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Boron doped diamond/metal nanocatalyst hybrid electrode arrays for analytical applications

MetadataDetails
Publication Date2017-05-01
AuthorsEmmanuel Scorsone, Dounia Belghiti, Massiel Habchi, P. Bergonzo
InstitutionsCommissariat à l’Énergie Atomique et aux Énergies Alternatives, CEA LIST
Citations1
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MPCVD Diamond Technical Analysis: Hybrid BDD Nano-Catalyst Electrode Arrays for Contaminant Detection

Section titled “MPCVD Diamond Technical Analysis: Hybrid BDD Nano-Catalyst Electrode Arrays for Contaminant Detection”

This document analyzes the research published by Scorsone et al. concerning the fabrication and testing of Boron Doped Diamond (BDD)/Metal Nanocatalyst Hybrid Electrode Arrays. The analysis connects the reported specifications and methodologies directly to the advanced MPCVD diamond solutions available from 6CCVD.


The reported study demonstrates a highly effective method for developing selective electrochemical sensor arrays using custom-engineered MPCVD Boron Doped Diamond (BDD) substrates.

  • Core Achievement: Development of a multi-sensor array using four BDD electrodes, each modified with a different metal or metal alloy nanoparticle (e.g., BDD, BDD-Pt, BDD-Ir, BDD-PtIr).
  • Material Foundation: The electrodes utilize heavily Boron-doped diamond (2.1021 at.cm-3) grown via MPECVD, enabling a wide potential window and high resilience required for analytical sensing.
  • Nanocatalyst Fabrication: A novel two-step process involving Physical Vapor Deposition (PVD) of a thin metal film (2-3 nm) followed by high-temperature hydrogen plasma de-wetting successfully produced well-adhered nanoparticles (~10 nm size).
  • Enhanced Selectivity: The BDD-PtIr alloy nanoparticles exhibited superior catalytic activity compared to single-metal nanoparticles or bare BDD, crucial for the highly sensitive detection and discrimination of multiple contaminants (DMMP, H2O2, Imidacloprid).
  • Application Demonstrated: The array was successfully tested for online detection and classification of contaminants in tap water using chronoamperometry and Principal Component Analysis (PCA).
  • 6CCVD Value Proposition: 6CCVD can replicate and optimize the critical BDD substrate synthesis and the necessary metal precursor deposition using its internal MPCVD and metalization capabilities.

ParameterValueUnitContext
Diamond MaterialBoron Doped Diamond (BDD)N/AElectrochemical working electrode material
Growth MethodMPECVDN/AMicrowave Plasma Enhanced CVD
Substrate Size (Pre-Cleaving)4 inchesDiameterHighly doped <100> silicon
BDD Film Thickness500nmMeasured via optical interferometry
Boron Doping Concentration2.1021at.cm-3Determined by SIMS, heavy doping
Electrode Dimensions1cm2Individual BDD electrodes, cleaved post-growth
Nanocatalyst Size (Mean)10nmParticle size after de-wetting (SEM/SAXS)
Precursor Film Thickness2-3nmInitial metal film thickness (Pt, Ir, Au, Rh)
Sputtering Pressure (Ar)6.10-3mbarPVD chamber pressure
Sputtering RF Power50WPower applied for PVD metal deposition
Sputtering Rate5 to 15nm.min-1Dependent on metal type
De-wetting Power900kWHydrogen plasma applied for 10 min
De-wetting Pressure40mbarHydrogen plasma chamber pressure
Measurement Voltage-0.1VPolarization voltage vs. pseudo-reference electrode
Flow Rate (Tap Water)300mL.min-1Used in the dedicated flow cell

The successful fabrication of the hybrid electrode arrays relies on precise control over two distinct processes: MPCVD diamond growth and subsequent metal nanocatalyst deposition.

  1. BDD Substrate Growth (MPCVD):

    • BDD film (500 nm thick) was grown onto 4-inch highly doped <100> silicon substrates using a proprietary Microwave Plasma Enhanced Chemical Vapor Deposition (MPECVD) process.
    • The films were intentionally heavily doped with Boron to a concentration of 2.1021 at.cm-3 to ensure high conductivity and a wide electrochemical window.
    • The wafer was cleaved to produce individual 1 cm2 electrodes.
  2. Thin Metal Film Deposition (PVD):

    • Thin films (2-3 nm) of metal precursors (Pt, Ir, Au, Rh, or alloys) were deposited onto the BDD surface.
    • This was achieved using Physical Vapor Deposition (PVD) via RF-sputtering, utilizing 50 W RF power and an Argon chamber pressure of 6.10-3 mbar.
  3. Nanoparticle Formation (De-wetting):

    • The metal-coated BDD samples were exposed to a Hydrogen plasma in a dedicated diamond growth reactor for 10 minutes.
    • Key parameters for this de-wetting step were: 900 kW microwave power and 40 mbar pressure.
    • This thermal treatment caused the metal thin film to restructure, forming well-adhered nanoparticles with a mean size of approximately 10 nm, verified by SEM and SAXS.
  4. Electrochemical Testing:

    • Four specialized working electrodes (WE: BDD, BDD-Pt, BDD-Ir, BDD-PtIr) were integrated into a 3D-printed flow cell setup, along with unmodified BDD counter (CE) and pseudo-reference (RE) electrodes.
    • Measurements were conducted using chronoamperometry at -0.1 V (vs. pseudo-RE) to detect and discriminate contaminants in flowing tap water (300 mL.min-1).

6CCVD is uniquely positioned to supply the foundational materials and advanced customization services required to replicate and scale this highly successful research endeavor, particularly for the development of multi-sensor arrays and e-tongue applications.

To replicate or extend the analytical performance achieved in this paper, researchers require heavily doped, high-quality BDD electrodes capable of high electron transfer rates.

6CCVD Product RecommendationSpecification Match/AdvantageCustomization Potential
Heavy Boron Doped Diamond (BDD) WafersDoping Level: We provide BDD with doping densities up to the 1021 at.cm-3 range, matching the required conductivity (2.1021 at.cm-3).Available as plates or wafers. We offer custom thicknesses from 0.1 ”m up to 500 ”m (as used in the paper) on Si, Quartz, or dedicated high-purity Diamond substrates.
High-Purity Polycrystalline Diamond (PCD)Platform Size: While the paper used 1 cm2 pieces, 6CCVD can supply large-area PCD up to 125mm (5 inches) for high-throughput array fabrication.Excellent polishing capability (Ra < 5nm) ensures optimal surface quality for subsequent thin-film PVD and de-wetting processes.
Custom Metalization ServicesPVD Match: The study relies on precise deposition of Pt, Ir, and alloys. 6CCVD offers internal, highly controlled PVD/sputtering and e-beam capabilities.We provide uniform thin-film deposition of Pt and Ir (and Pd, Au, Ti, W, Cu) at nanometer thicknesses (2-3 nm range) directly onto BDD, serving as the required precursor for the de-wetting step.

The development of reliable sensor arrays often requires tight dimensional control and specific surface modifications.

  • Custom Dimensions and Cleaving: The paper utilized 1 cm2 electrodes cleaved from a 4-inch wafer. 6CCVD offers precision laser cutting, scribing, and cleaving services to deliver BDD substrates in any custom shape or size required for microfluidic or sensor integration (e.g., 3D printed flow cells).
  • Targeted Metal Layering: 6CCVD can facilitate the precise deposition of alloy precursors (e.g., Pt/Ir layering) prior to the researcher’s de-wetting step, ensuring the precursor materials for the high-performance BDD-PtIr system are available in ultra-high purity.
  • Surface Preparation: For advanced electrode arrays, 6CCVD can provide atomically smooth SCD (Ra < 1nm) or PCD (Ra < 5nm) surfaces, minimizing background noise and maximizing adhesion uniformity prior to PVD.

The successful demonstration of the BDD-PtIr alloy’s superior catalytic properties for online contaminant detection confirms diamond’s role as the premier electrode material for environmental and industrial sensing.

6CCVD’s in-house team of PhD material scientists and engineers specializes in diamond chemistry and electrochemistry. We can assist researchers in:

  1. Optimizing Boron Doping: Tailoring the precise doping level to optimize the potential window and conductivity for specific redox reactions (e.g., DMMP reduction or H2O2 reduction).
  2. Substrate Selection: Advising on the optimal BDD thickness and substrate (Si, fused silica, or diamond) to meet mechanical, thermal, and electrical requirements for multi-sensor array deployment.
  3. Interface Engineering: Consulting on metalization strategies, including adhesion layers and capping layers, for durable nano-catalyst deposition in complex applications like water quality monitoring and e-tongue systems.

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

View Original Abstract

Conference of 2017 ISOCS/IEEE International Symposium on Olfaction and Electronic Nose, ISOEN 2017 ; Conference Date: 28 May 2017 Through 31 May 2017; Conference Code:129051