Growth Process of Hexagonal Boron Nitride in the Diffusion and Precipitation Method Studied by X-ray Photoelectron Spectroscopy

Satoru Suzuki; Yuichi Haruyama

arxiv: 1907.01123 · v1 · pith:XMAF6R2Knew · submitted 2019-07-02 · ❄️ cond-mat.mes-hall

Growth Process of Hexagonal Boron Nitride in the Diffusion and Precipitation Method Studied by X-ray Photoelectron Spectroscopy

Satoru Suzuki , Yuichi Haruyama This is my paper

Pith reviewed 2026-05-25 11:21 UTC · model grok-4.3

classification ❄️ cond-mat.mes-hall

keywords hexagonal boron nitrideh-BNdiffusion and precipitationX-ray photoelectron spectroscopynickel foilgrowth temperaturesurface decompositionboron rich

0 comments

The pith

Submonolayer h-BN on nickel forms at 600 C with a boron-rich surface and decomposes at 800 C.

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

The paper follows submonolayer hexagonal boron nitride growth on nickel foil by the diffusion and precipitation method in ultra-high vacuum, using x-ray photoelectron spectroscopy to monitor the process. Formation is first seen at 600 degrees Celsius, and the surface stays slightly boron-rich at every stage because boron dissolves and moves through the nickel by bulk diffusion while nitrogen does not. Both growth and breakdown of the h-BN occur at high temperatures, apparently set by how much nitrogen reaches the surface. Breakdown is recorded at 800 degrees Celsius on the nickel.

Core claim

The authors find that submonolayer h-BN formation on Ni foil is first observed at 600 C. The surface remains slightly B-rich throughout, matching the solubility of B in Ni at high temperature and its ability to diffuse while N cannot. Both formation and decomposition take place at elevated temperatures depending on provision of N atoms to the surface, with decomposition seen at 800 C on the Ni surface.

What carries the argument

X-ray photoelectron spectroscopy intensities of B 1s and N 1s peaks used to track submonolayer h-BN coverage and B/N ratio on Ni during temperature changes in the diffusion-precipitation process.

If this is right

h-BN layers can be produced at temperatures as low as 600 C on nickel using this method.
The persistent boron-rich surface follows directly from bulk diffusion of soluble boron through nickel.
Whether the layer grows or shrinks at high temperature is controlled by the supply of nitrogen atoms to the surface.
Any h-BN formed on nickel becomes unstable and decomposes once the temperature reaches 800 C in vacuum.

Where Pith is reading between the lines

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

Varying the nitrogen exposure during the process could be used to reach higher coverage or to stabilize the layer against decomposition.
The relatively low decomposition temperature on nickel may restrict the temperatures at which Ni-supported h-BN films can be processed or used.
The same solubility-driven mechanism could be tested on other metal substrates that dissolve boron but not nitrogen to see whether similar growth windows appear.

Load-bearing premise

XPS peak intensities give a direct quantitative measure of submonolayer h-BN coverage and surface B/N ratio with no large effects from subsurface atoms, contaminants, or matrix influences on nickel.

What would settle it

Depth-profiling XPS that finds substantial boron or nitrogen below the top atomic layer, or calibration spectra showing that known submonolayer h-BN produces intensity ratios different from those reported, would falsify the coverage and stoichiometry claims.

read the original abstract

Submonolayer h-BN was grown on Ni foil in ultra-high vacuum by the diffusion and precipitation method and the growth process was studied by x-ray photoelectron spectroscopy. Formation of h-BN started to be observed at 600 C. All through the process, the surface was always slightly B-rich, which is consistent with the fact that B which is soluble in Ni at a high temperature can diffuse in Ni by the conventional bulk diffusion and insoluble N cannot. Moreover, both formation and decomposition of h-BN were found to occur at elevated temperatures possibly depending on provision of N atoms to the surface. On the Ni surface, decomposition of h-BN was observed at a relatively low temperature of 800 C.

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.

Desk Editor's Note private letter to a colleague

XPS gives concrete 600 C formation and 800 C decomposition points for h-BN on Ni but the B-rich surface claim rests on uncalibrated peak ratios.

read the letter

The main things to know are that formation of submonolayer h-BN on Ni foil begins around 600 C and decomposition sets in near 800 C, with the surface staying slightly B-rich the whole time. These temperatures come from tracking B 1s and N 1s signals during the diffusion-precipitation process in UHV. The B-rich observation lines up with the known fact that boron diffuses readily through Ni while nitrogen does not, so the explanation holds without stretching. The paper does a straightforward job of mapping temperature steps to spectral changes and tying them to solubility differences already in the literature. That supplies usable process windows for anyone growing h-BN on nickel by this route. The soft spot is the direct jump from raw XPS intensities to coverage and stoichiometry. No reference spectra, sensitivity-factor checks, or escape-depth corrections appear in the description, and matrix effects from the Ni substrate could easily shift the apparent B/N ratio. Without those controls the “slightly B-rich” part and the exact thresholds are plausible but not tightly pinned down. Error bars and raw spectra are also absent, which is minor but adds to the need for caution. This is for surface scientists and 2D-materials growers who want practical temperature data rather than a new model. It deserves a serious referee because the experimental approach is simple and the claims are testable with added calibration, even if the paper will need revisions on the quantitative side.

Referee Report

2 major / 1 minor

Summary. The manuscript reports an in-situ XPS study of submonolayer h-BN growth on Ni foil via the diffusion-and-precipitation method in UHV. It claims that h-BN formation onsets at 600 °C, the surface remains slightly B-rich at all stages (attributed to bulk diffusion of soluble B versus insoluble N), both formation and decomposition occur at elevated temperatures depending on N supply, and decomposition is observed at 800 °C.

Significance. If the XPS intensity ratios can be shown to map reliably to submonolayer coverage and stoichiometry, the observations would supply useful temperature-dependent constraints on the diffusion-precipitation mechanism and on the stability window of h-BN on Ni. The work is otherwise limited to qualitative interpretation of peak intensities against known solubility facts.

major comments (2)

[Abstract] Abstract: the central claim that the surface is 'always slightly B-rich' and that this directly reflects bulk B diffusion versus N insolubility rests on equating B 1s / N 1s XPS intensity ratios to surface stoichiometry without any reported sensitivity-factor validation, reference spectra for submonolayer h-BN on Ni, or escape-depth corrections for the Ni matrix.
[Abstract] Abstract: the reported onset temperatures (formation at 600 °C, decomposition at 800 °C) are presented without error bars, raw spectra, or quantitative coverage calibration, leaving open the possibility that matrix effects, subsurface contributions, or minor contaminants dominate the observed intensity changes.

minor comments (1)

[Abstract] The abstract would be strengthened by a brief statement of the XPS photon energy, analyzer settings, and any background-subtraction procedure used to extract the B 1s and N 1s intensities.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for the careful reading and constructive comments on our XPS study of submonolayer h-BN growth. We address the two major comments point by point below, with revisions planned where appropriate.

read point-by-point responses

Referee: [Abstract] Abstract: the central claim that the surface is 'always slightly B-rich' and that this directly reflects bulk B diffusion versus N insolubility rests on equating B 1s / N 1s XPS intensity ratios to surface stoichiometry without any reported sensitivity-factor validation, reference spectra for submonolayer h-BN on Ni, or escape-depth corrections for the Ni matrix.

Authors: We acknowledge that the manuscript applies standard tabulated sensitivity factors for B 1s and N 1s without dedicated validation spectra or escape-depth corrections specific to the Ni matrix. The B-rich observation is therefore qualitative, based on relative intensity trends rather than absolute stoichiometry. This approach is consistent with the known bulk solubility contrast (B soluble, N insoluble) reported in the literature. In the revised manuscript we will explicitly state the use of standard factors, qualify the 'slightly B-rich' description as relative, and note the absence of matrix-specific corrections as a limitation of the present data set. revision: yes
Referee: [Abstract] Abstract: the reported onset temperatures (formation at 600 °C, decomposition at 800 °C) are presented without error bars, raw spectra, or quantitative coverage calibration, leaving open the possibility that matrix effects, subsurface contributions, or minor contaminants dominate the observed intensity changes.

Authors: The onset temperatures are defined by the first temperature at which the characteristic h-BN B 1s and N 1s components appear or vanish in the in-situ spectra. The manuscript already displays the relevant spectra in the figures; however, we agree that error bars, explicit discussion of matrix effects, and coverage calibration are missing. In revision we will add estimated uncertainties derived from peak-fitting residuals and signal-to-noise ratios, and we will discuss possible subsurface or contaminant contributions. Full quantitative calibration would require additional ex-situ techniques not available in the UHV setup, but the submonolayer regime is supported by the low absolute intensities relative to multilayer references. revision: partial

Circularity Check

0 steps flagged

No circularity: experimental XPS observations interpreted against external solubility facts

full rationale

The paper consists of direct experimental XPS intensity measurements during h-BN growth on Ni foil, reporting onset temperatures and B/N ratios from observed peaks. No equations, fitted parameters, derivations, or self-citations appear in the provided text. Claims rest on equating peak areas to surface composition using standard materials-science knowledge of B solubility and N insolubility in Ni, without any reduction of outputs to the paper's own inputs by construction. This is a standard experimental report with no load-bearing self-referential steps.

Axiom & Free-Parameter Ledger

0 free parameters · 1 axioms · 0 invented entities

Experimental surface-science study; no free parameters, no invented entities, and relies only on standard domain assumptions about XPS quantification and known solubility behavior of B and N in Ni.

axioms (1)

domain assumption XPS core-level intensities provide a reliable quantitative measure of surface B and N atomic ratios on Ni without major matrix or attenuation corrections for submonolayer coverages
Invoked when the abstract equates observed B-rich signals directly to solubility differences.

pith-pipeline@v0.9.0 · 5656 in / 1427 out tokens · 28299 ms · 2026-05-25T11:21:59.786353+00:00 · methodology

discussion (0)

Reference graph

Works this paper leans on

27 extracted references · 27 canonical work pages

[1]

C. R. Dean, A. F. Young, I. Meric, C. Lee, L. Wang, S. Sorgenfrei, K. Watanabe, T. Taniguchi, P. Kim, K. L. Shepard and J. Hone: Nat Nanotechnol. 5 (2010) 722

work page 2010
[2]

Petrone, C

N. Petrone, C. R. Dean, I. Meric, A. M. van der Zande, P. Y . Huang, L. Wang, D. Muller, K. L. Shepard and J. Hone: Nano Lett. 12 (2012) 2751

work page 2012
[3]

Decker, Y

R. Decker, Y . Wang, V . W. Brar, W. Regan, H. Z. Tsai, Q. Wu, W. Gannett, A. Zettl and M. F. Crommie: Nano Lett. 11 (2011) 2291

work page 2011
[4]

J. Wang, F. Ma, W. Liang and M. Sun: Materials Today Physics. 2 (2017) 6

work page 2017
[5]

K. H. Lee, H. J. Shin, J. Lee, I. Y . Lee, G. H. Kim, J. Y . Choi and S. W. Kim: Nano Lett. 12 (2012) 714

work page 2012
[6]

Britnell, R

L. Britnell, R. V . Gorbachev, R. Jalil, B. D. Belle, F. Schedin, A. Mishchenko, T. Georgiou, M. I. Katsnelson, L. Eaves, S. V . Morozov, N. M. Pe res, J. Leist, A. K. Geim, K. S. Novoselov and L. A. Ponomarenko: Science. 335 (2012) 947

work page 2012
[7]

Yadav, S

D. Yadav, S. B. Tombet, T. Watanabe, S. Arnold, V . Ryzhii and T. Otsuji: 2D Materials. 3 (2016) 045009

work page 2016
[8]

Piquemal-Banci, R

M. Piquemal-Banci, R. Galceran, S. Caneva, M. B. Martin , R. S. Weatherup, P. R. Kidambi, K. Bouzehouane, S. Xavier, A. Anane, F. Petroff, A. Fert, J. Robertson, S. Hofmann, B. Dlubak and P. Seneor: Appl. Phys. Lett. 108 (2016) 102404

work page 2016
[9]

V . M. Karpan, P. A. Khomyakov, G. Giovannetti, A. A. Starikov and P. J. K elly: Phys. Rev. B. 84 (2011) 153406

work page 2011
[10]

Piquemal-Banci, R

M. Piquemal-Banci, R. Galceran, M. -B. Martin, F. Godel, A. Anane, F. Petroff, B. Dlubak and P. Seneor: Journal of Physics D: Applied Physics. 50 (2017)

work page 2017
[11]

C. M. Orofeo, S. Suzuki and H. Hibino: Journal of Physica l Chemistry C. 118 (2014) 3340

work page 2014
[12]

Gleiman, C

S. Gleiman, C. K. Chen, A. Datye and P. J.: Journal of Materials Science. 37 (2002) 3429

work page 2002
[13]

Z. Liu, Y . Gong, W. Zhou, L. Ma, J. Yu, J. C. Idrobo, J. Jung, A. H. MacDonald, R. Vajtai, J. Lou and P. M. Ajayan: Nat Commun. 4 (2013) 2541

work page 2013
[14]

H. Cho, S. Park, D. I. Won, S. O. Kang, S. S. Pyo, D. I. Kim, S. M. Kim, H. C. Kim and M. J. Kim: Sci Rep. 5 (2015) 11985

work page 2015
[15]

Ismach, H

A. Ismach, H. Chou, P. Mende, A. Dolocan, R. Addou, S. Aloni, R. Wallace, R. Feenstra, R. S. Ruoff and L. Colombo: 2D Materials. 4 (2017) 025117

work page 2017
[16]

Lee, K.-K

Y.-H. Lee, K.-K. Liu, A.-Y . Lu, C.-Y . Wu, C.-T. Lin, W. Zhang, C.-Y . Su, C.-L. Hsu, T.-W. Lin, K.-H. Wei, Y . Shi and L.-J. Li: RSC Adv. 2 (2012) 111

work page 2012
[17]

C. M. Orofeo, S. Suzuki, H. Kageshima and H. Hibino: Nano Research. 6 (2013) 335

work page 2013
[18]

P. R. Kidambi, R. Blume, J. Kling, J. B. Wagner, C. Baehtz, R. S. Weatherup, R. Schloegl, B. C. Bayer and S. Hofmann: Chem Mater. 26 (2014) 6380

work page 2014
[19]

Suzuki, R

S. Suzuki, R. M. Pallares and H. Hibino: Journal of Physics D: Applied Physics. 45 (2012) 385304

work page 2012
[20]

Suzuki, R

S. Suzuki, R. Molto Pallares, C. M. Orofeo and H. Hibino: J. Vac. Sci. Technol. B. 31 (2013) 041804

work page 2013
[21]

Suzuki, Y

S. Suzuki, Y . Ogawa, S. Wang and K. Kumakura: Jpn. J. Appl. Phys. 56 (2017) 06GE06

work page 2017
[22]

Zhang, L

C. Zhang, L. Fu, S. Zhao, Y . Zhou, H. Peng and Z. Liu: Adv Mater. 26 (2014) 1776

work page 2014
[23]

P. C. Yang, J. T. Prater, W. Liu, J. T. Glass and R. F. Davis: Journal of Electronic Template for JJAP Regular Papers (Jan. 2014) 8 Materials. 34 (2005) 1558

work page 2014
[24]

Kowanda and M

C. Kowanda and M. O. Speidel: Scripta Materialia. 48 (2003) 1073

work page 2003
[25]

R. F. Abdulrahman and A. Hendry: Metallurgical and Materials Transactions B. 32 (2001) 1103

work page 2001
[26]

Rogl and J

P. Rogl and J. C. Schuster: Phase Diagrams of Ternary Boron Nitride and Silicon Nitride (American Society for Metals, OH, 1992)

work page 1992
[27]

Suzuki, Y

S. Suzuki, Y . Haruyama, M. Niibe, T. Tokushima, A. Yamaguchi, Y . Utsumi, A. Ito, R. Kadowaki, A. Maruta and T. Abukawa: Matrials Research Express. 6 (2019) 016301. Template for JJAP Regular Papers (Jan. 2014) 9 Figure Captions Fig. 1. Schematic of h -BN formation in UHV by the diffusion and precipitation method (left) and its XPS analysis (right) . The ...

work page 2019

[1] [1]

C. R. Dean, A. F. Young, I. Meric, C. Lee, L. Wang, S. Sorgenfrei, K. Watanabe, T. Taniguchi, P. Kim, K. L. Shepard and J. Hone: Nat Nanotechnol. 5 (2010) 722

work page 2010

[2] [2]

Petrone, C

N. Petrone, C. R. Dean, I. Meric, A. M. van der Zande, P. Y . Huang, L. Wang, D. Muller, K. L. Shepard and J. Hone: Nano Lett. 12 (2012) 2751

work page 2012

[3] [3]

Decker, Y

R. Decker, Y . Wang, V . W. Brar, W. Regan, H. Z. Tsai, Q. Wu, W. Gannett, A. Zettl and M. F. Crommie: Nano Lett. 11 (2011) 2291

work page 2011

[4] [4]

J. Wang, F. Ma, W. Liang and M. Sun: Materials Today Physics. 2 (2017) 6

work page 2017

[5] [5]

K. H. Lee, H. J. Shin, J. Lee, I. Y . Lee, G. H. Kim, J. Y . Choi and S. W. Kim: Nano Lett. 12 (2012) 714

work page 2012

[6] [6]

Britnell, R

L. Britnell, R. V . Gorbachev, R. Jalil, B. D. Belle, F. Schedin, A. Mishchenko, T. Georgiou, M. I. Katsnelson, L. Eaves, S. V . Morozov, N. M. Pe res, J. Leist, A. K. Geim, K. S. Novoselov and L. A. Ponomarenko: Science. 335 (2012) 947

work page 2012

[7] [7]

Yadav, S

D. Yadav, S. B. Tombet, T. Watanabe, S. Arnold, V . Ryzhii and T. Otsuji: 2D Materials. 3 (2016) 045009

work page 2016

[8] [8]

Piquemal-Banci, R

M. Piquemal-Banci, R. Galceran, S. Caneva, M. B. Martin , R. S. Weatherup, P. R. Kidambi, K. Bouzehouane, S. Xavier, A. Anane, F. Petroff, A. Fert, J. Robertson, S. Hofmann, B. Dlubak and P. Seneor: Appl. Phys. Lett. 108 (2016) 102404

work page 2016

[9] [9]

V . M. Karpan, P. A. Khomyakov, G. Giovannetti, A. A. Starikov and P. J. K elly: Phys. Rev. B. 84 (2011) 153406

work page 2011

[10] [10]

Piquemal-Banci, R

M. Piquemal-Banci, R. Galceran, M. -B. Martin, F. Godel, A. Anane, F. Petroff, B. Dlubak and P. Seneor: Journal of Physics D: Applied Physics. 50 (2017)

work page 2017

[11] [11]

C. M. Orofeo, S. Suzuki and H. Hibino: Journal of Physica l Chemistry C. 118 (2014) 3340

work page 2014

[12] [12]

Gleiman, C

S. Gleiman, C. K. Chen, A. Datye and P. J.: Journal of Materials Science. 37 (2002) 3429

work page 2002

[13] [13]

Z. Liu, Y . Gong, W. Zhou, L. Ma, J. Yu, J. C. Idrobo, J. Jung, A. H. MacDonald, R. Vajtai, J. Lou and P. M. Ajayan: Nat Commun. 4 (2013) 2541

work page 2013

[14] [14]

H. Cho, S. Park, D. I. Won, S. O. Kang, S. S. Pyo, D. I. Kim, S. M. Kim, H. C. Kim and M. J. Kim: Sci Rep. 5 (2015) 11985

work page 2015

[15] [15]

Ismach, H

A. Ismach, H. Chou, P. Mende, A. Dolocan, R. Addou, S. Aloni, R. Wallace, R. Feenstra, R. S. Ruoff and L. Colombo: 2D Materials. 4 (2017) 025117

work page 2017

[16] [16]

Lee, K.-K

Y.-H. Lee, K.-K. Liu, A.-Y . Lu, C.-Y . Wu, C.-T. Lin, W. Zhang, C.-Y . Su, C.-L. Hsu, T.-W. Lin, K.-H. Wei, Y . Shi and L.-J. Li: RSC Adv. 2 (2012) 111

work page 2012

[17] [17]

C. M. Orofeo, S. Suzuki, H. Kageshima and H. Hibino: Nano Research. 6 (2013) 335

work page 2013

[18] [18]

P. R. Kidambi, R. Blume, J. Kling, J. B. Wagner, C. Baehtz, R. S. Weatherup, R. Schloegl, B. C. Bayer and S. Hofmann: Chem Mater. 26 (2014) 6380

work page 2014

[19] [19]

Suzuki, R

S. Suzuki, R. M. Pallares and H. Hibino: Journal of Physics D: Applied Physics. 45 (2012) 385304

work page 2012

[20] [20]

Suzuki, R

S. Suzuki, R. Molto Pallares, C. M. Orofeo and H. Hibino: J. Vac. Sci. Technol. B. 31 (2013) 041804

work page 2013

[21] [21]

Suzuki, Y

S. Suzuki, Y . Ogawa, S. Wang and K. Kumakura: Jpn. J. Appl. Phys. 56 (2017) 06GE06

work page 2017

[22] [22]

Zhang, L

C. Zhang, L. Fu, S. Zhao, Y . Zhou, H. Peng and Z. Liu: Adv Mater. 26 (2014) 1776

work page 2014

[23] [23]

P. C. Yang, J. T. Prater, W. Liu, J. T. Glass and R. F. Davis: Journal of Electronic Template for JJAP Regular Papers (Jan. 2014) 8 Materials. 34 (2005) 1558

work page 2014

[24] [24]

Kowanda and M

C. Kowanda and M. O. Speidel: Scripta Materialia. 48 (2003) 1073

work page 2003

[25] [25]

R. F. Abdulrahman and A. Hendry: Metallurgical and Materials Transactions B. 32 (2001) 1103

work page 2001

[26] [26]

Rogl and J

P. Rogl and J. C. Schuster: Phase Diagrams of Ternary Boron Nitride and Silicon Nitride (American Society for Metals, OH, 1992)

work page 1992

[27] [27]

Suzuki, Y

S. Suzuki, Y . Haruyama, M. Niibe, T. Tokushima, A. Yamaguchi, Y . Utsumi, A. Ito, R. Kadowaki, A. Maruta and T. Abukawa: Matrials Research Express. 6 (2019) 016301. Template for JJAP Regular Papers (Jan. 2014) 9 Figure Captions Fig. 1. Schematic of h -BN formation in UHV by the diffusion and precipitation method (left) and its XPS analysis (right) . The ...

work page 2019