Diamond-like carbon (DLC) is a metastable form of amorphous carbon with significant sp3 bonding. DLC is a semiconductor with a high mechanical hardness, chemical inertness, and optical transparency. This review will describe the deposition methods, deposition mechanisms, characterisation methods, electronic structure, gap states, defects, doping, luminescence, field emission, mechanical properties and some applications of DLCs. The films have widespread applications as protective coatings in areas, such as magnetic storage disks, optical windows and micro-electromechanical devices (MEMs).

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Diamond-like amorphous carbon

The origin and interpretation of the Raman features of amorphous (hydrogenated) carbonfilmsdeposited at room temperature in the region of 1000–1700 cm−1 is discussed in this paper. Possible interpretations of the linewidths, positions of the ‘‘G’’ graphite peak and ‘‘D’’ disordered peak, and their intensity ratios are examined using results obtained from magnetron sputtered and magnetic field enhanced plasmadepositedfilms. It is shown that even small ‘‘clusters’’ of condensed benzene rings (cluster size below 20 A) in carbonfilms can explain the observed Raman scattering. Besides the care that should be taken in the correct interpretation of Raman results, the utility of Raman scattering in obtaining an estimate of cluster sizes in amorphous (hydrogenated) carbonfilms is discussed. Carbonfilms prepared by magnetron sputtering show two additional Raman features at 1180 and 1490 cm−1 in addition to the G and D peaks. It is shown that a correlation exists between the 1180 cm−1 peak and the sp 3 content in the films.

Raman spectroscopy on amorphous carbon films

A general framework for the interpretation of infrared and Raman spectra of amorphous carbon nitrides is presented. In the first part of this paper we examine the infrared spectra. The peaks around 1350 and 1550 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ found in the infrared spectrum of amorphous carbon nitride or hydrogenated and hydrogen-free amorphous carbon are shown to originate from the large dynamic charge of the more delocalized \ensuremath{\pi} bonding which occurs in more ${\mathrm{sp}}^{2}$ bonded networks. The IR absorption decreases strongly when the \ensuremath{\pi} bonding becomes localized, as in tetrahedral amorphous carbon. Isotopic substitution is used to assign the modes to $\mathrm{C}=\mathrm{C}$ skeleton modes, even those modes around 1600 ${\mathrm{cm}}^{\mathrm{\ensuremath{-}}1}$ which become strongly enhanced by the presence of hydrogen. The infrared spectrum of carbon nitride may resemble the Raman spectrum at some excitation energy, but the infrared activity does not primarily result from nitrogen breaking the symmetry. In the second part we examine the Raman spectra. A general model is presented for the interpretation of the Raman spectra of amorphous carbon nitrides measured at any excitation energy. The Raman spectra can be explained in terms of an amorphous carbon based model, without need of extra peaks due to CN, NN, or NH modes. We classify amorphous carbon nitride films in four classes, according to the corresponding N-free film: $a\ensuremath{-}\mathrm{C}:\mathrm{N},$ $a\ensuremath{-}\mathrm{C}:\mathrm{H}:\mathrm{N},$ $ta\ensuremath{-}\mathrm{C}:\mathrm{H}:\mathrm{N},$ and $ta\ensuremath{-}\mathrm{C}:\mathrm{N}.$ We analyze a wide variety of samples for the four classes and present the Raman spectra as a function of N content, ${\mathrm{sp}}^{3}$ content, and band gap. In all cases, a multiwavelength Raman study allows a direct correlation of the Raman parameters with the N content, which is not generally possible for single wavelength excitation. The G peak dispersion emerges as a most informative parameter for Raman analysis. UV Raman enhances the ${\mathrm{sp}}^{1}$ CN peak, which is usually too faint to be seen in visible excitation. As for N-free samples, UV Raman also enhances the C-C ${\mathrm{sp}}^{3}$ bonds vibrations, allowing the ${\mathrm{sp}}^{3}$ content to be quantified.

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Interpretation of infrared and Raman spectra of amorphous carbon nitrides

A review of the preparation of carbon nitride films

Mesoporous carbon nitrides (MCN) are fascinating materials with unique semiconducting and basic properties that are useful in many applications including photocatalysis and sensing. Most syntheses of MCN focus on creating theoretically predicted C3N4 stoichiometry with a band gap of 2.7 eV using a nano-hard templating approach with triazine-based precursors. However, the performance of the MCN in semiconducting applications is limited to the MCN framework with a small band gap, which would be linked with the addition of more N in the CN framework, but this remains a huge challenge. Here, we report a precursor with high nitrogen content, 3-amino-1,2,4-triazole, that enables the formation of new and well-ordered 3D MCN with C3N5 stoichiometry (MCN-8), which has not been predicted so far, and a low-band-gap energy (2.2 eV). This novel class of material without addition of any dopants shows not only a superior photocatalytic water-splitting performance with a total of 801 μmol of H2 under visible-light irradiation for 3 h but also excellent sensing properties for toxic acids.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/anie.201702386

Highly Ordered Nitrogen-Rich Mesoporous Carbon Nitrides and Their Superior Performance for Sensing and Photocatalytic Hydrogen Generation.

The effect of nitrogen addition on the structural and electronic properties of hydrogenated amorphous carbon (a-C:H) films has been characterized in terms of its composition, sp3 bonding fraction, infrared and Raman spectra, optical band gap, conductivity, and paramagnetic defect. The variation of conductivity with nitrogen content suggests that N acts as a weak donor, with the conductivity first decreasing and then increasing as the Fermi level moves up in the band gap. Compensated behavior is found at about 7 at. % N, for the deposition conditions used here, where a number of properties show extreme behavior. The paramagnetic defect density and the Urbach tailwidth are each found to decrease with increasing N content. It is unusual to find alloy additions decreasing disorder in this manner.

Nitrogen modification of hydrogenated amorphous carbon films

Nitrogenated amorphous carbon as a semiconductor

Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

Valence losses can be conveniently computed using classical dielectric excitation theory. In the non-relativistic case, the losses can be simulated using a distribution of surface and interface charges. These charges interact self-consistently with each other as well as with the incident electron. This method is used to analyse experimental STEM energy loss spectra for various incident beam positions near MgO cubes. The characteristic contributions of the cube edges are identified. 

Numerical simulation of valence losses in MgO cubes

The Bethe theory for inelastic scattering has been developed to understand the detailed shape of bandgap EELS spectra. The theory shows how the matrix elements for direct and indirect transitions can be decoupled from one another and have energy dependencies of (E - Eg)1/2 and (E - Eg)3/2 respectively. The zero loss peak was removed via a deconvolution routine which allowed this theory to be tested on a number of crystalline samples with bandgaps as low as 0.9 eV at an energy resolution of 0.22 eV. The agreement between theory and experiment is surprisingly good. 

B. Rafferty

Papers

Nitrogen modification of hydrogenated amorphous carbon films

Nitrogenated amorphous carbon as a semiconductor

Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

Numerical simulation of valence losses in MgO cubes

EELS in the region of the fundamental bandgap.