Skip to content

An alternative approach to the tribological analysis of Si-doped DLC coatings deposited with different bias voltages using Raman spectroscopy mapping

MetadataDetails
Publication Date2021-08-10
JournalEmergent Materials
AuthorsBruno J. Rodriguez, Parnia Navabpour, Daniela Proprentner, Marc Walker, Hailin Sun
InstitutionsTeer Coatings (United Kingdom), University of Warwick
Citations8
AnalysisFull AI Review Included

Technical Analysis and Documentation: High-Performance Carbon Materials for Extreme Tribology

Section titled “Technical Analysis and Documentation: High-Performance Carbon Materials for Extreme Tribology”

This document analyzes the research on Si-doped Diamond-Like Carbon (DLC) coatings and connects the findings to 6CCVD’s advanced MPCVD diamond capabilities, focusing on applications requiring extreme hardness, thermal stability, and controlled doping.


This study successfully demonstrates that increasing the bias voltage during magnetron sputtering deposition significantly enhances the structural and thermal properties of Si-doped DLC coatings, providing critical insights for high-temperature tribological applications.

  • Structural Enhancement: Increasing the bias voltage from 65 V to 85 V resulted in a measurable increase in the spÂł C-C content, rising from 21.9% to 23.1%.
  • Mechanical Doubling: Hardness (H) was nearly doubled, increasing from 13.6 GPa (65 V bias) to 27.2 GPa (85 V bias), accompanied by a corresponding increase in the Reduced Elastic Modulus (E’).
  • Thermal Stability Window: The maximum operational temperature before failure was extended by 150 °C, moving from 300 °C (65 V bias) up to 450 °C (85 V bias).
  • Tribological Trade-Off: Softer films (lower bias) exhibited the lowest Coefficient of Friction (COF), while the hardest film (85 V bias) provided superior wear resistance due to its higher H/E’ ratio and thermal stability.
  • Novel Analysis: Raman spectroscopy mapping of wear tracks was validated as an effective method for analyzing spÂČ configuration changes and estimating maximum flash temperatures reached during tribological contact.
  • 6CCVD Relevance: While DLC provides moderate performance, 6CCVD’s MPCVD Single Crystal Diamond (SCD) and Polycrystalline Diamond (PCD) offer intrinsic hardness and thermal stability far exceeding the limits demonstrated by these DLC films, making them ideal for next-generation extreme environment applications.

The following hard data points were extracted from the experimental results, detailing the relationship between deposition bias voltage and resulting material properties.

ParameterValueUnitContext
Deposition MethodMagnetron SputteringN/AUsed for Si-doped DLC coating
Bias Voltage Range65 to 85VControlled ion bombardment energy
Silicon Content1.3 ± 0.1 to 1.5 ± 0.2at. %Consistent doping level across samples
Hardness (H) Range13.6 ± 1.0 to 27.2 ± 1.5GPaIncreased with bias voltage
Reduced Elastic Modulus (E’) Range157.7 ± 15.9 to 243.5 ± 6.5GPaIncreased with bias voltage
sp³ C-C Content (XPS)21.9 ± 0.4 to 23.1 ± 0.6%Increased with bias voltage
Thermal Stability (Failure Temp)300 to 450°CMaximum operating temperature
G-Peak Position Range1556 ± 1 to 1570 ± 2cm-1Shifted with increasing bias
Tribological Load10NApplied during ball-on-disk testing
Sliding Speed1cm s-1Linear speed
Counterpart Material6.3 mm diameter Al2O3BallUsed for friction and wear tests

The experimental procedure focused on controlled deposition parameters, comprehensive structural characterization, and high-temperature tribological assessment.

  1. Coating Deposition: Silicon-doped DLC (a-C:Si) films were deposited onto M42 high-speed steel specimens (30 mm diameter) using magnetron sputtering. The primary variable was the applied bias voltage (65 V, 75 V, 85 V).
  2. Structural Characterization (Raman & XPS):
    • Raman spectroscopy (λ = 532 nm) was used to analyze the D and G modes, extracting parameters like G-peak position, FWHM (G), and the intensity ratio ID/IG, indicative of spÂČ configuration changes.
    • X-ray Photoelectron Spectroscopy (XPS) quantified the silicon content, identified silicon carbide (Si-C) and silicon oxide (Si-O-C) bonds, and measured the spÂł C-C content.
  3. Mechanical Testing: Hardness (H) and Reduced Elastic Modulus (E’) were measured using NanoTest Xtreme with a Berkovich indenter. Indentation depth was strictly controlled (< 200 nm) to minimize substrate influence.
  4. Tribological Testing (MFT-5000): Ball-on-disk friction tests were performed using a 10 N load and 6.3 mm Al2O3 balls as the counterpart. Tests were conducted at increasing temperatures (Room Temperature up to 450 °C) until coating failure.
  5. Wear Analysis: Specific Wear Rates (SWR) were calculated based on volume removal, measured using an Alicona InfiniteFocus instrument. Raman mapping was applied across the wear tracks to analyze localized graphitization and estimate maximum flash temperatures.
  6. High-Temperature Integrity: Cross-sections of tested coatings were analyzed using TEM (HAADF detector) and EDS to study oxygen diffusion depth and structural integrity after high-temperature annealing (300 °C).

The research highlights the need for materials with extreme hardness, superior thermal stability, and precise doping control for advanced tribological applications. 6CCVD’s MPCVD diamond materials offer performance metrics that significantly surpass the limits of the Si-doped DLC films studied.

Application Requirement6CCVD Material RecommendationTechnical Rationale
Extreme Hardness & Wear ResistanceElectronic Grade SCD (Single Crystal Diamond)Intrinsic hardness > 90 GPa, providing wear resistance orders of magnitude greater than the 27.2 GPa achieved by the best DLC film.
High Thermal Stability & Large AreaPolycrystalline Diamond (PCD) PlatesPCD is stable up to 700 °C in air and > 1000 °C in inert environments, vastly exceeding the 450 °C DLC limit. Available in large formats up to 125 mm diameter.
Controlled Surface Chemistry/ConductivityBoron-Doped Diamond (BDD) FilmsBDD allows for precise, tunable doping (light or heavy) to control electrical and electrochemical properties, essential for specialized tribological environments or sensor integration.
Optical/Raman AnalysisOptical Grade SCD WafersSCD offers ultra-low defect density and high transparency, ideal for advanced spectroscopic analysis (like the Raman mapping technique used in this paper) without background interference.

6CCVD provides comprehensive engineering services necessary to transition research findings into robust, scalable components:

  • Custom Dimensions and Substrates: While the paper used 30 mm steel specimens, 6CCVD can supply PCD plates up to 125 mm in diameter or SCD wafers up to 10 mm thick, allowing for the scaling of tribological components far beyond typical DLC limits.
  • Precision Thickness Control: 6CCVD offers precise thickness control for both SCD and PCD films, ranging from 0.1 ”m to 500 ”m, enabling optimization of the H/E’ ratio and compressive stress for specific load-bearing applications.
  • Integrated Metalization: The study utilized protective Pt layers and Cr-C interlayers. 6CCVD offers in-house metalization capabilities (including Au, Pt, Pd, Ti, W, and Cu) for creating robust electrical contacts, specialized interlayers, or protective caps on diamond surfaces.
  • Ultra-Low Roughness: To ensure accurate tribological measurements and minimize frictional energy generation, 6CCVD guarantees ultra-precision polishing (Ra < 1 nm for SCD and Ra < 5 nm for inch-size PCD).

6CCVD’s in-house PhD team specializes in the structural and electronic properties of MPCVD diamond. We can assist engineers and scientists in selecting the optimal diamond material (SCD, PCD, or BDD) and surface preparation techniques required to replicate or extend this research into high-performance High-Temperature Tribology projects.

Call to Action: For custom specifications or material consultation, visit 6ccvd.com or contact our engineering team directly.

View Original Abstract

Abstract A series of diamond-like carbon (DLC) coatings were deposited with increasing bias voltage using magnetron sputtering techniques. Structural changes were observed in the sp 2 -configuration across the films which were accompanied by a slight increase in the sp 3 fraction. With an increasing bias voltage, the thermal stability of the coatings increased from 300 to 450 °C. Oxygen diffusion was observed through the coating as a result of the high-temperature annealing and found to slow down with increasing bias voltage. Coefficients of friction (COF) remained stable with temperature for the individual coatings, with the softer films reporting the lowest COF. Our approach employed Raman spectroscopy to map the wear tracks at different temperatures, providing a deeper understanding of the coating performance and suggested maximum flash temperatures endured during testing.