Patent Publication Number: US-9884827-B2

Title: Selective placement of carbon nanotubes via coulombic attraction of oppositely charged carbon nanotubes and self-assembled monolayers

Description:
PRIORITY 
     This application is a continuation of and claims priority from U.S. patent application Ser. No. 13/248,176, filed on Sep. 29, 2011, entitled “SELECTION PLACEMENT OF CARBON NANOTUBES VIA COULOMBIC ATTRACTION OF OPPOSITELY CHARGED CARBON ANNAOTUBES AND SELF-ASSEMBLED MONOLAYERS”, the entire contents of which are incorporated herein by reference. 
    
    
     BACKGROUND 
     The present invention generally relates to a method of placing carbon nanotubes (herein after “CNTs”) on a substrate. In particular, the invention relates to selective placement of charged CNTs on a pre-patterned surface having an oppositely charged, self-assembled monolayer. 
     CNTs can be semiconducting and therefore are of interest as channel materials for Field Effect Transistors (herein after “FET”). Accordingly, methods of placing CNTs on a substrate for use in FETs are being explored. 
     One approach to placing CNTs on a substrate involves directed assembly of CNTs from a suspension. In this approach, a substrate is patterned to define areas to which the CNT will have an affinity. The affinity is due to functionalization of either the substrate or the CNT to promote bonding between the substrate and the CNT. 
     In one instance, to place CNTs on a substrate, the prior art stamps a substrate with an organic compound to create a substrate having hydrophilic and hydrophobic regions. The hydrophilic region is the original substrate surface and the hydrophobic region is the area stamped with the organic compound. The substrate is immersed in a solution of CNTs and dried to leave CNTs on the hydrophilic regions. However, the CNTs on the surface of the substrate are bundled (i.e. a group of CNTs twisted together in a rope-like fashion) and/or multilayered. Bundled or multilayered CNTs are undesirable because a transistor made from them requires higher voltage to turn on an off. The described method has another drawback in that a solution of CNTs is not able to reach recessed hydrophilic areas having small widths (around or less than 200 nm). As a result, CNTs will be placed in large hydrophilic areas while small hydrophilic features remain uncovered. Accordingly, a CNT placement method based upon hydrogen bonding (a type of dipole bonding) can result in poor selectivity. 
     In other methods, the prior art places CNTs on a substrate by first functionalizing the CNT and then placing the CNT directly on the substrate. However, such methods result in a low density of CNTs on the surface. 
     Therefore, a need exists for a method of selectively placing a monolayer of high density CNTs on a substrate with minimal bundling. 
     SUMMARY 
     An object of the invention is to provide a method of forming a structure having selectively placed carbon nanotubes (“CNTs”). The method includes providing a substrate having a surface and contacting the surface of the substrate and a solution of a precursor molecule to form a self-assembled monolayer having a first ionic charge moiety on the surface. Thereafter, the self-assembled monolayer and a dispersion of a plurality of CNTs having a second ionic charge moiety are contacted. 
     According to another aspect of the invention a structure having a CNT layer includes a substrate having a first region and a second region, a self-assembled monolayer on the first region, and a CNT layer on the self-assembled monolayer. The CNT layer has a density exceeding 1 CNT per square micron. 
     According to a further aspect of the invention, a bi-functional precursor molecule for making self-assembled monolayers is disclosed. A bi-functional precursor molecule includes a first functional group to anchor the monolayer to a substrate and a second functional group having a first ionic charge moiety. The first functional group is selected from the following group: a thiol, an isontrile, a phosphonic acid and a hydroxamic acid. The first ionic charge moiety can be an onium salt including an ammonium salt, a sulfonium salt, and phosphonium salt. 
     Advantages of the present invention include increased density of nanotubes, and reduced formation of multilayer CNTs or bundled CNTs. 
     Another advantage is better electrical performance of a CNTFET. 
     Other characteristics and advantages of the invention will become obvious in combination with the description of accompanying drawings, wherein the same number represents the same or similar parts in all figures. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a flow chart of a method of placing CNTs above a substrate according to an embodiment of the invention; 
         FIG. 2 a    illustrates a cross section of patterned substrate according to an embodiment of the invention; 
         FIG. 2 b    illustrates a top down view of the patterned substrate of  FIG. 2 a    according to an embodiment of the invention; 
         FIG. 3  illustrates bi-functional precursor material forming a self-assembled monolayer on regions of the substrate having a first isoelectric point according to an embodiment of the invention; 
         FIG. 4  illustrates a self-assembled monolayer with a first ionic charge moiety on the first region of the patterned substrate contacting a solution of CNTs having a second ionic charge moiety according to an embodiment of the invention; 
         FIG. 5  illustrates a CNT layer on a self-assembled monolayer formed by a method according to an embodiment of the invention; 
         FIG. 6  is a scanning electron microscope image of substrate with a layer of selectively placed CNTs according to an embodiment of the invention; 
         FIG. 7 a    illustrate a bi-functional precursor group having a first functional group and a second functional group which is an ammonium salt having a first ionic charge moiety according to an embodiment of the invention wherein the first ionic charge moiety is positively charged; 
         FIG. 7 b    illustrate a bi-functional precursor group having a first functional group and a second functional group which is an ammonium salt having a first ionic charge moiety according to an embodiment of the invention wherein the first ionic charge moiety is positively charged; 
         FIG. 7 c    illustrate a bi-functional precursor group having a first functional group and a second functional group which is a pyridinium salt having a first ionic charge moiety according to an embodiment of the invention wherein the first ionic charge moiety is positively charged; 
         FIG. 7 d    illustrate a bi-functional precursor group having a first functional group and a second functional group which is a sulfonium salt having a first ionic charge moiety according to an embodiment of the invention wherein the first ionic charge moiety is positively charged; 
         FIG. 7 e    illustrate a bi-functional precursor group having a first functional group and a second functional group which is a phosphonium salt having a first ionic charge moiety according to an embodiment of the invention wherein the first ionic charge moiety is positively charged; 
         FIG. 8 a    illustrates a first step in the method of forming a CNT having a second ionic charge moiety by functionalizing a CNT according to an embodiment of the invention, in the first step an organic salt is a diazonium salt (R—N2+X—) is combined with a CNT dispersion to form a functionalized CNT shown in  FIG. 8   b;    
         FIG. 8 b    illustrates a second step in a method of forming a CNT having a second ionic charge moiety by functionalizing a CNT according to an embodiment of the invention, in the second step KOH and water are mixed with the functionalized CNT to form the final product shown in  FIG. 8   c.    
         FIG. 8 c    illustrates the final product, the CNT having a second charge moiety, in a method of forming a CNT having a second ionic charge moiety by functionalizing a CNT according to an embodiment of the invention; and 
         FIG. 9  illustrates a method of forming a CNT having a second ionic charge moiety by coating a CNT with an ionic surfactant according to an embodiment of the invention; 
     
    
    
     DETAILED DESCRIPTION 
     The basic principle of the invention is a method for forming a high density monolayer of CNTs on a substrate with little or no bundling. The method, as well as the resulting structure, will be described in conjunction with  FIGS. 1-6 . The invention also includes a bi-functional precursor molecule for self-assembled monolayers used in the method of placing the CNTs on a substrate. An embodiment of the bi-functional precursor is described in conjunction with  FIG. 7 . The invention further includes methods for creating CNTs having a second ionic charge moiety embodiments of which are described in conjunction with  FIGS. 8-9 . A detailed description of the invention is made in combination with the following embodiments. Please note that reference numbers are merely reference numbers and, thus, do not necessarily restrict the method to the numerical order of the reference numbers. 
     Referring to  FIG. 1 , a flow chart of a method of placing CNTs above a substrate according to an embodiment of this invention is given. At reference numeral  10 , a patterned substrate is provided. Patterning the substrate creates a first region and a second region on the substrate. At reference numeral  20 , the patterned substrate is put in contact with a solution containing a precursor. The precursor is bi-functional, meaning it has two functional groups which serve two different purposes. The first functional group serves to anchor the precursor to the substrate and the second functional serves as (first) ionic charge moiety. By contacting the substrate to the precursor solution, the first functional group (the anchoring functional group) forms a bond with first region of the substrate thereby forming a self-assembled monolayer at that region; the second functional group remains in place, thus the monolayer has a first ionic charge moiety. At reference numeral  30 , the substrate with self-assembled monolayer, is put in contact with a dispersion containing CNTs having a second ionic charge moiety. The first and second charge moieties are opposites, thus the CNTs are electrostatically attracted to the self-assembled monolayer having the first ionic charge moiety which results in a layer of CNTs on the self-assembled monolayer. At reference numeral  50 , the substrate is rinsed to leave a CNT layer above the self-assembled monolayer, which in turn is above the first region of the substrate. 
     Referring to  FIG. 2 a   , a patterned substrate  200  is shown in cross-section. The substrate has a base  210 , a first region  220  and a second region  230 . Here, the second region  230  is shown as being higher than the first region  220 , however, the regions could be co-planar or the first region  220  could be higher than the second  230 . Here, the second region  230  is shown to be on top of a portion of the first region  220 . However, the opposite formation could also occur, or the regions could abut each other. Thus, the exact cross-sectional configuration of the regions relative to each other and the base may have many varieties (even beyond those varieties discussed above), of which  FIG. 2 a    is but one embodiment. 
     Referring to  FIG. 2 b   , the same patterned substrate  200  is shown from a top-down perspective. In  FIG. 2 b    the first region  220  is a simple strip that is flanked by the second regions  230 . However, the first and second regions may take on a variety of shapes or configurations. 
     Next, isoelectric properties of the first and second regions are discussed. An isoelectric point is the pH at which a surface carries no net electric charge. In this invention, the first region  220  has a first isoelectric point and the second region  230  has a second isoelectric point. The first and second isoelectric points are different from each other, with the first isoelectric point (i.e. isoelectric point of the first region  220 ) being greater than the second isoelectric point (i.e. isoelectric point of the second region  230 ). Preferably, the difference of the isoelectric point of the first region and that of the second region should be about four or greater. For example, a first region  220  of hafnium oxide having an isoelectric point around 7 and a second region  230  of silicon dioxide having an isoelectric point around 2 results in a difference in the isoelectric points of about 5. 
     Next, materials suitable as first and second regions of the patterned substrate are discussed. In a first embodiment, the first region  220  is a metal oxide and the second region  230  is a non-metal oxide such as, but not limited to, a silicon oxide (SixOzHz). The metal oxide includes at least one metal from group IVB, VB, VIB, VIIB, VIII or IIA (CAS version) of the Periodic Table of the Elements. Illustratively, the metal oxide first region  220  can be an aluminum oxide (Al2O3), a hafnium oxide (HfO2), a titanium oxide (TiOx), or a zinc oxide (ZnO). In a second embodiment, the first region  220  can be any oxide, including non-metal oxides and metal oxides. In the second embodiment, the second region  230  is a metal. Examples of metals for use in the second region include gold, palladium, copper, platinum, etc. 
     Referring to  FIG. 3 , the patterned substrate  200  comes in contact with a solution  240  containing a bi-functional precursor  250  to form a self-assembled monolayer (herein after “SAM”)  265  having a first ionic charge moiety  264 . The precursor  250  is bi-functional, meaning it has two functional groups ( 252 ,  254 ) which, in turn, serve two different purposes. 
     The first functional group  252  serves to anchor the precursor  250  to the first region  220  of the patterned substrate  200 . The second functional group  254  has a first ionic charge moiety  264  which serves to form a bond with a second ionic charge moiety of the CNT later in the process. By contacting the patterned substrate  200  to precursor solution  240 , the first functional group  252  (the anchoring functional group) forms a bond with first region  220  of the substrate thereby forming a self-assembled monolayer  265  having a first ionic charge moiety  264  at the first region  220 . (Specific examples of bi-functional precursors and the first and second functional groups are discussed later). 
     The first ionic charge moiety  264  can be either positively or negatively charged. In a preferred embodiment, the patterned substrate  200  has a hafnium oxide first region  220  and a silicon oxide (SiOx) second region  230 . In a preferred embodiment, the SAM  265  formed on the first region  220  (hafnium oxide) has a positive first ionic charge moiety  264 . As a result, at that point in the particular preferred embodiment, the entire surface of the substrate is now hydrophilic prior CNT layer formation. This is in contrast to prior art methods relying on hydrophilicity and hydrophobicity differences on a substrate surface to determine selectivity of CNT placement. Thus, in the present invention, selectivity is, in part, determined by the isoelectric point difference in the first and second regions of the substrate. 
     Referring to  FIG. 4 , a SAM  265  with a first ionic charge moiety  264  on the first region  220  of the patterned substrate  200 , contacts a solution  270  of CNTs  271  having a second ionic charge moiety  274 . Ways of formation of the CNT having a second ionic charge moiety are discussed later. Coulombic attraction between the oppositely charged first ionic moiety  264  and second ionic moiety  274  bonds  284  the CNT  271  to the SAM  265  in the first region  220  of the substrate (See  FIG. 5 ). The substrate is rinsed in water to form leave a CNT layer  290  selectively formed above the first region  220  of the patterned substrate  200 . The rinsing step removes any excess CNTs to preferably form a monolayer of CNT. The CNTs of the layer  209  may be single walled or multi-walled CNTs. A rinsing step is possible in the present invention method because the bond  284  created between the oppositely charged ions of the CNTs and SAM is stronger than a mere hydrogen bond found in prior are methods. Thus, the bond  284  will not dissociate in water like a hydrogen bond can. 
     An advantage to the present invention that the charge moiety on the CNT is from a charged functionality or charged surfactant around the CNT, as opposed to an induced charge of the nanotube itself. By using a charged functionality or surfactant attached to the CNT, interaction between the CNT and the SAM covered substrate is increased which results in increased CNT density on the desired region of the substrate  200 . 
     Still referring to  FIG. 5 , the CNT layer  290  exhibits a density of CNTs from about 10 CNT/μm2 to about 100 CNT/μm2 and ranges therebetween. The resulting CNT layer  290  exhibits a reduced bundle density of from about 0.1 bundles/μm2 to about 1 bundles/μm2 and ranges therebetween.  FIG. 6  is a scanning electron microscope image of substrate with selectively placed CNTs according to an embodiment of the invention. 
     Next, suitable bi-functional precursors  250  will be discussed. As stated earlier, the bi-functional precursor has a first functional group  252  for anchoring and a second functional group  254  for forming a first ionic charge moiety  264 . The identity of the first functional group (the anchoring group)  252  depends upon the material of the first region  220 . When the first region  220  material is a metal, the first functional group  252  is a thiol (—SH) or an isontrile (—NC). When the first region  220  material is a metal oxide, the first functional group  252  is a phosphonic acid (—PO3H2) or a hydroxamic acid (—CONHOH). 
     Next, the second functional group  254  of the bi-functional precursor  250  will be discussed. The second functional group  254  can be converted to the ionic charge moiety  264  (also referred to as charged ionic moiety in this application). The second functional group  254  can be converted to ionic charge moiety  264  either (1) before the precursor  250  anchors itself to the substrate to form a self-assembled monolayer, or (2) after the precursor  250  anchors itself to the substrate to form a self-assembled monolayer. In the first case, the self-assembled monolayer, as formed, has a first charge moiety  264 . In the second case, initially the self-assembled monolayer is uncharged, and must be converted to a SAM having a first ionic charge. 
     Referring to  FIGS. 7 a - e   , examples of bi-functional precursors  250  in which the second functional group  254  has been converted to a first ionic charge moiety  264  having a positive charged. All the bi-functional precursors  250  have an “R” group on the bottom which represents the first functional group  252  (i.e. the anchoring group) previously described. In  FIGS. 7 a - e   , the first ionic charge moieties  264  are all positively charged onium salts. Specifically,  FIGS. 7 a - b    illustrate ammonium salts,  FIG. 7 c    is an example of pyridinium salt,  FIG. 7 d    is a sulfonium salt, and  FIG. 7 e    is a phosphonium salt. Continuing, in  FIGS. 7 a  and 7 b   , “n” represents an integer from 2 to 16; in  FIG. 7 b    “Z” represents a single bond, oxygen, NH or sulfur; in  FIGS. 7 a , 7 b , 7 c  and 7 d   , “R1”, “R2”, and “R3” can independently be hydrogen, or an alkly group of one to ten carbons; in  FIG. 7 e    “Ar1”, “Ar2”, and “Ar3” can independently be phenyl or substituted phenyl rings; and in all  FIG. 7 , “X” is a halogen. The ammonium salts pictured in  FIGS. 7 a - b    are superior to a diazonium salt (—N2+) because a diazonium salt will form a covalent bond with a CNT (whether the CNT has a partial charge or full ionic charge). Covalent bonds degrade the electrical performance of a CNT in transistor and other electronic applications. 
     Second functional groups  254  that can be converted to positively charged moieties of  FIG. 7  are as follows: ammoniums salts ( FIGS. 7 a  and  b   ) can be made by reacting an amine with acids; pyridinium salt ( FIG. 7 c   ) can be made by reacting pyridine with alkyl halides; sulfonium salt ( FIG. 7 d   ) can be made by reacting sulfides with alkyl halides; and phosphonium salt ( FIG. 7 e    can be made by reacting triarylphosphines with alkyl halides. 
     While  FIGS. 7 a - e    illustrate examples of a first ionic charge moiety  264  having a positive charge, a bi-functional precursor  250  having a negatively charged first ionic charge moiety  264  is also within the scope of the present invention. In the case of a negatively charged first ionic moiety, the bi-functional molecules are the same as  FIGS. 7 a - e    with the exception that the positive charge moieties  264  are substituted with negative charged moieties such as —COO— or Ar—O—. Examples of second functional groups  254  that can be converted to negatively charged moieties  264  are carboxylic esters such as —COOCH3, and phenols. These groups are converted to the negatively charged moieties  264  by reacting with a strong base such as KOH to yield —COO— or Ar—O—, respectively. 
     Next, the term “ionic charge moiety” will be discussed. A moiety is a part of a molecule which has a charge. In the present invention, a charge is formed because one molecule takes an electron, or pair of electrons, from another; meaning the charge moiety is ionic. The ionically charged molecule of the present invention should be contrasted to a polar molecule (such as those found in water, —NH2, —NHNH2, —ONH2, —ONHOH, and —CONHO—). Polar molecules are molecules which have uneven electron distribution in a molecule. Because polar molecules have an uneven electron distribution, an atom in the molecule is sometimes referred to as partially charged or is said to have a dipole moment. However, the weak bonds which result from oppositely (partially) charged dipole-dipole attractions, should not be confused with the stronger bonds resulting from the attraction of oppositely charged ions of the present invention. 
     The discussion returns to the two ways of creating the second ionic charge moiety  274  on the CNTs  271 . Functionalization, the first way of creating the second ionic charge moiety  274  on the CNT can be accomplished by mixing an aryl diazonium salt with a CNT dispersion to form a CNT covalently bonded to an organic compound having a functional group. The CNT with functional group is then placed in an aqueous strong base solution to convert the functional group to the second ionic charge moiety  274 . Examples of strong bases include, but are not limited to, LiOH, NaOH, RbOH, CsOH, Ca(OH)2, Sr(OH)2, Ba(OH)2, and KOH, which is preferred. 
     Referring to  FIGS. 8 a - c   , a specific example of functionalizing a CNT to form a negatively charged ionic moiety  274  is shown. In  FIG. 8 a   , the organic salt is a diazonium salt (R—N2+X—) which is combined with a CNT  271  dispersion. Here, “R” of the diazonium salt is methyl benzoate. The salt bonds covalently with the CNT to form a CNT  271  having a functional group (i.e. a “functionalized CNT”) in  FIG. 8 b   . Continuing with  FIG. 8 b   , KOH and water are mixed with the functionalized CNT to convert a portion of the functional group (here, the carboxylic ester —COOCH3) to the second ionic charge moiety  274  (here, —COO—). 
     A specific example of functionalizing a CNT to form a positively charged ionic moiety  274  is not shown in  FIGS. 8 a - c   , however, a pyridine diazonium salt can be mixed with a CNT dispersion to form a functionalized CNT. Then the functionalized CNT is treated either with an acid to form pyridinium salt or with an alkyl halide (for example, but not limited to methyl iodide) to form N-alkylpyridinium halide. The treatments convert a portion of the functional group (here, pyridine) to the second ionic charge moiety  274  (here, CH3-X+). 
     Referring to  FIG. 9 , coating, the second way of creating the second ionic charge moiety  274  is shown. Coating on the CNT can be accomplished by mixing CNTs  271  with a solution of an ionic surfactant  276  having the second charged ionic moiety  274 . In  FIG. 9 , a water dispersion containing CNTs  271  is mixed with ionic surfactants  276 . Some of the ionic surfactant  276  material forms a monolayer around the CNTs as shown in  FIG. 9  as CNTs  271  with an overlapping ionic surfactant  276 . The solution containing the CNT dispersion and ionic surfactant under goes dialysis in pure water to remove any excess ionic surfactant. By removing the excess ionic surfactant  276 , the placement yield of the CNTs having a second ionic charge moiety on the SAM having a first ionic charge moiety increases because there is less likelihood that a SAM site will be occupied by an ionic surfactant  276  which is not associated with a CNT  271 . 
     The second ionic charge moiety  274  will be oppositely charged from the first charged ionic moiety  264 . Therefore, if the first ionic charge moiety  264  is positive, the ionic surfactant  276  will be anionic; if the first ionic charge moiety  264  is negative, the ionic surfactant  276  will be cationic. Examples of anionic surfactants include, but are not limited to DNA, sodium dodecyl sulfate and sodium cholate, in addition some lipids and phospholipids are useful as anionic surfactants. Examples of cationic surfactants include, but are not limited to, cetytlpyridinium chloride, diemthyldioctadecylammonium chloride. 
     The surfactants may be made ionic prior to coating the CNTs  271  or after coating the CNT  271 . For example, the anionic surfactants can be prepared by treating their acid form with base and the cationic surfactants can be prepared by treating tertiary amines with alkyl halides. 
     An advantage of the present invention is that a bond  284  between a two charged molecules is stronger than a charge between a polar molecule and a CNT. Furthermore, the first ionic charge moieties  264  disclosed are superior to alternative moieties (for example, Ar—N2+) because the current first ionic charge moieties do not from covalent bonds with the CNT like Ar—N2+ does. In some cases, covalent bonds to a CNT may interfere with the electronic properties of the CNT. One electrical property of a CNT field effect transistor is its transfer characteristic (Id(A) vs. Vg(V)). A low ON current equates to poor performance and is an indicator of a covalent bond to the CNT. A higher ON current (10-7 A or more) indicates return of the lattice of the CNT and thus, no to minimal covalent bonding. 
     Next, example embodiments of the present invention are given. 
     Example I—Positively charged bi-functional precursor molecules for self-assembly. Potassium cyanide (50 mg) was added to a solution of methyl isonicotinate (1.17 g, 0.01 mole) and 50% hydroxylamine in water (1.3 g, 0.02 mole) in 10 mL tetrahydrofuran and 5 mL methanol. After stirring the mixture at room temperature for 18 hours, the precipitate was filtered and washed with diethyl ether and dried to give analytically pure N-hydroxy isonicotinamide. The latter was added to 5% methyl iodide in methanol and stirred at room temperature for two days. Methanol was evaporated under reduced pressure and the solid residue was crystallized from ethanol resulting in pure 4-hydroxamido-N-methylpyridinium iodide. 
     Example II—Preparation of negatively-charged CNTs by functionalization Nitrosonium tetrafluoroborate (12 mg, 1 mmole) was added to a suspension of methyl 4-aminobenzoate (15 mg, 1 mmole) in 5 mL of acetonitrile. The resulting solution was added drop-wise to an aqueous suspension of single-walled carbon nanotubes (1 mg) in water containing 1% sodium dodecylsulfate. After standing for 18 hours, the solution was centrifuged and the sediments were added to 10 mL of 10% methanolic potassium hydroxide solution. After stirring for 4 hours, 20 mL of acetone was added and the mixture centrifuged. The supernatant liquid was discarded and the sediment was dissolved in de-ionized water resulting in an aqueous solution of negatively charged carbon nanotubes. 
     Example III—Preparation of an aqueous dispersion of CNTs coating in with a monolayer of anionic surfactant. Dispersion of carbon nanotubes in 1% sodium dodecylsulfate was dialyzed with pure water for several days, during which fresh water was used after 24 hours. After several times dialyzing with fresh water, the solution inside the filter contains no free surfactant and all surfactants are attached to carbon nanotubes. 
     Example IV—Selective placement of carbon nanotubes. A silicon substrate patterned with silicon oxide regions and hafnium oxide regions was immersed in a 2 mM solution of 4-hydroxamido-N-methylpyridinium iodide in ethanol. After one hour, the substrate was removed from the solution and rinsed with copious amount of ethanol and dried under stream of nitrogen. The substrate, now coated with a positively charged ionic monolayer on the hafnium oxide, was then immersed in a solution of negatively charged (ionic, not dipole) functionalized nanotubes of example II. After one hour, the substrate was removed and washed thoroughly with de-ionized water and dried under stream of nitrogen. Scanning electron microscopy ( FIG. 9 ) of the substrate showed selectively placed high density of carbon nanotubes on regions of hafnium oxide. 
     While the present invention has been described with reference to what are presently considered to be the preferred embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, the invention is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The scope of the following claims is to be accorded the broadcast interpretation so as to encompass all such modifications and equivalent structures and functions.