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Improved Thermal Resistance and Electrical Conductivity of a Boron-Doped DLC Film Using RF-PECVD

MetadataDetails
Publication Date2020-07-07
JournalFrontiers in Materials
AuthorsWanrong Li, Xing Tan, Yeong Min Park, Dong Chul Shin, Dae Weon Kim
InstitutionsSilla University, Pusan National University
Citations10
AnalysisFull AI Review Included

This research successfully developed boron-doped Diamond-like Carbon (B-DLC) films using Radio-Frequency Plasma-Enhanced Chemical Vapor Deposition (RF-PECVD) to significantly enhance thermal resistance and electrical conductivity, addressing limitations of conventional DLC.

  • Core Achievement: Boron doping (using B2H6/CH4) dramatically improved the thermal stability of DLC films and enabled high electrical conductivity.
  • Thermal Resistance: The thermal decomposition temperature (TGA onset) increased from approximately 300 °C (undoped DLC) to 460 °C for films doped with 30 vol% B2H6/CH4.
  • Structural Integrity: 30 vol% B-DLC films remained visually intact (no delamination or cracking via SEM) after heat treatment up to 400 °C, whereas undoped DLC delaminated at 350 °C.
  • Electrical Performance: Increasing boron concentration improved electrical conductivity. The 40 vol% B2H6/CH4 film exhibited the lowest sheet resistance, confirming the formation of a p-type semiconducting material.
  • Structural Mechanism: Boron doping promotes the formation of sp2 (graphite-like) bonds, which reduces internal compressive stress and facilitates electron tunneling, leading to higher conductivity.
  • Trade-off: The improved thermal and electrical properties came at the cost of reduced Vickers hardness (from 1572 HV for undoped to ~1176 HV for doped films).
  • Value Proposition: The resulting B-DLC films offer an optimal combination of thermal stability, mechanical robustness, and charge dissipation capability, making them highly suitable for demanding applications.
ParameterValueUnitContext
Substrate MaterialSi (100)N/AWafers used for deposition
Deposition MethodRF-PECVDN/ARadio-Frequency Plasma-Enhanced CVD
RF Power (Deposition)300WConstant power used for all samples
Working Pressure2.0 x 10-2TorrPressure during deposition and pretreatment
Optimal B2H6/CH4 Ratio (Thermal)30vol%Highest TGA stability (460 °C)
Optimal B2H6/CH4 Ratio (Electrical)40vol%Lowest electrical resistivity
Undoped DLC Hardness (Max)1572HVVickers Hardness
Doped DLC Hardness (Average)1176.3HVAverage Vickers Hardness
Undoped DLC Thermal Stability (TGA)~300°COnset of weight loss/decomposition
Optimal B-DLC Thermal Stability (TGA)460°COnset of weight loss (30 vol% B2H6)
B-DLC Film Growth Rate (40 vol% B2H6)897.6nm/hHigher than undoped film (799.6 nm/h)
Heat Treatment Temperatures300, 350, 400°CUsed for delamination testing (15 min hold)
Undoped DLC Delamination350°CFailure point observed via SEM
30 vol% B-DLC Integrity400°CRemained intact (highest temperature tested)
Boron XPS Peak (B1s) Range196.38-199.68eVConfirms boron incorporation
Undoped DLC ID/IG Ratio0.444N/ARaman analysis (low sp2 content)
Doped DLC ID/IG Ratio (Max)0.522N/ARaman analysis (30 vol% B2H6, higher sp2 content)

The B-DLC films were fabricated using a controlled RF-PECVD process, followed by rigorous thermal and structural characterization.

  1. Substrate Cleaning: Si (110) substrates (20 mm x 20 mm) were ultrasonically cleaned sequentially using acetone (C3H6O), ethanol (C2H5OH), and deionized water for 30 minutes each.
  2. Pretreatment (Plasma Etching): Substrates were pretreated in the chamber using Argon (Ar) plasma to enhance adhesion and ensure thermal stability during subsequent deposition.
    • Parameters: 30 sccm Ar flow, 300 W RF power, 30 minutes.
  3. DLC Deposition: Films were deposited using a mixture of methane (CH4) and diborane (B2H6).
    • Doping Ratios: B2H6/CH4 ratios were varied at 0, 10, 20, 30, and 40 vol%.
    • Process Parameters: 300 W RF power, 1 hour duration, 2.0 x 10-2 Torr pressure.
  4. Thermal Resistance Testing (Muffle Furnace): Samples were subjected to heat treatment to evaluate delamination and structural integrity.
    • Conditions: Heating rate of 10 °C/min, 15 minutes holding time at target temperatures (300 °C, 350 °C, 400 °C).
  5. Thermal Gravimetric Analysis (TGA): Used to determine the precise thermal decomposition temperature (onset of weight loss) for undoped and 30 vol% B-DLC films.
  6. Characterization:
    • Structural/Chemical: X-ray Photoelectron Spectroscopy (XPS) confirmed boron incorporation (B1s peak) and Scanning Electron Microscopy (SEM) monitored morphology and delamination post-heating.
    • Bonding Analysis: Raman Spectroscopy measured the shift and intensity ratio (ID/IG) of the D and G peaks to quantify the increase in sp2 bonding fraction.
    • Mechanical/Electrical: Nano-indenter measured Vickers hardness (HV), and the four-point probe method determined electrical conductivity (sheet resistance).

The improved thermal resistance and tunable electrical conductivity of B-DLC films make them critical for applications requiring stability under extreme conditions and effective charge management.

  • Outer Space Technology:
    • Charge Dissipation: High electrical conductivity is essential for dissipating charging electrons in plasma environments on orbit, protecting sensitive components.
    • Actuator Components: Used for long-term missions involving solar cell orientation, antenna azimuth, and propulsion gimbal adjustments, where high thermal and tribological stability is required.
  • High-Temperature Tribological Coatings: Used in engines, drills, or industrial machinery where conventional DLC fails due to graphitization and performance degradation above 300 °C.
  • Semiconductor Devices: The ability to create p-type semiconducting DLC films via boron doping opens avenues for use in thin-film transistors, photovoltaic cells, and advanced microelectronics.
  • High-Stress Environment Coatings: Applications requiring low internal stress (a benefit of boron doping) combined with improved thermal stability, such as protective layers in harsh chemical or thermal processing equipment.
View Original Abstract

Diamond-like carbon (DLC) film doped with boron has unique properties and displays higher thermal resistance, lower internal stress, and better electrical conductivity than un-doped DLC film; this makes it is suitable for various applications, especially in outer space. Radio-frequency plasma-enhanced chemical vacuum deposition of boron-doped DLC film was performed to determine the optimal percentage of boron for improving thermal resistance. Additional heat treatment and 40 vol% B2H6/CH4 yielded the best electrical conductivity. X-ray photoelectron spectroscopy, thermal gravimetric analysis, Raman spectroscopy, and the four-point probe method were utilized to analyze the properties of boron-doped DLC film. The boron-doped DLC film displayed outstanding performance in terms of thermal resistance and electrical conductivity.

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