Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium
Smoothing Graphene
Several methods have been reported for the growth of monolayer graphene into areas large enough for integration into silicon electronics. However, the electronic properties of the graphene are often degraded by grain boundaries and wrinkles. Lee et al. (p. 286, published online 3 April) showed that flat, single crystals of monolayer graphene can be grown by chemical-vapor deposition on silicon wafers covered by a germanium layer that aligns the grains. The graphene can be dry-transferred to other substrates, and the germanium layer can be reused for further growth cycles.
Abstract
The uniform growth of single-crystal graphene over wafer-scale areas remains a challenge in the commercial-level manufacturability of various electronic, photonic, mechanical, and other devices based on graphene. Here, we describe wafer-scale growth of wrinkle-free single-crystal monolayer graphene on silicon wafer using a hydrogen-terminated germanium buffer layer. The anisotropic twofold symmetry of the germanium (110) surface allowed unidirectional alignment of multiple seeds, which were merged to uniform single-crystal graphene with predefined orientation. Furthermore, the weak interaction between graphene and underlying hydrogen-terminated germanium surface enabled the facile etch-free dry transfer of graphene and the recycling of the germanium substrate for continual graphene growth.
Get full access to this article
View all available purchase options and get full access to this article.
Already a Subscriber?Sign In
Supplementary Material
Summary
Materials and Methods
Figs. S1 to S14
Resources
File (lee.sm.pdf)
References and Notes
1
Singh A. K., Yakobson B. I., Electronics and magnetism of patterned graphene nanoroads. Nano Lett. 9, 1540–1543 (2009).
2
Zhang C., Chen L., Ma Z., Orientation dependence of the optical spectra in graphene at high frequencies. Phys. Rev. B 77, 241402 (2008).
3
Emtsev K. V., Bostwick A., Horn K., Jobst J., Kellogg G. L., Ley L., McChesney J. L., Ohta T., Reshanov S. A., Röhrl J., Rotenberg E., Schmid A. K., Waldmann D., Weber H. B., Seyller T., Towards wafer-size graphene layers by atmospheric pressure graphitization of silicon carbide. Nat. Mater. 8, 203–207 (2009).
4
Berger C., Song Z., Li X., Wu X., Brown N., Naud C., Mayou D., Li T., Hass J., Marchenkov A. N., Conrad E. H., First P. N., de Heer W. A., Electronic confinement and coherence in patterned epitaxial graphene. Science 312, 1191–1196 (2006).
5
Li X., Cai W., An J., Kim S., Nah J., Yang D., Piner R., Velamakanni A., Jung I., Tutuc E., Banerjee S. K., Colombo L., Ruoff R. S., Large-area synthesis of high-quality and uniform graphene films on copper foils. Science 324, 1312–1314 (2009).
6
Kim K. S., Zhao Y., Jang H., Lee S. Y., Kim J. M., Kim K. S., Ahn J. H., Kim P., Choi J. Y., Hong B. H., Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706–710 (2009).
7
Bartelt N. C., McCarty K. F., Graphene growth on metal surfaces. MRS Bull. 37, 1158–1165 (2012).
8
Tsen A. W., Brown L., Levendorf M. P., Ghahari F., Huang P. Y., Havener R. W., Ruiz-Vargas C. S., Muller D. A., Kim P., Park J., Tailoring electrical transport across grain boundaries in polycrystalline graphene. Science 336, 1143–1146 (2012).
9
Wei Y., Wu J., Yin H., Shi X., Yang R., Dresselhaus M., The nature of strength enhancement and weakening by pentagon-heptagon defects in graphene. Nat. Mater. 11, 759–763 (2012).
10
Hao Y., Bharathi M. S., Wang L., Liu Y., Chen H., Nie S., Wang X., Chou H., Tan C., Fallahazad B., Ramanarayan H., Magnuson C. W., Tutuc E., Yakobson B. I., McCarty K. F., Zhang Y. W., Kim P., Hone J., Colombo L., Ruoff R. S., The role of surface oxygen in the growth of large single-crystal graphene on copper. Science 342, 720–723 (2013).
11
Materials and methods are available as supplementary materials on Science Online.
12
Sutter P. W., Flege J.-I., Sutter E. A., Epitaxial graphene on ruthenium. Nat. Mater. 7, 406–411 (2008).
13
Nie S., Wofford J. M., Bartelt N. C., Dubon O. D., McCarty K. F., Origin of the mosaicity in graphene grown on Cu(111). Phys. Rev. B 84, 155425 (2011).
14
Robinson Z. R., Tyagi P., Mowll T. R., Ventrice C. A., Hannon J. B., Argon-assisted growth of epitaxial graphene on Cu(111). Phys. Rev. B 86, 235413 (2012).
15
Zhang X., Xu Z., Hui L., Xin J., Ding F., How the orientation of graphene is determined during chemical vapor deposition growth. J. Phys. Chem. Lett. 3, 2822–2827 (2012).
16
Thanh Trung P., Joucken F., Campos-Delgado J., Raskin J.-P., Hackens B., Sporken R., Direct growth of graphitic carbon on Si(111). Appl. Phys. Lett. 102, 013118 (2013).
17
Loscutoff P. W., Bent S. F., Reactivity of the germanium surface: Chemical passivation and functionalization. Annu. Rev. Phys. Chem. 57, 467–495 (2006).
18
Scace R. I., Slack G. A., Solubility of carbon in silicon and germanium. J. Chem. Phys. 30, 1551–1555 (1959).
19
Wang G., Zhang M., Zhu Y., Ding G., Jiang D., Guo Q., Liu S., Xie X., Chu P. K., Di Z., Wang X., Direct growth of graphene film on germanium substrate. Sci. Rep 3, 2465 (2013).
20
Lieten R., Degroote S., Leys M., Posthuma N., Borghs G., Solid phase epitaxy of amorphous Ge on Si in N2 atmosphere. Appl. Phys. Lett. 94, 112113 (2009).
21
Bao W., Miao F., Chen Z., Zhang H., Jang W., Dames C., Lau C. N., Controlled ripple texturing of suspended graphene and ultrathin graphite membranes. Nat. Nanotechnol. 4, 562–566 (2009).
22
Gibbons D. F., Thermal expansion of some crystals with the diamond structure. Phys. Rev. 112, 136–140 (1958).
23
Ferrari A. C., Robertson J., Interpretation of Raman spectra of disordered and amorphous carbon. Phys. Rev. B 61, 14095–14107 (2000).
24
Gao L., Ren W., Xu H., Jin L., Wang Z., Ma T., Ma L. P., Zhang Z., Fu Q., Peng L. M., Bao X., Cheng H. M., Repeated growth and bubbling transfer of graphene with millimetre-size single-crystal grains using platinum. Nat. Commun. 3, 699 (2012).
25
Lahiri J., Lin Y., Bozkurt P., Oleynik I. I., Batzill M., An extended defect in graphene as a metallic wire. Nat. Nanotechnol. 5, 326–329 (2010).
26
Zhu W., Low T., Perebeinos V., Bol A. A., Zhu Y., Yan H., Tersoff J., Avouris P., Structure and electronic transport in graphene wrinkles. Nano Lett. 12, 3431–3436 (2012).
27
Hamada I., Otani M., Comparative van der Waals density-functional study of graphene on metal surfaces. Phys. Rev. B 82, 153412 (2010).
28
Kim J., Park H., Hannon J. B., Bedell S. W., Fogel K., Sadana D. K., Dimitrakopoulos C., Layer-resolved graphene transfer via engineered strain layers. Science 342, 833–836 (2013).
29
Kang J., Shin D., Bae S., Hong B. H., Graphene transfer: Key for applications. Nanoscale 4, 5527–5537 (2012).
30
Nair R. R., Blake P., Grigorenko A. N., Novoselov K. S., Booth T. J., Stauber T., Peres N. M., Geim A. K., Fine structure constant defines visual transparency of graphene. Science 320, 1308 (2008).
31
Zhang Y., Tan Y. W., Stormer H. L., Kim P., Experimental observation of the quantum Hall effect and Berry’s phase in graphene. Nature 438, 201–204 (2005).
32
Venugopal A., Chan J., Li X., Magnuson C. W., Kirk W. P., Colombo L., Ruoff R. S., Vogel E. M., Effective mobility of single-layer graphene transistors as a function of channel dimensions. J. Appl. Phys. 109, 104511 (2011).
33
Dimitrakopoulos C., Lin Y.-M., Grill A., Farmer D. B., Freitag M., Sun Y., Han S.-J., Chen Z., Jenkins K. A., Zhu Y., Liu Z., McArdle T. J., Ott J. A., Wisnieff R., Avouris P., Wafer-scale epitaxial graphene growth on the Si-face of hexagonal SiC (0001) for high frequency transistors. J. Vac. Sci. Technol. B 28, 985–992 (2010).
Information & Authors
Information
Published In
Science
Volume 344 | Issue 6181
18 April 2014
18 April 2014
Copyright
Copyright © 2014, American Association for the Advancement of Science.
Article versions
You are viewing the most recent version of this article.
Submission history
Received: 14 February 2014
Accepted: 20 March 2014
Published in print: 18 April 2014
Acknowledgments
We are grateful to J.-H. Ahn, B. H. Hong, and Y. J. Song for helpful discussions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (Ministry of Science, ICT, and Future Planning) (no. 2007-0054845). D.W. acknowledges support from the Basic Science Research Program through the NRF (no. 2009-0083540) and Samsung-SKKU graphene center.
Authors
Metrics & Citations
Metrics
Article Usage
Altmetrics
Citations
Export citation
Select the format you want to export the citation of this publication.
Cited by
- New Insight into the Metal-Catalyst-Free Direct Chemical Vapor Deposition Growth of Graphene on Silicon Substrates, The Journal of Physical Chemistry C, 125, 3, (1774-1783), (2021).https://doi.org/10.1021/acs.jpcc.0c07457
- Controlled growth of in-plane graphene/h-BN heterostructure on a single crystal Ge substrate, Applied Surface Science, 554, (149655), (2021).https://doi.org/10.1016/j.apsusc.2021.149655
- Epitaxial growth of wafer scale antioxidant single-crystal graphene on twinned Pt(111), Carbon, 181, (225-233), (2021).https://doi.org/10.1016/j.carbon.2021.05.027
- Growth and in situ characterization of 2D materials by chemical vapour deposition on liquid metal catalysts: a review , Nanoscale, 13, 6, (3346-3373), (2021).https://doi.org/10.1039/D0NR07330J
- The Fabrication of Wrinkle‐Free Graphene Patterns on Ge(110) Substrate, physica status solidi (b), 258, 5, (2000560), (2021).https://doi.org/10.1002/pssb.202000560
- Realizing the Intrinsic Anisotropic Growth of 1T′ ReS 2 on Selected Au(101) Substrate toward Large‐Scale Single Crystal Fabrication , Advanced Functional Materials, 31, 28, (2102138), (2021).https://doi.org/10.1002/adfm.202102138
- Suspended graphene on germanium: selective local etching via laser-induced photocorrosion of germanium, 2D Materials, 8, 3, (035043), (2021).https://doi.org/10.1088/2053-1583/abfedc
- Defect-Free Mechanical Graphene Transfer Using n- Doping Adhesive Gel Buffer , ACS Nano, 15, 7, (11276-11284), (2021).https://doi.org/10.1021/acsnano.0c10798
- Pristine Graphene Insertion at the Metal/Semiconductor Interface to Minimize Metal-Induced Gap States, ACS Applied Materials & Interfaces, 13, 19, (22828-22835), (2021).https://doi.org/10.1021/acsami.1c03299
- Emerging 2D Memory Devices for In‐Memory Computing, Advanced Materials, 33, 29, (2007081), (2021).https://doi.org/10.1002/adma.202007081
- See more
Loading...
View Options
Get Access
Log in to view the full text
AAAS login provides access to Science for AAAS Members, and access to other journals in the Science family to users who have purchased individual subscriptions.
- Become a AAAS Member
- Activate your AAAS ID
- Purchase Access to Other Journals in the Science Family
- Account Help
Log in via OpenAthens.
Log in via Shibboleth.
More options
Register for free to read this article
As a service to the community, this article is available for free. Login or register for free to read this article.
Buy a single issue of Science for just $15 USD.
View options
PDF format
Download this article as a PDF file
Download PDF