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The Effect of Chromium on the Microstructure and Transparency of Diamond-like Carbon Films

MetadataDetails
Publication Date2025-04-06
JournalProcesses
AuthorsVilius Dovydaitis, Mindaugas MilieĹĄka, Johnny Chimborazo, Enrico Gnecco, Liutauras Marcinauskas
InstitutionsJagiellonian University, Universidad Yachay Tech
Citations2
AnalysisFull AI Review Included
  • Objective: Investigate the impact of Chromium (Cr) concentration on the elemental composition, microstructure, and optical transparency of Diamond-like Carbon (DLC) films deposited via magnetron sputtering (MS).
  • Compositional Trend: Increasing Cr content (from 7.4 at.% to 13.1 at.%) resulted in a significant, proportional increase in oxygen (O) concentration (from 34.6 at.% to 51.0 at.%), suggesting active Cr-O bond formation.
  • Surface Morphology: The surface roughness (Ra) was optimally minimized (~10% reduction compared to pure DLC, Ra = 1.63 nm) at an intermediate Cr concentration of 9.2 at.%.
  • Structural Changes (Graphitization): Raman spectroscopy indicated that Cr addition promoted graphitization (increased sp2 C=C bonds), evidenced by the G peak shifting to higher wavenumbers and a reduction in the G band dispersion (DG) from 0.206 cm-1/nm (pure DLC) to 0.109 cm-1/nm (highest Cr content).
  • Optical Performance: Optical transmittance was reduced by up to 30% compared to pure DLC due to the enhanced sp2 bond fraction. However, the high co-doping of oxygen helped compensate for sp3 loss, maintaining transmittance values greater than 70% in the infrared (IR) wavelength range.
ParameterValueUnitContext
Deposition MethodDirect Current Magnetron Sputtering (DCMS)N/AUsed 99.99% Cr and 99.9% Graphite targets
Substrates UsedSilicon (100) and GlassN/ALocated 60 mm from magnetrons
Working Pressure (Ar)2-3PaSynthesis atmosphere
Base Pressure< 0.01PaChamber vacuum level
Graphite Target Current1.5AFixed deposition parameter
Chromium Target Current0.5AFixed deposition parameter
Film Thickness Range220 to 250nmAs-deposited films
Cr Concentration Range7.4 to 13.1at.%Measured via EDS (Cr-DLC15 to Cr-DLC17)
Oxygen Concentration Range34.6 to 51.0at.%Increased with Cr doping
Minimum Average Roughness (Ra)1.63nmAchieved at 9.2 at.% Cr (Cr-DLC16)
Pure DLC Roughness (Ra)1.82nmBaseline DLC film
G Peak Dispersion (DG) Range0.206 to 0.109cm-1/nmReduced with Cr increase (enhanced clustering)
Transmittance ReductionUp to 30%Compared to pure DLC coatings
Transmittance (Cr-DLC17, 500 nm)38%Lowest visible light transparency
IR Transmittance (High Cr/O)> 70%Maintained in the infrared range
Raman Excitation Wavelengths458, 514, 633nmUsed for structural analysis
  1. Deposition Setup: Films were deposited using Direct Current Magnetron Sputtering (DCMS) onto Si(100) and glass substrates.
  2. Target Materials: High-purity (99.99% Cr and 99.9% Graphite) 3-inch disc targets were used.
  3. Process Parameters: Graphite and Chromium target currents were set at 1.5 A and 0.5 A, respectively. The process was conducted in an Argon atmosphere at a working pressure of 2-3 Pa for 10 minutes.
  4. Pre-treatment: Cathodes were etched for 5 minutes in Ar plasma (2-3 Pa) after achieving a base pressure less than 0.01 Pa.
  5. Elemental Composition: Energy-Dispersive X-ray Spectroscopy (EDS) was performed using a 15 kV accelerating voltage over a 1.25 mm2 surface area.
  6. Surface Morphology: Atomic Force Microscopy (AFM) was used to measure the average (Ra) and root mean square (Rq) roughness.
  7. Bonding Structure Analysis: Micro-Raman spectroscopy was conducted using three distinct laser wavelengths (458 nm, 514 nm, and 633 nm) to determine the ID/IG ratio, G peak position, and G band dispersion (DG).
  8. Optical Transparency: Transmittance spectra were captured between 400 nm and 1300 nm using a UV-VIS-NIR spectrophotometer.
Industry/ApplicationTechnical Benefit Provided by Cr-DLC
Industrial Tooling & MoldsEnhanced mechanical and tribological performance (hardness, wear resistance) combined with improved adhesion due to Cr incorporation.
Automotive and AerospaceLow coefficient of friction and excellent wear resistance for moving parts, crucial for reducing energy loss and extending component lifespan.
Optical Devices and SensorsControlled optical transparency in the VIS-NIR range. The high oxygen content allows for protective coatings that maintain high IR transmittance (>70%).
Corrosion ProtectionImproved corrosion resistance, particularly relevant for components exposed to harsh environments, such as bipolar plates in Proton Exchange Membrane Fuel Cells (PEMFCs).
High-Stress ComponentsThe ability to tailor the sp2/sp3 ratio and cluster size (via Cr doping) allows for the creation of coatings with optimized internal stress and elasticity modulus.
View Original Abstract

Cr-doped diamond-like carbon (DLC) films were formed on silicon and glass substrates by magnetron sputtering (MS). The surface morphology, elemental composition, bonding structure, and transparency of the as-deposited films were analyzed by atomic force microscopy (AFM), the energy-dispersive X-ray spectroscopy (EDS), multiwavelength micro-Raman spectrometer, and UV-VIS-NIR spectrophotometer. The study revealed that the oxygen concentration in the Cr-DLC films increased as the Cr content increased. The surface roughness of the films was slightly reduced when the Cr content was ~9.2 at.%, and further increase in the Cr content up to 13.1 at.% stimulated the growth of the highest-roughness Cr-DLC films. The micro-Raman analysis showed that the G peak position shifted to a higher wavenumber, and the sp² bond fraction increased as the Cr concentration in the DLC films rose. The optical transmittance of the Cr-DLC films was reduced by up to 30% compared to DLC coatings due to the increased graphitization process caused by chromium addition.

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