• 한국재료학회지
• /
• 제24권12호
• /
• pp.694-699
• /
• 2014

We report the chemical vapor deposition growth characteristics of graphene on various catalytic metal substrates such as Ni, Fe, Ag, Au, and Pt. 50-nm-thick metal films were deposited on $SiO_2/Si$ substrates using dc magnetron sputtering. Graphene was synthesized on the metal/$SiO_2$/Si substrates with $CH_4$ gas (1 SCCM) diluted in mixed gases of 10% $H_2$ and 90 % Ar (99 SCCM) using inductively-coupled plasma chemical vapor deposition (ICP-CVD). The highest quality of graphene film was achieved on Ni and Fe substrates at $900^{\circ}C$ and 500 W of ICP power. Ni substrate seemed to be the best catalytic material among the tested materials for graphene growth because it required the lowest growth temperature ($600^{\circ}C$) as well as showing a low ICP power of 200W. Graphene films were successfully grown on Ag, Au, and Pt substrates as well. Graphene was formed on Pt substrate within 2 sec, while graphene film was achieved on Ni substrate over a period of 5 min of growth. These results can be understood as showing the direct CVD growth of graphene with a highly efficient catalytic reaction on the Pt surface.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
• /
• pp.130.2-130.2
• /
• 2013

Today, chemical vapor deposition (CVD) of hydrocarbon gases has been demonstrated as an attractive method to synthesize large-area graphene layers. However, special care should be taken to precisely control the resulting graphene layers in CVD due to its sensitivity to various process parameters. Therefore, a facile synthesis to grow graphene layers with high controllability will have great advantages for scalable practical applications. In order to simplify and create efficiency in graphene synthesis, the graphene growth by thermal annealing process has been discussed by several groups. However, the study on growth mechanism and the detailed structural and optoelectronic properties in the resulting graphene films have not been reported yet, which will be of particular interest to explore for the practical application of graphene. In this study, we report the growth of few-layer, large-area graphene films using rapid thermal annealing (RTA) without the use of intentional carbon-containing precursor. The instability of nickel films in air facilitates the spontaneous formation of ultrathin (<2~3 nm) carbon- and oxygen-containing compounds on a nickel surface and high-temperature annealing of the nickel samples results in the formation of few-layer graphene films with high crystallinity. From annealing temperature and ambient studies during RTA, it was found that the evaporation of oxygen atoms from the surface is the dominant factor affecting the formation of graphene films. The thickness of the graphene layers is strongly dependent on the RTA temperature and time and the resulting films have a limited thickness less than 2 nm even for an extended RTA time. The transferred films have a low sheet resistance of ~380 ${\Omega}/sq$, with ~93% optical transparency. This simple and potentially inexpensive method of synthesizing novel 2-dimensional carbon films offers a wide choice of graphene films for various potential applications.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2012년도 제42회 동계 정기 학술대회 초록집
• /
• pp.128-128
• /
• 2012

We investigated the atomic and electronic properties of graphene grown by Pd silicidation and intercalation using LEED, STM, and ARPES. Pd was deposited on the 6H-SiC(0001) surface at RT. The formation of Pd silicide gives rise to breaking of Si-C bonds of the SiC crystal, which enables to release C atoms at low temperature. The C atoms are transformed into graphene from $860^{\circ}C$ according to the LEED patterns as a function of annealing temperature. Even though the graphene spots were observed in the LEED pattern and the Fourier transformed STM images after annealing at $870^{\circ}C$, the topography images showed various superstructures so that graphene is covered with Pd silicide residue. After annealing at $950^{\circ}C$, monolayer graphene was revealed at the surface. The growth of graphene is not limited by surface obstacles such as steps and defects. In addition, we observed that six protrusions consisting of the honeycomb network of graphene has same intensity meaning non-broken AB-symmetry of graphene. The ARPES results in the vicinity of K point showed the non-doped linear ${\pi}$ band structure indicating monolayer graphene decoupled from the SiC substrate electronically. Note that the charge neutrality of graphene grown by Pd silicidation and intercalation was sustained regardless of annealing temperature in contrast with quasi-free- standing graphene induced by H and Au intercalation. Further annealing above $1,000^{\circ}C$ accelerates sublimation of the Pd silicide layer underneath graphene. This results in appearance of the $(6r3x6r3)R30^{\circ}$ structure and dissolution of the ${\pi}$ bands for quasi-free-standing graphene.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2012년도 제43회 하계 정기 학술대회 초록집
• /
• pp.391-392
• /
• 2012

Graphene is a perfectly two-dimensional (2D) atomic crystal which consists of sp2 bonded carbon atoms like a honeycomb lattice. With its unique structure, graphene provides outstanding electrical, mechanical, and optical properties, thus enabling wide variety of applications including a strong potential to extend the technology beyond the conventional Si based electronic materials. Currently, the widespread application for electrostatically switchable devices is limited by its characteristic of zero-energy gap and complex process in its synthesis. Several groups have investigated nanoribbon, strained, or nanomeshed graphenes to induce a band gap. Among various techniques to synthesize graphene, chemical vapor deposition (CVD) is suited to make relatively large scale growth of graphene layers. Direct growth of graphene on hexagonal boron nitride (h-BN) using CVD has gained much attention as the atomically smooth surface, relatively small lattice mismatch (~1.7％) of h-BN provides good quality graphene with high mobility. In addition, induced band gap of graphene on h-BN has been demonstrated to a meaningful value about ~0.5 eV.[1] In this paper, we report the synthesis of grpahene / h-BN bilayer in a chemical vapor deposition (CVD) process by controlling the gas flux ratio and deposition rate with temperature. The h-BN (99.99％) substrate, pure Ar as carrier gas, and $CH_4$ are used to grow graphene. The number of graphene layer grown on the h-BN tends to be proportional to growth time and $CH_4$ gas flow rate. Epitaxially grown graphene on h-BN are characterized by scanning electron microscopy, atomic force microscopy, and Raman spectroscopy.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2009년도 제38회 동계학술대회 초록집
• /
• pp.80-80
• /
• 2010

Graphene has attracted tremendous attention for the last a few years due to it fascinating electrical, mechanical, and chemical properties. Up to now, several methods have been developed exclusively to prepare graphene, which include micromechanical cleavage, polycrystalline Ni employing chemical vapor deposition technique, solvent thermal reaction, thermal desorption of Si from SiC substrates, chemical routes via graphite intercalation compounds or graphite oxide. In particular, polycrystalline Ni foil and conventional chemical vapor deposition system have been widely used for synthesis of large-area graphene. [1-3] In this study, synthesis of mono-layer graphene on a Ni foil, the mixing ratio of hydrocarbon ($CH_4$) gas to hydrogen gas, microwave power, and growth time were systemically optimized. It is possible to synthesize a graphene at relatively lower temperature ($500^{\circ}C$) than those (${\sim}1000^{\circ}C$) of previous results. Also, we could control the number of graphene according to the growth conditions. The structural features such as surface morphology, crystallinity and number of layer were investigated by scanning electron microscopy (SEM) and atomic force microscopy (AFM), transmission electron microscopy (TEM) and resonant Raman spectroscopy with 514 nm excitation wavelength. We believe that our approach for the synthesis of mono-layer graphene may be potentially useful for the development of many electronic devices.

• 반도체디스플레이기술학회지
• /
• 제21권3호
• /
• pp.114-118
• /
• 2022

The stabilized all-solid-state battery structure indicate a fundamental alternative to the development of next-generation energy storage devices. Existing liquid electrolyte structures severely limit battery stability, creating safety concerns due to the growth of Li dendrites during rapid charge/discharge cycles. In this study, a low-dimensional graphene quantum dot layer structure was applied to demonstrate stable operating characteristics based on Li+ ion conductivity and excellent electrochemical performance. Transmission electron microscopy analysis was performed to elucidate the microstructure at the interface. The low-dimensional structure of GQD-based solid electrolytes has provided an important strategy for stable scalable solid-state lithium battery applications at room temperature. This study indicates that the low-dimensional carbon structure of Li-GQDs can be an effective approach for the stabilization of solid-state Li matrix architectures.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
• /
• pp.181.2-181.2
• /
• 2014

A single-layer graphene has been uniformly grown on a Cu surface at elevated temperatures by thermally processing a poly (methyl methacrylate) (PMMA) film in a rapid thermal annealing (RTA) system under vacuum. The detailed chemistry of the transition from solid-state carbon to graphene on the catalytic Cu surface was investigated by performing in-situ residual gas analysis while PMMA/Cu-foil samples being heated, in conjunction with interrupted growth studies to reconstruct ex-situ the heating process. We found that the gas species of mass/charge (m/e) ratio of 15 ($CH_3{^+}$) was mainly originated from the thermal decomposition of PMMA, indicating that the formation of graphene occurs with hydrocarbon molecules vaporized from PMMA, such as methane and/or methyl radicals, as precursors rather than by the direct graphitization of solid-state carbon. We also found that the temperature for dominantly vaporizing hydrocarbon molecules from PMMA and the length of time, the gaseous hydrocarbon atmosphere is maintained, are dependent on both the heating temperature profile and the amount of a solid carbon feedstock. From those results, we strongly suggest that the heating rate and the amount of solid carbon are the dominant factors to determine the crystalline quality of the resulting graphene film. Under optimal growth conditions, the PMMA-derived graphene was found to have a carrier (hole) mobility as high as ${\sim}2,700cm^2V^{-1}s^{-1}$ at room temperature, which is superior to common graphene converted from solid carbon.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2013년도 제45회 하계 정기학술대회 초록집
• /
• pp.131-131
• /
• 2013

A single-layer graphene has been uniformly grown on a Cu surface at elevated temperatures by thermally processing a poly(methyl methacrylate) (PMMA) film in a rapid thermal annealing (RTA) system under vacuum. The detailed chemistry of the transition from solid-state carbon to graphene on the catalytic Cu surface was investigated by performing in-situ residual gas analysis while PMMA/Cu-foil samples being heated, in conjunction with interrupted growth studies to reconstruct ex-situ the heating process. The data clearly show that the formation of graphene occurs with hydrocarbon molecules vaporized from PMMA, such as methane and/or methyl radicals, as precursors rather than by the direct graphitization of solid-state carbon. We also found that the temperature for vaporizing hydrocarbon molecules from PMMA and the length of time the gaseous hydrocarbon atmosphere is maintained, which are dependent on both the heating temperature profile and the amount of a solid carbon feedstock are the dominant factors to determine the crystalline quality of the resulting graphene film. Under optimal growth conditions, the PMMA-derived graphene was found to have a carrier (hole) mobility as high as ~2,700 cm2V-1s-1 at room temperature, superior to common graphene converted from solid carbon.

• Applied Science and Convergence Technology
• /
• 제26권6호
• /
• pp.179-183
• /
• 2017

The direct growth method is simplified manufacturing process used to avoid damages and contaminants from the graphene transfer process. In this paper, graphene nano-walls (GNWs) were direct synthesized using electron cyclotron resonance (ECR) plasma by varying the $CH_4/H_2$ gas flow rate on the copper foil at low temperature (without substrate heater). Investigations were carried out of the changes in the morphology and characteristic of GNWs due to the relative intensity of hydrocarbon radical and molecule in the ECR plasma. The results of these investigations were then discussed.

• 한국진공학회:학술대회논문집
• /
• 한국진공학회 2015년도 제49회 하계 정기학술대회 초록집
• /
• pp.109.2-109.2
• /
• 2015

Graphene, as a single layer of $sp^2$-bonded carbon atoms packed into a 2D honeycomb crystal lattice, has attracted much attention due to its outstanding properties such as high carrier mobility, chemical stability, and optical transparency. In order to synthesize high quality graphene, transition metals, such as nickel and copper, have been widely employed as catalysts, which need transfer to desired substrates for various applications. However, the transfer steps inevitably induce defects, impurities, wrinkles, and cracks of graphene. Here, we report a facile transfer-free graphene synthesis method through nickel and carbon co-deposited layer, which does not require separately deposited catalytic nickel and carbon source layers. The 100 nm NiC layer was deposited on the top of $SiO_2/Si$ substrates by nickel and carbon co-deposition. When the sample was annealed at $1000^{\circ}C$, the carbon atoms diffused through the NiC layer and deposited on both sides of the layer to form graphene upon cooling. The remained NiC layer was removed by using nickel etchant, and graphene was then directly obtained on $SiO_2/Si$ without any transfer process. Raman spectroscopy was carried out to confirm the quality of resulted graphene layer. Raman spectra revealed that the resulted graphene was at high quality with low degree of $sp^3$-type structural defects. Furthermore, the Raman analysis results also demonstrated that gas flow ratio (Ar : $CH_4$) during the NiC deposition and annealing temperature significantly influence not only the number of graphene layers but also structural defects. This facile non-transfer process would consequently facilitate the future graphene research and industrial applications.