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Structural and Physical Characterization of Nanodiamond Composite Thin Films Synthesized by Pulsed-Laser Ablation Method (A Review)

MetadataDetails
Publication Date2021-10-21
JournalProceedings of International Exchange and Innovation Conference on Engineering & Sciences (IEICES)
AuthorsLama Osman, Abdelrahman Zkria, Tsuyoshi Yoshitake
InstitutionsKyushu University
Citations1
AnalysisFull AI Review Included

Structural and Physical Characterization of Nanodiamond Composite Thin Films (A Review)

Section titled “Structural and Physical Characterization of Nanodiamond Composite Thin Films (A Review)”

This analysis summarizes the synthesis and characterization of Ultrananocrystalline Diamond/Hydrogenated Amorphous Carbon Composite (NDC) thin films fabricated using Pulsed-Laser Ablation (PLD).

  • Material System: Nanodiamond Composite (NDC) films, consisting of diamond crystallites (< 10 nm) embedded in an amorphous carbon (a-C) matrix.
  • Synthesis Advantage: PLD was utilized to synthesize high-quality NDC films at a relatively low substrate temperature (550 °C), enabling deposition on diverse solid-state substrates, unlike high-temperature Chemical Vapor Deposition (CVD).
  • Structural Quality: Undoped films exhibited a high sp3 bonding fraction (68%) and sharp sp3 peak FWHM (0.91 eV), confirming the presence of dense, homogeneous nanodiamond crystallites (~5 nm).
  • Electronic Properties: The films displayed a large direct optical band gap of 2.2 eV, attributed to the grain boundaries between the NDCs and the a-C matrix.
  • Doping Effects (Boron): Boron incorporation successfully enhanced the sp3 bonding fraction up to 74%, correlating with an enlargement of the NDC grain sizes.
  • Doping Effects (Nitrogen): Nitrogen incorporation increased the sp2 fraction (reducing sp3 content to 60%), primarily integrating into the grain boundaries (C-N and C=N bonds).
  • Method Efficacy: The review validates PLD as an advanced physical vapor deposition technique for controlling the structural and electronic properties of NDC films through ambient gas (hydrogen) and doping.
ParameterValueUnitContext
Optimum Substrate Temperature550°CPLD deposition condition
Ambient Hydrogen Pressure53.3PaPLD deposition (equivalent to 4 Torr)
Laser TypeArF ExcimerN/AUsed for ablation
Laser Wavelength193nmArF Excimer Laser
Laser Pulse Duration24nsArF Excimer Laser
Laser Fluence5J/cm2Target irradiation
Undoped Crystallite Diameter5nmObserved via TEM
Undoped Film Thickness2”mDeposited on sapphire (0001)
Direct Optical Band Gap2.2eVUndoped NDC film
Indirect Optical Band Gap1.0eVUndoped NDC film (attributed to a-C matrix)
Undoped sp3/(sp2+sp3) Ratio68%Determined by XPS
N-Doped sp3/(sp2+sp3) Ratio60.4%7.9 atm.% N-doped film
B-Doped sp3/(sp2+sp3) Ratio74%13 atm.% B-doped film (highest sp3 content)
Undoped sp3 FWHM (XPS)0.91eVIndicates high crystallite homogeneity
Characteristic Raman Peak1149cm-1Specific to NDCs

The NDC films were synthesized and characterized using the following procedures:

  1. Pulsed-Laser Ablation (PLD) Synthesis:

    • Target: Graphite target was irradiated by an ArF excimer laser (193 nm, 24 ns).
    • Environment: Deposition occurred under an ambient hydrogen pressure (53.3 Pa) at 550 °C. Hydrogen was critical for selectively etching sp2 bonds, promoting sp3 diamond growth, and improving film morphology (surfactant effect).
    • Doping: Nitrogen and Boron were incorporated to tune electronic properties. Nitrogen content was controlled by gas inflow ratio (up to 7.9 atm.%), while Boron was incorporated via doped targets (up to 13 atm.%).
  2. Structural and Morphological Characterization:

    • Transmission Electron Microscopy (TEM): Used in dark-field and high-resolution modes to confirm the presence and size (~5 nm) of diamond crystallites within the amorphous matrix.
    • Selected Area Electron Diffraction (SAED): Confirmed diamond phases ((111), (220), (311)) without evidence of graphite rings.
  3. Chemical Bonding and Electronic Characterization:

    • X-ray Photoemission Spectroscopy (XPS): Measured the C1s core level spectra. Decomposition of the C1s peak into sp3, sp2, and C-O/C=O components allowed precise determination of the sp3/(sp2+sp3) ratio.
    • Near-Edge X-ray Absorption Fine Structure (NEXAFS): Utilized synchrotron radiation to probe the local atomic bonding configuration (π* and σ* transitions), confirming the sp3 fraction and revealing specific doping-induced bonds (e.g., σ* C-B and σ* C=N).
    • Fourier Transform Infrared Spectroscopy (FTIR): Examined CHn vibration peaks, confirming hydrogen termination at the grain boundaries, especially the intense sp3-CH peak in NDC films.
  4. Optical Characterization:

    • UV-Vis Spectroscopy: Measured transmittance (T) and reflectance (R) to calculate the absorption coefficient (α), leading to the determination of direct (2.2 eV) and indirect (1.0 eV) optical band gaps.

The unique combination of high hardness, smoothness, high thermal conductivity, and tunable electronic properties makes NDC films suitable for advanced engineering applications:

Application AreaRelevant NDC PropertySpecific Use Cases
Advanced ElectronicsTunable wide band gap, high thermal conductivityHigh-power/High-frequency transistors, heat spreaders, passive components.
Field Emission TechnologyLow electron affinity, high conductivity (when doped)Cold cathodes, flat panel displays, electron sources for vacuum microelectronics.
Biomedical DevicesBio-compatibility, chemical inertness, smoothnessProtective coatings for medical implants, biosensors, drug delivery platforms.
Mechanical/TribologyExtreme hardness, low frictionWear-resistant coatings for micro-tools, MEMS components, protective layers in harsh environments.
Optics and SensorsWide optical transparency, doping-induced defectsUV detectors, optical windows, quantum sensing platforms (if NV centers are formed).
View Original Abstract

Ultrananocrystalline diamond/hydrogenated amorphous carbon composite (so called Nanodiamond composite) thin films were deposited on diverse substrate materials at optimum substrate temperature of 550℃ and ambient hydrogen pressure of 53.3 Pa by pulsed-laser deposition technique. The structural and physical characterization of the undoped, nitrogen-doped and boron-doped films were well-discussed through this review.