Submitted Successfully!
To reward your contribution, here is a gift for you: A free trial for our video production service.
Thank you for your contribution! You can also upload a video entry or images related to this topic.
Version Summary Created by Modification Content Size Created at Operation
1 -- 1273 2022-06-24 11:45:38 |
2 Format correction -2 word(s) 1271 2022-06-27 02:39:14 |

Video Upload Options

Do you have a full video?

Confirm

Are you sure to Delete?
Cite
If you have any further questions, please contact Encyclopedia Editorial Office.
Hagendoorn, Y.;  Pandraud, G.;  Vollebregt, S.;  Morana, B.;  Sarro, P.;  Steeneken, P. Integration of CVD Graphene on Silicon Wafers. Encyclopedia. Available online: https://encyclopedia.pub/entry/24475 (accessed on 04 October 2024).
Hagendoorn Y,  Pandraud G,  Vollebregt S,  Morana B,  Sarro P,  Steeneken P. Integration of CVD Graphene on Silicon Wafers. Encyclopedia. Available at: https://encyclopedia.pub/entry/24475. Accessed October 04, 2024.
Hagendoorn, Yelena, Gregory Pandraud, Sten Vollebregt, Bruno Morana, Pasqualina Sarro, Peter Steeneken. "Integration of CVD Graphene on Silicon Wafers" Encyclopedia, https://encyclopedia.pub/entry/24475 (accessed October 04, 2024).
Hagendoorn, Y.,  Pandraud, G.,  Vollebregt, S.,  Morana, B.,  Sarro, P., & Steeneken, P. (2022, June 25). Integration of CVD Graphene on Silicon Wafers. In Encyclopedia. https://encyclopedia.pub/entry/24475
Hagendoorn, Yelena, et al. "Integration of CVD Graphene on Silicon Wafers." Encyclopedia. Web. 25 June, 2022.
Integration of CVD Graphene on Silicon Wafers
Edit

The exceptional electronic, optical and mechanical properties of graphene can lead to revolutionary new devices. Since the transfer process of graphene from a dedicated growth substrate to another substrate is prone to induce defects and contamination and can increase costs, there is a large interest in methods for growing graphene directly on silicon wafers. It has become clear that chemical vapor deposition (CVD) is the most promising process to guarantee large-area high-quality graphene.

graphene synthesis CVD nanofabrication thin films silicon technology

1. Introduction

Since the discovery of graphene in 2004, it has become increasingly clear that the exceptional electronic, optical and mechanical properties of this material can lead to revolutionary new devices. Next generation transistors, RF circuits, optoelectronic devices and sensors with huge performance merits might become feasible. For producing such devices in high-volume and creating hybrid circuits comprising both graphene and silicon devices, it is highly desirable to integrate them with advanced complementary metal-oxide-semiconductor (CMOS) technology.
To realize this integration [1], production methods for fabricating graphene layers with dimensions equal to the size of a silicon wafer, up to 300 mm diameter, need to be developed. Moreover, it is required that the graphene can be deposited and patterned on silicon wafers without degrading its quality. After intense scientific and industrial research during the last decade, it now has become clear that chemical vapor deposition (CVD) is probably the most promising process to guarantee large-area high-quality graphene [2].

2. Transfer-Based Integration

In modern CVD processes, graphene is grown on foils, or thin films of transition metals, the most common of which are: Cu, Ni, Mo and Pt. For CMOS integration, the graphene needs to be transferred from these foils onto a silicon wafer. There are several ways to achieve this [3], but the procedure usually follows these steps: first a transfer polymer layer such as Poly Methyl Methacrylate (PMMA) is coated on the graphene, and the transition metal foil is selectively removed with a suitable etchant, after which the transfer polymer with graphene is placed on a silicon wafer (Figure 1a top). As the last step, graphene can be patterned using conventional lithography methods (Figure 1a bottom).
Figure 1. Schematic flows for transfer-based and transfer-free integration of CVD graphene on silicon wafers. (a) Transfer-based integration flow. (b) Transfer-free integration flow, growing graphene locally on top of a seed layer (purple). (c) Transfer-free integration flow growing graphene under a seed layer, where the yellow blocking structure layer is used to define the local graphene growth region. The blue layer in the figure can be the CMOS backend SiO2 layer, or any other interface of choice.
This transfer-based CVD graphene integration route has the advantage that the growth of graphene can be optimized completely independently from the substrate, enabling high-quality graphene to be integrated, without exposing the substrate to high temperatures. However, it also poses challenges, since the transfer procedure can result in imperfections in the CVD graphene due to (polymer) contamination, membrane fracture, wrinkling, and strain non-uniformities [4]. The grain boundaries in the polycrystalline transition metal foils or films that are used to grow the CVD graphene can also be a source of imperfections [5]. Although transfer-based CMOS integration is still the method of choice [2], these challenges have not been fully solved, such that actual device performance, and device-to-device uniformity continue to be limited by transfer related imperfections.

3. Transfer-Free Integration

Considering the aforementioned drawbacks of transfer-based graphene flows, it is of interest to investigate alternative ’transfer-free’ methodologies, where the graphene is grown directly on the substrate, such that the transfer process can be eliminated. However, the number of substrates on which graphene can be grown has appeared to be limited. Moreover, the high electrical conductivity and reflectivity of the transition metal substrates that are commonly used for graphene growth prohibit many device applications. A notable exception appeared to be silicon carbide, which allows direct growth of single-layer graphene on its surface and is still a strong contender for enabling graphene integration, despite the high price of crystalline silicon carbide wafers limiting production volumes.
An alternative route towards transfer-free graphene growth on silicon wafers is the use of a seed layer that is deposited on top of the substrate wafer for growing graphene. For such growth using a seed layer, the transition metals Cu, Ni, Mo and Pt, on which CVD graphene growth has been established, are logical choices. With Mo and Pt being the preferred seed materials, since Ni and Cu tend to form silicides or diffuse into the silicon faster.
During the last years, it was shown that few-layer CVD graphene can be grown on Mo seed layers [6] that are as thin as 50 nm (Figure 1b top). Moreover, it was demonstrated that after graphene growth it was possible to remove (Figure 1b bottom) the seed layer by underetching [7][8][9]. This resulted in locally patterned, transfer-free graphene structures on the substrate that, after electrical contacting, function as gas sensors [7] and pressure sensors [9][10]. This transfer-free growth of graphene certainly has a strong potential, in particular for micromechanical sensor applications, even though it does not offer very high electronic mobility and cannot be used for growing single monolayers of graphene.
Another route toward transfer-free graphene integration is by using Pt seed layers in a process flow where graphene grows beneath the seed layer, at the SiO2/Pt interface, as shown in Figure 1c. This process is combining the benefits of CVD graphene growth on Pt with a transfer-free integration on silicon wafers. The process involves local graphene growth at the Pt/SiO2 interface, after which the Pt seed layer is removed. This process reduces organic contamination, mechanical stress and other potential challenges of transfer-based process flows. Moreover, an additional intermediate, adhesion layer of thin film of Ta metal between Pt and SiO2 can locally inhibit the graphene growth with designed patterns. A similar study has been done by implementing a Ni thin film as a seed layer [11]; however, in that work the high carbon solubility of the metal was an impactful bottleneck towards control of the number of graphene layers.
Platinum was one of the first transition metals that was used as a substrate for graphene CVD growth [12][13][14][15][16][17][18][19]. It follows from simulations that the distance between the graphene layer and the Pt substrate is 3.1 Å, which is significantly larger than that of CVD on Cu or Ni (2.24 Åand 2.01 Å) [14][20][21][22][23]. This large distance results in a small average adhesive energy per carbon atom (∼39 meV) [14][20], minimizing effects of the substrate on the graphene layer. Moreover Pt is more resistant to oxidation than Cu and Ni substrates. These properties have enabled the growth of large single-crystalline graphene islands on the platinum surface.
When graphene is grown on Cu or Ni foils, the foil is often etched away after the growth process. However, Pt foils are costly, and reuse of the foils is therefore often preferred, which has led to the development of processes to delaminate the graphene from the Pt surface [24], or grow it on much thinner Pt layers [25]. Growth on Pt can thus yield high-quality graphene, if the transfer challenges discussed in Section 2 can be dealt with. 

4. Conclusion and Outlook

Due to the difficulties related to transfer-based integration of graphene, transfer-less or direct growth approaches for integrating graphene on silicon and CMOS have been gaining growing attention. The drawback of these transfer-less schemes is however that the growth temperatures are so high that they will lead to detrimental diffusion of the p and n-type dopants in CMOS transistors. For that reason other 2D materials, that can be grown directly on silicon substrates, are also receiving increasing attention as potential materials for CMOS integration and might thus might have a better chance for playing an important role in next-generation nano-electronic devices. 

References

  1. Akinwande, D.; Huyghebaert, C.; Wang, C.H.; Serna, M.I.; Goossens, S.; Li, L.J.; Wong, H.S.P.; Koppens, F.H. Graphene and two-dimensional materials for silicon technology. Nature 2019, 573, 507–518.
  2. Neumaier, D.; Pindl, S.; Lemme, M.C. Integrating graphene into semiconductor fabrication lines. Nat. Mater. 2019, 18, 525–529.
  3. Ullah, S.; Yang, X.; Ta, H.Q.; Hasan, M.; Bachmatiuk, A.; Tokarska, K.; Trzebicka, B.; Fu, L.; Rummeli, M.H. Graphene transfer methods: A review. Nano Res. 2021, 14, 3756–3772.
  4. Wagner, S.; Weisenstein, C.; Smith, A.D.; Östling, M.; Kataria, S.; Lemme, M.C. Graphene transfer methods for the fabrication of membrane-based NEMS devices. Microelectron. Eng. 2016, 159, 108–113.
  5. Zhu, W.; Low, T.; Perebeinos, V.; Bol, A.A.; Zhu, Y.; Yan, H.; Tersoff, J.; Avouris, P. Structure and elctronic transport in graphene wrinkles. Nano Lett. 2012, 12, 3431–3436.
  6. Grachova, Y.; Vollebregt, S.; Lacaita, A.L.; Sarro, P.M. High Quality Wafer-scale CVD Graphene on Molybdenum Thin Film for Sensing Application. Procedia Eng. 2014, 87, 1501–1504.
  7. Ricciardella, F.; Vollebregt, S.; Polichetti, T.; Alfano, B.; Massera, E.; Sarro, P.M. High sensitive gas sensors realized by a transfer-free process of CVD graphene. In Proceedings of the 2016 IEEE SENSORS, Orlando, FL, USA, 30 October–3 November 2016; pp. 1–3.
  8. Vollebregt, S.; Alfano, B.; Ricciardella, F.; Giesbers, A.J.M.; Grachova, Y.; van Zeijl, H.W.; Polichetti, T.; Sarro, P.M. A transfer-free wafer-scale CVD graphene fabrication process for MEMS/NEMS sensors. In Proceedings of the 2016 IEEE 29th International Conference on Micro Electro Mechanical Systems (MEMS), Shanghai, China, 24–28 January 2016; pp. 17–20.
  9. Vollebregt, S.; Dolleman, R.J.; van der Zant, H.S.J.; Steeneken, P.G.; Sarro, P.M. Suspended graphene beams with tunable gap for squeeze-film pressure sensing. In Proceedings of the 2017 19th International Conference on Solid-State Sensors, Actuators and Microsystems (TRANSDUCERS), Kaohsiung, Taiwan, 18–22 June 2017; pp. 770–773.
  10. Romijn, J.; Dolleman, R.J.; Singh, M.; van der Zant, H.S.J.; Steeneken, P.G.; Sarro, P.M.; Vollebregt, S. Multi-layer graphene pirani pressure sensors. Nanotechnology 2021, 32, 335501.
  11. McNerny, D.Q.; Viswanath, B.; Copic, D.; Laye, F.R.; Prohoda, C.; Brieland-Shoultz, A.C.; Polsen, E.S.; Dee, N.T.; Veerasamy, V.S.; Hart, A.J. Direct fabrication of graphene on SiO2 enabled by thin film stress engineering. Sci. Rep. 2014, 4, 5049.
  12. Kang, B.J.; Mun, J.H.; Hwang, C.Y.; Cho, B.J. Monolayer graphene growth on sputtered thin film platinum. J. Appl. Phys. 2009, 106, 104309.
  13. Sutter, P.; Sadowski, J.T.; Sutter, E. Graphene on Pt (111): Growth and substrate interaction. Phys. Rev. B 2009, 80, 245411.
  14. Gao, M.; Pan, Y.; Huang, L.; Hu, H.; Zhang, L.; Guo, H.; Du, S.; Gao, H.J. Epitaxial growth and structural property of graphene on Pt (111). Appl. Phys. Lett. 2011, 98, 033101.
  15. Gao, T.; Xie, S.; Gao, Y.; Liu, M.; Chen, Y.; Zhang, Y.; Liu, Z. Growth and atomic-scale characterizations of graphene on multifaceted textured Pt foils prepared by chemical vapor deposition. ACS Nano 2011, 5, 9194–9201.
  16. Addou, R.; Batzill, M. Defects and domain boundaries in self-assembled terephthalic acid (TPA) monolayers on CVD-grown graphene on Pt (111). Langmuir 2013, 29, 6354–6360.
  17. Lee, B.J.; Jeong, G.H. Comparative study on graphene growth mechanism using Ni films, Ni/Mo sheets, and Pt substrates. Appl. Phys. A 2014, 116, 15–24.
  18. Ma, T.; Ren, W.; Liu, Z.; Huang, L.; Ma, L.P.; Ma, X.; Zhang, Z.; Peng, L.M.; Cheng, H.M. Repeated growth–etching–regrowth for large-area defect-free single-crystal graphene by chemical vapor deposition. ACS Nano 2014, 8, 12806–12813.
  19. Weatherup, R.S.; Shahani, A.J.; Wang, Z.J.; Mingard, K.; Pollard, A.J.; Willinger, M.G.; Schloegl, R.; Voorhees, P.W.; Hofmann, S. In situ graphene growth dynamics on polycrystalline catalyst foils. Nano Lett. 2016, 16, 6196–6206.
  20. Preobrajenski, A.; Ng, M.L.; Vinogradov, A.; Mårtensson, N. Controlling graphene corrugation on lattice-mismatched substrates. Phys. Rev. B 2008, 78, 073401.
  21. Xu, Z.; Buehler, M.J. Interface structure and mechanics between graphene and metal substrates: A first-principles study. J. Phys. Condens. Matter 2010, 22, 485301.
  22. Gao, M.; Pan, Y.; Zhang, C.; Hu, H.; Yang, R.; Lu, H.; Cai, J.; Du, S.; Liu, F.; Gao, H.J. Tunable interfacial properties of epitaxial graphene on metal substrates. Appl. Phys. Lett. 2010, 96, 053109.
  23. Adamska, L.; Lin, Y.; Ross, A.J.; Batzill, M.; Oleynik, I.I. Atomic and electronic structure of simple metal/graphene and complex metal/graphene/metal interfaces. Phys. Rev. B 2012, 85, 195443.
  24. Verguts, K.; Coroa, J.; Huyghebaert, C.; De Gendt, S.; Brems, S. Graphene delamination using ‘electrochemical methods’: An ion intercalation effect. Nanoscale 2018, 10, 5515–5521.
  25. Verguts, K.; Defossez, Y.; Leonhardt, A.; De Messemaeker, J.; Schouteden, K.; Van Haesendonck, C.; Huyghebaert, C.; De Gendt, S.; Brems, S. Growth of millimeter-sized graphene single crystals on Al2O3 (0001)/Pt (111) template wafers using chemical vapor deposition. ECS J. Solid State Sci. Technol. 2018, 7, M195.
More
Information
Contributors MDPI registered users' name will be linked to their SciProfiles pages. To register with us, please refer to https://encyclopedia.pub/register : , , , , ,
View Times: 723
Revisions: 2 times (View History)
Update Date: 27 Jun 2022
1000/1000
ScholarVision Creations