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In the realm of chemistry, the concept of allotropy unveils the mesmerizing ability of an element to exist in multiple forms, known as allotropes, each exhibiting distinct physical and chemical properties. Among the myriad elements that showcase this intriguing phenomenon, carbon stands out as a versatile and captivating element with a plethora of allotropes. Understanding the diverse carbon allotropes, their mechanical and chemical properties, as well as the characterization methods used to unveil their secrets, is essential for unlocking their potential in various scientific and technological applications.

Carbon Allotropes: A Kaleidoscope of Structures and Properties

Carbon, with its ability to form strong covalent bonds and diverse molecular structures, manifests in several allotropes, each with unique properties and applications. Here are some of the prominent carbon allotropes:

1. Diamond: The epitome of elegance and durability, diamond features a three-dimensional network of carbon atoms arranged in a tetrahedral structure. Renowned for its exceptional hardness, thermal conductivity, and optical properties, diamond finds applications in jewellery, cutting tools, and industrial abrasives.

2. Graphite: In contrast to diamond’s rigid structure, graphite embodies layers of carbon atoms arranged in hexagonal rings, imparting lubricating properties. Graphite is commonly used in pencil leads, lubricants, and electrodes due to its soft and slippery nature.

3. Graphene: A single layer of graphite arranged in a two-dimensional hexagonal lattice structure, graphene boasts remarkable mechanical strength, electrical conductivity, and thermal properties. This wonder material holds promise for applications in electronics, energy storage, and sensors.

4. Carbon Nanotubes: These cylindrical structures composed of rolled-up graphene sheets exhibit exceptional mechanical strength, electrical conductivity, and thermal properties. Carbon nanotubes find applications in nanotechnology, composites, and electronics due to their unique structural characteristics.

5. Fullerenes: Hollow carbon molecules with cage-like structures, fullerenes like Buckminsterfullerene (C60) possess intriguing properties such as high electron affinity and reactivity. Fullerenes are utilized in diverse fields ranging from drug delivery to superconductors.

Mechanical and Chemical Properties of Carbon Allotropes

Each carbon allotrope showcases a distinctive set of mechanical and chemical properties based on its unique structure and bonding arrangement:

– Diamond: Exceptional hardness, transparency, high thermal conductivity.
– Graphite: Softness, lubricating properties, opaque nature.
– Graphene: High electrical conductivity, mechanical strength, thermal conductivity.
– Carbon Nanotubes: Exceptional mechanical strength, electrical conductivity, and thermal properties.
– Fullerenes: High electron affinity, reactivity, unique cage-like structures.

Characterization Methods for Carbon Allotropes

To unravel the mysteries of carbon allotropes and understand their properties at a molecular level, various sophisticated characterization techniques are employed:

1. Fourier Transform Infrared Spectroscopy (FTIR)

Fourier-transform infrared (FTIR) spectroscopy is another powerful analytical technique that can aid in the characterization of different allotropies of carbon by providing information about their chemical bonding, functional groups, and structural properties. Here’s how FTIR analysis can be utilized to study various carbon allotropes:

a. Functional Group Identification: FTIR spectroscopy can be used to identify specific functional groups present in different carbon allotropes based on the characteristic absorption bands observed in their infrared spectra. For example, the presence of sp2 and sp3 hybridized carbon bonds in graphene, carbon nanotubes, and diamond can be distinguished by analyzing the peaks corresponding to C=C and C-H stretching vibrations, respectively. Additionally, functional groups such as hydroxyl (-OH), carbonyl (C=O), carboxyl (-COOH), and epoxy (-O-) groups can be detected in carbon materials through their distinctive IR absorption bands, allowing researchers to assess the surface chemistry and reactivity of the allotropes.

b. Structural Analysis: FTIR spectroscopy can provide insights into the structural characteristics of carbon allotropes by probing the vibrational modes of carbon-carbon bonds and other chemical interactions within the materials. The presence of sp2 and sp3 hybridized carbon atoms, aromatic rings, double bonds, and functional groups can be inferred from the intensity, position, and shape of the absorption bands in the FTIR spectrum. By correlating the vibrational frequencies of carbon allotropes with their structural features, researchers can elucidate the bonding configurations, lattice arrangements, and crystallographic orientations of the materials.

c. Surface Modification and Functionalization: FTIR spectroscopy is a valuable tool for studying surface modifications, functionalization reactions, and chemical interactions on the surface of carbon allotropes. By comparing the FTIR spectra of pristine and modified carbon samples, researchers can identify changes in the absorption bands associated with functional groups introduced during surface treatments, chemical derivatization, or doping processes. This enables the characterization of surface functionalization strategies, quantification of surface coverage, and evaluation of chemical stability in functionalized carbon materials.

d. Quantitative Analysis: FTIR spectroscopy can be utilized for quantitative analysis of functional groups, impurities, and contaminants in carbon allotropes by measuring the absorbance intensities at specific wavenumbers corresponding to characteristic vibrational modes. By establishing calibration curves or using peak area integration methods, researchers can quantify the relative concentrations of different functional groups or impurities in a carbon sample, providing valuable information about its chemical composition, purity, and quality.

e. Stability and Degradation Studies: FTIR spectroscopy can be employed to investigate the stability, degradation mechanisms, and chemical reactivity of carbon allotropes under various environmental conditions. By monitoring changes in the FTIR spectra over time or upon exposure to external factors (e.g., temperature, humidity, oxidation), researchers can assess the material’s resistance to degradation, identify degradation products or by-products, and elucidate the underlying chemical processes that influence its performance and longevity.

2. Raman Spectroscopy

By studying the vibrational modes of carbon materials, Raman spectroscopy offers valuable information about their structural properties and defects. Raman spectroscopy is a powerful analytical technique that can provide valuable insights into the structural and vibrational properties of different carbon allotropes. Here’s how Raman spectroscopy can help characterize various carbon allotropes:

a. Structural Analysis: Raman spectroscopy can distinguish between different carbon allotropes based on their unique structural characteristics. Each allotrope exhibits specific Raman-active vibrational modes, allowing researchers to identify and differentiate between diamond, graphite, graphene, carbon nanotubes, and fullerenes.

b. Defect Detection: Carbon allotropes may contain defects or impurities that can influence their properties. Raman spectroscopy can detect and characterize these defects by analyzing changes in the Raman spectra, such as shifts in peak positions or intensity variations. This information is crucial for understanding the quality and purity of carbon materials.

c. Quantitative Analysis: Raman spectroscopy can be used for quantitative analysis of carbon allotropes, providing information about the relative abundance of different phases or structures within a sample. By correlating Raman spectral features with specific carbon allotropes, researchers can quantitatively assess the composition and distribution of various forms of carbon in a sample.

d. Chemical Functionalization: Raman spectroscopy is sensitive to chemical modifications and functional groups present on the surface of carbon allotropes. By analyzing changes in Raman spectra upon functionalization or chemical treatment, researchers can characterize the interaction between carbon materials and other substances, enabling the design of tailored functionalized carbon materials for specific applications.

3. X-ray Photoelectron Spectroscopy (XPS)

XPS is another valuable technique that can aid in the characterization of different allotropies of carbon. Here’s how XPS analysis can provide insights into the structural and chemical properties of various carbon allotropes:

a. Elemental Composition: XPS analysis can determine the elemental composition of carbon allotropes by measuring the binding energies of core-level electrons, such as the carbon 1s peak. Different carbon allotropes exhibit distinct binding energy values for their core-level electrons due to variations in the local chemical environment and bonding configurations. By comparing the XPS spectra of carbon allotropes with reference data, researchers can identify the presence of specific elements and quantify their relative concentrations.

b. Chemical State Analysis: XPS analysis can reveal information about the chemical state and bonding characteristics of carbon allotropes. The peak shapes, positions, and intensities in the XPS spectra provide insights into the oxidation state, functional groups, and bonding configurations present in a carbon sample. For example, XPS can differentiate between sp2 and sp3 hybridized carbon atoms in graphene and diamond, respectively, based on their distinct chemical environments and electronic structures.

c. Surface Sensitivity: XPS analysis is a surface-sensitive technique that probes the top few nanometers of a material, making it well-suited for characterizing the surface chemistry of carbon allotropes. By analyzing the elemental composition and chemical states at the surface of a carbon sample, researchers can gain valuable information about surface contaminants, functionalization, and modifications that may influence the material’s properties and reactivity.

d. Dopant Identification: XPS analysis can help identify dopants or impurities incorporated into carbon allotropes to modify their electronic, optical, or catalytic properties. By analyzing the XPS spectra of doped carbon materials, researchers can detect changes in the core-level binding energies and chemical states of the dopant atoms, providing insights into their distribution, concentration, and interaction with the host carbon lattice.

e. Depth Profiling: XPS analysis can also be combined with depth profiling techniques to investigate the chemical composition and structure of carbon allotropes as a function of depth below the surface. Depth profiling methods, such as angle-resolved XPS or sputter depth profiling, allow researchers to study the layer-by-layer composition, doping profiles, and interface properties of carbon materials, enabling a comprehensive understanding of their structure-property relationships.

4. Ultraviolet-Visible Spectroscopy (UV-Vis)

UV-Vis spectroscopy aids in studying the optical properties of carbon allotropes, including absorption and emission spectra.

UV-Vis spectroscopy is another valuable technique that can aid in the characterization of different allotropies of carbon by providing insights into their electronic and optical properties. Here’s how UV-Vis analysis can be utilized to study various carbon allotropes:

a. Bandgap Determination: UV-Vis spectroscopy can be used to determine the bandgap energy of carbon allotropes, which is a crucial parameter that influences their electronic and optical properties. By measuring the absorption spectrum of a carbon sample in the UV and visible regions, researchers can identify the onset of absorption (i.e., the bandgap energy) and characterize the material’s semiconducting or insulating behavior. Different carbon allotropes, such as graphene, carbon nanotubes, and diamond, exhibit distinct bandgap energies due to variations in their electronic structure and bonding configurations.

b. Optical Absorption Features: UV-Vis spectroscopy can reveal information about the optical absorption features of carbon allotropes, such as excitonic transitions, interband transitions, and localized electronic states. The absorption spectrum of a carbon sample can exhibit characteristic peaks, shoulders, or broad absorption bands corresponding to specific electronic transitions within the material. By analyzing the shape, intensity, and position of these absorption features, researchers can gain insights into the electronic structure, energy levels, and optical properties of different carbon allotropes.

c. Defects and Functional Groups: UV-Vis spectroscopy can be used to detect defects, functional groups, and chemical modifications in carbon allotropes that affect their electronic and optical properties. Defect-induced states, surface functionalization, and doping can introduce additional absorption features or modify the intensity of existing peaks in the UV-Vis spectrum of a carbon sample. By comparing the UV-Vis spectra of pristine and modified carbon materials, researchers can identify changes in the electronic structure, bandgap energy, and optical response resulting from defects or functionalization.

d. Quantitative Analysis: UV-Vis spectroscopy can also be employed for quantitative analysis of carbon allotropes by correlating the absorption intensity with the concentration of specific components or impurities in a sample. By measuring the absorbance at characteristic wavelengths and establishing calibration curves for different carbon species or dopants, researchers can quantify the relative abundance of components in a complex mixture or determine the doping level in doped carbon materials.

e. Stability and Degradation Studies: UV-Vis spectroscopy can provide valuable information about the stability, degradation, and photochemical behavior of carbon allotropes under various environmental conditions. By monitoring changes in the UV-Vis absorption spectrum over time or under different exposure conditions (e.g., light irradiation, temperature variations), researchers can assess the material’s photochemical stability, degradation mechanisms, and resistance to environmental factors that may impact its performance and longevity.

5. X-ray Diffraction (XRD)

X-ray diffraction (XRD) analysis is another powerful technique that can provide valuable insights into the structural properties of different carbon allotropes. Here’s how XRD analysis can help characterize various allotropies of carbon:

a. Crystal Structure Determination: XRD analysis can be used to determine the crystal structure of carbon allotropes by analyzing the diffraction patterns generated when X-rays interact with the periodic arrangement of atoms in a material. Different carbon allotropes have distinct crystal structures, such as the hexagonal lattice of graphite, the cubic structure of diamond, and the helical structure of carbon nanotubes. By comparing experimental XRD patterns with reference data, researchers can identify and confirm the crystal structure of a carbon allotrope.

b. Phase Identification: XRD analysis can help identify and distinguish between different phases or polymorphs of carbon allotropes present in a sample. By analyzing the positions and intensities of diffraction peaks in the XRD pattern, researchers can determine the presence of specific allotropes, such as graphite, diamond, graphene, carbon nanotubes, and fullerenes. This information is essential for characterizing the composition and phase distribution within a carbon sample.

c. Crystallite Size and Orientation: XRD analysis can provide information about the crystallite size and orientation of carbon allotropes. By analyzing the broadening of XRD peaks, researchers can estimate the average crystallite size of a material, which is crucial for understanding its structural properties. Additionally, XRD can reveal information about the preferred orientation or texture of crystallites within a sample, offering insights into the growth and alignment of carbon allotropes.

d. Strain Analysis: XRD analysis can also be used to investigate the presence of strain or defects in carbon allotropes. Changes in the peak positions and peak shapes in the XRD pattern can indicate the presence of lattice strain, dislocations, or defects in the crystal structure of a material. By quantifying these structural imperfections, researchers can assess the mechanical stability and performance of carbon allotropes.

e. Thermal Stability and Phase Transitions: XRD analysis can be employed to study the thermal stability and phase transitions of carbon allotropes under varying temperature and pressure conditions. By monitoring changes in the XRD patterns as a function of temperature or pressure, researchers can identify phase transformations, melting points, and structural changes in carbon materials, providing crucial information for understanding their behaviour under different environmental conditions.

Conclusion

In conclusion, the captivating world of carbon allotropes unveils a treasure trove of possibilities for scientific exploration and technological innovation. By delving into the diverse structures and properties of carbon allotropes and employing advanced characterization methods, researchers can unlock the full potential of these fascinating materials across a wide range of applications. The allure of carbon allotropes continues to inspire groundbreaking discoveries and advancements in materials science and beyond.

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Adsorption is a process where a solid or liquid substance is attracted and held onto the surface of another material. It is an essential process in many industries, including water treatment, food processing, and pharmaceuticals. The effectiveness of adsorption depends on the properties of the adsorbent material, such as its surface area, pore size distribution, and chemical composition. Therefore, finding an optimum adsorbent material is crucial to achieving efficient and cost-effective adsorption processes.

One of the most powerful tools for determining the properties of an adsorbent material is the BET analysis. The BET (Brunauer-Emmett-Teller) analysis is a technique used to measure the specific surface area of a material by measuring the amount of gas adsorbed onto its surface at different pressures. The data obtained from BET analysis can be used to calculate the pore size distribution and other critical parameters that determine the adsorption capacity and efficiency of the material.

BET analysis can be used to evaluate various types of materials, including activated carbon, zeolites, silica gels, and metal-organic frameworks. By using BET analysis, researchers can determine the optimum conditions for preparing and using these materials as adsorbents. Here are some ways BET analysis can help in finding an optimum material for using as an adsorbate:

1. Determining the Specific Surface Area

The specific surface area of an adsorbent material is one of the most critical parameters that affect its adsorption capacity. BET analysis can accurately measure the specific surface area of a material by analyzing the amount of gas adsorbed onto its surface at different pressures. The higher the specific surface area, the more adsorption sites are available for attracting and holding onto target molecules.

2. Calculating Pore Size Distribution

The pore size distribution of an adsorbent material is another crucial factor that affects its adsorption capacity. BET analysis can provide information about the pore size distribution of a material by analyzing the adsorption isotherm data. The pore size distribution can be used to determine the optimum pore size range for the target molecules to be adsorbed.

3. Evaluating Adsorption Capacity

BET analysis can also be used to evaluate the adsorption capacity of an adsorbent material. By measuring the amount of gas adsorbed onto the material at different pressures, researchers can determine the maximum amount of target molecules that can be adsorbed onto the material. This information can be used to optimize the adsorption process and determine the most effective operating conditions.

4. Comparing Different Materials

BET analysis can also be used to compare the properties of different adsorbent materials. By analyzing the specific surface area, pore size distribution, and other parameters, researchers can determine which material is most suitable for a specific application. This information can help in selecting the best material for a particular adsorption process and improve its efficiency and cost-effectiveness.

In conclusion, BET analysis is a powerful tool for evaluating the properties of adsorbent materials and finding an optimum material for using as an adsorbate. By analyzing the specific surface area, pore size distribution, and other parameters, researchers can determine the most effective operating conditions and select the best material for a specific application. BET analysis can help in improving the efficiency and cost-effectiveness of adsorption processes in various industries, making it an essential technique for researchers and engineers working in this field.

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We present here results on a Raman spectroscopic study of the deposited defected graphene on Si substrates by chemical vapor deposition (thermal decomposition of acetone). The graphene films are not deposited on the (001) Si substrate directly but on two types of interlayers of mixed phases unintentionally deposited on the substrates: а diamond-like carbon (designated here as DLC) and amorphous carbon (designated here as αC) are dominated ones.

The performed thorough Raman spectroscopic study of as-deposited as well as exfoliated specimens by two different techniques using different excitation wavelengths (488, 514, and 613 nm) as well as polarized Raman spectroscopy establishes that the composition of the designated DLC layers varies with depth: the initial layers on the Si substrate consist of DLC, nanodiamond species, and C₇₀fullerenes while the upper ones are dominated by DLC with an occasional presence of C₇₀ fullerenes. The αC interlayer is dominated by turbostratic graphite and contains a larger quantity of C₇₀ than the DLC-designated interlayers. The results of polarized and unpolarized Raman spectroscopic studies of as-grown and exfoliated graphene films tend to assume that single- to three-layered defected graphene is deposited on the interlayers. It can be concluded that the observed slight upshift of the 2D band as well as the broadening of 2D band should be related to the strain and doping.

1. Introduction

Graphene is a one-atom-thick layered material that consists of completely sp²-bonded carbon atoms tightly packed into a honeycomb lattice. It has a lot of unique properties promising a huge number of possible applications (see, e.g., [1]). A lot of different ways of synthesizing graphene were experimentally tested during the last decade; however, only thermally and plasma-assisted chemical vapor deposition (CVD/PECVD) on metal substrates (copper, nickel, etc.) [2, 3] as well as epitaxial growth on SiC substrates and so on [4, 5] were developed for industrial application. The latter method is based on C (or Si) termination of the (0001)_C (or (0001)_Si) SiC surface and requires high temperature and expensive SiC substrates. The CVD method is based on the plasma-enhanced thermal decomposition of a carbon-containing precursor on a catalytic metal surface. This method provides high reliability and relatively high quality of graphene films, and now, there are a lot of suppliers of reactors for PECVD of graphene. The most preferred precursor is methane (CH₄) as the chemical bond in CH₄ is relatively strong and prevents fast decomposition of the reagent at temperatures below 1000°C (see, e.g., [6]). However, production for microelectronic applications requires transfer of the graphene layers on an insulating surface and, consequently, a large number of additional defects affecting the properties of graphene can be introduced. Therefore, the problem with the deposition of graphene on silicon (or surfaces compatible with silicon technology such as SiO₂) still remains unsolved. We demonstrated the possible application of acetone as a precursor in a thermally assisted CVD and showed that few-layered defected graphene/folded graphene can be deposited on commercially available metal foils—Ni, (Cu_0.5Ni_0.5), μ-metal, and stainless steel SS 304 in a recently published work [7]. Further, we established (see [8]) by Raman spectroscopy, scanning electron microscopy (SEM), X-ray diffraction (XRD), and grazing incidence X-ray diffraction (GIXRD) as well as by X-ray photoelectron spectroscopy (XPS) the presence of single- to few-layered defected graphene on two different types of interlayers deposited on (100) Si surface: (i) a diamond-like carbon (DLC) layer with some SiC contents (in the range below 5w%) and some residual quantities of SiO₂, and (ii) a complex amorphous carbon layer consisting of a mixture of sp²– and sp³-hybridized carbon as well as very small amount of fullerenes, SiO, and so on.

Here, we focus our experimental study on the Raman spectroscopic characterization of defected as-deposited graphene layers (including polarized spectroscopy) as well as graphene flakes exfoliated from similar specimens by two different ways using 488, 514, and 633 nm excitation laser wavelengths aiming at unambiguous confirmation of the graphene deposition of as well as the identification of the exact composition of the interlayers between the Si substrate and graphene layer/s.

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2. Experimental

2.1. CVD Process

We use 2 inches in diameter (001) Si substrates and a horizontal tube quartz CVD reactor with an internal diameter of approximately 70 mm. The experimental setup also consists of a gas-supply system (inlet and outlet parts), a thermostat with acetone evaporation alert/indication system, a quartz substrate holder, and a resistive heating furnace. The CVD process is based on thermal decomposition of acetone in Ar main gas flow. The deposition temperature was in the range 1150–1160°C. The temperature of the thermostat was kept at 12°C. In order to prevent the supersaturation in the high-temperature zone of the reactor, we used a “pulsed” regime in experiments by alternating the flow of the gas mixture of Ar + C₃H₆O) for 3 min on top of the main flow of pure Ar of about 150–180 cm³/min for 1.5 min for each pulse. The optimal results (predominantly single-layered graphene) were obtained after two deposition pulses.

2.2. Exfoliation

We exfoliated the carbon films deposited on (001) Si substrates by the following two different techniques:(i)The Scotch tape method (see, e.g., [9]): we put tightly the adhesive Scotch tape on the multilayered graphene side of the specimens. After peeling the tape off the specimen, a single- to few-layered graphene remains on the tape’s surface and the interlayer between the upper few layers of graphene and the substrate becomes accessible for spectroscopic examination. Then, we put tightly the Scotch tape with graphene flakes either on 320 nm SiO₂/Si or on glass substrate. About 30–50% of the graphene flakes remain adhered to the SiO₂ or glass substrate after removing the tape due to the Van der Waals force.(ii)We also adhered the multilayered graphene side of the specimens to epoxy resin. After careful cleavage, the most part of the graphene layer/s remains on the surface of the resin. Then, the adhered to the resin graphene film becomes accessible for spectroscopic examination. The Raman spectrum of the epoxy resin does not contain strong peaks around the 2D band of graphene (the area around 2630–2670 cm⁻¹). We established that the 2D band of graphene is clearly distinguishable for graphene regions lying on gas bubbles close to the surface of the resin; otherwise, the 2D band of graphene is weak.

2.3. Characterization

The Raman measurements were carried out in backscattering geometry at a micro-Raman HORIBA Jobin Yvon Labram HR 800 visible spectrometer equipped with a Peltier-cooled CCD detector with a He-Ne (633 nm wavelength and 0.5 mW) laser excitation. The 514 nm (about 23 mW) as well as 488 nm (about 24 mW) lines of an external Ar laser were also used. The laser beam was focused on a spot of about 1 μm in diameter, the spectral resolution being 0.5, 0.7, and 1 cm⁻¹, respectively, or better.

The Raman spectrum of graphene is a clearly established fingerprint of this 2D material (see [10]). The main first-order features in the Raman spectra of graphene and defect-infested graphene excited at 633 nm wavelength are the following:(i)G band (~1582 cm⁻¹) is the only band in graphene allowed by selection rules for first-order Raman effect; it is ascribed to optical (iTO and LO) doubly degenerate phonons of E_2g symmetry at the Γ point (initially described by Tuinstra and Koenig [11]).(ii)D band (~1330 cm⁻¹) is due to breathing-like bands of C hexagonal rings (corresponding to transverse optical phonons near the K point) and requires a defect for its activation via an intervalley double-resonance Raman process (see [12]).(iii)D’ band (at about 1615 cm⁻¹; defect induced similarly to the D band) occurs via an intravalley double-resonance process (see, e.g., [13]).(iv)D” band (at about 1145 cm⁻¹) is resulting from double-resonance intervalley scattering of LA phonons on defects (see [14]). The intensity of this band should be about 100 times lower than that of the D band.

Overtones and combination bands:(i)2D band (historically known from graphite and carbon nanotube-related literature as G’- peak) appears at about 2648–2665 cm⁻¹. It is clearly shown [15–20] that the shape and width of the 2D band can be used for the identification of the mono-, bi-, and three-layered graphene.(ii)The overtone of the D’- peak (2D’) and combination G (phonons), as well as (D+D’) bands, occur around 3230, 2450, and 2930 cm⁻¹, respectively (see [21]).

3. Results and Discussion

Two areas with different surface morphologies are observed by optical microscopy (Figure 1(a)): a clear relief (ridge-like formations) lying along <001> directions covers the first area denoted as DLC while the second area (denoted as αC) is covered by an inhomogeneous film with a constant depth. It should be also mentioned that optical inhomogeneities are observed on the DLC as well as αC-marked areas.
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(e)Figure 1Optical microscopy image of the surface morphology of (a) as-deposited graphene and graphene-related phases on diamond-like carbon (DLC) and amorphous carbon (αC) interlayers. The arrows remarked [100] and [010] directions of the Si substrate. The marker represents 20 μm. (b) The exfoliated and transferred graphene flakes on 320 nm SiO₂. The Raman spectra are taken from “+”-marked positions. The marker represents 30 μm. (c) The layers remaining on the surface of the substrate after exfoliation by Scotch tape. The Raman spectra are taken from the “+”-marked positions near points 1, 2, and 3. The marker represents 30 μm. (d) The exfoliated and transferred graphene flakes on glass substrate. The Raman spectra are taken from the “+”-marked positions near points 1 and 2. The marker represents 20 μm. (e) A graphene flake on air bubble near the epoxy resin surface. The Raman spectra are taken from the square-marked position. The marker represents 20 μm.

It should be recalled that the Raman spectrum (excited at 633 nm laser wavelength) taken from αC- and DLC-denoted areas (see [8]) contains all features typical for graphene: symmetric and clearly pronounced 2D band with full width at a half maximum (FWHM) of 40–56 cm⁻¹, I_2D/I_G ratio between 2 and 3.5, and I_2D/I_D ratio between 2 and 4. However, the 2D band appears at about 2660–2668 cm⁻¹ (for single- and bilayered graphene, respectively), that is, it is blueshifted by about 20 cm⁻¹ relative to the results presented in [15, 22, 23].

Due to the double-resonance origin of most of the monitored spectral features, we perform a Raman spectroscopy examination of as-deposited defected graphene at 488, 514, and 633 nm excitation wavelengths and the results are presented in Figure 2. The 2D bands are blueshifted by about 20 cm⁻¹ and can be typically deconvoluted into (a) a single Lorentzian with FWHM of about 40-41 cm⁻¹ (see Figure 3(a)); (b) four Lorentzians (FWHM of 22 (±1) cm⁻¹) for 2D band with total width of 45–56 cm⁻¹ (see Figure 3(b)); and (c) six Lorentzians (Figure 3(c)) for 2D band with total width larger than 56 cm⁻¹. The results of the deconvolution indicate the presence of single-, bi-, and three-layered defected graphene, respectively (see [15–20]). We did not establish a clear difference between the graphene layers deposited on αC and DLC interlayers; however, bi- and three-layered areas were more frequently observed on DLC interlayers. The results for predominantly single-layered (SL) and bilayered (BL) defected graphene (according to the deconvolution of 2D bands) are summarized in Table 1.

Figure 2Raman spectra taken from as-grown films excited at 633 nm (red trace), 514 nm (blue trace), and 488 nm (green trace) laser wavelengths.
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(c)Figure 3Deconvolution of 2D band identified as coming from single-layered (a), bilayered (b), and three-layered defected graphene deposited on αC. The spectrum is excited at 633 nm laser wavelength.Table 1Summarized results of Raman spectroscopy examination of as-deposited defected graphene films.

In order to access the interlayers as well as graphene flakes for Raman examination, the so-called Scotch tape method was initially used for exfoliation. The Raman spectra of the graphene flakes exfoliated in this way with some occasional amorphous (αC) interlayers transferred to Si/SiO₂ (300 nm) or glass substrate are shown in Figures 4 and 5, respectively.

Figure 4The Raman spectrum of defected 1-2-layered graphene transferred on 320 nm SiO₂. The 2D band is symmetric and appears at 2658-2659 cm⁻¹ with FWHM of 38–40 cm⁻¹ (measured in point 2) and 40–42 cm⁻¹ (measured in point 1).

Figure 5The Raman spectrum of the interlayer (point 1, Figure 1(c)) of αC after exfoliation by Scotch tape. The features observed at about 1450 and 1530 cm⁻¹ are typical for C₇₀ fullerenes.

A lot of flakes (of the order of 10²) were transferred on Si/SiO₂ and examined by Raman spectroscopy. The Raman spectra are enhanced due to interference effects caused by the SiO₂ 300 nm layer over the Si substrate, and I_2D/I_G varies in the range 3.5-6.0. However, it was impossible to isolate single-layered graphene flake (or to obtain clear Raman response of single-layered graphene) in this way. The exfoliated flakes were never transparent (see point 1 in Figure 1(b)). The best spectra were recorded from the points in a darker contrast (point 2 in Figure 1(b)), but the FWHM of 2D Raman band remains >35 cm⁻¹. Moreover, the D” band slightly overlaps with the second order of Si substrate when the spectrum is excited at 514 as well as 488 nm laser wavelengths.

After peeling the tape off the specimen, the interlayer between the upper flake and the substrate is accessed. The remaining interlayers have different optical contrasts (see Figure 1(c)) and Raman spectra: the spectrum of typically retained interlayer (point 1 in Figure 1(c)) in Figure 5 is very similar to that of turbostratic graphite (see [24]), but weak peaks of C₇₀ fullerenes (the features observed at about 1450 and 1530 cm⁻¹ (see [25, 26])) are also clearly distinguished (Figure 5). The strong modes of fullerenes C₇₀ at about 1180 and 1568 cm⁻¹ are merged with D” and G bands.

The Raman spectra (Figure 6) taken from points 2 and 3 (Figure 1(c)) are similar as they contain the most prominent modes of C₇₀ peaks at 1160, 1220, 1454, 1526, and 1565 cm⁻¹ [25, 26], nanodiamond (Nd) peaks at 1330 and 1620 cm⁻¹ (see [27]), and turbostratic graphite. The D, G, and D’ bands are found at 1335, 1590, and 1612 cm⁻¹, respectively, but in a different proportion: the spectrum from point 3 is dominated by the peaks of C₇₀ and Nd while the spectrum from point 2 is dominated by turbostratic graphite (see Figure 6). It should be also remarked that features of C₆₀ fullerenes (see, e.g., [25, 26]) were not observed.

Figure 6Raman spectra of the interlayer that remains on the substrate after exfoliation by the Scotch tape method taken from points 2 and 3 (Figure 1(c)).

As it was mentioned above, the D” band overlaps with the second-order band of Si substrate especially when the spectrum is excited at 488 and 514 nm laser wavelengths. In order to distinguish the dispersion of the D” band of several Scotch tape methods, exfoliated flakes were transferred on glass substrates. The flakes have very similar surface morphology to those transferred on SiO₂/Si substrates (Figure 1(d)). The Raman spectrum of such flakes is not significantly different from that of the as-deposited layers (Figure 7); however, the D” band appears at 1096 (for 488 nm excitation) and at 1135 cm⁻¹ (for 633 nm excitation), respectively, that is, they coincide with the data of Herziger et al. [14].

Figure 7The Raman spectra of as-grown graphene on αC excited at 488 nm (green trace) and 633 nm (black trace) wavelengths. The similar spectra of exfoliated graphene transferred on a glass substrate excited at 488 nm (blue trace) and 633 nm (red trace). The inset: magnified part of the region 900–1200 cm⁻¹.

According to the above results, we conclude that the exfoliation by the Scotch tape method does not enable splitting up between the defected graphene and the interlayers (especially the αC-designated one). Another way for exfoliation was probed (by exfoliation on epoxy resin), and the optical micrograph image of the area of the edge of a resin bubble and the Raman spectrum taken from this area (excited at 633 nm) are shown in Figures 1(e) and 8, respectively. The Raman spectrum of epoxy resin does not contain any features in the 2D region of graphene (upper trace in Figure 8); hence, 2D bands of a single- and bilayered graphene were identified at the edge of a lot of bubbles on the surface of the resin (Figure 1(e)). It should be clearly remarked that the measured FWHM of the 2D band of such single-layered graphene is about 27–29 cm⁻¹, but it is situated at 2654–2656 cm⁻¹, that is, it remains upshifted with about 10–15 cm⁻¹.

Figure 8Raman spectra of graphene films situated on air bubbles/cavities. The 2D band is situated at 2655 cm⁻¹ and has FWHM ~28 cm⁻¹ (i.e., it corresponds to single-layered graphene—blue trace).

Recently, Li et al. [28] established that the intensity of 2D band varies as a cosine to the fourth power when the laser propagation direction is parallel to the graphene layer and the polarization is rotated around it. They also derived the orientation distribution function of monolayered graphene as well as that of graphene paper and highly oriented pyrolytic graphite. We perform similar measurements in X(Y_φY_φ)X geometry, φ being the angle between the incident laser beam polarization and the graphene layer plane; Z is the axis perpendicular to the graphene plane, and the laser beam propagates transversely to the graphene layer along the X direction (see Figure 9(a)). The excitation laser beam was focused in a manner to comprise no more than 30% of the edge of the Si substrate and graphene film (Figure 9(a)). The parallel scattering geometry was used. The measurements were performed starting from φ = 0° (corresponding to X(YY)X in Porto notations) and finished at φ = 180°. The preliminary results of these rotational angle-dependent Raman measurements of as-deposited specimen are presented in Figure 9. The signal significantly drops upon changing the angle from 0° to 90° and increases again in the interval between 90 and 180° which resembles indeed the cos⁴ law. At 90° (corresponding to X(ZZ)X in Porto notations), the Raman signal is very weak but still observable (Figure 9), and the rotational angle-independent features of C₇₀ fullerenes and nanodiamond (Nd) dominate the spectrum. The residual features in the Raman spectra taken at φ = 90° point out that the measured polarized Raman spectra are taken from graphene deposited on DLC interlayer. The measurements in this scattering geometry (X(YY)X in Porto notations) access measurements of the interlayer/s without exfoliation. On the other hand, the polarized Raman study confirms the deposition of graphene because the intensities of the most prominent Raman features of graphite (D, G, and 2D bands) show similar behavior in similar conditions as those of graphene. However, the intensity of the Raman features of graphene decreases significantly slower than those of graphene as it is shown in [28].
(a)
(b)
(a)
(b)Figure 9(a) Optical photography of the specimen in X(YY)X geometry (in Porto notations). The inset: optical photography of the specimen in Z(YY)Z geometry (in Porto notations). The arrow-remarked laser spots are eye guide showing the real area of the laser spot during measurements. The marker represents 10 μm. (b) Spatially resolved Raman spectra of as-deposited defected graphene at 633 nm excitation.

It is worth noting that the 2D band from the single-layered graphene regions is symmetric and strong, but it is somewhat broadened with FWHM of about 40–42 cm⁻¹and is blueshifted by 15–20 cm⁻¹ in as-grown specimens. It is well known that such behavior is usually related to strain (see [29–32]) and doping [33]. Moreover, Lee et al. [34] and Bouhafs et al. [35] experimentally studied the influence of these parameters on the position and FWHM of G and 2D bands in single- and bi-/multilayered graphene, respectively. The deduced simple plot of the 2D versus G band positions enables distinguishing the influence of doping and strain on the positions of G and 2D bands. In our single-layered specimens, the G band is slightly uphifted by 1-2 cm⁻¹ while the 2D band is more significantly blueshifted and broadened by 10–20 cm⁻¹. Therefore it can be assumed that the 2D band blueshift and broadening are due to the lattice strain predominantly as well as to the doping. It can be suggested that the lattice strain is due to the bonding between graphene and the interlayers while the doping should be related to charge transfer from the interlayers/interfaces to graphene as well as to different intrinsic (grain boundaries, etc.) and extrinsic (trapped nitrogen, oxygen, and impurities during the deposition) defects, that is, it can be related to the influence of the interlayers/substrates as well as of the deposition process.

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4. Conclusions

We extended the analysis of defected graphene deposited by CVD as well as the two types of interlayers between the defected graphene layer/s and Si substrates by both unpolarized and polarized Raman spectroscopy. The performed Raman spectroscopy examination of as-deposited defected graphene at 488, 514, and 633 nm excitation wavelengths enables the most of the monitored spectral features of double-resonance origin (D, D”, and 2D bands). The Raman studies of exfoliation by the so-called Scotch tape method revealed that (a) the composition of the designated DLC interlayers varies with depth: the initial layers on the Si substrate consist of a mixed phase of turbostratic graphite, nanodiamond/diamond-like carbon, and C₇₀ fullerenes while the upper ones are dominated by diamond-like carbon and some C₇₀ fullerenes and (b) the amorphous carbon interlayer is dominated by turbostratic graphite and contains a larger quantity of C₇₀ than the DLC-designated interlayers. Single- and bilayered defected graphene flakes were exfoliated on epoxy resin. The preliminary results of polarized Raman experiments show that the intensity of the 2D band varies as a cosine to the fourth power when the laser propagation direction is parallel to the graphene layer and the polarization is rotated around it which is an additional indication of the deposition of single-layered graphene. The results of Raman spectroscopic studies of as-grown and exfoliated graphene films tend to assume that the observed slight upshift of the 2D band as well as the broadening of 2D band is due to the strain and can be related to the bonding between the graphene and the interlayers, that is, it could be regarded as an influence of the interlayers between the defected graphene and the Si substrates.

Conflicts of Interest

The authors declare that there is no conflict of interest regarding the publication of this paper.

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Authors: T. I. Milenov,¹ E. Valcheva,² and V. N. Popov²