skip to main content


Title: Effects of direct current bias on nucleation density of superhard boron-rich boron carbide films made by microwave plasma chemical vapor deposition
Abstract

We report bias enhanced nucleation and growth of boron-rich deposits through systematic study of the effect of a negative direct current substrate bias during microwave plasma chemical vapor deposition. The current flowing through a silicon substrate with an applied bias of −250 V was investigated for a feedgas containing fixed hydrogen (H2) flow rate but with varying argon (Ar) flow rates for 1330, 2670, and 4000 Pa chamber pressure. For 1330 and 2670 Pa, the bias current goes through a maximum with increasing Ar flow rate. This maximum current also corresponds to a peak in substrate temperature. However, at 4000 Pa, no maximum in bias current or substrate temperature is observed for the range of argon flow rates tested. Using these results, substrate bias pre-treatment experiments were performed at 1330 Pa in an Ar/H2plasma, yielding the maximum bias current. Nucleation density of boron deposits were measured after subsequent exposure to B2H6in H2plasma and found to be a factor of 200 times higher than when no bias and no Ar was used. Experiments were repeated at 2670 and 4000 Pa (fixed bias voltage and Ar flow rate) in order to test the effect of chamber pressure on the nucleation density. Compared to 4000 Pa, we find nearly 7 times higher boron nucleation densities for both 1330 and 2670 Pa when the substrate was negatively biased in the Ar/H2plasma. Results are explained by incorporating measurements of plasma optical emission and by use of heterogeneous nucleation theory. The optimal conditions at 1330 Pa for nucleation were used to grow boron-rich amorphous films with measured hardness as high as 58 GPa, well above the 40 GPa threshold for superhardness.

 
more » « less
Award ID(s):
1655280
NSF-PAR ID:
10362417
Author(s) / Creator(s):
; ;
Publisher / Repository:
IOP Publishing
Date Published:
Journal Name:
Materials Research Express
Volume:
8
Issue:
4
ISSN:
2053-1591
Page Range / eLocation ID:
Article No. 046401
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. A microwave plasma chemical vapor deposition system was used to synthesize cubic boron nitride (cBN) coatings on diamond seeded silicon substrates using direct current (DC) bias. Effects of the argon (Ar) flow rate and bias voltage on the growth of the cBN coatings were investigated. Hydrogen (H2), argon (Ar), a mixture of diborane in H2 (95% H2, 5% B2H6), and N2 were used in the feed gas. A DC bias system was used for external biasing of the sample, which facilitates the goal of achieving sp3 bonded cBN. Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) revealed the existence of sp3-bonded BN in the produced samples. With increasing Ar flow, the cBN content in the coating increases and reaches a maximum at the maximum Ar flow of 400 SCCM used in this study. High-resolution XPS scans for B1s and N1s indicate that the deposited coating contains more than 70% cBN. This study demonstrates that energetic argon ions generated in a microwave-induced plasma significantly increase cBN content in the coating. 
    more » « less
  2. Abstract

    As in lamellibranch bivalves, individuals of the common Atlantic slippersnailCrepidula fornicatabeat cilia on their gill filaments to produce a suspension‐feeding current. Having only one shell and no siphons with which to direct water flow, however, individuals ofC. fornicatamust adhere to a solid substrate to facilitate normal feeding. Thus, what hydrodynamic role does substrate attachment play in producing, regulating, and directing the suspension‐feeding current for this species? Here, a combined particle image velocimetry and computational fluid dynamics study was conducted to address this question. Three findings were obtained: (1) Juveniles ofC. fornicata(shell length 6.0–10.6 mm) whose foot was attached to a solid surface generated a strong, fan‐like exhalant current and an almost equally strong, convergent inhalant current, both being spatially well extended; (2) juveniles ofC. fornicatathat were prevented from adhering to any surface also generated a strong, fan‐like exhalant current but a much weaker and spatially limited inhalant current; and (3) whether or not they were attached to a solid surface, juveniles ofC. fornicatahad almost the same performance or system characteristics of the ciliary water pump, including the relationship between flow pressure rise Δpacross the ciliary zone and volume flow rateQ, pump resistance Δp/Q, and pressure coefficient for laminar flowCp,l. These results indicate that the primary hydrodynamic effect of substrate attachment inC. fornicatais to form a complete inhalant chamber with a narrowed opening, such that negative flow pressure develops in the inhalant chamber, and a strong, convergent, spatially well‐extended inhalant current is generated to effectively bring in food particles from farther distances and to reduce refiltration of the outflowing water. Finally, ecological trade‐offs are discussed regarding the two distinct shell configuration strategies: (1) that of the single‐shelledC. fornicata, with only a naturally formed exhalant chamber and opening but not a morphologically defined inhalant chamber and opening, and (2) that of two‐shelled bivalves, with naturally formed exhalant and inhalant chambers.

     
    more » « less
  3. Abstract

    A knowledge-based understanding of the plasma-surface-interaction with the aim to precisely control (reactive) sputtering processes for the deposition of thin films with tailored and reproducible properties is highly desired for industrial applications. In order to understand the effect of plasma parameter variations on the film properties, a single plasma parameter needs to be varied, while all other process and plasma parameters should remain constant. In this work, we use the Electrical Asymmetry Effect in a multi-frequency capacitively coupled plasma to control the ion energy at the substrate without affecting the ion-to-growth flux ratio by adjusting the relative phase between two consecutive driving harmonics and their voltage amplitudes. Measurements of the ion energy distribution function and ion flux at the substrate by a retarding field energy analyzer combined with the determined deposition rateRdfor a reactive Ar/N2(8:1) plasma at 0.5 Pa show a possible variation of the mean ion energy at the substrateEmigwithin a range of 38 and 81 eV that allows the modification of the film characteristics at the grounded electrode, when changing the relative phase shiftθbetween the applied voltage frequencies, while the ion-to-growth flux ratio Γiggrcan be kept constant. AlN thin films are deposited and exhibit an increase in compressive film stress from −5.8 to −8.4 GPa as well as an increase in elastic modulus from 175 to 224 GPa as a function of the mean ion energy. Moreover, a transition from the preferential orientation (002) at low ion energies to the (100), (101) and (110) orientations at higher ion energies is observed. In this way, the effects of the ion energy on the growing film are identified, while other process relevant parameters remain unchanged.

     
    more » « less
  4. Boron nitride (BN) is primarily a synthetically produced advanced ceramic material. It is isoelectronic to carbon and, like carbon, can exist as several polymorphic modifications. Microwave plasma chemical vapor deposition (MPCVD) of metastable wurtzite boron nitride is reported for the first time and found to be facilitated by the application of direct current (DC) bias to the substrate. The applied negative DC bias was found to yield a higher content of sp3 bonded BN in both cubic and metastable wurtzite structural forms. This is confirmed by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Nano-indentation measurements reveal an average coating hardness of 25 GPa with some measurements as high as 31 GPa, consistent with a substantial fraction of sp3 bonding mixed with the hexagonal sp2 bonded BN phase. 
    more » « less
  5. Cubic boron nitride (c-BN), with a small 1.4% lattice mismatch with diamond, presents a heterostructure with multiple opportunities for electronic device applications. However, the formation of c-BN/diamond heterostructures has been limited by the tendency to form hexagonal BN at the interface. In this study, c-BN has been deposited on free standing polycrystalline and single crystal boron-doped diamond substrates via electron cyclotron resonance plasma enhanced chemical vapor deposition (ECR-PECVD), employing fluorine chemistry. In situ x-ray photoelectron spectroscopy (XPS) is used to characterize the nucleation and growth of boron nitride (BN) films as a function of hydrogen gas flow rates during deposition. The PECVD growth rate of BN was found to increase with increased hydrogen gas flow. In the absence of hydrogen gas flow, the BN layer was reduced in thickness or etched. The XPS results show that an excess of hydrogen gas significantly increases the percent of sp2 bonding, characteristic of hexagonal BN (h-BN), particularly during initial layer growth. Reducing the hydrogen flow, such that hydrogen gas is the limiting reactant, minimizes the sp2 bonding during the nucleation of BN. TEM results indicate the partial coverage of the diamond with thin epitaxial islands of c-BN. The limited hydrogen reaction is found to be a favorable growth environment for c-BN on boron-doped diamond.

     
    more » « less