Open Access Article
Michael
Fralaide
abc,
Yuanchen
Chi
ab,
Shen
Chen
ab,
Raghunandan
B-Iyer
bc,
Yilong
Luan
ab,
Ruth
Shinar
c,
Joseph
Shinar
abc,
Cai-Zhuang
Wang
ab,
Marek
Kolmer
b,
Michael C.
Tringides
*ab and
Zhe
Fei
*ab
aDepartment of Physics and Astronomy, Iowa State University, Ames, Iowa 50011, USA. E-mail: zfei@iastate.edu; mctringi@iastate.edu
bAmes Laboratory, U.S. Department of Energy, Iowa State University, Ames, Iowa 50011, USA
cDepartment of Electrical & Computer Engineering, Iowa State University, Ames, Iowa 50011, USA
First published on 20th March 2026
We report nano-infrared (IR) imaging and spectroscopy of epitaxial bilayer graphene (BLG) on silicon carbide (SiC) partially intercalated with gadolinium (Gd). Gd intercalation produces a high density of nanoscale conducting domains that exhibit pronounced IR enhancement at frequencies above the SiC phonon resonance and pronounced amplitude suppression at the resonance. Both effects originate from the increased local optical conductivity induced by Gd. Quantitative modeling of the nano-IR spectra shows that the conductivity of intercalated regions is enhanced by more than a factor of two relative to pristine BLG. This enhancement is attributed to the electronic decoupling of the graphene layers combined with substantial charge transfer from the intercalated atoms. These results demonstrate that controlled metal intercalation enables spatially resolved tuning of the electronic and optical responses of wafer-scale graphene, providing a versatile platform for graphene-based optoelectronic and nanophotonic applications.
Metal intercalation has emerged as a powerful method to tune the properties of epitaxial graphene on SiC.8 By inserting metal atoms at the graphene–substrate interface or between adjacent graphene layers, intercalation can electronically decouple graphene from SiC and modify the interlayer coupling of FLG. As a result, carrier density, Fermi-level position, and band structure can be precisely tailored. Depending on the choice of the intercalant, additional functionalities—such as magnetism, superconductivity, and topologically nontrivial phases—can be introduced,9–16 significantly expanding the capabilities of graphene-based heterostructures for spintronics, nanoelectronics, and emerging quantum technologies.
Among the various intercalants studied, gadolinium (Gd) stands out due to its large magnetic moment and strong interaction between localized 4f states and itinerant electrons. Intercalating Gd beneath epitaxial graphene may induce magnetic ordering and spin polarization while preserving the high mobility of graphene. The presence of Gd also modifies interlayer coupling and graphene doping via charge transfer, creating spatial variations in carrier density and work function.17,18 These effects provide opportunities to investigate spin-dependent transport, magneto-optical phenomena, and nanoscale electronic inhomogeneity in graphene.
To date, research on Gd-intercalated epitaxial graphene has relied largely on X-ray photoelectron spectroscopy, low-energy electron diffraction, scanning tunneling microscopy (STM), and angle-resolved photoemission spectroscopy,18–20 which offer valuable insights into atomic configuration and band-structure evolution. However, how Gd intercalation modifies the local optical response and infrared dynamics at the nanoscale remains largely unexplored. A deeper understanding of how Gd intercalation modifies optical responses and infrared dynamics is essential for advancing its use in optoelectronic and photonic devices and for revealing how nanoscale variations in intercalation drive local electronic inhomogeneities.
In this work, we performed systematic nano-infrared (IR) imaging and spectroscopy studies of Gd-intercalated epitaxial bilayer graphene (BLG) on SiC by using a scattering-type scanning near-field optical microscope (s-SNOM). The s-SNOM was built based on a tapping-mode atomic force microscope (AFM), so we can collect both topography and IR images of the sample simultaneously. By coupling the s-SNOM with various IR sources, we performed both nano-IR imaging and spectroscopy on the sample with a spatial resolution of ∼25 nm, which enables visualization and quantitative mapping of nanoscale domains with distinct IR responses. Prior to the nano-IR measurements, we characterized the surface morphology at different stages of growth using STM. By combining nano-IR, AFM, and STM techniques, we obtained a comprehensive understanding of the nanoscale surface features and electronic properties of Gd-intercalated BLG. All nano-IR and AFM measurements were performed at room temperature (293 K). For STM imaging, the large-area (Fig. 1a and b) and high-resolution (Fig. 1c and d) scans were performed at 293 K and 77 K, respectively.
After deposition, the sample was annealed at 850 °C for 20 minutes. Fig. 1b presents an STM image acquired after annealing, showing that most of the fractal clusters observed in Fig. 1a have significantly decreased in size. Only a small number of large clusters remain (e.g., those marked by blue arrows), and these features are stable for many days even under ambient conditions. In addition, several relatively flat domains are visible in Fig. 1b (e.g., those marked by green arrows). These domains correspond to Gd-intercalated regions, where Gd atoms occupy the interlayer spacing between graphene layers during the annealing process. Near the centers of these domains, additional step-like features are observed, suggesting the formation of a second Gd layer beneath the surface. As shown by the line profile, the thickness of each Gd layer is approximately 0.25 nm.
These distinct topographic features are likely the result of a defect-assisted intercalation mechanism.25,26 In this process, Gd atoms initially penetrate the graphene layers through vacancy defects and subsequently spread laterally to form the first intercalated layer. Continued incorporation of Gd atoms through the same defect can lead to the formation of an additional intercalated layer. Fig. 1(c) shows a zoomed-in STM image at the boundary of an intercalated domain, where pristine bilayer graphene (BLG) exhibiting the characteristic 6 × 6 moiré pattern (center right) is surrounded by intercalated regions with increased surface roughness. Similar intercalation-induced surface morphologies have been reported previously.17,18 Finally, Fig. 1d presents a higher-resolution STM image acquired on a flat intercalated domain, in which the graphene lattice is clearly resolved, confirming that the Gd atoms reside beneath the top graphene layer.
From the AFM topography image (Fig. 2b), one can see again the stepper terrain as well as the big Gd clusters, like those on the STM image (Fig. 1b). The Gd clusters are also seen in the AFM phase image (Fig. 2c), where the majority part appears to be brownish, corresponding to “near-pristine” BLG not affected by the Gd intercalation process. For convenience, we set the phase value (ψ) of the majority region to be zero in Fig. 2c. The Gd clusters (e.g., a pair of such particles marked with blue arrows) appear to have a very high AFM phase (ψ ∼ 0.3 rad.), indicating they are stiffer than the relatively softer pristine BLG. From the nano-IR image (Fig. 2d), we observe that these clusters appear to be darker (i.e., lower IR amplitude), signaling that they are less conductive than BLG. Therefore, Gd clusters are likely not fully crystalline and hence not very metallic.
Another type of feature in the AFM phase image (Fig. 2c) corresponds to patches of domains with sizes varying from tens to hundreds of nanometers. For convenience, we mark a typical one with green arrows in all data images in Fig. 2. These domains have an intermediate phase signal of ψ ∼ 0.1 rad. Indicating they are slightly stiffer than graphene layers. They also appear to be slightly higher (0.3–0.5 nm) than adjacent BLG regions from the AFM topography image (seen more clearly in the zoomed-in images in Fig. 3). Based on these characteristics, we conclude that these domains are Gd-intercalated regions like those seen previously in the STM images (see Fig. 1b and c). From the nano-IR image (Fig. 2d), one can see that these domains appear to have higher IR signals than the rest of the sample areas, so they are more conductive. In addition, we found that the IR contrast of these bright domains varies dramatically from one to another (see Fig. 2d), indicating that they exhibit different conductivities. The variation of IR signals and conductivities is likely due to the differences in the amount of intercalated Gd atoms within each domain.
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| Fig. 3 (a and b) Zoomed-in AFM topography and AFM phase images of the sample region marked by the white dashed square in Fig. 2b. (c–f) Nano-IR imaging data of the sample when varying the incident light from 9.2 to 10.7 μm. (g) Line profiles extracted along the dashed lines in panels c–f. The profiles are displaced vertically for clarity. | ||
To better visualize all these features, we performed higher-resolution imaging of the sample area marked with a dashed square in Fig. 2b at various excitation wavelengths (λ0). The imaging results are shown in Fig. 3, where we plot the AFM topography (Fig. 3a), AFM phase (Fig. 3b), and nano-IR images (Fig. 3c–f). Here, one can see more clearly Gd-intercalated domains in the AFM and nano-IR images. Again, we pay attention to the large domain at the lower part of the images (marked with a green arrow). Upon close inspection of the nano-IR images, we find that the distribution of the IR signals within the domain is non-uniform. The center of the domain appears to be brighter than the edges. This might be due to a denser distribution of Gd atoms at the center of the domain, where the graphene properties are more dramatically altered.
Now we examine the λ0-dependence of IR images (Fig. 3c–f), where one can see that the domain contrast clearly changes with varying IR wavelengths. For quantitative analysis, we plot in Fig. 3g the line profiles extracted across the domain (along the dashed lines in Fig. 3c–f). These profiles are normalized to the background signal of non-intercalated BLG. From Fig. 3g, one can see that the maximum IR contrast increases from ∼70% to ∼130% from 9.2 to 9.6 μm and then drops to about 40% at 10.7 μm. The change in IR contrast among different IR wavelengths, as discussed in detail below, is due to the optical phonon on SiC that peaks around 11.5 μm.
From Fig. 4c and d, one can spot the Gd-intercalated domain (centered at around x = 800 nm) due to its different IR contrast. At the phonon resonance (Fig. 4c), the domain region appears to be darker compared to neighboring pristine BLG regions. Away from the phonon resonance (Fig. 4d), on the other hand, the domain is brighter. The λ0-dependent IR contrast of the domain can be visualized more clearly in the horizontal line profiles (Fig. 4e and f) extracted directly from the hyperspectral images. These profiles serve the same purpose as those of Fig. 3g but were taken with a different approach and cover a broader wavelength region. From both the hyperspectral images and profiles, one can see that the Gd-intercalated domain has a positive IR contrast relative to pristine BLG off the SiC phonon (e.g., λ0 < 10.5 μm), which is consistent with the results shown in Fig. 3g. Nevertheless, when it is on top of the phonon (e.g., λ0 > 11 μm), the domain shows a negative IR contrast.
The unique IR contrasts can be seen more clearly in Fig. 5a, where we plot together the nano-IR spectra of the Gd-intercalated BLG domain, pristine BLG region, and a bare SiC substrate. As shown in the spectra (Fig. 5a), the SiC phonon resonance, which peaked at 11.5 μm, is the dominant feature within the spectroscopic window. At shorter wavelengths below the phonon resonance, Gd-intercalated BLG has higher signals than pristine BLG and the bare SiC substrate. On top of the phonon resonance, in contrast, the signal of SiC is higher than that of the pristine and intercalated BLG. The distinct IR contrasts on and off the phonon resonance both originate from the high conductivity of the two types of BLG. Away from the phonon, the graphene layers are the main contributors to the s-SNOM signal, so higher conductivity leads to a higher IR amplitude signal. Atop the phonon, SiC is the dominant source of the s-SNOM signal, and graphene layers quench the SiC signal due to the electronic screening effect. Enhanced conductivity of the graphene layers due to Gd intercalation results in more effective screening and consequently a weaker phonon resonance.
The key modeling parameter of the BLG sample (with or without Gd-intercalation) is the optical conductivity σ(E), where E is the IR energy. Note that the Fermi energy (EF) of epitaxial BLG is high (>0.3 eV) (see ref. 10), the interband transitions (only enabled at energies above 2EF) are far above our energy range (0.1–0.15 eV). Therefore, we only consider the intraband transitions when formulating the optical conductivity. For pristine BLG, the Drude conductivity can be written as:30
![]() | (1) |
Based on the BLG modeling result, we can now evaluate the conductivity enhancement by Gd intercalation. Here, we set the optical conductivity of Gd-intercalated BLG in the model to be
| σGd-BLG = ησBLG, | (2) |
The sizable enhancement of conductivity is a direct signature of the significant change of electronic properties of BLG due to Gd intercalation. According to the previous study,21 the Gd atoms are likely intercalated between the top two graphene layers when annealed at a relatively low temperature (≤1000 °C). In other words, BLG is decoupled and becomes two isolated SLG due to Gd intercalation (see Fig. 2a). In addition, the intercalated Gd atoms can also significantly dope the adjacent graphene layers due to charge transfer.21,31 Therefore, the conductivity enhancement observed in our work is likely due to the contribution from both the decoupling and doping of the top two graphene layers by Gd.
For example, in the case of η = 2.4, the two decoupled graphene layers contribute to a total of 2.4 times of σBLG(EF = 0.34 eV). Assuming that the two SLG layers are equally doped by Gd atoms, they each contribute 1.2 times of σBLG. Similar to BLG, the interband transitions only occur at very high energies (≥2EF), so we only need to consider the Drude component of the optical conductivity, as written below:
![]() | (3) |
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