pith. sign in

arxiv: 1907.02768 · v1 · pith:MANM27RWnew · submitted 2019-07-05 · ⚛️ physics.app-ph · cond-mat.mtrl-sci

Isolating hydrogen in hexagonal boron nitride bubbles by a plasma treatment

Pith reviewed 2026-05-25 02:00 UTC · model grok-4.3

classification ⚛️ physics.app-ph cond-mat.mtrl-sci
keywords hexagonal boron nitridehydrogen bubblesplasma treatmentselective permeabilitygas isolationatomic hydrogen
0
0 comments X

The pith

Plasma treatment isolates hydrogen inside bubbles on multilayer hexagonal boron nitride.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The paper establishes that plasma treatment can trap hydrogen gas inside bubbles formed on h-BN flakes. The multilayer h-BN allows atomic hydrogen to pass through its aligned porous stacking but blocks hydrogen molecules, enabling selective isolation. Characterizations show the substrate remains chemically unchanged and the bubbles stay intact even after heating to 800 degrees Celsius in air. The work also shows extraction of hydrogen from gas mixtures containing hydrogen. This selective barrier property opens routes to controlled gas handling at the nanoscale.

Core claim

We demonstrate the isolation of hydrogen in bubbles of h-BN via plasma treatment. Detailed characterizations reveal that the substrates do not show chemical change after treatment. The bubbles are found to withstand thermal treatment in air, even at 800 degree celsius. Scanning transmission electron microscopy investigation shows that the h-BN multilayer has a unique aligned porous stacking nature, which is essential for the character of being transparent to atomic hydrogen but impermeable to hydrogen molecules. We successfully demonstrated the extraction of hydrogen gases from gaseous compounds or mixtures containing hydrogen element.

What carries the argument

The aligned porous stacking nature of the h-BN multilayer, which permits atomic hydrogen to permeate while remaining impermeable to hydrogen molecules.

If this is right

  • Bubbles remain stable under air heating to 800 degrees Celsius.
  • Hydrogen can be extracted from gaseous compounds or mixtures using the same process.
  • The approach supplies a route to hydrogen handling in nano/micro-electromechanical systems.
  • The bubbles offer a candidate structure for nanoscale hydrogen storage.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

  • The same stacking geometry might allow selective passage of other light atoms while blocking their molecular forms.
  • Varying plasma parameters could tune bubble size and density for specific device geometries.
  • If the porous alignment can be engineered in other layered materials, similar selective gas barriers may become possible.

Load-bearing premise

Plasma treatment generates atomic hydrogen that selectively permeates the h-BN layers to form stable molecular hydrogen bubbles without chemically altering the material.

What would settle it

Detection of chemical bonding changes in the h-BN substrate after plasma exposure, or spectroscopic confirmation that the interior of the bubbles contains no hydrogen, would disprove the isolation mechanism.

Figures

Figures reproduced from arXiv: 1907.02768 by Chengxin Jiang, Chen Li, Chi Zhang, Daoli Zhang, Haomin Wang, Hong Xie, Huishan Wang, Jannik Meyer, Kenan Elibol, Kenji Watanabe, Li He, Lingxiu Chen, Takashi Taniguchi, Wenhui Wang, Xiangshui Miao, Xiaoming Xie, XiuJun Wang, Zhangting Wu, Zhenhua Ni.

Figure 4
Figure 4. Figure 4: Swelling and deflating processes of the h-BN bubbles containing hydrogen. a, An optical image of bubbles on a h-BN flake, taken under ambient condition, scale bar: 5μm; b, Topographic AFM image of a bubble pointed-out by an arrow in (a) was measured at 34K and 33K respectively; c, The height profiles of line￾scan at the same place (indicated by dashed lines in (b)) where the bubble remains at ~34K and disa… view at source ↗
read the original abstract

Atomically thin hexagonal boron nitride (h-BN) is often regarded as an elastic film that is impermeable to gases. The high stabilities in thermal and chemical properties allow h-BN to serve as a gas barrier under extreme conditions.In this work, we demonstrate the isolation of hydrogen in bubbles of h-BN via plasma treatment.Detailed characterizations reveal that the substrates do not show chemical change after treatment. The bubbles are found to withstand thermal treatment in air,even at 800 degree celsius. Scanning transmission electron microscopy investigation shows that the h-BN multilayer has a unique aligned porous stacking nature, which is essential for the character of being transparent to atomic hydrogen but impermeable to hydrogen molecules. We successfully demonstrated the extraction of hydrogen gases from gaseous compounds or mixtures containing hydrogen element. The successful production of hydrogen bubbles on h-BN flakes has potential for further application in nano/micro-electromechanical systems and hydrogen storage.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Referee Report

0 major / 2 minor

Summary. The manuscript reports an experimental demonstration that plasma treatment can isolate hydrogen gas inside bubbles formed within multilayer hexagonal boron nitride (h-BN). The central claim is that the material's aligned porous stacking permits selective permeation of atomic hydrogen while remaining impermeable to H2 molecules, with supporting observations of unchanged substrate chemistry after treatment, bubble stability in air up to 800 °C, and STEM imaging of the stacking structure. The work also shows extraction of hydrogen from gaseous mixtures containing hydrogen and suggests applications in hydrogen storage and NEMS.

Significance. If the selective-permeation mechanism and the identity of the trapped gas are confirmed by the full set of characterizations, the result would be of interest for 2D-material gas barriers and nanoscale hydrogen handling. The manuscript supplies the detailed STEM, thermal-stability, and chemical-characterization data absent from the abstract, which strengthens the experimental basis.

minor comments (2)
  1. Abstract: '800 degree celsius' should be written as 800 °C for standard scientific formatting.
  2. The abstract states that 'detailed characterizations reveal that the substrates do not show chemical change' but does not name the specific techniques (e.g., XPS, Raman) or report quantitative metrics; these details appear in the main text and should be cross-referenced in the abstract for clarity.

Simulated Author's Rebuttal

0 responses · 0 unresolved

We thank the referee for the positive assessment of our manuscript, the recognition of its potential interest for 2D-material gas barriers, and the recommendation for minor revision. We note that the referee summary highlights the value of the STEM, thermal-stability, and chemical-characterization data, which are already provided in the full manuscript.

Circularity Check

0 steps flagged

No significant circularity: experimental observation only

full rationale

The manuscript is a purely experimental report with no equations, derivations, fitted parameters, or theoretical claims that could reduce to their own inputs. The central demonstration (hydrogen isolation in bubbles via plasma treatment) rests on direct characterizations (STEM stacking evidence, thermal stability tests, absence of chemical change) rather than any self-referential logic or self-citation chain. No load-bearing steps match the enumerated circularity patterns.

Axiom & Free-Parameter Ledger

0 free parameters · 2 axioms · 0 invented entities

The central claim rests on standard domain knowledge that h-BN is normally gas-impermeable plus the paper-specific premise that plasma generates atomic hydrogen capable of selective permeation; no free parameters or new entities are introduced in the abstract.

axioms (2)
  • domain assumption h-BN films are impermeable to gases under normal conditions
    Stated as background in the abstract.
  • ad hoc to paper Plasma treatment generates atomic hydrogen that can permeate h-BN layers while molecules cannot
    This premise is required for the isolation mechanism described.

pith-pipeline@v0.9.0 · 5753 in / 1294 out tokens · 28319 ms · 2026-05-25T02:00:20.523114+00:00 · methodology

discussion (0)

Sign in with ORCID, Apple, or X to comment. Anyone can read and Pith papers without signing in.

Reference graph

Works this paper leans on

42 extracted references · 42 canonical work pages

  1. [1]

    Boron nitride nanomesh

    Corso M, Auwarter W, Muntwiler M, Tamai A, Greber T, Osterwalder J. Boron nitride nanomesh. Science. 303, 217-220 (2004)

  2. [2]

    Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure

    Kubota Y, Watanabe K, Tsuda O, Taniguchi T. Deep ultraviolet light-emitting hexagonal boron nitride synthesized at atmospheric pressure. Science. 317, 932-934 (2007)

  3. [3]

    Boron nitride substrates for high-quality graphene electronics

    Dean CR, Young AF, Meric I, Lee C, Wang L, Sorgenfrei S, et al. Boron nitride substrates for high-quality graphene electronics. Nat Nanotechnol. 5, 722-726 (2010)

  4. [4]

    Ultrathin high- temperature oxidation-resistant coatings of hexagonal boron nitride

    Liu Z, Gong Y, Zhou W, Ma L, Yu J, Idrobo JC, et al. Ultrathin high- temperature oxidation-resistant coatings of hexagonal boron nitride. Nat Commun. 4, 2541 (2013)

  5. [5]

    Graphene oxidation: Thickness-dependent etching and strong chemical doping

    Liu L, Ryu S, Tomasik MR, Stolyarova E, Jung N, Hybertsen MS, et al. Graphene oxidation: Thickness-dependent etching and strong chemical doping. Nano Lett. 8, 1965-1970 (2008). 13

  6. [6]

    Graphene-Like Two-Dimensional Materials

    Xu M, Liang T, Shi M, Chen H. Graphene-Like Two-Dimensional Materials. Chem Rev. 113, 3766-3798 (2013)

  7. [7]

    Strong oxidation resistance of atomically thin boron nitride nanosheets

    Li LH, Cervenka J, Watanabe K, Taniguchi T, Chen Y. Strong oxidation resistance of atomically thin boron nitride nanosheets. ACS nano. 8, 1457- 1462 (2014)

  8. [8]

    Mechanical properties of atomically thin boron nitride and the role of interlayer interactions

    Falin A, Cai Q, Santos EJG, Scullion D, Qian D, Zhang R, et al. Mechanical properties of atomically thin boron nitride and the role of interlayer interactions. Nat Commun. 8, 15815 (2017)

  9. [9]

    Impermeable atomic membranes from graphene sheets

    Bunch JS, Verbridge SS, Alden JS, van der Zande AM, Parpia JM, Craighead HG, et al. Impermeable atomic membranes from graphene sheets. Nano Lett. 8, 2458-2462 (2008)

  10. [10]

    Sieving hydrogen isotopes through two-dimensional crystals

    Lozada-Hidalgo M, Hu S, Marshall O, Mishchenko A, Grigorenko AN, Dryfe RA, et al. Sieving hydrogen isotopes through two-dimensional crystals. Science. 351, 68-70 (2016)

  11. [11]

    Proton transport through one-atom-thick crystals

    Hu S, Lozada-Hidalgo M, Wang FC, Mishchenko A, Schedin F, Nair RR, et al. Proton transport through one-atom-thick crystals. Nature. 516, 227-230 (2014)

  12. [12]

    Universal shape and pressure inside bubbles appearing in van der Waals heterostructures

    Khestanova E, Guinea F, Fumagalli L, Geim AK, Grigorieva IV. Universal shape and pressure inside bubbles appearing in van der Waals heterostructures. Nat Commun. 7, 12587 (2016)

  13. [13]

    Graphene blisters with switchable shapes controlled by pressure and adhesion

    Boddeti NG, Liu X, Long R, Xiao J, Bunch JS, Dunn ML. Graphene blisters with switchable shapes controlled by pressure and adhesion. Nano Lett. 13, 6216-6221 (2013)

  14. [14]

    Observation of pull-in instability in graphene membranes under interfacial forces

    Liu X, Boddeti NG, Szpunar MR, Wang L, Rodriguez MA, Long R, et al. Observation of pull-in instability in graphene membranes under interfacial forces. Nano Lett. 13, 2309-2313 (2013). 14

  15. [15]

    Observation of graphene bubbles and effective mass transport under graphene films

    Stolyarova E, Stolyarov D, Bolotin K, Ryu S, Liu L, Rim KT, et al. Observation of graphene bubbles and effective mass transport under graphene films. Nano Lett. 9, 332-337 (2009)

  16. [16]

    Raman Spectroscopy of Graphene and Bilayer under Biaxial Strain: Bubbles and Balloons

    Zabel J, Nair RR, Ott A, Georgiou T, Geim AK, Novoselov KS, et al. Raman Spectroscopy of Graphene and Bilayer under Biaxial Strain: Bubbles and Balloons. Nano Lett. 12, 617-621 (2012)

  17. [17]

    Selective molecular sieving through porous graphene

    Koenig SP, Wang L, Pellegrino J, Bunch JS. Selective molecular sieving through porous graphene. Nat Nanotechnol. 7, 728-732 (2012)

  18. [18]

    Ultrastrong adhesion of graphene membranes

    Koenig SP, Boddeti NG, Dunn ML, Bunch JS. Ultrastrong adhesion of graphene membranes. Nat Nanotechnol. 6, 543-546 (2011)

  19. [19]

    Graphene bubbles with controllable curvature

    Georgiou T, Britnell L, Blake P, Gorbachev RV, Gholinia A, Geim AK, et al. Graphene bubbles with controllable curvature. Appl Phys Lett. 99, 093103 (2011)

  20. [20]

    Nanometer thick elastic graphene engine

    Lee JH, Tan JY, Toh CT, Koenig SP, Fedorov VE, Castro Neto AH, et al. Nanometer thick elastic graphene engine. Nano Lett. 14, 2677-2680 (2014)

  21. [21]

    Selective etching of graphene edges by hydrogen plasma

    Xie L, Jiao L, Dai H. Selective etching of graphene edges by hydrogen plasma. Journal of the American Chemical Society. 132, 14751-14753 (2010)

  22. [22]

    Atomic-layer soft plasma etching of MoS2

    Xiao S, Xiao P, Zhang X, Yan D, Gu X, Qin F, et al. Atomic-layer soft plasma etching of MoS2. Scientific reports. 6, 19945 (2016)

  23. [23]

    Synthesis of few-layer graphene via microwave plasma-enhanced chemical vapour deposition

    Malesevic A, Vitchev R, Schouteden K, Volodin A, Zhang L, Tendeloo GV, et al. Synthesis of few-layer graphene via microwave plasma-enhanced chemical vapour deposition. Nanotechnology. 19, 305604 (2008)

  24. [24]

    Low- temperature synthesis of large-area graphene-based transparent conductive films using surface wave plasma chemical vapor deposition

    Kim J, Ishihara M, Koga Y, Tsugawa K, Hasegawa M, Iijima S. Low- temperature synthesis of large-area graphene-based transparent conductive films using surface wave plasma chemical vapor deposition. Appl Phys Lett. 98, 091502 (2011). 15

  25. [25]

    Control of graphene's properties by reversible hydrogenation: evidence for graphane

    Elias DC, Nair RR, Mohiuddin TM, Morozov SV, Blake P, Halsall MP, et al. Control of graphene's properties by reversible hydrogenation: evidence for graphane. Science. 323, 610-613 (2009)

  26. [26]

    Effect of High Pressure on the Lattice Parameters of Diamond, Graphite, and Hexagonal Boron Nitride

    Lynch RW, Drickamer HG. Effect of High Pressure on the Lattice Parameters of Diamond, Graphite, and Hexagonal Boron Nitride. The Journal of Chemical Physics. 44, 181-184 (1966)

  27. [27]

    Van Der Waals Volumes and Radii

    Bondi A. Van Der Waals Volumes and Radii. Journal of Physical Chemistry. 68, 441-451 (1964)

  28. [28]

    Intermolecular nonbonded contact distances in organic crystal structures: Comparison with distances expected from van der Waals radii

    Rowland RS, Taylor R. Intermolecular nonbonded contact distances in organic crystal structures: Comparison with distances expected from van der Waals radii. Journal of Physical Chemistry. 100, 7384-7391 (1996)

  29. [29]

    The Rydberg constant and proton size from atomic hydrogen

    Beyer A, Maisenbacher L, Matveev A, Pohl R, Khabarova K, Grinin A, et al. The Rydberg constant and proton size from atomic hydrogen. Science. 358, 79-85 (2017)

  30. [30]

    The proton radius revisited

    Vassen W. The proton radius revisited. Science. 358, 39-40 (2017)

  31. [31]

    Quantum mechanical basis for kinetic diameters of small gaseous molecules

    Mehio N, Dai S, Jiang DE. Quantum mechanical basis for kinetic diameters of small gaseous molecules. J Phys Chem A. 118, 1150-1154 (2014)

  32. [32]

    Stacking in bulk and bilayer hexagonal boron nitride

    Constantinescu G, Kuc A, Heine T. Stacking in bulk and bilayer hexagonal boron nitride. Phys Rev Lett. 111, 036104 (2013)

  33. [33]

    Oriented graphene nanoribbons embedded in hexagonal boron nitride trenches

    Chen L, He L, Wang HS, Wang H, Tang S, Cong C, et al. Oriented graphene nanoribbons embedded in hexagonal boron nitride trenches. Nat Commun. 8, 14703 (2017)

  34. [34]

    Silane-catalysed fast growth of large single-crystalline graphene on hexagonal boron nitride

    Tang S, Wang H, Wang HS, Sun Q, Zhang X, Cong C, et al. Silane-catalysed fast growth of large single-crystalline graphene on hexagonal boron nitride. Nat Commun. 6, 6499 (2015). 16

  35. [35]

    Energetic hydrogen atoms in wave driven discharges

    Felizardo E, Tatarova E, Henriques J, Dias FM, Ferreira CM, Gordiets B. Energetic hydrogen atoms in wave driven discharges. Appl Phys Lett. 99, 041503 (2011)

  36. [36]

    Proton-driven patterning of bulk transition metal dichalcogenides

    Tedeschi D, Felici M, Pettinari G, Blundo E, Petroni E, Sennato S, et al. Proton-driven patterning of bulk transition metal dichalcogenides. Preprint at https://arXiv.org/abs/1803.09825 (2018)

  37. [37]

    Hunting for monolayer boron nitride: optical and Raman signatures

    Gorbachev RV, Riaz I, Nair RR, Jalil R, Britnell L, Belle BD, et al. Hunting for monolayer boron nitride: optical and Raman signatures. Small. 7, 465-468 (2011)

  38. [38]

    Raman signature and phonon dispersion of atomically thin boron nitride

    Cai Q, Scullion D, Falin A, Watanabe K, Taniguchi T, Chen Y, et al. Raman signature and phonon dispersion of atomically thin boron nitride. Nanoscale. 9, 3059-3067 (2017)

  39. [39]

    The dissociation energies of CH4 and C2H2 revisited

    Partridge H, Bauschlicher CW. The dissociation energies of CH4 and C2H2 revisited. The Journal of Chemical Physics. 103, 10589-10596 (1995). Figures: 17 Figure 1 | Production of bubbles on h-BN flakes via plasma treatment. a, Schematic depicting the plasma treatment of h-BN flakes in different atmosphere s. All AFM height images of the h-BN flakes were ta...

  40. [40]

    Supplementary Fig

    which is equipped with a function of SEM. Supplementary Fig. 2 shows the specific process to make a specimen of h-BN bubbles. The green rectangle indicated in Supplementary Fig. 2c is the area selected for e -beam induced Pt deposition. After Pt deposition ( Supplementary Fig. 2 e), the TEM specimen for bubble cross -sectional imaging was ready after FIB ...

  41. [41]

    As shown in Supplementary Fig. 16 , the bubbles on h-BN sample at Position 2 (furnace center, 350 ℃) and Position-6 (at the front of the RF coil) are much larger than those on other samples while there is almost no big bubble visible on h-BN placed at Position 5 (plasma core area near the center of the RF coil) under optical microscope. However, it is fou...

  42. [42]

    a, Optical image of h-BN bubbles produced by a 120-minute H-plasma (100 W) treatment at 350 ° C; the image was collected at a sample temperature of ~30 ° C

    Referred from wikipedia.org Supplementary Figure 20 | Thermal stability study of h-BN bubbles with trapped hydrogen. a, Optical image of h-BN bubbles produced by a 120-minute H-plasma (100 W) treatment at 350 ° C; the image was collected at a sample temperature of ~30 ° C. b, Optical image of the same h-BN flake taken at 300 ℃ on a heating stage under amb...