The detailed chemistry of the solid-state carbon-to-graphene transition on the Cu catalytic surface was investigated by performing in situ residual gas analyzes while heating PMMA/Cu sheet samples, in conjunction with interrupted growth studies to reconstruct the ex- in situ heating process. The data clearly show that graphene formation occurs with hydrocarbon molecules vaporized from PMMA, such as methane and/or methyl radicals, as precursors and not by direct graphitization of carbon in the solid state. We also found that the temperature for vaporization of hydrocarbon molecules from PMMA and the retention time of the hydrocarbon gas atmosphere, which depend on both the heating temperature profile and the amount of solid carbon feedstock, are the dominant factors for determine the crystalline quality. of the resulting graphene film.
Representative low-magnification TEM image of a graphene film grown at 1000 °C for 3 min, then transferred to a TEM support hole. As the total pressure increases, the intensity of the D band increases, indicating that the amount of effective carbon sources may not be sufficient. If the total pressure was greater than 1 Torr, the Raman spectrum (black line) shows no features associated with carbon above a. a) Schematic representation of our experimental setup to investigate the growth mechanism of graphene using a solid-state carbon source.
With different concentration of PMMA in toluene, the thickness of PMMA film was deposited on SiO2/Si by spin coating at 5000 rpm for 1 min. Note that all vertical axes represent the logarithm of the partial pressure. e–h) Representative Raman spectra of graphene films transferred onto a SiO2/Si substrate after heating the samples to a 1 wt%. a) An AFM image of a bare Cu foil.
Introduction
Solid carbon sources
Each PMMA solution was spin-coated onto Cu foil at 5000 rpm for 1 minute. PMMA-coated Cu foil samples were cured on a hot plate at 180 °C for 1 minute and loaded into the RTA chamber.
RTA process
Graphene transfer
The diagrams represent the elementary steps in graphene formation, including PMMA deposition on Cu foil, RTA annealing in vacuum, and graphene formation respectively. To investigate the basic nature of the gaseous products, we used the residual gas analyzer (RGA) equipped with a quadrupole mass spectrometer (QMS 200F1, Pfeiffer Vacuum) to monitor changes in the chamber atmosphere during in-situ baking. The sheet resistance of the graphene layers was measured using transmission line model measurement (TLM), which is the way to accurately measure the contact resistance and sheet resistance of the graphene layer.
After measuring the total resistance of the TLM structure as a function of distance, we extracted a sheet resistance value of graphene from the slope. We used a wet transfer TEM sampling method for plan view imaging of graphene films to minimize damage and/or contamination of the films. To ensure efficient contact at Quantifoil graphene/substrate pairs, isopropyl alcohol (IPA) was dropped on top of the grids and the couples were heated on a hot plate at 120 °C for 10–20 min to evaporate any remaining IPA .
Then the couples were dipped in a buffered oxide etchant (BOE) solution to slightly etch the SiO2 layer until the couples floated free from the substrate. The objective aperture was placed over one of the diffracted beams, and the DF image was acquired using an acquisition time of 2–5 sec.
Results and Discussions
Electrical properties of graphene on SiO 2 -Si substrates
Now, careful consideration should be given to how high quality graphite can be formed on Cu foil using solid state carbon sources. Because direct graphitization of solid carbon sources is not a feasible mechanism from our experiment, and Cu does not induce solid carbon graphitization at temperatures up to 950 °C.26,27 So, we assumed that nutrients gases erupted from the thermal decomposition of PMMA can play an important role in graphitization on a catalytic Cu surface.28 From our assumption, we implemented the following experiment, methodology similar to that presented by Ji et al.16 in vacuum, as shown in Figure 3-7a. Three pieces of Cu foil were placed in the hot zone area with similar temperature profiles, which are accurate within 10 °C at 1000 °C.
The PMMA was deposited only on the piece of Cu foil in the middle and both left and right side pieces of Cu foil were bare. Due to the physical gap between Cu foils, it is expected that gaseous precursors, such as CxHy, CxOy and Hx, are produced from thermal decomposition of PMMA at the elevated temperature and then those gaseous precursors are converted to the graphene layers on Cu surfaces. From previous experimental data, we have convinced that gaseous precursors are generated from thermal decomposition of PMMA.
In order to investigate the basic nature of the gaseous products, such as what types of gaseous products and when they are formed, a residual gas analyzer (RGA) equipped with a quadrupole mass spectrometer (QMS 200F1, Pfeiffer Vacuum) was used for monitoring. changes in chamber atmosphere during in situ annealing of PMMA/Cu foil. But the bare copper foil did not evolve any gaseous species during the heating process as expected (Figure 3-10). Therefore, we confirmed that gaseous species are produced by the thermal decomposition of PMMA. From this analysis, we suggest that methane and/or methyl radicals are the main precursor for the formation of graphene converted from PMMA to Cu foil.
We also attempted the same RGA analysis using a piece of Cu foil deposited with a 20nm-thcik amorphous carbon (a-C) film (Figure 3-11). a-C films were deposited using an e-beam evaporator at room temperature with a base pressure of ∼10-6 Torr. In addition, we adjusted the thickness of PMMA films by changing the concentration of PMMA solutions. From the value of ID/IG in the Raman spectra in Figure 3-15e~h, we observed that the crystalline quality of graphene was significantly improved when a high concentration of PMMA was used.
In order to adjust the outgassing temperature depending on the thickness of PMMA films, interrupted growth studies were performed using atomic force microscopy (AFM) to monitor the heating process for the samples with 1 wt. As a reference, a bare Cu foil surface was examined by AFM indicating a step flow growth morphology with regularly spaced atomic steps (Figure 3-17a). After deposition of PMMA on Cu, Surface morphology always leads to a flattening according to the AFM data.
The step height and surface RMS roughness of PMMA-coated Cu foils decreased suddenly after PMMA deposition on Cu and remained fairly constant, until heating temperatures reached 750 °C and 900 °C at 1 wt. Given the relatively very low thermal conductivity of PMMA (0.19 W/m K at room temperature)32 compared to Cu (398 W/m K at room temperature),33 the heat transfer in PMMA is extremely slow so that the thickness of the PMMA films make a difference in the outgassing temperature. a) An AFM image of a bare Cu foil.
Conclusion
Repeated growth and bubbling transfer of graphene with millimeter-sized single-crystal grains using platinum. Rational design of a binary metal alloy for chemical vapor deposition growth of uniform single-layer graphene.
