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Structures, Wettability, and Corrosion Resistance of Annealed Platinum/Ruthenium/Nitrogen Co-Doped Diamond-like Carbon Nano-Composite Thin Film at Different Temperatures

MetadataDetails
Publication Date2025-01-01
JournalJournal of Materials and Engineering
Authors
AnalysisFull AI Review Included

This analysis summarizes the effects of Rapid Thermal Annealing (RTA) temperature (RTAT) on Platinum/Ruthenium/Nitrogen co-doped Diamond-like Carbon Nano-Composite Thin Films (Pt/Ru/N-DLCNC-TF) for protective coating applications, particularly micro-molds.

  • Core Material: Pt/Ru/N-DLCNC-TF deposited on Si via DC magnetron sputtering, subsequently annealed (100-400 °C).
  • Structural Changes: Increasing RTAT promotes significant graphitization (increased sp2 fraction) and surface segregation of PtRu aggregates.
  • Optimal Corrosion Resistance: The film annealed at 200 °C exhibited the best corrosion performance, achieving a polarization resistance (Rp) 15.2 times higher than the as-deposited film, attributed to reduced residual stress and structural defects.
  • Surface Property Trend: Higher RTAT (up to 400 °C) increases surface roughness (Ra increases by 21.4%) and hydrophobicity (Water Contact Angle increases by 6%).
  • High-Temperature Degradation: Annealing at 400 °C severely decreased corrosion resistance (Rp was 18.2 times lower than the 200 °C sample), due to degraded structural integrity, increased galvanic corrosion risk, and localized film delamination.
  • Chemical Composition: Increased RTAT leads to higher surface Pt and Ru content but decreased surface N content, which correlates with reduced surface polarity and increased hydrophobicity.
ParameterValueUnitContext
Film TypePt/Ru/N-DLCNC-TFN/ADiamond-like Carbon Nano-Composite
Substratep-type Si (100)N/AUsed for deposition
Annealing Range (RTAT)100 - 400°CRapid Thermal Annealing (RTA)
Annealing Duration2minRTA process time
Temperature Ramping Rate25°C/sRTA process parameter
Temperature Cooling Rate6°C/sRTA process parameter
As-Deposited Ra1.4nmArithmetic average roughness
Ra at 400 °C1.7nm21.4% increase due to PtRu segregation
As-Deposited WCA78°Water Contact Angle
WCA at 400 °C82.7°6% increase (increased hydrophobicity)
As-Deposited ID/IG Ratio2.3N/ARaman spectroscopy (indicates aromatic rings)
400 °C ID/IG Ratio2.8N/AConfirms increased graphitization
Corrosion Electrolyte0.5 M HClN/ASolution used for polarization tests
Corrosion Resistance (200 °C)15.2x Higher RpN/ACompared to as-deposited film
Corrosion Resistance (400 °C)18.2x Lower RpN/ACompared to 200 °C annealed film
As-Deposited C 1s FWHM1.88eVFull-width-at-half-maximum
400 °C C 1s FWHM1.65eVDecrease indicates reduced bond angle disorder

The Pt/Ru/N-DLCNC-TF was prepared using DC magnetron sputtering followed by Rapid Thermal Annealing (RTA).

  • Targets: Graphite (99.999% C) and Pt50Ru50 (99.99%).
  • Power Density:
    • Graphite Target: 52 W/in2.
    • Pt50Ru50 Target: 2.5 W/in2.
  • Gases and Flow Rates:
    • Working Gas: Argon (Ar) at 50 sccm.
    • Reactive Gas: Nitrogen (N2) at 1 sccm.
  • Deposition Environment:
    • Background Pressure: 7.5 x 10-6 Torr.
    • Deposition Pressure: 3 x 10-3 Torr.
  • Substrate Conditions: Substrate bias of -30 V, rotated at 22 rpm.
  • Duration: 120 minutes.
  • Equipment: Jipelec Jetfirst 100 RT processor.
  • Temperature Range: 100 °C, 200 °C, 300 °C, and 400 °C (RTATs).
  • Duration: 2 minutes at peak temperature.
  • Atmosphere: Nitrogen environment supplied at 2000 sccm.
  • Chemical Composition/Bonding: X-ray Photoelectron Spectroscopy (XPS, Kratos Axis Ultra).
  • Amorphous Structure: Renishaw S2000 micro-Raman spectroscopy (He-Ne laser, 632.8 nm).
  • Surface Topography/Roughness: Digital Instruments S-3000 Atomic-Force-Microscopy (AFM) in tapping mode (1 ”m x 1 ”m scan size).
  • Wettability: FTA200 system using distilled water droplets (Water Contact Angle).
  • Corrosion Resistance: EG & G 263A potentiostat/galvanostat workstation in 0.5 M HCl solution (Tafel slopes, Polarization Resistance Rp).

The development of highly durable, low-adhesion, and wear-resistant coatings is critical for extending the service life of precision tools. This Pt/Ru/N-DLCNC-TF technology is directly applicable to:

  • Micro-Molding and Micro-Fluidics: The primary application cited. DLC coatings are essential for reducing adhesion and friction in miniature micro-molds (e.g., Si and steel molds) used for fabricating micro-fluidic devices, which typically suffer from short service life due to high adhesion and wear.
  • Protective Coatings: General use as a protective coating for steel components susceptible to corrosion, especially in environments containing moisture or chlorides (e.g., industrial equipment, marine applications).
  • High-Wear Components: Due to the high hardness and excellent wear resistance inherent to DLC films, these nano-composite coatings can be used on moving parts requiring low friction and high durability.
  • Catalysis and Electrochemistry: The incorporation and surface segregation of Pt and Ru aggregates suggest potential applications in electrocatalytic systems, where the metal content and structure are crucial for reaction efficiency.