Characterizing Local Electronic States of Twin Boundaries in Copper.

Grain boundaries (GBs) and twin boundaries (TBs) in copper (Cu) are two major planar defects that influence electrical conductivity due to their complex electron transport characteristics, involving electron scattering and electron concentration. Understanding their local electronic states is crucial for the design of future conductor materials. In this study, we characterized electron behaviors at TBs and GBs within one Cu grain using atomic force microscopy. Our findings revealed that, compared with GBs, TBs exhibit better current transport capability (direct-current mode) and larger electromagnetic loss (high-frequency microwave mode). Both kelvin probe force microscopy and theoretical analysis suggested that TBs with smaller lattice disorder possess lower density of states at the Fermi level. The reduced density of states may result in decreased electron scattering and a lower electron concentration at TBs. The latter can be highlighted by the high-frequency skinning effect, manifested as larger electromagnetic loss and weaker high-frequency conductivity.

Electrical Resistivity Measurements of Surface-Coated Copper Foils.

Due to the direct contact between the probe and sample, the contact of the four-probe method is important for the structural integrity of the sample and the accuracy of electrical resistivity measurements, especially for surface-coated metal foils with multilayered structures. Here, we analyzed the accuracy and stability of four-probe method probing on different sides of copper (Cu) foils covered with graphene (Gr). Theoretical simulations showed similar potential distributions on the probe tip when probing on the Cu and Gr sides. The resistivity of the Gr/Cu foil was 2.31 ± 0.02 µΩ·cm when measured by probing on the Cu side, and 2.30 ± 0.10 µΩ·cm when measured by probing on the Gr side. The major difference in the mean deviation is attributed to surface damage. In addition, the method of probing on the Cu side was sensitive to the resistivity changes of Gr induced by polymers with a dielectric constant range of 2~12, which is consistent with the calculations based on the random phase approximation theory. Our results demonstrated that the probing position on the metal side in the four-probe method can effectively protect the structural integrity of the functional surface-coated layer and maintain the high sensitivity of the measurement, providing guidance for the resistivity measurements of other similarly heterogeneous materials.

Radio-Frequency Conductivity Characteristics and Corresponding Mechanism of Graphene/Copper Multilayer Structures.

High-radio-frequency (RF) conductivity is required in advanced electronic materials to reduce the electromagnetic loss and power dissipation of electronic devices. Graphene/copper (Gr/Cu) multilayers possess higher conductivity than silver under direct current conditions. However, their RF conductivity and detailed mechanisms have rarely been evaluated at the micro scale. In this work, the RF conductivity of copper-copper (P-Cu), monolayer-graphene/copper (S-Gr/Cu), and multilayer-graphene/copper (M-Gr/Cu) multilayer structures were evaluated using scanning microwave impedance microscopy (SMIM) and dielectric resonator technique. The results indicated that the order of RF conductivity was M-Gr/Cu < P-Cu < S-Gr/Cu at 3 GHz, contrasting with P-Cu < M-Gr/Cu < S-Gr/Cu at DC condition. Meanwhile, the same trend of M-Gr/Cu < P-Cu < S-Gr/Cu was also observed using the dielectric resonator technique. Based on the conductivity-related Drude model and scattering theory, we believe that the microwave radiation can induce a thermal effect at S-Gr/Cu interfaces, leading to an increasing carrier concentration in S-Gr. In contrast, the intrinsic defects in M-Gr introduce additional carrier scattering, thereby reducing the RF conductivity in M-Gr/Cu. Our research offers a practical foundation for investigating conductive materials under RF conditions.

Effect of Copper Surface Roughness on the High-Temperature Structural Stability of Single-Layer-Graphene.

Graphene (Gr) has shown great potential in the field of oxidation protection for metals. However, numerous studies have shown that Gr will suffer structural degradation on metal surface during high-temperature oxidation, which significantly limited the effectiveness of their oxidation protection. Therefore, understanding the degradation mechanism of Gr is of great interest to enhance their structural stability. Here, the effect of copper (Cu) surface roughness on the high-temperature structural stability of single-layer graphene (SLG) was examined using Cu covered with SLG as a model material. SLG/Cu with different roughness values was obtained via high-temperature annealing of the model material. After high-temperature oxidation at 500 °C, Raman spectra analysis showed that the defect density of the oxidized SLG increased from 41% to 81% when the surface roughness varied from 37 nm to 81 nm. Combined with density functional theory calculations, it was found that the lower formation energy of the C-O bond on rough Cu surfaces (0.19 eV) promoted the formation of defects in SLG. This study may provide guidance for improving the effectiveness of SLG for the oxidation protection of metallic materials.

Two-Step Thermal Transformation of Multilayer Graphene Using Polymeric Carbon Source Assisted by Physical Vapor Deposited Copper.

Direct in situ growth of graphene on dielectric substrates is a reliable method for overcoming the challenges of complex physical transfer operations, graphene performance degradation, and compatibility with graphene-based semiconductor devices. A transfer-free graphene synthesis based on a controllable and low-cost polymeric carbon source is a promising approach for achieving this process. In this paper, we report a two-step thermal transformation method for the copper-assisted synthesis of transfer-free multilayer graphene. Firstly, we obtained high-quality polymethyl methacrylate (PMMA) film on a 300 nm SiO2/Si substrate using a well-established spin-coating process. The complete thermal decomposition loss of PMMA film was effectively avoided by introducing a copper clad layer. After the first thermal transformation process, flat, clean, and high-quality amorphous carbon films were obtained. Next, the in situ obtained amorphous carbon layer underwent a second copper sputtering and thermal transformation process, which resulted in the formation of a final, large-sized, and highly uniform transfer-free multilayer graphene film on the surface of the dielectric substrate. Multi-scale characterization results show that the specimens underwent different microstructural evolution processes based on different mechanisms during the two thermal transformations. The two-step thermal transformation method is compatible with the current semiconductor process and introduces a low-cost and structurally controllable polymeric carbon source into the production of transfer-free graphene. The catalytic protection of the copper layer provides a new direction for accelerating the application of graphene in the field of direct integration of semiconductor devices.

Quantifying Interfacial Bonding Using Thermal Boundary Conductance at Cubic Boron Nitride/Copper Interfaces with a Large Mismatch of Phonon Density of States.

Interfacial bonding that directly influences the functional and mechanical properties of metal/nonmetal composites is commonly estimated by destructive pull-off measurements such as scratch tests, etc. However, these destructive methods may not be applicable under certain extreme environments; it is urgently necessary to develop a nondestructive quantification technique to determine the composite's performance. In this work, the time-domain thermoreflectance (TDTR) technique is applied to study the inter-relationship between interfacial bonding and interface characteristics through thermal boundary conductance (G) measurements. We think that interfacial phonon transmission capability plays a decisive role in influencing interfacial heat transport, especially for scenarios with a large mismatch of phonon density of states (PDOS). Moreover, we demonstrated this method at (100) and (111) cubic boron nitride/copper (c-BN/Cu) interfaces by both experimental and simulation efforts. The results show that the TDTR-measured G of the (100) c-BN/Cu interface (30 MW/m2·K) is about 20% higher than that of the (111) c-BN/Cu (25 MW/m2·K), which is ascribed to that higher interfacial bonding of the (100) c-BN/Cu endows it with better interfacial phonon transmission capability. In addition, detailed comparison of 10+ other metal/nonmetal interfaces exhibits similar positive relationship for interfaces with a large PDOS mismatch but negative relationship for interfaces with a small PDOS mismatch. The latter one is attributed to that extra inelastic phonon scattering and electron transport channels abnormally promoting interfacial heat transport. This work may provide some insights into quantitatively establishing inter-relationship between interfacial bonding and interface characteristics.