Chapter 1 Introduction
2.1 Carbon Nanotubes Fabrication Method
2.1.1 CVD growth method
Vertically aligned CNT arrays are typically grown using the CVD technique inside a CVD reactor. There are many different variations of CVD reactors, including high pressure or low pressure CVD, hot wall or cold wall CVD, and many more. A high pressure CVD reactor utilizes a near-atmospheric pressure to achieve carbon saturation and CNT nucleation. In contrast, a low pressure CVD reactor allows CNT growth to be performed at a reduced pressure in the range of hundreds of mtorr. In a hot wall CVD reactor, both precursor gas and substrates are heated simultaneously inside a furnace. On the other hand, in a cold wall CVD reactor, the precursor gas is not heated inside the same furnace as the substrates. In fact, this gas may not need to be heated at all since a non-thermal source is used to initiate the gas dissociation.
A cold wall CVD reactor is typically associated with plasma-assisted CVD because the dissociation of the precursor gas is not initiated thermally, but instead by plasma generated by RF coils at a frequency of several MHz.
All CNT arrays used in this study are grown in-house using a custom made hot wall thermal CVD reactor. This CVD reactor consists of two main parts: precursor delivery system and reaction chamber (Figure 2.1). Each part consists of several sub- systems that are assembled into one working system. The precursor delivery system for this in-house CVD reactor connects the precursor gas feedstock to the reaction chamber through a series of cleaned stainless steel swagelok tubing. The flow rate and pressure of the precursor gas are maintained by electronic mass flow controllers (MKS π MFC) and a pressure controller (MKS π PC). Here, these controllers are connected to a computer to allow precise and accurate control of the mass flow rate and pressure with a fast response time. The mass flow controllers are located up- stream of the reaction chamber, while the pressure controller is located downstream of the reaction chamber. The downstream part of the pressure controller is connected to a vacuum pump (Leybold AMEB 90). CNT arrays are grown inside the reaction chamber of this in-house CVD reactor, which is made of a quartz tube with diameter of 1 inch and length of 24 inches. This quartz tube is housed inside a tube furnace
Table 2.1. List of materials and equipment used in the in-house CVD reactor.
Name Company Model number Key parameter
Tube furnace Lindberg Blue M - Thermo Scientific
Mini Mite TF- 55030A
D: 1 inch
Electronic mass flow controllers
MKS PFC-50 MFC 0 - 1000 sccm
Electronic pressure controller
MKS PC-90 PC 0 - 1000 torr
Vacuum pump Leybold AMEB 90 135 L / min
Quartz tube MTI Corp. EQ-QZTube-
25GE-610
OD: 1 inch, L: 24 inch
Hydrogen gas Airgas HY UHP200 99.999% purity
Ethylene gas Matheson G2250101 99.95% purity
Argon gas Airgas AR UHP200 99.999% purity
(Lindberg/BlueM Single-Zone Tube Furnace), capable of heating the reaction cham- ber up to 1100 ◦C. The temperature of the tube furnace is controlled electronically by the furnace’s PID controller. Materials and equipments used in this in-house CVD reactor are listed in Table 2.1.
These CNT arrays are grown using a common CVD method on silicon wafer substrates. Prior to growth, these silicon wafers are coated with layers of support, buffer, and catalyst several nanometers thick. Acting as the support layer is 300nm silicon oxide layer. This layer can be grown thermally as native oxide or deposited using an electron beam evaporator. A 10 nm aluminum oxide layer and a 1 nm iron layer are used as the buffer and catalyst layers, respectively. These buffer and catalyst layers have to be deposited using an electron beam evaporator (Temescal BJD 1800 or CHA Industries Mk40) to ensure the correct thickness and coverage uniformity. Subsequent to the deposition of these layers, the silicon substrates are diced into smaller samples, typically 1x1 cm2. Materials and equipment used for substrate preparation and catalysts deposition are listed in Table 2.2.
Up to now, there are countless numbers of growth recipes that have been published for fabrication of CNT arrays, and each of them is different. Because of the uniqueness of each CVD reactor, none of these growth recipes can be used as is without any modification. The growth recipe used in this study is basically a modified version of previously published growth recipes (Bronikowski, 2006; Sansom et al., 2008). The growth recipe used in this study is divided into four periods: heating, sintering, growth, and cooling, and summarized in Table 2.3.
The CNT arrays fabrication process is started by placing several pieces of silicon substrates on a quartz boat inside the quartz reaction chamber. The reaction chamber is then evacuated of ambient air using vacuum until it reaches a pressure lower than 10 torr and purged with argon gas for several minutes. Subsequently, the temperature of the reaction chamber is increased to a temperature of 750◦C at a heating rate of about 50◦C/minute. During this heating period, argon gas is flowed into the reaction chamber at a flow rate of 500 sccm and a pressure of 600 torr. Once the temperature reaches 750◦C, the flow of argon gas is reduced to a flow rate of 200 sccm and hydrogen
Table 2.2. List of materials and equipment used for substrate preparation and cata- lysts deposition.
Name Company Model number Key parameter
Silicon wafer El-Cat 2449 300nm polished
thermal oxide layer Iron pellets Kurt J Lesker EVMFE35EXEA 99.95% purity Aluminum oxide pel-
lets
Kurt J Lesker EVMALO- 1220B
99.99% purity
E-beam evaporator CHA Industries Mark 40 10 nm Al2O3 and 1 nm Fe
E-beam evaporator Temescal BJD 1800 10 nm Al2O3 and 1 nm Fe
Scriber breaker Dynatex GST-150 1 x 1 cm2
Figure 2.2. Schematic of CNT growth process using a common thermal chemical vapor deposition method.
gas is flowed simultaneously into the reaction chamber at a flow rate of 285 sccm.
The pressure of the reaction chamber is maintained at 600 torr. During this period, the buffer and catalyst layers are reduced by the hot hydrogen gas and sintered into catalyst nanoparticles (Figure 2.2). These catalyst nanoparticles will later act as the nucleation sites for CNT growth during the growth period. This sintering period is considered as the most important part of the fabrication process and has to be performed for exactly five minutes to ensure the correct size, roughness, and distribution of these catalyst nanoparticles.
Subsequent to the sintering period, the flow of argon gas is completely shut off and the flow of hydrogen gas is reduced to a flow rate of 210 sccm. Ethylene gas is then flowed into the reaction chamber at a flow rate of 490 sccm. The pressure and temperature of the reaction chamber is maintained at 600 torr and 750◦C respectively.
During this period, the catalyst nanoparticles are saturated with carbon, and CNTs start to nucleate and grow on them (Figure 2.2). Because of the tight distribution of the catalysts nanoparticles, CNTs are grown in a densely packed manner. Limitation of lateral space for CNTs to grow means that the growth in vertical direction is more preferable, resulting in vertically aligned, densely packed CNT arrays. The length of CNT arrays grown using this growth recipe can be varied between 10µm and 1 mm by controlling their growth time. Longer growth time results in longer CNT arrays.
However, the growth rate is not linear but rather hyperbolic, with a maximum length of 1-1.2 mm. CNT arrays grow very quickly in the first couple of minutes and start to slow down afterwards. The growth process itself seems to be self-terminated after the CNT arrays reach an average length of 1-1.2 mm. Subsequent to the growth period, the flow of both ethylene and hydrogen gasses is shut off completely and the temperature of the reaction chamber is brought back to room temperature by turning off the furnace. This passive cooling allows the reaction chamber temperature to decrease at a rate of about 25◦C/minute. During this cooling period, argon gas is flowed into the reaction chamber at a flow rate of 360 sccm. Once the temperature of the reaction chamber reaches room temperature, the flow of argon gas is shut off and ambient air is flowed into the reaction chamber. The vacuum pump is then turned
Table 2.3. CVD growth parameters.
Step Parameters Value
Heating Pressure 600torr
Temperature room - 750◦C Ar 500 sccm
Heating rate about 50◦C / min Sintering Pressure 600torr
Temperature 750◦C Ar 200 sccm H2 285 sccm Pretreatment time 5 min
Growth Pressure 600torr
Temperature 750◦C C2H4 490 sccm
H2 210 sccm Growth time 5 - 60 min
Cooling Pressure 600torr
Temperature 750 C - room Ar 360 sccm
Cooling rate about 25◦C / min
off and the pressure regulator is released to allow the pressure inside the reaction chamber to equilibrate with the ambient pressure. The grown CNT arrays can then be taken from the reaction chamber and are ready to be used.