METHODS FOR FORMING A FIELD EMISSION CATHODE

Abstract

A method for fabricating an electron field emission cathode, the field emission cathode including a substrate having a field emission material layer engaged therewith, where the field emission material incorporates a carbon nanotube material and a metal oxide. The field emission material is produced via a sol-gel process to improve field emission characteristics of the field emission cathode and field emission cathode devices implementing such cathodes.

Claims

1. A method of forming a field emission cathode, comprising: mixing a plurality of carbon nanotubes and a solution at a particular ratio to form a base mixture, the solution comprising a water stable conducting polymer in a liquid medium; exposing the base mixture to an ultrasonic dispersion process at a power of greater than 1 W/cm.sup.2 and at a frequency of 20-50 kHz; introducing a metal oxide sol solution to the base mixture to form a field emission material precursor; exposing the field emission material precursor to an ultrasonic dispersion process at a power of less than 1 W/cm.sup.2 and at a frequency of greater than 50 kHz to form a stable solution of the field emission material precursor; introducing a polar additive into the stable solution of the field emission material precursor to form a final sol solution as a final field emission material precursor; depositing a layer of the final field emission material precursor on at least a portion of a substrate; drying the layer of the final field emission material precursor and the substrate at a temperature of 30 C. to 150 C. at atmosphere or under a vacuum such that the layer of the final field emission material precursor forms a uniform gel layer on the substrate; annealing the gel layer and the substrate at a temperature of 500 C. to 1000 C. under a vacuum such that the gel layer forms a field emission material; and activating the field emission material to form the field emission cathode.

2. The method of claim 1, wherein mixing the plurality of carbon nanotubes and the solution comprises mixing the plurality of carbon nanotubes and the solution comprising a poly(3,4-ethylendioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) polymer and the liquid medium.

3. The method of claim 2, wherein mixing the plurality of carbon nanotubes and the solution comprises mixing the plurality of carbon nanotubes and the PEDOT:PSS solution such that the particular ratio of carbon nanotubes to PEDOT:PSS polymer solution is from 10:1 to 1:10 by weight.

4. The method of claim 1, wherein mixing the plurality of carbon nanotubes and the solution comprises mixing the plurality of carbon nanotubes and the solution, with the liquid medium of the solution comprising water.

5. The method of claim 1, wherein depositing the layer of the final field emission material precursor on the substrate comprises depositing the layer on to the substrate via dip-coating, spin-coating, air knife coating, gravure coating, slot die coating, inkjet printing, spray coating, Meyer bar coating, lithography coating, flexography coating, or combinations thereof.

6. The method of claim 1, wherein introducing the metal oxide sol solution to the base mixture comprises introducing the metal oxide sol solution selected from the group consisting of aluminum oxide (Al.sub.2O.sub.3), silicon dioxide (SiO.sub.2), titanium dioxide (TiO.sub.2), zinc oxide (ZnO), magnesium oxide (MgO), barium oxide (BaO), lead dioxide (PbO.sub.2), zirconium dioxide (ZrO.sub.2), molybdenum dioxide (MoO.sub.2), copper oxide (CuO), vanadium pentoxide (V.sub.2O.sub.5), tin dioxide (SnO.sub.2), indium tin oxide (ITO), indium zinc oxide (IZO), and aluminum zinc oxide (AZO), or a combination thereof.

7. The method of claim 1, wherein introducing the polar additive into the stable solution comprises introducing the polar additive, selected from the group consisting of an alcohol, a polyol, ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol, dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), Dimethylsulfone (DMSO.sub.2), N-methyl-2-pyrrolidone (NMP), an ionic liquid, or combinations thereof, into the stable solution.

8. The method of claim 1, wherein depositing the layer of the final field emission material precursor on the substrate comprises depositing the layer of the final field emission material precursor on the substrate comprising a metal, stainless steel, an alloy, a conductive glass, or a ceramic.

9. The method of claim 1, wherein activating the layer of the field emission material comprises: applying an adhesive tape to a surface of the field emission material; and removing the adhesive tape from the surface.

10. The method of claim 1, wherein activating the layer of the field emission material comprises: applying a curable adhesive to a surface of the field emission material; exposing the adhesive to a heat source or an ultraviolet light to cure the adhesive and form the adhesive into an adhesive film; and removing the adhesive film from the surface.

11. A method of forming a field emission material precursor, comprising: introducing a plurality of carbon nanotubes into a liquid medium; introducing a water stable conducting polymer into the liquid medium comprising the plurality of carbon nanotubes, wherein the plurality of carbon nanotubes is present at a particular ratio to a solution comprising the liquid medium and the polymer; mixing the plurality of carbon nanotubes and the water stable conducting polymer in the liquid medium via an ultrasonic dispersion process at a power of greater than 1 W/cm.sup.2 and at a frequency of 20-50 kHz to form a base mixture; introducing a metal oxide sol solution into the base mixture; exposing the base mixture including the metal oxide sol solution to an ultrasonic dispersion process at a power of less than 1 W/cm.sup.2 and at a frequency of greater than 50 kHz to form a stable solution of a field emission material precursor; and introducing a polar additive into the stable solution of the field emission material precursor to form a final field emission material precursor.

12. The method of claim 11, wherein introducing the plurality of carbon nanotubes into the liquid medium comprises introducing the plurality of carbon nanotubes into water.

13. The method of claim 11, wherein introducing the water stable conducting polymer comprises introducing a poly(3,4-ethylendioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) polymer into the liquid medium.

14. The method of claim 13, wherein mixing the plurality of carbon nanotubes and the solution comprises mixing the plurality of carbon nanotubes and the PEDOT:PSS solution such that the particular ratio of carbon nanotubes to PEDOT:PSS solution is from 10:1 to 1:10 by weight.

15. The method of claim 11, wherein introducing the metal oxide sol solution to the base mixture comprises introducing the metal oxide sol solution selected from the group consisting of aluminum oxide (Al.sub.2O.sub.3), silicon dioxide (SiO.sub.2), titanium dioxide (TiO.sub.2), zinc oxide (ZnO), magnesium oxide (MgO), barium oxide (BaO), lead dioxide (PbO.sub.2), zirconium dioxide (ZrO.sub.2), molybdenum dioxide (MoO.sub.2), copper oxide (CuO), vanadium pentoxide (V.sub.2O.sub.5), tin dioxide (SnO.sub.2), indium tin oxide (ITO), indium zinc oxide (IZO), an Azo compound, or a combination thereof.

16. The method of claim 11, wherein introducing the polar additive into the stable solution comprises introducing the polar additive, selected from the group consisting of an alcohol, a polyol, ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol, dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), Dimethylsulfone (DMSO.sub.2), N-methyl-2-pyrrolidone (NMP), an ionic liquid, or combinations thereof, into the stable solution.

17. A method of forming a field emission cathode, comprising: depositing the final field emission material precursor of claim 11 on at least a portion of a substrate; drying the final field emission material precursor and the substrate at a temperature of 30 C. to 150 C. at atmosphere or under a vacuum such that the final field emission material precursor forms a layer on the substrate; annealing the layer and the substrate at a temperature of 500 C. to 1000 C. under a vacuum such that the layer forms a field emission material; and activating the field emission material to form the field emission cathode.

18. The method of claim 17, wherein depositing the final field emission material precursor on the at least a portion of the substrate comprises depositing the final field emission material precursor on the at least a portion of the substrate comprising a metal, stainless steel, an alloy, a conductive glass, or a ceramic.

19. The method of claim 17, wherein depositing the final field emission material precursor on the at least a portion of the substrate comprises depositing the final field emission material precursor on the at least a portion of the substrate via dip-coating, spin-coating, air knife coating, gravure coating, slot die coating, inkjet printing, spray coating, Meyer bar coating, lithography coating, flexography coating or combinations thereof.

20. The method of claim 17, wherein activating the field emission material comprises: applying an adhesive tape to a surface of the field emission material; and removing the adhesive tape from the field emission material.

21. The method of claim 17, wherein activating the field emission material comprises: applying a curable adhesive to a surface of the field emission material; exposing the adhesive to a heat source or an ultraviolet light to cure the adhesive and form the adhesive into an adhesive film; and removing the adhesive film from the surface.

22. (canceled)

Description

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING(S)

[0034] Having thus described the disclosure in general terms, reference will now be made to the accompanying drawings, which are not necessarily drawn to scale, and wherein:

[0035] FIG. 1 schematically illustrates an example of a field emission cathode and the nature of the field emission material deposition layer engaged with the cathode substrate, according to one or more aspects of the present disclosure;

[0036] FIG. 2 illustrates one example of a method of forming a field emission material precursor, according to one or more aspects of the present disclosure; and

[0037] FIG. 3 illustrates one example of a method of forming a field emission cathode, according to one or more aspects of the present disclosure.

DETAILED DESCRIPTION OF THE DISCLOSURE

[0038] The present disclosure now will be described more fully hereinafter with reference to the accompanying drawings, in which some, but not all aspects of the disclosure are shown. Indeed, the disclosure may be embodied in many different forms and should not be construed as limited to the aspects set forth herein; rather, these aspects are provided so that this disclosure will satisfy applicable legal requirements. Like numbers refer to like elements throughout.

[0039] FIG. 1 illustrates one example of a field emission cathode 100 that includes a substrate 102 and a layer of a field emission material 104 disposed on the substrate 102, and, if necessary, an additional layer of an adhesion material (not shown) disposed between the substrate 102 and the field emission material 104. The substrate 102 may be made of an electrically conductive material, such as a metallic material, such as a solid metal or alloy (e.g., stainless steel, doped silicon), conductive glass (e.g., Indium Tin Oxide (ITO) coated glass or other fused glass having a conductive coating on the surface); or a conductive ceramic (e.g., a metalized ceramic, such as aluminum oxide, beryllium oxide, and aluminum nitride). The field emission material 104 includes a plurality of carbon nanotubes (CNT) disposed within a matrix material. Typical CNT/matrix field emission materials have a high surface roughness, for example, surfaces with emitters disposed on different height layers across the surface of the cathodes and contamination of the emitters disposed on the lower height layers, because many loose particles are not removed therefrom during the activation process.

[0040] By forming the layer of field emission material 104 via a sol-gel process and incorporating a metal oxide sol solution results in a gel layer of a CNT/PEDOT:PSS/metal oxide matrix in a nanometer composite structure, which is uniform in texture, formed on the surface of the substrate 102. After drying, annealing, and activation, a field emission cathode is obtained with less roughness of the field emission material layer and the characteristics of high emitter density, high emission current, low turn on voltage and long lifetime. In particular, the incorporation of the metal oxide sol solution, instead of matrix particles, results in a homogeneous precursor solution that can be deposited on the surface of a substrate. The deposition of the field emission material on to the substrate 102 may be carried out via any of the coating processes disclosed herein. After activation, the surfaces of the cathodes have low surface roughness (e.g., less variation of emitter heights and most of the loose particles removed. The two layers (high roughness layer 104 and low roughness layer 104) are depicted in FIG. 1 for comparative purposes.

[0041] Thus, the cathodes have not only high density and uniformity of emitters but also improved field emission properties with low batch to batch variation that can meet requirements of large production for industrial applications. FIG. 2 illustrates a method 200 of forming a field emission material precursor including carbon nanotubes and a metal oxide. In one aspect of the method, a liquid medium, such as water, is provided (step 210) into which a plurality of carbon nanotubes and a poly(3,4-ethylendioxythiophene)-poly(styrene sulfonic acid) (PEDOT:PSS) polymer are introduced at a particular ratio, such as, for example, a ratio of the plurality of carbon nanotubes to a solution comprising the liquid medium and the polymer that ranges from about 10:1 to about 1:10 by weight (step 220). In some embodiments, other liquid mediums comprising a water stable conducting polymer may be used. At step 230, the plurality of carbon nanotubes and the PEDOT:PSS solution are mixed via a strong ultrasonic dispersion process to form a base mixture. The mixing may be carried out at low frequency (20-50 kHz) and high power (>1 W/cm.sup.2) for a period of time ranging from about 1 min to about 30 min. Next, a metal oxide sol solution is introduced into the base mixture (step 240) to form a modified base mixture. The modified base mixture (i.e., with the inclusion of the metal oxide sol) is exposed to a mild ultrasonic dispersion process to form a stable solution of the field emission material precursor (i.e., a homogenous precursor sol) (step 250). The mild ultrasonic dispersion process may be carried out at high frequency (>50 kHz) low power (<1 W/cm.sup.2) and for a period of time ranging from about 30 minutes to about 24 hours. At step 260, a polar additive is introduced to the stable solution to form a final sol solution as a final field emission material precursor. In various embodiments, the final field emission material precursor may include the carbon nanotubes, the PEDOT:PSS, the metal oxide sol, and one or more additives.

[0042] The specific composition and quantities of the components may vary to suit a particular application. For example, in some embodiments, the metal oxide sol solution comprises, for example, aluminum oxide (Al.sub.2O.sub.3), silicon dioxide (SiO.sub.2), titanium dioxide (TiO.sub.2), zinc oxide (ZnO), magnesium oxide (MgO), barium oxide (BaO), lead dioxide (PbO.sub.2), zirconium dioxide (ZrO.sub.2), molybdenum dioxide (MoO.sub.2), copper oxide (CuO), vanadium pentoxide (V.sub.2O.sub.5), tin dioxide (SnO.sub.2), indium tin oxide (ITO), indium zinc oxide (IZO), and aluminum zinc oxide (AZO) The metal oxide sol may be dispersed into the base mixture at about to about 20 wt % of total liquid medium. In various embodiments, the polar additive may include one or more of alcohols, polyols, such as ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol, dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), Dimethylsulfone (DMSO.sub.2), N-methyl-2-pyrrolidone (NMP), an ionic liquid, or combinations thereof. The concentration of the polar additive may be about 0.1 wt % to about 20 wt % of total liquid medium. The carbon nanotubes may be manufactured by a chemical vapor deposition process, a laser ablation process, and/or an arc discharge method.

[0043] Once the final field emission material precursor has been created in a stable sol solution, the final field emission material precursor may be deposited on at least a portion of the substrate (step 270). The layer of the final field emission material precursor is deposited on to the substrate via dip-coating, spin-coating, air knife coating, gravure coating, slot die coating, inkjet printing, spray coating, Meyer bar coating, lithography coating, flexography coating, or combinations thereof. The substrate may comprise a metal, stainless steel, an alloy, a conductive glass, or a ceramic. The substrate may be provided to the appropriate equipment via, for example, a robotic material handling system or manually by a user. The substrate is configured to receive a layer of the final field emission material precursor thereon.

[0044] The sol layer may be subjected to one or more other processes after deposition on the substrate, such as drying, annealing, and activating processes. After drying, a uniform gel layer of a CNT/PEDOT:PSS/metal oxide matrix material is formed from the sol layer on the surface of the substrate, which is then annealed. The field emission cathode is formed after activating the deposition layer on the substrate to form the field emission material.

[0045] FIG. 3 illustrates a method 300 of forming a field emission cathode using a field emission material comprising carbon nanotubes and a metal oxide. In one aspect of the method, a substrate, such as those described hereinabove, is provided to equipment configured for carrying out a deposition process (step 310). The method further includes forming a field emission material from a field emission material precursor (step 320). In some cases, the field emission material is created as a field emission material precursor prior to the substrate being provided, e.g., as the final field emission material precursor disclosed herein. A layer of the final field emission material precursor is deposited on to at least a portion of the substrate (step 330). The substrate may be made of a metal, such as stainless steel, an alloy, a conductive glass, or a metalized ceramic. The substrate may be provided to the appropriate equipment via, for example, a robotic material handling system or manually by a user.

[0046] The substrate and the layer of final field emission material precursor deposited thereon is then exposed to a drying process (step 340) and an annealing process (step 350) to form the field emission material. The drying process may be carried out at a temperature of about 30 C. to about 150 C. at atmosphere or under a vacuum. The annealing process may be carried out at a temperature of about 500 C. to about 1000 C. under a vacuum. At step 360, the layer of the field emission material is activated to obtain the field emission cathode. Activation may be carried out by applying an adhesive (e.g., an adhesive tape or a curable adhesive material) on to a surface of the layer of the field emission material and removing the adhesive from the layer of the field emission material.

[0047] Step 370 illustrates one example of a method of forming a field emission material precursor. At step 370, a plurality of carbon nanotubes and a PEDOT:PSS polymer are mixed into a liquid medium, such as water, at a particular ratio (e.g., from about 1:10 to about 10:1 by weight) of the plurality of carbon nanotubes to a solution comprising the liquid medium and the polymer. The components can be mixed via a strong ultrasonic dispersion process to form a base mixture, as described above. Next, a metal oxide sol solution is dispersed within the base mixture. The modified base mixture can be exposed to a mild ultrasonic dispersion process to form a stable suspension of the field emission material precursor, as described above. Next, a polar additive is added to the stable solution to form a final sol solution as a final field emission material precursor. In various embodiments, the final field emission material precursor may include the carbon nanotubes, the PEDOT:PSS, the metal oxide sol, and one or more additives.

[0048] The specific composition and quantities of the components may vary to suit a particular application. For example, in some embodiments, the metal oxide sol solution comprises, for example, aluminum oxide (Al.sub.2O.sub.3), silicon dioxide (SiO.sub.2), titanium dioxide (TiO.sub.2), zinc oxide (ZnO), magnesium oxide (MgO), barium oxide (BaO), lead dioxide (PbO.sub.2), zirconium dioxide (ZrO.sub.2), molybdenum dioxide (MoO.sub.2), copper oxide (CuO), vanadium pentoxide (V.sub.2O.sub.5), tin dioxide (SnO.sub.2), indium tin oxide (ITO), indium zinc oxide (IZO), an Azo compound, or combinations thereof. The metal oxide sol may be dispersed into the base mixture at about 0.1 wt % to about 20 wt % of total liquid medium. In various embodiments, the polar additive may include one or more of alcohols, polyols, such as ethylene glycol, glycerol, meso-erythritol, xylitol, and D-sorbitol, dimethylformamide (DMF), Dimethyl sulfoxide (DMSO), Dimethylsulfone (DMSO.sub.2), N-methyl-2-pyrrolidone (NMP), an ionic liquid, or combinations thereof. The concentration of the polar additive may be about 0.1 wt % to about 20 wt % of total liquid medium. The carbon nanotubes may be manufactured by a chemical vapor deposition process, a laser ablation process, and/or an arc discharge method.

[0049] The foregoing methods provide for a CNT/PEDOT:PSS/metal oxide matrix material layer in a nanometer composite structure, which is uniform in texture when formed on the surface of a substrate. After drying and annealing in a vacuum, the resulting field emission cathode is activated. The formed field emission material layer of the cathode has a low roughness surface with the characteristics of high emitter density, high emission current, low turn on voltage and long lifetime. The batch to batch variation of cathodes is significantly decreased, which is important for industrialized production and application.

[0050] Many modifications and other embodiments of the inventions set forth herein will come to mind to one skilled in the art to which these disclosed embodiments pertain having the benefit of the teachings presented in the foregoing descriptions and the associated drawings. Therefore, it is to be understood that embodiments of the invention are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the invention. Moreover, although the foregoing descriptions and the associated drawings describe example embodiments in the context of certain example combinations of elements and/or functions, it should be appreciated that different combinations of elements and/or functions may be provided by alternative embodiments without departing from the scope of the disclosure. In this regard, for example, different combinations of elements and/or functions than those explicitly described above are also contemplated within the scope of the disclosure. Although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

[0051] It should be understood that although the terms first, second, etc. may be used hereinto describe various steps or calculations, these steps or calculations should not be limited by these terms. These terms are only used to distinguish one operation or calculation from another. For example, a first calculation may be termed a second calculation, and, similarly, a second step may be termed a first step, without departing from the scope of this disclosure. As used herein, the term and/or and the I symbol includes any and all combinations of one or more of the associated listed items.

[0052] As used herein, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises, comprising, includes, and/or including, when used herein, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Therefore, the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.