METHOD FOR MAKING CARBON NANOTUBE-BASE DEVICE
A method for making a carbon nanotube-based device is provided. A substrate having a shadow mask layer to define an unmasked surface area thereon is provided. A sputter source is disposed on the shadow mask layer. The sputter source is configured for supplying a catalyst material and depositing the catalyst material onto the substrate. A catalyst layer including at least one catalyst block is formed on the substrate. A thickness of the at least one catalyst block is gradually decreased from one end to another opposite end thereof. The at least one catalyst block has a region with a thickness proximal or equal to an optimum thickness. A carbon source gas is introduced. At least one carbon nanotube array extending from the catalyst layer using a chemical vapor deposition process is formed. The at least one carbon nanotube array is arc-shaped, and bend in a direction of deviating from the region.
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This application is related to one copending U.S. patent application entitled “METHOD FOR MAKING CARBON NANOTUBE-BASED DEVICE”, concurrently filed here with (Docket No. US7938), and having the same assignee as the instant application. The disclosure of the above-indentified application is incorporated herein by reference.
TECHNICAL FIELDThe present invention generally relates to a method for making a carbon nanotube-based device.
BACKGROUNDCarbon nanotubes are very small tube-shaped structures essentially having the composition of a graphite sheet, formed as a tube. Carbon nanotubes produced by arc discharge between graphite rods were first discovered and reported in an article by Sumio Iijima entitled “Helical Microtubules of Graphitic Carbon” (Nature, Vol. 354, Nov. 7, 1991, pp. 56-58). Carbon nanotubes have very good electrical conductance due to their structure. They are also chemically stable, and have very small diameters (less than 100 nanometers) and large aspect ratios (length/diameter). Due to these and other properties, it has been suggested that carbon nanotubes can play an important role in fields such as microscopic electronics, materials science, biology and chemistry.
Although carbon nanotubes promise to have a wide range of applications, better control is needed over the building and organization of nanotube-based architectures. Normally, the orientation of growing nanotubes is controlled such that the nanotubes are rectilinear and parallel to each other. Chemical vapor deposition has been used to produce nanotubes vertically aligned on catalyst-printed substrates.
There have been reports of growth of aligned carbon nanotubes using chemical vapor deposition, for instance, Z. F. Ren et al. entitled “Synthesis of large arrays of well-aligned carbon nanotubes on glass” (Science, Vol. 282, Nov. 6, 1998, pp. 1105-1107), S. S. Fan et al. entitled “Self-oriented regular arrays of carbon nanotubes and their field emission properties” (Science, Vol. 283, Jan. 22, 1999, pp. 512-514), B. Q. Wei et al. entitled “Organized assembly of carbon nanotubes” (Nature, Vol. 416, Apr. 4, 2002, pp. 495-496), Yoon-Taek Jang et al. entitled “Lateral growth of aligned mutilwalled carbon nanotubes under electric field” (Solid State Communications, Vol. 126, 2003, pp. 305-308), and Ki-Hong Lee et al. entitled “Control of growth orientation for carbon nanotubes” (Appl. Phys. Lett., Vol. 82, Jan. 20, 2003, pp. 448-450).
However, carbon nanotubes obtained by the above-mentioned methods are aligned along a linear direction, and/or extend perpendicularly from the substrates. Furthermore, the method of using an external field such as an electric field or a magnetic field, to control a direction of growth of the carbon nanotubes is difficult to apply in generating localized complicated structures with plural orientations of the carbon nanotubes. Accordingly, the range of diversity of different kinds of carbon nanotube-based devices is limited.
What is needed is to provide a method for making a carbon nanotube-based device with plural orientations of carbon nanotubes.
SUMMARYIn a preferred embodiment, a method for making a carbon nanotube-based device is provided. The method includes the following steps of: providing a substrate having a shadow mask layer formed thereon, the shadow mask layer being configured for defining an unmasked surface area on the substrate; disposing a sputter source on the shadow mask layer, the sputter source being configured for supplying a catalyst material and depositing the catalyst material onto the substrate; forming a catalyst layer including at least one catalyst block on the unmasked surface area of the substrate, a thickness of the at least one catalyst block being gradually decreased from a first end thereof to an opposite second end thereof, and the at least one catalyst block having a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest; introducing a carbon source gas; and forming at least one carbon nanotube array extending from the catalyst layer using a chemical vapor deposition process, wherein the at least one carbon nanotube array being arc-shaped, and bending in a direction of deviating from the region.
Theoretically, the growth rate of carbon nanotubes is associated with a thickness of the catalyst layer used to grow them on. Under certain conditions for growing carbon nanotubes by a chemical vapor deposition process, the carbon nanotubes grow fastest when the catalyst layer has a certain optimum thickness. In particular, when the thickness of the catalyst layer is greater than the optimum thickness, the thicker the catalyst layer, the slower the growth rate of carbon nanotubes; when the thickness of the catalyst layer is less than the optimum thickness, the thinner the catalyst layer, the slower the growth rate of carbon nanotubes. If the thickness of the catalyst layer is deliberately controlled, so that the thickness gradually varies from a first end to an opposite second end, and somewhere the catalyst layer has a thickness proximal or equal to the optimum thickness for growing carbon nanotube; additionally, carbon nanotubes have inherently strong Van der Waals force interactions therebetween. Thereby, a carbon nanotube-based device with plural orientations of carbon nanotubes is obtainable.
Other advantages and novel features will become more apparent from the following detailed description of embodiments when taken in conjunction with the accompanying drawings.
The components in the drawings are not necessarily to scale, the emphasis instead being placed upon clearly illustrating the principles of the present method for making a carbon nanotube-based device. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
The exemplifications set out herein illustrate at least one preferred embodiment, in one form, and such exemplifications are not to be construed as limiting the scope of the present method for making a carbon nanotube-base device in any manner.
DETAILED DESCRIPTION OF THE EMBODIMENTS Embodiment 1Referring to
A shadow mask layer 40 is formed on the substrate 10 and located at one end portion thereof to define an unmasked surface area 12 of the substrate 10 to be exposed. The shadow mask layer 40 is usually made from photo-resist, metal, metallic oxide, or metallic nitride. The shadow mask layer 40 has a suitable height (as denoted by h in
where, d is a diameter of the catalyst atom, p is an operating pressure of the sputter-deposition process, k is the Boltzmann constant (1.38066×10−23 J/K (Joule per kelvin)), T is an operating absolute temperature of the sputter-deposition process. For example, when the T≈273.15 kelvin, p=1 pascal; the mean free path S of a catalyst iron atom is approximately equal to 13.5×10−3 meters.
The sputter source 20 is configured for supplying a catalyst material and depositing the catalyst material onto the substrate 10, so as to form a catalyst layer having a gradient thickness via a sputter-deposition process. The catalyst material is usually selected from iron (Fe), cobalt (Co), nickel (Ni), or alloys thereof. Generally, a distance from the sputter source 20 to the substrate 10 is greater than the mean free path of a catalyst atom generated from the sputter source 20 under a predetermined sputter-deposition process. The sputter source 20 usually includes a surface sputter target made from a catalyst material, or a linear sputter target made from a catalyst material. In the case of the sputter source 20 having a linear sputter target, an optimum solution is that a reciprocating movement of the substrate 10 relative to the sputter source 20 along a direction perpendicular to the linear sputter target is implemented. In the illustrated embodiment, the sputter source 20 has a surface sputter target.
Referring to
Generally, a thickness T(λ) of a position of the catalyst layer 30 distant from the shadow mask layer 40 with a distance of λ approximately satisfies the following condition (2):
T(λ)=T0/2×(1+λ/√{square root over (λ2+h2)}) (2)
where, T0 is a thickness of the position under a situation that no shadow mask layer 40 exists on the substrate 10 during the sputter-deposition process; h is a height of the shadow mask layer 40.
It is realized from the condition (2) that an obvious gradient thickness exists in the region where λ varies from 0 to 2h. The size of the region is correlated with the height of the shadow mask layer 40. For example, when the height h of the shadow mask layer 40 is in the range from 0.1 micrometers to 10 millimeters; correspondingly, the length (starting from the shadow mask layer 40) of the region having obvious gradient thickness is in the range from 0.2 micrometers to 20 millimeters In practice, the region having obvious gradient thickness usually fully covers a region used for growing carbon nanotubes of an expected carbon nanotube-base device.
Referring to
Referring to
Advantageously, when the patterned catalyst layer 30 is made from iron, a thickness of the thickest end of each of the catalyst blocks is in the range from 5 nm to 20 nm, and a thickness of the thinnest end of each the catalyst blocks is in the range from 1 nm to 10 nm. In the illustrated embodiment, the patterned catalyst layer 30 includes a plurality of catalyst blocks 33, 34 staggeringly positioned at opposite sides of the region of optimum thickness 32. A thinnest end of each of the catalyst blocks 34 has a thickness approximately equal to the optimum thickness, and a thickest end of each of the catalyst blocks 33 has a thickness approximately equal to the optimum thickness. The pattern is defined using a photolithography process.
It is understood that, a catalyst layer having a predetermined pattern can be directly formed, without the patterning step as above-mentioned. The formation of such a catalyst layer is actually the product of a series of substeps. A shadow mask layer having a reverse pattern corresponding to the predetermined pattern is formed on the substrate 10, to define an unmasked surface area same to the pretermined pattern. After a catalyst layer sputter-deposition process similar to the process as above-mentioned being implemented, and the shadow mask layer being removed using a lift-off process, a catalyst layer having the predetermined pattern can be directly obtained.
Referring to
Subsequently, the treated substrate 10 is placed in a furnace (not shown), a carbon source gas is continuously introduced into the furnace, and then a chemical vapor deposition process similar to that of defining the region 32 of the catalyst layer 30 is implemented. In particular, the carbon source gas with a protective gas together are continuously introduced into the furnace at a predetermined temperature (e.g. 500-900° C.). The carbon source gas can be acetylene, ethylene, methane or any suitable carbon-containing gas. The protective gas can be a noble gas or nitrogen. The protective gas and carbon source gas are introduced at suitable flow rates respectively (e.g. 160 sccm and 80 sccm respectively).
Referring to
Referring to
Referring to
A shadow mask layer 80 is formed on the substrate 70 and located at a middle portion thereof, to define an unmasked surface area 72 of the substrate 70 to be exposed. The shadow mask layer 80 is usually made from photo-resist, metal, metallic oxide, or metallic nitride. The shadow mask layer 80 has a suitable height (as denoted by h in
The sputter source 60 is configured for supplying a catalyst material and depositing the catalyst material onto the substrate 70, so as to form a catalyst layer having a gradient thickness via a sputter-deposition process. The catalyst material is usually selected from iron (Fe), cobalt (Co), nickel (Ni), or alloys thereof. Generally, a distance from the sputter source 60 to the substrate 70 is greater than the mean free path of a catalyst atom generated from the sputter source 60 under a predetermined sputter-deposition process. The sputter source 60 usually includes a surface sputter target made from a catalyst material, or a linear sputter target made from a catalyst material. In the case of the sputter source 60 having a linear sputter target, an optimum solution is that a reciprocating movement of the substrate 70 relative to the sputter source 60 along a direction perpendicular to the linear sputter target is implemented. In the illustrated embodiment, the sputter source 60 has a surface sputter target.
Referring to
Generally, a thickness T(λ) of a position of the catalyst layer 90 distant from the shadow mask layer 80 with a distance of λ approximately satisfies the condition (2) as the above-described. It is realized from the condition (2) that an obvious gradient thickness exists in the region where λ varies from 0 to 2h; and the size of the region is correlated with the height of the shadow mask layer 80. In practice, the region having obvious gradient thickness usually fully covers a region used for growing carbon nanotubes of an expected carbon nanotube-base device.
Referring to
Referring to
In the illustrated embodiment, the patterned catalyst layer 90 includes a plurality of catalyst blocks 93, 94, 95, 96 each positioned at a side of the region 92. A thinnest end of each of the catalyst blocks 93, 96 has a thickness proximal or equal to the optimum thickness, and a thickest end of each of the catalyst blocks 94, 95 has a thickness proximal or equal to the optimum thickness. The pattern is defined using a photolithography process.
It is understood that, a catalyst layer having a predetermined pattern can be directly formed, without the patterning step as above-mentioned. The formation of such a catalyst layer is actually the product of a series of substeps. A shadow mask layer having a reverse pattern corresponding to the predetermined pattern is formed on the substrate 90, to define a unmasked surface area same to the predetermined pattern. After a catalyst layer sputter-deposition process similar to the process as above-mentioned being implemented, and the shadow mask layer being removed using a lift-off process, a catalyst layer having the predetermined pattern can be directly obtained.
Referring to
Subsequently, the treated substrate 70 is placed in a furnace (not shown), a carbon source gas is introduced into the furnace, and then a chemical vapor deposition process similar to that of defining the region 92 of the catalyst layer 90 is implemented.
Referring to
Referring to
It is believed that the present embodiments and their advantages will be understood from the foregoing description, and it will be apparent that various changes may be made thereto without departing from the spirit and scope of the invention or sacrificing all of its material advantages, the examples hereinbefore described merely being preferred or exemplary embodiments of the invention.
Claims
1. A method for making a carbon nanotube-based device, the method comprising the steps of:
- providing a substrate having a shadow mask layer formed thereon, the shadow mask layer being configured for defining an unmasked surface area on the substrate;
- disposing a sputter source on the shadow mask layer, the sputter source being configured for supplying a catalyst material and depositing the catalyst material onto the substrate;
- forming a catalyst layer comprising at least one catalyst block on the unmasked surface area of the substrate, a thickness of the at least one catalyst block being gradually decreased from a first end thereof to an opposite second end thereof; the at least one catalyst block having a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes growing fastest, a thicker region having a thickness that is thicker than the optimum thickness, and a thinner region having a thickness that is thinner than the optimum thickness, such that the carbon nanotubes in the thicker and thinner regions grow slower than the carbon nanotubes at the region;
- introducing a carbon source gas; and
- forming at least one carbon nanotube array extending from the catalyst layer using a chemical vapor deposition process, wherein the at least one carbon nanotube array being arc-shaped, and bending in a direction of deviating from the region.
2. The method of claim 1, wherein the step of forming the catalyst layer comprising the sub-steps of:
- sputter-depositing a catalyst material on the substrate to form an initial catalyst layer;
- removing the shadow mask layer from the substrate; and
- patterning the initial catalyst layer to form the catalyst layer.
3. The method of claim 2, further comprising a step of marking the region of the initial catalyst layer, before patterning the initial catalyst layer.
4. The method of claim 2, wherein the sputter source comprising a sputter target made from the catalyst material, the sputter target being selected from the group consisting of a surface sputter target and a linear sputter target.
5. The method of claim 2, wherein the catalyst material is selected from the group consisting of iron, cobalt, nickel, and alloys thereof.
6. The method of claim 2, wherein the shadow mask layer has a plurality of sidewalls substantially perpendicular to the substrate.
7. The method of claim 2, wherein a thickness of a position of the initial catalyst layer distant from the shadow mask layer with a distance of λ satisfies the condition:
- T(λ)=T0/2×(1+λ/√{square root over (λ2+h2)})
- where, the T(λ) is a thickness of the position of the initial catalyst layer distant from the shadow mask layer with a distance of λ, T0 is a thickness of the position under a situation that no shadow mask layer formed on the substrate during the sputter-deposition process; h is a height of the shadow mask layer.
8. The method of the claim 1, wherein a thickness of the first end of the at least one catalyst block is in the range from 5 to 20 nanometers; a thickness of the second end of the at least one catalyst block is in the range from 1 to 10 nanometers.
9. (canceled)
10. The method of claim 1, wherein the step of forming the catalyst layer comprising the sub-steps of:
- sputter-depositing a catalyst material on the substrate to form the catalyst layer; and
- removing the shadow mask layer from the substrate.
11. The method of claim 1, further comprising a step of annealing the substrate with the catalyst layer in an oxygen-containing environment to form nano-sized catalyst oxide particles before introducing the carbon source gas.
12. The method of claim 1, wherein the substrate is made from a material selected from the group consisting of silicon, glass, and metal.
13. (canceled)
14. The method of claim 1, wherein the step of forming at least one carbon nanotube array extending from the catalyst layer using a chemical vapor deposition process further comprises forming at least two carbon nanotube arrays bending in two different directions of deviating from the region.
15. The method of claim 2, wherein the step of patterning the initial catalyst layer to form the catalyst layer further comprises patterning the initial catalyst layer to form a plurality of first catalyst blocks and second catalyst blocks, a thinnest end of the first catalyst blocks comprises of a thickness approximately equal to the optimum thickness, and a thickest end of the second catalyst blocks comprises of a thickness approximately equal to the optimum thickness.
16. The method of claim 15, wherein the plurality of first catalyst blocks and second catalyst blocks is patterned to be staggeringly positioned at opposite sides of the region with the thickness proximal or equal to the optimum thickness.
17. The method of claim 1, wherein a height of the shadow mask layer is less than mean free path of a catalyst atom generated from the sputter source under a predetermined sputter-deposition process, wherein the mean free path S of a catalyst atom satisfies the condition: S = kT 2 π d 2 p
- where d is a diameter of the catalyst atom, p is an operating pressure of the sputter-deposition process, k is the Boltzmann constant (1.38066×10−23 J/K (Joule per Kelvin)), T is an operating absolute temperature of the sputter-deposition process.
18. The method of claim 1, wherein a distance from the sputter source to the substrate is greater than the mean free path of the catalyst atom generated from the sputter source under the predetermined sputter-deposition process.
19. The method of claim 6, wherein the catalyst layer is formed around the shadow mask layer.
20. The method of claim 1, wherein the catalyst material is iron, the carbon source gas is ethylene, a temperature at which the carbon nanotubes are grown is about 700° C., the optimum thickness of the catalyst layer is about 5 nanometers.
21. A method for making a carbon nanotube-based device, the method comprising the steps of:
- forming a catalyst layer comprising a gradient thickness being gradually decreased from a first end of the catalyst layer to an opposite second end of the catalyst layer, wherein the catalyst layer comprises a region with a thickness proximal or equal to an optimum thickness at which carbon nanotubes grow fastest;
- patterning the catalyst layer to form a plurality of first catalyst blocks and second catalyst blocks staggeringly positioned at opposite sides of the region with the thickness proximal or equal to the optimum thickness, wherein a thinnest end of the first catalyst blocks comprises of a thickness approximately equal to the optimum thickness, and a thickest end of the second catalyst blocks comprises of a thickness approximately equal to the optimum thickness;
- introducing a carbon source gas; and
- forming a plurality of carbon nanotube arrays extending from the first catalyst blocks and second catalyst blocks using a chemical vapor deposition process, wherein the carbon nanotube arrays extending from the first catalyst blocks bend toward a thickest end of the first catalyst blocks, and the carbon nanotube arrays extending from the second catalyst blocks bend toward a thinnest end of the second catalyst blocks.
Type: Application
Filed: May 3, 2006
Publication Date: Aug 5, 2010
Applicants: Tsinghua University (Beijing City), HON HAI Precision Industry CO., LTD. (Tu-Cheng City)
Inventors: Liang Liu (Beijing), Shou-Shan Fan (Beijing)
Application Number: 11/416,724
International Classification: C23C 14/34 (20060101); C23C 16/00 (20060101);