind or agitating the nanotubes in the selected solvent and sonication may enhance solubilization.

[0045] The solution is appropriate for use as a spin-on SWNT solution for electronic and electronic packaging applications. The inventors envision that the addition of various optional additives may be useful to facilitate long term storage and stabilization properties of carbon nanotube solutions. Such additives include, but are not limited to stabilizers, surfactants and other chemicals known or accepted as additives to solutions used for fabrication of electronics. The nanotube solution according to one or more embodiments of the present invention and the methods of making the solution of nanotubes have been standardized for CMOS compatibility as required in conventional semiconductor fabrication systems, i.e. the chemicals, spin coating tracks and other related machineries necessary to create the solutions of the present invention may be found in typical CMOS
processing facilities or more generally may be present in many types of services common to the electronics industry including fabrication and packaging facilities.

[0046] The nanotube composition can be placed or applied on a substrate to obtain a nanotube film, fabric or other article. A conductive article includes an aggregate of nanotubes (at least some of which are conductive), in which the nanotubes contact other nanotubes to define a plurality of conductive pathways in the article. The nanotube fabric or film desirably has a uniform porosity or density. In many applications, the nanotube fabric is a monolayer.

[0047] Many methods exist for the application procedure including spin coating, spray coating, dipping and many others known for dispersing solutions onto substrates. For thicker fabrics beyond a monolayer, more applications or more concentrated solutions may be required. In fact other techniques for application of the fabric may be required as has been outlined elsewhere (See Nanotube Films and Articles (U.S. Pat. No. 6,706,402) filed April 23, 2002 and Methods of Nanotube Films and Articles (U.S. Pat. No. 6,835,591) filed April 23, 2002).

[0048] In one aspect of the invention, a highly purified nanotube article is provided. The article contains a network of contacting nanotubes for form pathway through the article. The nanotube network may form a ribbon or non-woven fabric. The article contains less than 0.2 wt% or 0.1 wt% free metal, or even less.

[0049] In one or more embodiments, the nanotubes article contains less than about 1018 atoms/cm2 of metal impurities, or less than about 1016 atoms/cm2 of metal impurities, or less than about 1014 atoms/Cm2 of metal impurities, or less than about 1012 atoms/cm2 of metal impurities, or less than about 1010 atoms/cm2 of metal impurities.
Compositions having lower levels of metallic impurities, e.g. ca. 1010 - 1012 atoms/cm2, may be used in the manufacture of advanced devices having fine features, for example, devices having features of less than or equal to 250 rim.

[0050] Heavy metals, for examples metals having a specific gravity of 5 g/nil, are generally toxic in relatively low concentrations to plant and animal life and tend to accumulate in the food chain. Examples include lead, mercury, cadmium, chromium, and arsenic. Such compounds are carefully regulated in the semiconductor fabrication industry and are desirably maintained at minimum levels. In one or more embodiments, the nanotube article includes less than about 1018 atoms/cm2 of heavy metal impurities, or even less than about 15 x 1010 atoms/cm2 of heavy metal impurities.

[0051] Similarly, the concentration of group I and group II elements is regulated due to the deleterious effect of elements such as sodium, potassium, magnesium and calcium, and the like, on the performance characteristics of the electronic device. In one or more embodiments, the nanotube article includes less than about 1018 atoms/cm2 of group I and group II element impurities, or even less than about 15 x 1010 atoms/cm2 of group I and group II element impurities.

[0052] Lastly, transition metals are also avoided due to their ready migration and the deleterious effect of such migration to the device performance. As is the case for heavy metals and group I and group II metals, it is desired to maintain the impurity level of transition metals, such as copper, iron, cobalt, molybdenum, titanium, and nickel, to less than preselected values. In one or more embodiments of the present invention, the nanotube article includes less than about 1018 atoms/cm2 of transition metal impurities, or even less than about 15 x 1010 atoms/cm2 of transition metal impurities.

[0053] The use of the term "about" reflects the variation that occurs in measurement and can range up to 30% of the measured value. For example, when determining metal impurity levels using VPD ICP-MS, the accuracy of the measurement is related to the precision of analytical signals, the recovery of trace metals from the wafer surface, and the accuracy of the standards used. Overall accuracy of the VPD ICP-MS technique varies from 15%, at concentration levels higher than 10 times above the method detection limit, to 30% or higher at concentration levels lower than 10 times the detection limits.
Similar variability is expected in other measurements.

[0054] The following example are provided to illustrate the invention, which is not intended to be limiting of the invention, the scope of which is set forth in the claims which follow.

[0055] This example describes the purification of nanotubes.

[0056] Single-walled carbon nanotubes (SWNTs) were purified by stirring in 7.7M
HNO3 for 8h followed by refluxing at 125 C for 12h. The acid refluxed material was washed with DI water three times by a sonication-centrifugation-decantation cycle.
The DI water washed material was then vacuum filtered over a 5 micron filter until a dried SWNT
membrane was obtained on the filter paper. This purified SWNT material was collected and used for making a SWNT composition.

[0057] This example describes the preparation of a nanotube composition and a nanotube article.

[0058] In order to avoid recontamination of the nanotubes, clean room conditions, for example, Class 100 or greater, were maintained during preparation and processing of the nanotube composition. Twenty-one mg of single-walled nanotubes (SWNTs), purified as described above in Example 1 were soaked in 10 mL ethyl lactate (electronics grade-Sigma), ground with a mortar and pestle, sonicated and centrifuged to remove the supernatant. These steps were repeated as necessary to solubilize the carbon nanotubes. The solubilized nanotubes had a final concentration of 21 mg carbon nanotubes per 250mL ethyl lactate, and the optical density at 550 nm of the solution was measured to be 1.001.

[0059] Each individual step of the solubilization process is detailed in the Table 1 for the solubilization of SWNTs in ethyl lactate (EL). This protocol is illustrative of one means of forming a solubilized nanotube solution. Many other methods of forming such a solution are possible by adding or subtracting steps involving agitation and solubilization depending upon the specific requirements for concentration, solution stability and ultimate performance metrics of the desired fabric.

TABLE 1: Process Flow Chart for SWNT solubilization in Ethyl-Lactate Step Process Duration Remarks 1 Soak in 10 ml EL 30 min In mortar 2 Grind 10 min In mort ar 3 Soak in 10ml EL lh 20min In mortar 4 Add 90 ml EL After transfer to 250 ml flask Bath sonicate 0.5 h 5 C

6 Centrifuge (10 krpm, 20 C) 0.5 h In Teflon container 7 Decant supernatant Collect in 500 ml flask (100 ml); 25C
8 Grind sediment in 10 ml EL 10 min In mortar 9 Soak 50 min In mortar Add 90 ml EL After transfer to 250 ml flask 11 Bath sonicate 0.5 h 5 C

12 Centrifuge (10 krpm, 20 C) 0.5 h In Teflon container 13 Decant supernatant Collect in 500 ml flask (200 ml); 25 C
14 Grind sediment in 10 ml EL 10 min In mortar Soak 50 min In mortar 16 Add 90 ml EL After transfer to 250 ml flask 17 Bath sonicate 0.5 h 5 C

18 Centrifuge (10 krpm) 0.5 h In Teflon container 19 Decant supernatant Collect in 500 ml flask (300 ml); 25 C
Allow to stand 12 h At 25 C in closed flask 21 Sonicate 1 h 5 C

22 Metrics NA Check for sheet resistance and SEM

23 Storage conditions NA In 250 ml polypropylene (PP) bottle; 5 C

[0060] This example describes an alternative method of preparing a nanotube composition.

[0061] Twenty-one mg carbon nanotubes were mixed in 10mL EL and subjected to sonication, centrifugation, decanting of the supernatant and remixing of carbon nanotubes in EL for repeated sonication until the tubes were sufficiently solubilized;
i.e., the nanotubes were subjected essentially the same steps as in Example 2, without grinding with mortar and pestle. The steps of the process are shown in Table 2.

TABLE 2: Alternate Process Flow Chart for SWNT solubilization in Ethyl-Lactate Step Process Duration Remarks 1 Place 100 mg in 800 ml EL N/A In 1L polypropylene (PP) bottle.
2 Add Teflon impellers N/A In 1L PP bottle 3 Place on autoshaker 100h Powered through a timer 4 Collect in a 1L RB N/A HF cleaned flask, in cleanroom Bath sonicate lh 5 C

6 Centrifuge (15 krpm, 15 C) 2 h 6x250; Beckman PP bottles 7 Decant supernatant -15 min Collect in 1000 ml flask 8 Check for optical density at 550 N/A If above 1.25 this needs to be adjusted to anometer. 1.25 by adding neat EL

9 Bath sonicate 2h 5 C

Centrifuge (25000 rpm, 15 C) 2h 8x50 cc, Beckman PP in 3 batches 12 Decant supernatant N/A Collect in 1000 ml flask (200 ml); 25 C
13 Check for final metrics N/A Bottled in a 1L PP bottle rinsed with including sheet resistance and CMOS grade EL, SEM

[0062] This example describes the preparation of a nanotube article on a silicon substrate.
[0063] The solution prepared in Example 2 was spin coated onto a 100 mm oxide-coated silicon wafer. For comparison, a nanotube solution in EL using as-prepared, i.e., unpurified, nanotubes was spin coated onto a similar 100 mm oxide-coated silicon wafer.
Six applications were used to generate a fabric or film onto the wafer surface.
Figures 1 and 3 illustrate SEM images of unpurified SWNT material and purified SWNT material, respectively coated from a solution of SWNTs in ethyl lactate. The presence of particulate impurities is apparent in the unpurified sample (Fig. 1).

[0064] The purified SWNT film showed significant reduction in amorphous carbon contamination after completion of the purification process (Fig. 2). The figures do not necessarily represent ideal electronics grade fabrics, but are shown simply to represent spun-on fabrics created from ethyl lactate.

[0065] Upon generation of a fabric the sheet resistance was measured to be 70 kOhm (center); 129+/-22 kOhm (edge). The following table (Table 3) summarizes several metric parameters including the optical density of a typical purified SWNT solution as well as the resistivity of a SWNT fabric on a 100 mm silicon wafer coated with a thick gate oxide.
TABLE 3: Metrics of Typical SWNT Fabric Metrics Data Remarks Optical Density (550 nm) 1.001 Sheet Resistance 70 kohm (center), 6 spins:
129+/-22 kohm (edge) 60 rpm, 500 rpm, 4000 rpm [0066] The solution can be used to form a component of NRAM memories, such as described in U.S. Patent No. 6919592, entitled "Electromechanical Memory Array Using Nanotube Ribbons and Method for Making Same", filed July 25, 2001; U.S.
Patent No. 6643165, entitled "Electromechanical Memory Having Cell Selection Circuitry Constructed with Nanotube Technology", filed July 25, 2001; U.S. Patent No.
6944054, entitled "NRAM Bit Selectable Two-Drive Nanotube Array", filed March 29, 2003;
and U.S. Patent No. 7113426, entitled "NRAM Byte/Block Released Bit Selectable One-Device Nanotube Array," filed March 29, 2003. The solution holds potential as a stand alone commercial product to serve the research and development laboratories that work on single walled carbon nanotubes as well other applications.

[0067] This example describes the testing of trace metals on the surface of a nanotube article that is deposited on a silicon wafer.

[0068] A nanotube composition was prepared from nanotubes that had been purified of metallic and particulate impurities as described in Example 1 by dispersing the nanotubes in ethyl lactate medium as described in Example 2. The nanotube compositions were analyzed for surface metallic impurities by Vapor Phase Decomposition and Inductively-Coupled Plasma Mass Spectrometry (VPD, ICP/MS) by Chemtrace, Fremont, CA.

[0069] Silicon wafers, with and without a deposited nanotube layer, were placed in a pre-cleaned high purity chamber saturated with hydrofluoric acid (HF) vapor.
Untreated silicon wafers and ethyl lactate coated wafers were used as controls. The native or thermal oxide on the silicon wafer or deposited layer was dissolved in the presence of the HF
vapor. Metal impurities incorporated into the layer were released and dissolved in the acid during the scanning process.

[0070] A drop of an ultrapure acid etchant is added to the surface and the analysis area is scanned in a reproducible manner. The scanning solution was then collected for ICP-MS
analysis. The analysis area was the entire surface on one side of the wafer with 2 mm edge exclusion. Strict cleanroom practices were followed at all times. The VPD
process was performed in a near Class 1 laminar flow mini-environment located in a Class 10 cleanroom.
The ICP-MS instrument was operated in a Class 1000 cleanroom to minimize environmental source contamination.

[0071] A pre-cleaned silicon wafer was used as the control. In order to evaluate the source of metallic impurities in the solvent, a silicon wafer was treated (spin-coated) with electronics grade ethyl lactate alone (EL Control). Samples 1 through 3 represent three different nanotube compositions purified and prepared according to the methodology set out in Examples 1 and 2. The test results demonstrate that comparable levels of purity were achieved over a number of samples tested. Most of the metals tested were near the detection limit of the method. Notable exceptions to this were boron, calcium, cobalt, nickel potassium and sodium. However, the total and individual metals content were well below the lower limit of 15 x 1010 atoms/cm3 set by the ITS. Care must be taken in post purification processing in order to preserve the purity levels thus attained. For example, it was observed that rinsing the as-deposited nanotubes with DI water reintroduced several metal impurities.
[0072] The results of trace metal analysis recording the elemental content SWNTs after being coated on silicon substrates are reported in Table 4. Measurements are recorded as the number of atoms for a given element (X 1010 atoms per cm).

TABLE 4 (Number Of Atoms For A Given Element X 1010 Atoms Per cm2).

Method Detection Sample 1 Sample 2 Sample 3 Limits Control EL Control Batch 14 Batch 15 Batch 16 Aluminum (AI) 0.3 0.91 0.57 0.78 0.33 <0.3 Antimony (Sb) 0.003 <0.003 <0.003 <0.003 <0.003 <0.003 Arsenic (As) 0.03 0.065 0.32 <0.03 <0.03 <0.03 Barium (Ba) 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Beryllium (Be) 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Bismuth (Bi) 0.002 <0.002 <0.002 <0.002 <0.002 <0.002 Boron (B) 1 140 220 5.7 5.9 5.3 Cadmium (Cd) 0.005 <0.005 <0.005 <0.005 <0.005 <0.005 Calcium (Ca) 0.2 0.34 2.4 0.83 1.3 1.8 Chromium (Cr) 0.1 <0.1 0.11 <0.1 <0.1 <0.1 Cobalt (Co) 0.02 <0.02 <0.02 0.57 0.45 0.22 Copper (Cu) 0.05 <0.05 0.080 <0.05 0.34 <0.05 Gallium (Ga) 0.005 <0.005 <0.005 <0.005 <0.005 <0.005 Germanium (Ge) 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Iron (Fe) 0.1 <0.1 0.54 0.24 0.19 0.14 Lead (Pb) 0.003 <0.003 0,012 <0.003 0.011 <0.003 Lithium (Li) 0.08 <0.08 <0.08 <0.08 <0.08 <0.08 Magnesium (Mg) 0.3 <0.3 <0.3 <0.3 <0.3 <0.3 Manganese (Mn) 0.03 <0.03 0.069 <0.03 <0.03 <0.03 Molybdenum (Mo) 0.01 <0.01 0.014 <0.01 <0.01 <0.01 Nickel (Ni) 0.05 <0.05 <0.05 0.79 0.96 0.48 Potassium (K) 0.2 <0.2 3.5 0.30 1.2 0.73 Sodium (Na) 0.2 <0.2 7.1 1.2 2.1 1.5 Strontium (Sr) 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 Tin (Sn) 0.02 <0.02 <0.02 <0.02 <0.02 <0.02 Titanium (Ti) - 0.1 <0.1 <0.1 <0.1 <0.1 <0.1 Tungsten (W) 0.005 <0.005 <0.005 <0.005 <0.005 <0.005 Vanadium (V) 0.03 <0.03 <0.03 <0.03 <0.03 <0.03 Zinc (Zn) 0.06 <0.06 1.4 0.088 0.095 0.078 Zirconium (Zr) 0.003 0.050 <0.003 <0.003 <0.003 <0.003 Other Embodiments [0073] In certain embodiments concentrations of metallic or carbonaceous contamination that are above those required for CMOS fabrication may be acceptable. The present invention serves to exemplify creation of nanotube solutions with stringent requirements that meet or exceed those of a CMOS process flow but can be modified in applications that have relaxed requirements.

[0074] In certain embodiments the SWNT solutions may be modified or tailored to form thick nanotube coatings up to 100 microns thick or more and as thin as a monolayer of SWNTs. Such nanotube fabrics can be characterized by resistivity or capacitance measurements to meet the requirements of the specific electronics application.

[0075] As described herein, certain applicator liquids and application techniques are described, which can be used to form nanotube films or fabrics of controlled properties. For example, certain proposals have been made suggesting the benefits of substantially monolayers of nanotubes with substantially uniform porosity. Techniques have been provided in which one or more parameters may be controlled or monitored to create such films. Moreover, these liquids are intended for industrial environments, which require that the liquids be usable, i.e., that the nanotube suspension is stable, for periods of days, weeks and even months.

[0076] What is claimed is:

Claims

CLAIMS:

1. An applicator liquid for preparation of a nanotube film or fabric, comprising a controlled concentration of nanotubes dispersed in ethyl lactate, wherein the controlled concentration is sufficient to form a nanotube fabric or film of preselected density and uniformity and the applicator liquid is free of polymer and particle impurities having a diameter of greater than about 500 nm, and the applicator liquid comprises less than 1 x 10 18 atoms/cm3 of metal impurities.

2. The applicator liquid of claim 1, wherein the nanotubes are at a concentration of greater than 1 mg/L.

3. The applicator liquid of claim 1, wherein the nanotubes are at a concentration of greater than 100 mg/L.

4. The applicator liquid of claim 1, wherein the nanotubes are at a concentration of greater than 1000 mg/L.

5. The applicator liquid of claim 1, wherein the nanotubes are homogeneously distributed in ethyl lactate without precipitation or flocculation.

6. The applicator liquid of claim 1, wherein the applicator liquid is free of particle impurities having a diameter of greater than about 100 nm.

7. The applicator liquid of claim 1, wherein the particle impurities comprise carbonaceous particles.

8. The applicator liquid of claim 1, wherein the liquid comprises less than 15 x 10 10 atoms/cm3 of metal impurities.

9. An applicator liquid for preparation of a nanotube film, comprising a distribution of nanotubes in ethyl lactate, wherein the nanotubes remain separate from one another without precipitation or flocculation for a time sufficient to apply the applicator liquid to a surface and the applicator liquid is free of polymer and particle impurities having a diameter greater than about 500 nm, and the applicator liquid comprises less than 1 x 10 18 atoms/cm3 of metal impurities.

10. The applicator liquid of claim 9, wherein the nanotubes are at a concentration of greater than 1 mg/L.

11. The applicator liquid of claim 9, wherein the nanotubes are at a concentration of greater than 10 mg/L.

12. The applicator liquid of claim 9, wherein the nanotubes are at a concentration of greater than 100 mg/L.

13. The applicator liquid of claim 9, wherein the nanotubes remain separate from one another for at least one hour.

14. The applicator liquid of claim 9, wherein the nanotubes remain separate from one another for at least 24 hours.

15. The applicator liquid of claim 9, wherein the nanotubes remain separate from one another for at least one week.

16. The applicator liquid of claim 9, wherein the applicator liquid is free of particle impurities having a diameter greater than about 100 nm.

17. The applicator liquid of claim 9, wherein the liquid comprises less than 15 x 10 10 atoms/cm3 of metal impurities.

18. A nanotube composition comprising a plurality of nanotubes in ethyl lactate medium, wherein the nanotubes are separate from one another and homogeneously distributed throughout the ethyl lactate medium and the applicator liquid is free of polymer and particle impurities having a diameter greater than about 500 nm, and the nanotube composition comprises less than 1 x 10 18 atoms/cm3 of metal impurities.

19. The nanotube composition of claim 18, wherein the nanotubes remain distributed without precipitation or flocculation.

20. The nanotube composition of claim 18, wherein the nanotubes are at a concentration of greater than 1 mg/L.

21. The nanotube composition of claim 18, wherein the nanotubes are at a concentration of greater than 10 mg/L.

22. The nanotube composition of claim 18, wherein the nanotubes are at a concentration of greater than 100 mg/L.

23. The nanotube composition of claim 18, wherein the nanotubes remain homogeneously distributed for at least one hour.

24. The nanotube composition of claim 18, wherein the nanotubes remain homogeneously distributed for at least 24 hours.

25. The nanotube composition of claim 18, wherein the nanotubes remain homogeneously distributed for at least one week.

26. The nanotube composition of claim 18, wherein the composition is free of particle impurities having a diameter greater than about 100 nm.

27. The nanotube composition of claim 18, wherein the composition comprises less than 15 x 10 10 atoms/cm3 of metal impurities.

28. A fullerene composition, comprising: a liquid medium containing a distribution of fullerenes, wherein the fullerenes remain separate from one another without precipitation or flocculation for a time sufficient to apply the fullerene composition to a surface, and wherein the composition comprises less than 1 x 10 18 atoms/cm3 of metallic impurities.

29. The fullerene composition of claim 28, wherein the composition comprises less than about 1 x 10 18 atoms/cm3 of heavy metal impurities.

30. The fullerene composition of claim 28, wherein the composition comprises less than about 1 x 10 18 atoms/cm3 of group I and group II element impurities.

31. The fullerene composition of claim 28, wherein the composition comprises less than about 1 x 10 18 atoms/cm3 of transition metal impurities.

32. The fullerene composition of claim 28, wherein the composition comprises less than about 15 x 10 10 atoms/cm3 of heavy metal impurities.

33. The fullerene composition of claim 28, wherein the composition comprises less than about 15 x 10 10 atoms/cm3,of group I and group II element impurities.

34. The fullerene composition of claim 28, wherein the composition comprises less than about 15 x 10 10 atoms/cm3 of transition metal impurities.

35. An applicator liquid comprising: a liquid medium containing a controlled concentration of purified nanotubes, wherein the controlled concentration is sufficient to form a nanotube fabric or film of preselected density and uniformity, wherein the purified nanotubes are substantially free of functionalization that deplete .pi. electrons so that desired electrical properties of the nanotubes are maintained, wherein the applicator liquid is substantially free of surfactants and polymers, and wherein the applicator liquid comprises less than 1 x 10 18 atoms/cm3 of metallic impurities.

36. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 1 x 10 15 atoms/cm3 of metallic impurities.

37. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of metal impurities.

38. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of heavy metal impurities.

39. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of heavy metal impurities.

40. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of group I and group II element impurities.

41. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of group I and group II element impurities.

42. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of transition metal impurities.

43. The applicator liquid of claim 35, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of transition metal impurities.

44. The applicator liquid of claim 35, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 500 nm.

45. The applicator liquid of claim 35, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 300 nm.

46. The applicator liquid of claim 35, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 45 nm.

47. The applicator liquid of claim 35, wherein the purified nanotubes are homogeneously distributed in the liquid medium without substantial precipitation or flocculation.

48. The applicator liquid of claim 35, wherein the liquid medium is a non-halogen solvent.

49. The applicator liquid of claim 35, wherein the liquid medium is a non-aqueous solvent.

50. The applicator liquid of claim 35, wherein the liquid medium is selected for compatibility with an electronics manufacturing process.

51. The applicator liquid of claim 35, wherein the liquid medium comprises ethyl lactate.

52. The applicator liquid of claim 35, wherein the purified nanotubes comprise conductive nanotubes.

53. The applicator liquid of claim 35, wherein the purified nanotubes are single-walled nanotubes.

54. An applicator liquid comprising:

a liquid medium containing a distribution of purified nanotubes, wherein the purified nanotubes remain separate from one another without precipitation or flocculation for a time sufficient to apply the applicator liquid to a surface, wherein the purified nanotubes are substantially free of functionalization that deplete .pi. electrons so that desired electrical properties of the nanotubes are maintained, wherein the applicator liquid is substantially free of surfactants and polymers, and wherein the wherein the purified nanotubes are substantially free of functionalization that deplete .pi. electrons so that desired electrical properties of the nanotubes are maintained, wherein the applicator liquid is substantially free of surfactants and polymers, liquid is substantially free of particle impurities having a diameter of greater than about 500 nm.

55. The applicator liquid of claim 54, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 300 nm.

56. The applicator liquid of claim 54, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 100 nm.

57. The applicator liquid of claim 54, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 45 nm.

58. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of metallic impurities.

59. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of metallic impurities.

60. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of transition metal impurities.

61. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of transition metal impurities.

62. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of heavy metal impurities.

63. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of heavy metal impurities.

64. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 10 x 10 17 atoms/cm3 of group I and group II element impurities.

65. The applicator liquid of claim 54, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of group I and group II element impurities.

66. The applicator liquid of claim 54, wherein the liquid medium is a non-halogen solvent.

67. The applicator liquid of claim 54, wherein the liquid medium is a non-aqueous solvent.

68. The applicator liquid of claim 54, wherein the liquid medium is selected for compatibility with an electronics manufacturing process.

69. The applicator liquid of claim 54, wherein the liquid medium comprises ethyl lactate.

70. The applicator liquid of claim 54, wherein the purified nanotubes comprise conductive nanotubes.

71. The applicator liquid of claim 54, wherein the purified nanotubes are single-walled nanotubes.

72. An applicator liquid for use in an electronics manufacturing process, comprising: an electronics-grade solvent and a plurality of nanotubes, wherein the applicator liquid is free of polymers and is free of surfactant, wherein the nanotubes are at a concentration of greater than or equal to 10 mg/L, wherein the nanotubes are separated from one another and are distributed in the solvent without precipitation or flocculation and can remain separated for about at least one week; wherein the nanotubes are pretreated to reduce a level of metal impurities to less than about 1 x 10 18 atoms/cm3, and wherein said applicator liquid is free of particulates having a diameter greater than about 500 nm.

73. The applicator liquid of claim 72, wherein the solvent is selected for compatibility with the electronics manufacturing process.

74. The applicator liquid of claim 72, wherein the solvent is selected for compatibility with a semiconductor manufacturing process.

75. The applicator liquid of claim 72, wherein the applicator liquid is compatible with a semiconductor manufacturing process.

76. The applicator liquid of claim 72, wherein the nanotubes are at a concentration of greater than 100 mg/L.

77. The applicator liquid of claim 72, wherein the nanotubes are at a concentration of greater than 1000 mg/L.

78. The applicator liquid of claim 72, wherein the solvent is a non-halogen solvent.

79. The applicator liquid of claim 72, wherein the solvent is a non-aqueous solvent.

80. The applicator liquid of claim 72, wherein the solvent comprises ethyl lactate.

81. The applicator liquid of claim 72, wherein the nanotubes are single-walled nanotubes.

82. The applicator liquid of claim 72, wherein the applicator liquid is free of particulate impurities having a diameter greater than about 200 nm.

83. The applicator liquid of claim 72, wherein the applicator liquid is free of particulate impurities having a diameter greater than about 100 nm.

84. The applicator liquid of claim 72, wherein the applicator liquid is free of particulate impurities having a diameter greater than about 45 nm.

85. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of transition metal impurities.

86. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of heavy metal impurities.

87. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 1 x 10 18 atoms/cm3 of group I and group II metal impurities.

88. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3,of metal impurities.

89. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of transition metal impurities.

90. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of heavy metal impurities.

91. The applicator liquid of claim 72, wherein the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of group I and group II metal impurities.

92. A nanotube film comprising:

a solution-deposited network of connected and purified nanotubes on a substrate, wherein the nanotubes form a film of substantially uniform porosity, the film is free of amorphous carbon, the film is free of polymer and surfactants, the film comprises less than about 1 x 10 18 atoms/cm2 of metallic impurities, and the film is free of particle impurities having a diameter of greater than about 500 nm.

93. The nanotube film of claim 92, wherein the film comprises less than about 15 x 10 10 atoms/cm2 of metallic impurities.

94. The nanotube film of claim 92, wherein the film comprises less than about 15 x 10 10 atoms/cm2 of heavy metal impurities.

95. The nanotube film of claim 92, wherein the film comprises less than about 15 x 10 10 atoms/cm2 of group I and group II element impurities.

96. The nanotube film of claim 92, wherein the film comprises less than about 15 x 10 10 atoms/cm2 of transition metal impurities.

97. The nanotube film of claim 92, wherein the film comprises less than about 1 x 10 18 atoms/cm2 of heavy metal impurities.

98. The nanotube film of claim 92, wherein the film comprises less than about 1 x 10 18 atoms/cm2 of group I and group II element impurities.

99. The nanotube film of claim 92, wherein the film comprises less than about 1 x 10 18 atoms/cm2 of transition metal impurities.

100. The nanotube film of claim 92, wherein the film is free of particle impurities having a diameter of greater than about 300 nm.

101. The nanotube film of claim 92, wherein the nanotubes comprise conductive nanotubes.

102. The nanotube film of claim 92, wherein the film comprises a mono-layer of nanotubes.

103. The nanotube film of claim 92, wherein the film comprises a multilayer of nanotubes.

104. An assembly comprising a substrate and a conductive element disposed on the substrate, wherein the conductive element comprises a solution-deposited network of purified nanotubes having a substantially uniform porosity contacting other purified nanotubes to define a plurality of conductive pathways along the conductive element, the conductive element is free of amorphous carbon, the conductive element is free of polymer and surfactants, the conductive element comprises less than 1 x 10 18 atoms/cm2 of metal impurities and the conductive element is free of particle impurities greater than about 500 nm.

105. The assembly of claim 104, wherein the assembly comprises less than about 15 x 10 10 atoms/cm2 of metal impurities.

106. The assembly of claim 104, wherein the assembly comprises less than about 1 x 10 18 atoms/cm2 of heavy metal impurities.

107. The assembly of claim 104, wherein the assembly comprises less than about 15 x 10 10 atoms/cm2 of heavy metal impurities.

108. The assembly of claim 104, wherein the assembly comprises less than about 1 x 10 18 atoms/cm2 of group I and group II element impurities.

109. The assembly of claim 104, wherein the assembly comprises less than about 1 x 10 18 atoms/cm2 of transition metal impurities.

110. The assembly of claim 104, wherein the assembly comprises less than about 15 x 10 10 atoms/cm2 of group I and group II element impurities.

111. The assembly of claim 104, wherein the assembly comprises less than about 15 x 10 10 atoms/cm2 of transition metal impurities.

112. The assembly of claim 104, wherein the nanotubes comprise conductive nanotubes.

113. The assembly of claim 104, wherein the assembly comprises a mono-layer of nanotubes.

114. The assembly of claim 104, wherein the assembly comprises a multilayer of nanotubes.

115. A method of making an applicator liquid containing nanotubes of high purity while achieving a stable distribution of nanotubes in the liquid for use in an electronics fabrication process, comprising: dispersing nanotubes into a solvent at a concentration of at least one milligram of nanotubes per liter solvent without addition of surfactants or polymers to form the applicator liquid; wherein the applicator liquid is substantially free of particulates having a diameter greater than about 500 nm; wherein the applicator liquid has a level of metal impurities that is less than about 1 x 10 18 atoms/cm3; and wherein the nanotubes are distributed in the solvent without substantial precipitation or flocculation.

116. The method of claim 115, wherein the electronics fabrication process comprises a semiconductor fabrication.

117. The method of claim 115, wherein the electronics fabrication process comprises an advanced logic and memory fabrication.

118. The method of claim 115, wherein the electronics fabrication process comprises interconnect fabrication.

119. The method of claim 115, wherein the electronics fabrication process comprises chemical or biological sensor fabrication.

120. The method of claim 115, wherein said dispersing the nanotube into the solvent comprises: introducing a plurality of nanotube into the solvent to form a mixture; and agitating the mixture to disperse the nanotubes.

121. The method of claim 120, wherein said agitating the mixture comprises sonicating the mixture.

122. The method of claim 121, further comprising: centrifuging the sonicated mixture to separate a sediment from a supernatant, and collecting the supernatant containing nanotubes.

123. The method of claim 122, further comprising mixing the sediment with an additional portion of the solvent, sonicating the mixture, centrifuging the sonicated mixture to separate a sediment from a supernatant, and collecting the supernatant containing nanotubes.

124. The method of claim 123, wherein said mixing, sonicating, centrifuging and collecting are repeated one or more times.

125. The method of claim 115, wherein nanotubes are pretreated to remove metallic impurities to provide nanotubes that have a level of metal impurities that is less than about 1 x 10 18 atoms/cm3.

126. The method of claim 125, wherein the pretreatment comprises dispersing the nanotubes in an acid solution to dissolve metal impurities.

127. The method of claim 125, wherein the the nanotubes have a level of metal impurities that is less than about 15 x 10 10 atoms/cm2.

128. The method of claim 115, wherein the nanotubes are pretreated to remove particle impurities to provide nanotubes that are substantially free of particulates having a diameter greater than about 500 nm.

129. The method of claim 128, wherein the pretreatment comprises removing particle impurities by filtration.

130. The method of claim 128, wherein the nanotubes are substantially free of particulate impurities having a diameter of greater than about 300 nm.

131. The method of claim 128, wherein the nanotubes are substantially free of particulate impurities having a diameter of greater than about 100 nm.

132. The method of claim 128, wherein the nanotubes are substantially free of particulate impurities having a diameter of greater than about 45 nm.

133. The method of claim 115, wherein said dispersing the nanotubes into the solvent comprises: introducing a plurality of nanotube into the solvent to form a mixture; and sonicating the mixture; centrifuging the sonicated mixture; and removing the supernatant containing dispersed nanotubes.

134. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 17 atoms/cm3 of metal impurities.

135. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 17 atoms/cm3 of heavy metal impurities.

136. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 17 atoms/cm3 of group I and group II element impurities.

137. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 17 atoms/cm3 of transition metal impurities.

138. The method of claim 133, wherein, the applicator liquid comprises less than about 15 x 10 10 atoms/cm3 of metal impurities.

139. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 10 atoms/cm3 of heavy metal impurities.

140. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 10 atoms/cm3 of group I and group II element impurities.

141. The method of claim 133, wherein the applicator liquid comprises less than about 10 x 10 10 atoms/cm3 of transition metal impurities.

142. The method of claim 133, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 300 nm.

143. The method of claim 133, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 100 nm.

144. The method of claim 133, wherein the applicator liquid is substantially free of particle impurities having a diameter of greater than about 45 nm.