Electro-Precipitation of Actinides on Boron-Doped Diamond Thin Films for Solid Sources Preparation for High-Resolution Alpha-Particle Spectrometry
Round 1
Reviewer 1 Report
The article conveys a very laid-back approach of authors regarding explaining science. First of all, BDD has three categories: Ultra nanocrystalline, nanocrystalline and microcrystalline. With each type has specific fabrication techniques. Also, boron doping levels alter the conductivity. It can be semiconductive, highly conductive depending upon the particular doping level. Diamond itself has a heterogeneous surface morphology with grain and grain boundaries, doping. Such things change the surface reactivity under any specific electrochemical deposition condition for a specifically doped sample. Authors never mentioned such specificities. Also, it is unclear what kind of boron doped diamond with particular surface chemistry they got. Authors need to say these things in the text.
Also, authors need to convey why they used boron-doped diamond for electrodeposition.
Rewrite the conclusion. The conclusion should sink with high-quality results, and explanation authors have provided.
Try to consider adding some supplementary materials if required and refer them in the main text.
Comments for author File: 
Comments.pdf
Author Response
Review 1:
Summary: This article deals with exploring a novel way to deal with getting a superior alpha-molecule strong source created on the doped diamond, a low-Z material with less corrosion and more mechanical hardness. The boron-doped diamond (BDD) substrate showed excellent exhibitions in the autoradiography and spectroscopic than stainless steel. A precipitation process in the Na2SO4 or NaNO3 electrolytes under mild test conditions with a low current density mANaN- 2 was sufficient to create a single 241Am as well as 239Pu, 241Am and 244Cm mixed radionuclides onto BDD substrates. The outcomes reveal that BDD substrates exhibit comparable performance than steel substrates with incredible consistency and high-resolution spectroscopy. Here the strength, chemical resilience and X-beam transparency of a doped diamond integrated to achieve desirable performance. Alpha-molecule spectra displaying a low full width at half most extreme (FWHM) of 12.5 keV at the vitality of 5.485 MeV (241Am) shows the benefit of using BDD substrates.
à We appreciate the deep analysis the reviewer has made on our manuscript and agree that he has appreciated the scientific approach.
Broad comments:
Strength: The unique application being doped diamond used in radioactive measurements.
Weakness: Article conveys a very nonchalant approach of authors regarding explaining science. First of all, BDD has three categories: Ultra nanocrystalline, nanocrystalline and microcrystalline. With each type has specific fabrication techniques. Also, boron doping levels alter the conductivity. It can be semiconductive, highly conductive depending upon the specific doping level. Diamond itself has a heterogeneous surface morphology with grain and grain boundaries, doping. Such things change the surface reactivity under any specific electrochemical deposition condition for a specifically doped sample. Authors never mentioned such specificities.
à Indeed diamond coatings of polycrystalline form can take form with several granularity, however in the case of microcrystalline and nanocrystalline, both consist of the same material according to their thickness. Polycrystalline diamond has been called microcrystalline when its grain size is of the order of micrometric size, and since in normal consideration of polycrystalline diamond, the grain size is about 10% of the thickness, it corresponds to layer thicknesses of several microns. It used to be the conventional material in the 2000 decade. Then late 2000s, seed techniques have appeared, and have enabled the growth of thinner continuous films, of the order of a few 100s nm, so called nanocrystalline as the grain size is of the order of a few 10s to 100s of nm. On the principle, both material are exactly of the same physico-chemical composition, and here as described in the manuscript, since we are considering layers of 400 to 500nm in thickness (see first line section 2.2), it is clear for a reader of the field that we refer nanocrystalline diamond.
Then ultrananocrystalline diamond is a very different material that is grown using Ar and high secondary nucleation, a material much smoother but with low electronic conductivity, that is made conductive when hoping transport is promoted with N doping, which is not the case here as we are always referring to BDD, a highly doped B type nanocrystalline material, well known for electrochemical applications.
Also, it is unclear what kind of boron doped diamond with specific surface chemistry they got.
à BDD is recognised as a B doped material above the metallic transition, as now described in the text, with a nanocrystalline nature. There is no surface chemistry used, the BDD electrodes are used bared, i.e. with no surface functionalization.
Authors need to mention these things in the text. Also, authors need to convey why they used boron-doped diamond for electrodeposition. Authors can consider the following articles like “Dutta, G., Siddiqui, S., Zeng, H., Carlisle, J.A. and Arumugam, P.U., 2015. The effect of electrode size and surface heterogeneity on electrochemical properties of ultrananocrystalline diamond microelectrode. Journal of Electroanalytical Chemistry, 756, pp.61-68.”; “Dutta, G., Tan, C., Siddiqui, S. and Arumugam, P.U., 2016. Enabling long term monitoring of dopamine using dimensionally stable ultrananocrystalline diamond microelectrodes. Materials Research Express, 3(9), p.094001.”; “Tan, C., Dutta, G., Yin, H., Siddiqui, S. and Arumugam, P.U., 2018. Detection of neurochemicals with enhanced sensitivity and selectivity via hybrid multiwall carbon nanotube-ultrananocrystalline diamond microelectrodes. Sensors and Actuators B: Chemical, 258, pp.193- 203.” for a better explanation regarding boron-doped diamond surface. They need to mention the doped diamond growth conditions specifically, or they can cite the specific journal from they have adopted the fabrication of doped diamond.
à Nanocrystalline diamond with high B doping has been well established in the community, and we deeply recognize the papers listed by the reviewer which are well known in the community. The authors themselves have published more than 20 papers where such BDD electrodes were used to detect TNT, pesticides, neurotransmitters, pollutants, biochemicals etc in a broad range of complex fluids such as blood, wine, urine, sea water, tap water, etc. However since the object of the current manuscript is alpha particle detection there was no real reason to cite those. However as motivated by the review a few references were added accordingly
Also, an ambiguity regarding current densities found that sometimes they are 8.0 mANaN-2, 3.3 mANaN-2, 5.0 mANaN-2 simultaneously changing the pH also. Authors should clearly explain to readers about selecting that particular current density and pH depending upon the diamond surface. Not sure about the profile they got using the mixture of radionuclides.
à Following to our previous work demonstrated that suitable pH values for Na2SO4 and NaNO3 electrolytes were found to be of 4.0 and 3.0 respectively [see Ref. 36]. Also there are some limit values for current density in order to generate hydroxide layer.
Consider rewriting the conclusion in a more better way.
Specific comments:
Line 14: It appears that high performance is missing a hyphen. Consider adding the hyphen(s). à Noted and updated
Line 21 and 24: Consider adding a comma before and. Authors have missed adding a comma before and in the whole article. Please change it. à Noted and updated
Line 23: Replace goo with excellent — overuse of “good” word. à Noted and updated
Line 25: The noun phrase diamond seems to be missing a determiner before it. Consider adding an article. à Noted and updated
Line 28: It should be Keywords. à Noted and updated
Line 40: “a very important” can be written as “ a significant feature. à Noted and updated
Line 53: Should be “the cathodic.” It should be “reacts.” à Noted and updated
Line 58: “ very important.” - The intensifier very modifies the weak adjective important. Consider replacing the phrase with a strong adjective in order to sharpen the writing. Like significant can be used. à Noted and updated
Line 60: Should be “, e.g.” à Noted and updated
Line 63: It appears that High resolution is missing a hyphen. Change it in text wherever is necessary. Consider adding the hyphen(s). Also, consider removing a before FWHM. à Noted and updated
Line 66: Consider adding a comma before and. Remove extra commas after “etc.” à Noted and updated
Line 69: “The subordinate phrase To alleviate these issues does not appear to be modifying the subject some works. Rewrite the sentence to avoid a dangling modifier.” à Noted and updated: For electrochemical precipitation process, some works ……
Line 73: Should be “resulted from” not “ resulted that”. à Noted and updated
Line 77 to 80: Sentence unnecessarily complexed by adding and. Try to split up in simple sentences. It appears that missing a comma after the introductory phrase Further. Consider adding a comma. à Noted and updated: Still, one limitation is arising and stands in the necessity for the process to use conductive materials with high corrosion resilience. Several metals are offering these properties, several may be noble metals thus expensive.
Line 83: It appears that the modifiers in the noun phrase synthetic thin layers are in the wrong order. Consider changing the word order to a thin synthetic layer. à Noted and updated
Line 84: Either “a or the.” The word hereby may be considered archaic or unnecessary legal jargon by readers. Consider changing the wording to now. à Noted and updated
Line 89: Should be “the diamond.” à Noted and updated
Line 94: It appears that Boron Doped is missing a hyphen. Consider adding the hyphen(s). Change it in the title too. à Noted and updated
Line 108: The plural verb were did not appear to agree with the singular subject Doping. Consider changing the verb form for subject-verb agreement. Like, write was. à Noted and updated
Line 120: The phrase Prior to sounding wordy. Consider changing the wording to Before. à Noted and updated
Line 133: The word high does not seem to fit this context. Consider replacing it with a different one like highly. à Noted and updated
Line 138: “ to obtain” should be “ obtaining.” à Noted and updated
Line 139: The indefinite article, a, may be redundant when used with the uncountable noun radioactivity in the sentence. Consider removing it. à Noted and updated
Line 149: Should be “the geometrical.” à Noted and updated
Line 158: Should be “ the whole.” à Noted and updated
Line 160: Should be “a result.” Consider changing it in the following sentences. à Noted and updated
Line 164: The plural verb have does not appear to agree with the singular subject deposited BDD substrate. Consider changing the verb form for subject-verb agreement to has. The phrase with respect to sounds wordy consider changing the wording only “to/concerning.” Follow the same in the following sentences. à Noted and updated
Line 165: It appears that the verb produce should be in the to-infinitive form. Consider adding the word “to.” à Noted and updated
Line 167: Add a comma after case. à Noted and updated
Line 170: It appears that the verb generates incorrectly used with the helping verb do. Consider changing it to the base form. à Noted and updated
Line 172: Can authors add some color scale in the profile image of Figure 2 — A and B to differentiate between the yellow, red and green. Do the similar for all the following graphs. à Noted and updated
Line 182: Should be “ has grown.” à Noted and updated
Line 190: Should be “were grown.” à Noted and updated
Line 204: Should be “ was estimated.” à Noted and updated
Line 207: The “are” should be replaced with is. Consider adding with before standard. à Noted and updated
Line 208: It appears that clearly may be unnecessary in this sentence. Consider removing it. Follow the same for the following sentences. à Noted and updated
Line 211: Should be “display.” à Noted and updated
Line 226: The alpha-particle. à Noted and updated
Line 231: The cathode. à Noted and updated
Line 256: It appears that high quality is missing a hyphen. Consider adding the hyphen(s). à Noted and updated
Line 257: The word Especially is often overused. Consider using a more specific synonym to improve the sharpness of the writing like add Notably. Replace it with its. à Noted and updated
Line 258: Should be “the nuclear.” à Noted and updated
Author Response File: Author Response.pdf
Reviewer 2 Report
This manuscript describe physical results of great interest for the diamond community. I hereby recommend it for publication in the present form.
Author Response
This manuscript describes physical results of great interest for the diamond community. I hereby recommend it for publication in the present form.
à We acknowledge the reviewer remarks.
Reviewer 3 Report
I would recommend the publication after the revision of minor objections that are included below.
Line 206, it is written that FWHM varying from 12.5-14.5 keV for 241Am source on BDD substrate. However, table 1 shows FWHM values of 13.2-14.5 keV for diamond. Similarly, in line 207 it is written a value of 13.2 keV for stainless steel, but one cannot see that value in the column of Stainless-steel of the same table.
I would suggest to change the name of the 4th column of table 1, use BDD instead of "diamond".
FWHM values should be shown for the different peaks of figure 6A & 6B.
Line 259, the given value of 12.5 keV should be follow by the type of substrate so readers can identify it easily.
Author Response
Line 206, it is written that FWHM varying from 12.5-14.5 keV for 241Am source on BDD substrate. However, table 1 shows FWHM values of 13.2-14.5 keV for diamond. Similarly, in line 207 it is written a value of 13.2 keV for stainless steel, but one cannot see that value in the column of Stainless-steel of the same table.
à The manuscript was edited and updated.
I would suggest to change the name of the 4th column of table 1, use BDD instead of "diamond".
à The manuscript was edited and updated.
FWHM values should be shown for the different peaks of figure 6A & 6B.
à For comparison, we should take the data for a same radioactive source e.g. 241Am deposited onto BDD (Figure 6A), stainless-steel (data not shown) substrates concerning 241Am standard source. The Figure 6B displays alpha-particle spectrum of the mixed actinides (239Pu, 241Am, and 244Cm) for demonstrating a clear identification of these three actinides.
Line 259, the given value of 12.5 keV should be follow by the type of substrate so readers can identify it easily.
à This value of 13.2 keV for BDD substrate was updated in the manuscript.
Round 2
Reviewer 1 Report
Technologies regarding radioisotope tracing in saline and further in the physiological sample has a high potential not only in the nuclear industry but also in terms of environment and health too. Authors need to be commended for pursuing research in such direction and providing an article. Authors claim BDD has a great potential to use as a microelectrode in such tracing.
Comments for author File: Comments.pdf
Author Response
Technologies regarding radioisotope tracing in saline and further in the physiological sample has a great potential not only in the nuclear industry but also in terms of environment and health too. Authors need to commended for pursuing research in such direction and providing an interesting article. Authors claim BDD has a great potential to use as a microelectrode in such tracing. Authors mentioned in the review response that “Also there are some limit values for current density to generate hydroxide layer.” I think they should include that sentence in the main text for clarity regarding choosing such specific current densities in the context of a range of current density. It will be great if they also mention (in a couple of sentences) how does it affect electro-precipitation of actinides or any other materials in the context of boron doped diamond with proper siting articles.
Response: There are some minimum values for current density to generate a hydroxide layer for precipitation as actinide hydroxide compounds [see ref. 1]. Our previous study demonstrated that the current density should be above 3 mANaN-2 and 1 mANaN-2 for NaNO3 pH 3 and Na2SO4 pH 4 electrolytes respectively [see ref. 2]. This content was mentioned in the manuscript.
1. V. Tsoupko-Sitnikov, F. Dayras, J. de Sanoit, and D. Filossofov, “Ap- plication of rotating disk electrode technique for the preparation ofNp, Pu and Am -sources,” J. Appl. Radiat. Isot., vol. 52, pp. 357–364, Mar. 2000.
2. Tran, Q.T.; Pomorski, M.; de Sanoit, J.; Scorsone, E.; Bergonzo, P. Optimization of Actinides Trace Precipitation on Diamond/Si PIN Sensor for Alpha-Spectrometry in Aqueous Solution, Trans. Nucl. Sci. 2014, 61(4), 2082–2089.
Line 89: Add a comma before and.
Response: noted and updated.
Line 113: “a broad range of applications.” Site some relevant articles which mention a broad range of application if possible.
Response: some relevant articles were performed by our groups. Therefore, its were cited in the manuscript.
1. Scorsone, E., Belghiti, D., Habchi, M., & Bergonzo, P. (2017). Boron doped diamond/metal nanocatalyst hybrid electrode arrays for analytical applications. ISOEN 2017 - ISOCS/IEEE International Symposium on Olfaction and Electronic Nose, Proceedings. doi:10.1109/ISOEN.2017.7968907
2. Belghiti, D. K., Zadeh-Habchi, M., Scorsone, E., & Bergonzo, P. (2016). Boron Doped Diamond/Metal Nanoparticle Catalysts Hybrid Electrode Array for the Detection of Pesticides in Tap Water. Procedia Engineering, 168, 428-431. doi:10.1016/j.proeng.2016.11.536
3. Hébert, C., Cottance, M., Degardin, J., Scorsone, E., Rousseau, L., Lissorgues, G., . . . Picaud, S. (2016). Monitoring the evolution of boron doped porous diamond electrode on flexible retinal implant by OCT and in vivo impedance spectroscopy. Materials Science and Engineering C, 69, 77-84. doi:10.1016/j.msec.2016.06.032
4. Belghiti, D. K., Scorsone, E., de Sanoit, J., & Bergonzo, P. (2016). Simultaneous detection of indole and 3-methylindole using boron-doped diamond electrodes. Physica Status Solidi (A) Applications and Materials Science, 213 (10), 2662-2671. doi:10.1002/pssa.201600187
5. Piret, G., Hébert, C., Mazellier, J. P., Rousseau, L., Scorsone, E., Cottance, M., . . . Yvert, B. (2015). 3D-nanostructured boron-doped diamond for microelectrode array neural interfacing. Biomaterials, 53, 173-183. doi:10.1016/j.biomaterials.2015.02.021
6. Tran, Q. T., De Sanoit, J., Pierre, S., Arnault, J. C., & Bergonzo, P. (2014). Diamond electrodes for trace alpha pollutant sequestration via covalent grafting of nitrilotriacetic acid (NTA) ligand. Electrochimica Acta, 136, 430-434. doi:10.1016/j.electacta.2014.05.087
7. de Sanoit, J., Vanhove, E., Mailley, P., & Bergonzo, P. (2009). Electrochemical diamond sensors for TNT detection in water. Electrochimica Acta, 54 (24), 5688-5693. doi:10.1016/j.electacta.2009.05.013
Line114: “Bare BDD electrodes are used, i.e., with no particular surface functionalization, as promoted by the ability to clean the surface in complex media.” Support this claim, site relevant articles.
Response: some relevant articles were cited in the manuscript.
1. R. Kiran, J. de Sanoit and E. Scorsone, Patent application no: 11 51341, (2011).
2. Kiran, R., Scorsone, E., De Sanoit, J., Arnault, J. C., Mailley, P., & Bergonzo, P. (2013). Boron doped diamond electrodes for direct measurement in biological fluids: An in situ regeneration approach. Journal of the Electrochemical Society, 160 (1). doi:10.1149/2.014302jes
3. Kiran, R., Scorsone, E., Mailley, P., & Bergonzo, P. (2012). Quasi-real time quantification of uric acid in urine using boron doped diamond microelectrode with in situ cleaning. Analytical Chemistry, 84 (23), 10207-10213. doi:10.1021/ac301177z
Line 133: Change “increasing” to “increase.”
Response: noted and updated.
Line 268: “a valuable behavior for practical application in the nuclear industry using highly acidic solutions.” Site some relevant articles to support this claim.
Response: some relevant articles were cited in the manuscript.
1. Bergonzo, P., Foulon, F., Brambilla, A., Tromson, D., Jany, C., & Haan, S. (2000). Corrosion hard CVD diamond alpha particle detectors for nuclear liquid source monitoring. Diamond and Related Materials, 9 (3-6), 1003-1007. doi:10.1016/S0925-9635(99)00257-5
2. Mer, C., Tromson, D., De Sanoit, J., Pomorski, M., & Bergonzo, P. (2009). Diamond detectors for alpha monitoring in corrosive media for nuclear waste activity monitoring. ANIMMA 2009 - 2009 1st International Conference on Advancements in Nuclear Instrumentation, Measurement Methods and their Applications. doi:10.1109/ANIMMA.2009.5503796
Author Response File: 
Author Response.docx
