Graphene nanowalls (GNWs) are wall-like graphene nanosheets that are oriented vertically on a substrate. GNWs have a unique structure and special optoelectronic properties, which enables their use in photodetectors. In this paper, we use plasma-enhanced chemical vapor deposition to directly grow GNWs onto the surface of an n-type lightly doped Si substrate and to optimize the quality of the GNWs by adjusting the growth time and temperature. Furthermore, after the GNWs are lithographically patterned, we use a GNW-Si Schottky structure to develop photodetector arrays which are capable of detecting light from the visible to infrared light spectral range. Throughout the process, GNWs are directly synthesized on a Si substrate without using a catalyst or a transfer step. The process is simple and efficient. Under laser illumination at a wavelength of 792 nm, the highest on/off ratio at zero bias is approximately 105, and the specific detectivity is 7.85 × 106 cm Hz1/2/W. Under a reverse bias of 4 V, the measured responsivity of the detector reaches 1 A/W at room temperature. The device can also produce a light response in the near-infrared band. Upon laser illumination at a wavelength of 1550 nm, the detector shows a responsivity of 12 mA/W at room temperature.
A technique for the in situ growth of patterned graphene by CVD has been achieved directly on insulating substrates at 800 °C. The graphene growth is catalyzed by a Ni−Cu alloy sacrificial layer, which integrates many advantages such as being lithography-free, and almost wrinkle-free, with a high repeatability and rapid growth. The etching method of the metal sacrificial layer is the core of this technique, and the mechanism is analyzed. Graphene has been found to play an important role in accelerating etching speeds. The Ni−Cu alloy exhibits a high catalytic activity, and thus, high-quality graphene can be obtained at a lower temperature. Moreover, the Ni−Cu layer accommodates a limited amount of carbon atoms, which ensures a high monolayer ratio of the graphene. The carbon solid solubility of the alloy is calculated theoretically and used to explain the experimental findings. The method is compatible with the current semiconductor process and is conducive to the industrialization of graphene devices.
Vertically oriented graphene (VG) has attracted attention for years, but the growth mechanism is still not fully revealed. The electric field may play a role, but the direct evidence and exactly what role it plays remains unclear. Here, we conduct a systematic study and find that in plasma-enhanced chemical vapor deposition, the VG growth preferably occurs at spots where the local field is stronger, for example, at GaN nanowire tips. On almost round-shaped nanoparticles, instead of being perpendicular to the substrate, the VG grows along the field direction, that is, perpendicular to the particles' local surfaces. Even more convincingly, the sheath field is screened to different degrees, and a direct correlation between the field strength and the VG growth is observed. Numerical calculation suggests that during the growth, the field helps accumulate charges on graphene, which eventually changes the cohesive graphene layers into separate three-dimensional VG flakes. Furthermore, the field helps attract charged precursors to places sticking out from the substrate and makes them even sharper and turn into VG. Finally, we demonstrate that the VG-covered nanoparticles are benign to human blood leukocytes and could be considered for drug delivery. Our research may serve as a starting point for further vertical two-dimensional material growth mechanism studies.
Chemical vapor deposited graphene suffers from two problems: transfer from metal catalysts to insulators, and photoresist induced degradation during patterning. Both result in macroscopic and microscopic damages such as holes, tears, doping, and contamination, translated into property and yield dropping. We attempt to solve the problems simultaneously. A nickel thin film is evaporated on SiO as a sacrificial catalyst, on which surface graphene is grown. A polymer (PMMA) support is spin-coated on the graphene. During the Ni wet etching process, the etchant can permeate the polymer, making the etching efficient. The PMMA/graphene layer is fixed on the substrate by controlling the surface morphology of Ni film during the graphene growth. After etching, the graphene naturally adheres to the insulating substrate. By using this method, transfer-free, lithography-free and fast growth of graphene realized. The whole experiment has good repeatability and controllability. Compared with graphene transfer between substrates, here, no mechanical manipulation is required, leading to minimal damage. Due to the presence of Ni, the graphene quality is intrinsically better than catalyst-free growth. The Ni thickness and growth temperature are controlled to limit the number of layers of graphene. The technology can be extended to grow other two-dimensional materials with other catalysts.
A method for direct growth of graphene nanowalls (GNWs) on an insulating substrate by plasma enhanced chemical vapor deposition (PECVD) is reported. The effects of growth temperature, plasma power, carbon source concentration, gas ratio and growth time on the quality of GNWs are systematically studied. The Raman spectrum shows that the obtained GNWs have a relatively high quality with a D to G peak ratio (ID/IG) of 0.42. Based on the optimization of the quality of GNWs, a field-effect transistor (FET) photodetector is prepared for the first time, and its photo-response mechanism is analyzed. The responsivity of the photodetector is 160 mA/W at 792 nm and 55 mA/W at 1550 nm. The results reveal that the GNWs are promising for high performance photodetectors.
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