1. Field of the Invention
This invention relates to nanotube (NT) growth of carbon and other materials using a chemical vapor deposition (CVD) process.
2. Description of the Related Art
Carbon nanotubes (CNTs) have stimulated a great deal of interest in the microelectronic and other industries because of their unique properties including tensile strengths above 35 GPA, elastic modulus reaching 1 TPa, higher thermal conductivity than diamond, ability to carry 1000× the current of copper, densities below 1.3 g/cm3 and high chemical, thermal and radiation stability. CNTs have great promise for devices such as field effect transistors, field emission displays, single electron transistors in the microelectronic industry, and uses in other industries. Commercialization of CNTs will depend in large part on the ability to grow and network CNTs on a large cost-effective scale without compromising these properties.
As illustrated in
CNTs are commonly grown using several techniques such as arc discharge, laser ablation and chemical vapour deposition (CVD). In CVD the growth of a CNT is determined by the presence of a catalyst, usually a transition metal such as Fe, Co or Ni, which causes the catalytic dehydrogenation of hydrocarbons and consequently the formation of a CNT. CVD generally produces MWNTs or SWNTs of relatively poor quality due mostly to the poorly controlled diameters of the nanotubes. T However, CVD is relatively easy to scale up and can be integrated with conventional microelectronic fabrication, which favors commercialization.
The way in which nanotubes are formed is not precisely known. The growth mechanism is still a subject of scientific debate, and more than one mechanism might be operative during the formation of CNTs. As shown in
As shown in
The present invention provides a system and method for growing nanotubes out of carbon and other materials using a CVD process that facilitates sustained rapid growth of high quality nanotubes with greater control over the geometry of the nanotubes and arrays of nanotubes, the ability to control defects in the nanotubes and the capability to observe nanotube growth using electron gun and optical equipment in-situ.
This is accomplished with a catalytic transmembrane that separates a feedstock chamber from a growth chamber and provides a catalyst with separate catalytic surfaces to absorb carbon atoms from the feedstock chamber and to grow carbon nanotubes in the growth chamber. Separation of the feedstock and growth chambers and of the absorption and growth surfaces provides for greater flexibility to independently control both the gas environment and pressure in the chambers to optimize absorption and growth and to provide instrumentation in the growth chamber for in-situ control of defects or observation of the carbon nanotube growth.
These and other features and advantages ofthe invention will be apparent to those skilled in the art from the following detailed description of preferred embodiments, taken together with the accompanying drawings, in which:
a-2b, as described above, are diagrams illustrating root and tip CNT growth;
a and 7b are section and plan views of an exemplary catalytic transmembrane including an array of catalytic nano-particles in membrane pores;
a through 8g are diagrams of an exemplary process for fabricating the catalytic transmembrane;
a-9b are section and plan views of an exemplary strip heater for heating the catalytic transmembrane; and
a through 10h are different configurations of material catalysts in the membrane pores.
The present invention provides a system and method for growing nanotubes out of carbon and other materials using CVD that facilitates sustained rapid growth of high quality nanotubes with greater control over the geometry of the nanotubes and nanotube arrays, ability to control defects in the nanotubes and the capability to observe nanotube growth using electron gun and optical equipment in-situ.
Efforts to improve the growth of CNTs have revealed a number of drawbacks in the conventional CVD approach. The surface area for absorbing carbon atoms is limited by the desired geometry and growth of the CNT from the catalytic nano-particle. To grow a SWNT the nano-particle must be very small, approximately 1-10 nm in diameter. The presence of the growing CNT further reduces the available surface area. Furthermore, the absorption process itselfcauses the surface of the catalytic nano-particle to become encrusted with amorphous carbon and graphite which slows and eventually stops absorption of feedstock carbon and growth of the CNT. The effectiveness of the scrubber gas to clean the surface of the nano-particle is limited because the scrubber gas tends to attack the CNT necessitating a lower concentration of scrubber gas. The conventional process cannot be sustained indefinitely, which places a limit on the length of CNT growth. Likewise the growth rate in the conventional process is limited by the absorption rate and a viscous force produced by the process gases that opposes the extrusion force. Growth rate will be important to commercialization of CNTs. In theory, the CNT structure is formed of pure carbon atoms. However, in the conventional process CNT growth in the presence of the impurities in the process gases can introduce contaminants into the CNT structure of 2% or more. Furthermore, the high-pressure noxious gas environment is not hospitable to in-situ annealing of defects using electron guns or in-situ observation of CNT growth using electron gun microscopes or optical sensors.
As we have discovered, many of these deficiencies are attributable to the fact that in conventional CVD , the catalytic surface at which absorption of carbon feedstock takes place and at which growth of the CNTs occurs are one and the same. However, the desired conditions for absorption of reactive carbon atoms into the catalytic material and for growth of CNTs are quite different. For efficient absorption, a system should provide a relatively large unobstructed and clean absorption surface on which to absorb the reactive carbon. The chamber would preferably be operated at higher pressure and higher concentrations of scrubber gas to keep the surface clean to sustain growth indefinitely. For efficient growth, a system should provide a growth surface that is not exposed to the growth or scrubber gases and which may be controlled to provide a small or no opposing viscous force. The system would preferably be conducive to the introduction of electron guns and optical sensors in-situ to control defects in the growing CNT and observe the growth of the CNT. In-situ observation of CNT growth is particularly important to further the science of CNT growth.
As shown in
An embodiment of a system for CVD synthesis of CNTs is illustrated in
A feedstock environmental control system includes gas feeds 71 to introduce process gases into the feedstock chamber 52, a pump system 72 including a vacuum and/or pressure pump to control the pressure of the feedstock chamber, and an energy source 74 to heat the gases and/or catalytic material to separate carbon atoms 62 from the growth gas molecules 64 for absorption into the catalytic material at absorption surface 58. The process gas typically includes a mixture of a carbon-containing growth gas 76, typically a hydrocarbon CxHy such as Ethylene (C2H4), Methane (CH4), Acetylene (C2H2) or Ethanol (C2H5OH) or possibly a non-hydrocarbon such as carbon-monoxide (CO), a buffer gas 78 such as an inert gas, e.g. Argon (Ar), to control pressure inside the chamber and prevent released hydrogen atoms from exploding, and possibly a scrubber gas 80 such as H2O or O2 to periodically clean the surface of the catalyst. In some applications the buffer and or scrubber gases may not be required. A number of electrical ports 82 are provided to accommodate pressure sensors, thermocouples and the like to monitor conditions inside both chambers.
Because the CNT is not grown inside feedstock chamber 52 the CVD process can be modified for more efficient absorption and growth control. First, the concentration of the scrubber gas 80 can be increased from less than 1% from conventional CVD to greater than 10% without the risk of attacking the CNT. As a result, the unobstructed absorption surface 58 can be cleaned and the process sustained indefinitely. In an alternate embodiment, an Ar ion beam 84 can be used to clean the absorption surface. The ion beam is suitably generated external to the chamber and routed through a port in the chamber. Second, the chamber pressure can be elevated, typically 0.1 to 100 Torr, to increase the supply of carbon atoms and improve absorption of carbon atoms into the catalytic material.
A growth environmental control system includes a pump system 90 including a vacuum and/or pressure pump to control the pressure of growth chamber 54 and possibly one or more gas feeds 92 to introduce a gas 94 such as an inert gas or possibly functionalizing gases for attaching doping materials to CNTs to modify or enhance their mechanical, electrical, optical, or chemical properties for further processing into electronic or sensor devices. Eliminating the hot noxious gases, particularly the carbon-containing growth gas, from the growth chamber has several benefits. First, these gases tend to attack and contaminate the CNT as it grows. The contaminant level can be reduced to less than 1% for the configuration shown here. Second, electron guns 96 and 98 can be used in-situ to selectively fix and create defects in the CNT as it grows. Electron gun 96 can be used to anneal defects in the NT structure to provide missing carbon atoms. Electron gun 98 can be used, for example, to rotate pairs of common atoms to move the bonds and change the bond structure of the CNT. Lastly, the environment facilitates in-situ observation of the growth process using, for example, an electron microscope 100 and optical equipment 102 for Raman spectroscopy, fluorescent spectroscopy or other appropriate measurements. The electron guns and observation equipment are suitably located outside the chamber and routed through ports in the chamber.
The growth chamber may be operated in a vacuum or gases may be introduced and the pressure controlled to be nearer atmospheric pressure. Pure vacuum is 0 Torr, less than 10−6 is considered to be ultra-high vacuum and less than 10−2 a good vacuum. For example, if the transmembrane is sufficiently strong or the feedstock chamber can be operated at a low enough pressure, a vacuum can be pulled (created) on the growth chamber. Vacuum conditions may provide an optimal environment for carbon growth and for use of the electron guns. Alternately, an inert gas can be introduced into the growth chamber to lower the pressure differential across the transmembrane. The inert gas can be selected to be a different inert gas such as He than that used in the feedstock chamber to provide a lower viscous force to resist extrusion of the carbon atoms and/or to provide better optical absorption properties for observation of carbon growth.
For simplicity of explanation, the catalytic transmembrane has been described as having a single catalyst or nano-particle embedded therein. For purposes of scientific research and some commercial applications it may be desirable to grow a single CNT. In other cases, it may be desirable to grow an array of CNTs and in some cases a very large array, perhaps upwards to billions of separate NTs in a single structure. The transmembrane is well suited for either single CNTs or arrays of CNTs. The ‘pore’ structures in which the catalysts (nano-particles) are formed can be controlled using standard processing techniques. As will be discussed later, this allows for control over the geometry of the nano-particle and particularly the geometry of the absorption and growth surfaces. In conventional CVD, drops of catalytic material are formed on the surface of the support making it difficult to control the individual drops and overall array.
In one embodiment as shown in
A method of fabricating transmembrane 50 is illustrated in
In an exemplary embodiment, a 500 nm thick layer 114 of SiO2 is grown on both sides of a silicon wafer 110. On the backside of the wafer, the SiO2 is patterned using standard photolithography techniques to form an etch mask 130 for the membrane formation process. The frontside oxide is then removed, and a high quality three layer film stack 132 (20 nm SiO2/15 nm a-Si/20 nm SiO2) is deposited on the front surface using RF magnetron sputtering. To form the pnc-Si membranes, the substrate is briefly exposed to high temperature in a rapid thermal processing chamber, crystallizing the a-Si into a nanocrystalline film thereby forming the pores. The patterned wafer back side is then exposed to a highly selective silicon etchant, EDP, which removes the silicon wafer along crystal planes until it reaches the first SiO2 layer of the front side film stack to form cavity 116. Exposing the three layer membrane to buffered oxide etchant removes the protective oxide layers, leaving the freely suspended ultra thin pnc-Si membrane 112. Thereafter, iron is evaporated at high temperature, which, upon heating, forms droplets that are drawn into the pores via capillary action leaving a catalytic transmembrane whose pores are sealed with catalytic material 56. Many other methods to fill the nm pores can be found in the scientific literature dealing with nano capillarity such as solution evaporation and sublimination methods, sputtering or atomic layer deposition, or electrolytic deposition.
As described above, an energy source is used to heat the catalytic material and/or growth gas to ‘crack’ the molecules and provide the reactive carbon atoms and to maintain the temperature needed for absorption into and bulk or surface diffussion through the catalytic material. In general, this can be done with a heat source that heats the transmembrane and/or the process gases. Within the sealed chamber, heating the process gases will have the effect of heating the catalytic material and vice-versa. As shown in
Another potential benefit to the use of the catalytic transmembrane is the capability to control the geometry of the nano-particle(s) and more particularly the geometry of the particle's absorption and growth surfaces that are exposed to the feedstock and growth chambers, respectively. This may be used to improve the efficiency of absorption and growth and to control the geometry of the CNT. As illustrated in
The following examples exemplify the flexibility provided by independent feedstock and growth chambers. However, there are many variations on the transmembrane configuration and feedstock and growth parameters that may be used.
Transmembrane: 400 micron thick silicon with approximately 1 million 10 nm diameter pores filled with Fe.
Feedstock Chamber: 10-45% Ethylene growth gas, 30-85% Argon buffer gas (purged before growth or introduced continuously), 5-25% Hydrogen scrubber gas (purged before growth or introduced continuously), 1E−1 to 1E+2 Torr, 500-900 C.
Growth Chamber: Vacuum (<1E−2) or Argon/Helium inert gases at 1E−1 to 1E+2 Torr
Transmembrane: 400 micron thick silicon with approximately 1 million 10 nm diameter pores filled with Fe.
Feedstock Chamber: 15-100% Ethanol growth gas, 75-90% Argon buffer gas (purged before growth or introduced continuously), 5-25% Hydrogen scrubber gas (purged before growth or introduced continuously), 1E−1 to 1E+2 Torr, 500-900 C.
Growth Chamber: Vacuum (<1E−2) or Argon/Helium inert gases at 1E−1 to 1E+2 Torr
Transmembrane: 20-100 micron thick alumina with approximately 1 trillion 13-18 nm diameter pores filled with Fe.
Feedstock Chamber: 10-45% Ethylene growth gas, 30-85% Argon buffer gas (purged before growth or introduced continuously), 5-25% Hydrogen scrubber gas (purged before growth or introduced continuously), 1E−1 to 1E+2 Torr, 500-900 C.
Growth Chamber: Vacuum (<1E−2) or Argon/Helium inert gases at 1E−1 to 1E+2 Torr
Transmembrane: 20-100 micron thick alumina with approximately 1 million 10 nm diameter pores filled with Fe.
Feedstock Chamber: 15-100% Ethanol growth gas at 5-20 Torr, 75-90% Argon buffer gas (purged before growth or introduced continuously), 5-25% Hydrogen scrubber gas (purged before growth or introduced continuously), 1E−1 to 1E+2 Torr, 500-900 C.
Growth Chamber: Vacuum (<1E−2) or Argon/Helium inert gases at 1E−1 to 1E+2 Torr
Although the description of the invention has focused on the growth of carbon nanotubes the approach is viable for growing nanotubes from other materials such as Germanium (Ge), Boron (B), or Boron-Nitride (BN). The interest in and development of carbon nanotube technology is well beyond that of other materials, hence the focus on carbon nanotubes. However, the approach of using a catalytic transmembrane to separate the feedstock and growth chambers is just as applicable for growing nanotubes from these other discovered or yet to be discovered materials.
While several illustrative embodiments of the invention have been shown and described, numerous variations and alternate embodiments will occur to those skilled in the art. Such variations and alternate embodiments are contemplated, and can be made without departing from the spirit and scope of the invention as defined in the appended claims.