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Orientation-dependent electric transport and band filling in hole co-doped epitaxial diamond films

MetadataDetails
Publication Date2020-06-08
JournalApplied Surface Science
AuthorsErik Piatti, A. Pasquarelli, R. S. Gonnelli
InstitutionsUniversitÀt Ulm, Polytechnic University of Turin
Citations11
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Technical Documentation & Analysis: Orientation-Dependent Hole Co-Doping in Epitaxial Diamond

Section titled “Technical Documentation & Analysis: Orientation-Dependent Hole Co-Doping in Epitaxial Diamond”

This document analyzes the research detailing orientation-dependent electric transport in hole co-doped epitaxial diamond films, focusing on the combination of ionic gating and Boron substitution. The findings are leveraged to showcase 6CCVD’s superior material science capabilities for advanced quantum and electronic device engineering.


  • Novel Co-Doping Approach: The research successfully demonstrates a co-doping technique combining ionic gating (Electric Double Layer Transistors, EDLTs) and Boron (B) substitution to tune free hole density in H-terminated epitaxial diamond films.
  • Strong Orientation Dependence: Electric transport properties, particularly gate capacitance (C$_{G}$) and mobility ($\mu$), show extreme sensitivity to crystal orientation, comparing (111) and (110) facets.
  • Capacitance Enhancement: B-doping led to a five-fold increase in C$_{G}$ in the (110)-oriented films (up to 2.53 ”F cm-2), linking directly to the energy-dependence of the electronic density of states (DOS).
  • Mobility Suppression: While B-doping increased intrinsic hole density (up to 1.5 $\cdot$ 1014 h+cm-2), it significantly suppressed mobility, particularly in the (111) orientation ($\mu$ dropped to $\approx 3$ cm2V-1s-1).
  • Metallicity Frustration: The co-doping approach resulted in a frustrated insulator-to-metal transition (IMT) in the (110) surface and a re-entrant IMT in the (111) surface, falling short of the required carrier density (6 $\cdot$ 1014 h+cm-2) for predicted high-Tc superconductivity.
  • Material Requirement: Achieving robust metallicity and high-Tc superconductivity requires optimizing crystal growth to minimize disorder and precisely control ultra-thin B-doped layer thickness (nominal 2 nm used).

The following hard data points were extracted from the gate-dependent transport measurements and DFT calculations:

ParameterValueUnitContext
Operating Temperature (T)$\approx 240$KOptimal EDLT operation (above PES glass transition)
Maximum Total Carrier Density (n2D)$\lt 2.1 \cdot 10^{14}$h+cm-2Achieved maximum (Target for SC is $6 \cdot 10^{14}$ h+cm-2$) |
| Intrinsic Hole Density (n0) | $1.5 \pm 0.4 \cdot 10^{14}$ | h+cm-2Highest value (B-doped (111) surface)
H-Terminated C$_{G}$ (111)$1.36 \pm 0.41$”F cm-2Gate Capacitance (H-terminated)
H-Terminated C$_{G}$ (110)$0.44 \pm 0.13$”F cm-2Gate Capacitance (H-terminated)
B-Doped C$_{G}$ (111)$2.06 \pm 0.62$”F cm-2Gate Capacitance (B-doped)
B-Doped C$_{G}$ (110)$2.53 \pm 0.76$”F cm-2Gate Capacitance (B-doped)
H-Terminated Mobility ($\mu$)$53 \div 145$cm2V-1s-1Range across (111) and (110) surfaces
B-Doped Mobility ($\mu$)$1.9 \div 3.3$cm2V-1s-1Lowest range (B-doped (111) surface)
Epitaxial Buffer Layer Thickness$100$nmUndoped intrinsic layer
B-Doped Layer Thickness$2$nmNominal thickness of the active layer
CVD Reactor Pressure$2$kPaMPCVD growth parameter
CVD Reactor Temperature$750$°CMPCVD growth parameter

The experimental procedure combined advanced MPCVD growth with ionic gating techniques (EDLT architecture) and ab initio Density Functional Theory (DFT) calculations.

  1. Substrate Preparation: Commercial Ib-type single crystal diamond substrates ((111) and (110) orientation) were thoroughly cleaned using a multi-step chemical process (Acetone, Isopropanol, Chromosulphuric acid, HCl:H2O2, H2O2:NH4OH, HCl:HNO3, H2SO4:H2O2).
  2. Epitaxial Growth (MPCVD):
    • A nominally undoped, 100 nm thick intrinsic buffer layer was grown first.
    • An additional 2 nm thick B-doped layer was subsequently grown on half the samples.
    • Parameters: Pressure 2 kPa, Reactor Temperature 750°C, Plasma RF Power 750 W, H2 flow 200 sccm, varying CH4 concentration. Boron supplied via a solid B-coated wire.
  3. Surface Termination: Growth was performed in H2/CH4 atmosphere, resulting in H-termination of the diamond surfaces.
  4. Device Fabrication (EDLT):
    • Four-wire electrical contacts (source, drain, longitudinal voltage probes) were realized using silver conductive paste.
    • A side gate (thin gold leaf) and a reference electrode (thin gold wire) were incorporated.
    • The Polymer-Electrolyte System (PES) was drop-casted and UV-cured (BEMA and EMIM-TFSI ionic liquid).
  5. Transport Measurement: Gate-dependent electric transport measurements were performed at $T \approx 240$ K.
    • Sheet conductance ($\sigma_{2D}$) was measured via four-wire resistance.
    • Gate-induced hole density ($\Delta n_{2D}$) and gate capacitance (C$_{G}$) were determined using Double-Step Chronocoulometry (DSCC).
  6. Theoretical Modeling: Ab initio DFT calculations (using the Jellium model) were performed to determine the electronic band structure and Density of States (DOS) for H-terminated, hole-doped (111) and (110) slabs.

The research highlights the critical need for ultra-precise material control—specifically, crystal orientation, doping concentration, and layer thickness—to manipulate quantum capacitance and carrier mobility in diamond EDLTs. 6CCVD is uniquely positioned to supply the advanced MPCVD diamond materials necessary to replicate, optimize, and extend this research toward achieving robust metallicity and high-temperature superconductivity.

Research Requirement6CCVD SolutionMaterial Specification
Substrate & Buffer LayerOptical Grade SCDHigh-purity, low-disorder Single Crystal Diamond (SCD) wafers. Essential for minimizing extrinsic disorder noted in the paper.
Active Doping LayerPrecisely Doped SCD (BDD)Ultra-thin, highly controlled Boron-Doped Diamond (BDD) epitaxial layers. Required for achieving high intrinsic hole density ($n_0$) without excessive lattice disorder.
Crystal OrientationCustom Oriented SCD WafersSCD wafers available in standard (100), (111), and custom (110) orientations up to inch size, critical for exploiting orientation-dependent DOS effects.
Surface QualitySCD PolishingPolishing to achieve surface roughness Ra < 1 nm, significantly improving upon the $S_q \approx 2.4$ nm to $3.8$ nm reported in the paper, thereby reducing discontinuities in the conducting surface layer.

The paper emphasizes that optimizing the crystal growth and B doping process is necessary to avoid discontinuities and minimize mobility degradation. 6CCVD offers bespoke engineering services to address these challenges:

  • Ultra-Precise Thickness Control: 6CCVD guarantees SCD layer thickness control from 0.1 ”m up to 500 ”m. We can reliably produce the required 100 nm buffer layer and the critical 2 nm B-doped active layer with superior uniformity and repeatability.
  • Custom Doping Profiles (BDD): We offer tailored Boron doping concentrations (BDD) to fine-tune the intrinsic hole density ($n_0$) and optimize the quantum capacitance, crucial for overcoming the IMT frustration observed in this study.
  • Advanced Metalization Services: The EDLT architecture requires precise electrical contacts (Au gate, Ag paste contacts). 6CCVD provides in-house metalization capabilities, including Au, Pt, Pd, Ti, W, and Cu, allowing researchers to integrate robust, high-quality contacts directly onto the diamond surface.
  • Large Area PCD: While this study focused on SCD, 6CCVD offers Polycrystalline Diamond (PCD) plates up to 125 mm diameter with polishing down to Ra < 5 nm, suitable for scaling up EDLT or other field-effect device architectures.

6CCVD’s in-house team of PhD material scientists and CVD experts can provide comprehensive engineering support for projects targeting High-Density 2D Hole Gas (2DHG) and Field-Induced Superconductivity in diamond. We assist clients in selecting the optimal substrate orientation, doping concentration, and layer stack design to maximize carrier density and mobility simultaneously, addressing the trade-offs identified in this research.

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

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  2. 2004 - Dependence of the superconducting transition temperature on the doping level in single-crystalline diamond films [Crossref]
  3. 2005 - Origin of the metallic properties of heavily boron-doped superconducting diamond [Crossref]
  4. 2004 - Superconductivity in diamond thin films well above liquid helium temperature [Crossref]
  5. 2007 - Observation of a superconducting gap in boron-doped diamond by laser-excited photoemission spectroscopy [Crossref]
  6. 2008 - Superconducting diamond: an introduction [Crossref]
  7. 2015 - Signature of high Tc above 25 K in high quality superconducting diamond [Crossref]
  8. 2004 - Three-dimensional MgB2-type superconductivity in hole-doped diamond [Crossref]
  9. 2004 - Superconductivity in boron-doped diamond [Crossref]