Carbon Nanotubes Use for the Semiconductors ZnSe and ZnS Material Surface Modification via the Laser-Oriented Deposition Technique

Round 1

Reviewer 1 Report

I have read through the latest version completely. The manuscript is carefully revised and the quality has been improved. I would recommend it for publication.

Author Response

Dear Referee!

Thanks a lot for your job to make the comments for our paper. Thank you for your kind relation, which is positive and permits to us to continue the research with other semiconducting materials.

I have improved a little bit the English used for our paper. All corrections have been colored with red.

Thank you once again!

Best Regards,

Natalia Kamanina

Author Response File: Author Response.pdf

Reviewer 2 Report

In this work, authors study the process of ZnSe and ZnS substrates surface modification in presence of carbon nanotubes. For it, laser oriented deposition technique which authors have successfully used with other substrates, has been used. The final purpoise of this materials is to be used in optoelectronic devices.

In order to investigate the improvement of the modified materials transmittance in IR range, micro-hardness and contact angle of the modified substrates, have been selected as control properties.

Results indicate a decrease of the IR range light absorption and increase in the number of revolutions which generate a distinct ring and the contact angle.

However, although I don’t have any important criticism about the structure, the presentation or the experimental approach, I have the following comment/disagreement which must be revised to accept the manuscript for publication.

1. In line 246, authors argue the “the experimental results can partially supported by the molecular dynamic simulation ". Is it possible to obtain an electronic microscopy image of the modified surface? I think that the image could experimentally prove the results.

Author Response

Dear Referee!

Thanks a lot for your kind and useful job to make the comments for our paper. It can improve it, indeed!

I have improved a little bit the English used for our paper. All corrections have been colored with red.

Sorry, I cannot present now the scanning microscopy images for your structures. In my experimental Lab we have no this device. For the future study I will ask my colleagues from Novosibirsk or Petrozavodsk to help to me with this job. We have the data for the different semiconducting systems treated by out laser technique, maybe I will interest my colleagues in conducting such joint experiments. I wrote at the end of the article about it, also painted it in red

Thank you once again!

Best Regards,

Natalia Kamanina

Author Response File: Author Response.pdf

This manuscript is a resubmission of an earlier submission. The following is a list of the peer review reports and author responses from that submission.

Round 1

Reviewer 1 Report

The presented manuscript discusses the surface treatment of ZnS and ZnSe with carbon nanotubes to increase transparency. After consideration, I have to suggest that this work should not be published in the Journal of Carbon Research.

The motivation and the shown results are not conclusive and mostly unclear. The characterization is only done very superficially and do not allow any detailed interpretation. Various additional measurement should be included Especially, missing errors bars forbid a comparison of the results to each other. Differences in the depicted data thus cannot be interpreted. Furthermore, the language style is not sufficiently fine and has to be improved.

Author Response

Reply to referee 1.

Thank you for your useful remarks and recommendation. I hope that the paper can be improved. Please see added parts, which are colored with yellow.

 

I reworked the article, added a drawing with our technology, corrected the descriptions to the graphs, checked the grammar, etc.

 

Thank you once again for your job to read the paper and to make the referee’s remarks.

Best Regards,

Natalia Kamanina

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Natalia V. Kamanina (Prof., Dr.Sci., PhD)

Head of the lab for Photophysics of media with nanoobjects

Vavilov State Optical Institute

Kadetskaya Liniya V.O., dom.5, korpus 2,

St.- Petersburg, 199053, Russia

Professor of the St.-Petersburg Electrotechnical University (“LETI”),

Part-time Leading Researcher at Nuclear Physics Institute (Gatchina)

Job phone: +7 (812) 327-00-95

Fax: +7 (812) 331-75-58 (for N.V.Kamanina)

e-mail:  [email protected]

http://www.photophysics-lab.org/ 

https://publons.com/researcher/1696479/natalia-kamanina/

https://sciprofiles.com/news-feed

http://rusnor.org/network/webinars/10203.htm

http://www.npkgoi.ru/?module=articles&c=profil&b=7

http://www.nanometer.ru/2007/08/09/liquid_crystal_3905.html

http://www.eltech.ru/ru/fakultety/fakultet-elektroniki/sostav-fakulteta/kafedra-kvantovoy-elektroniki-i-optiko-elektronnyh-priborov/sostav-kafedry

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Author Response File: Author Response.pdf

Reviewer 2 Report

Kamanina et al. showed a study of ‘Semiconductors ZnSe and ZnS materials nanostructuring via laser oriented deposition technique (LOD)’.

The topic is interesting. LOD approach seems quite perspective in the surface treatment of semiconductor materials. However, the results that the authors presented in this article lack enough details to demonstrate the respective experimental data, which stops the reviewer from doing a positive review. 

For instance,   the authors mentioned that electrical fields were applied to orient the nanotubes vertically during the deposition process. However, it is difficult to justify from the optical image in Figure 1.  The authors should show SEM or TEM images to prove that instead of optical images.

The authors showed the mechanical properties of the studied materials in Table 1 and Table2.  Why is there no microhardness data from ZnS materials shown in Table 1, no surface hardness data from ZnSe shown in Table 2?

Wetting data from ZnS is shown in Figure 3. How about wetting behavior from ZnSe?

The MD simulation data is shown in Figure4 and Figure 5 but without any discussion. In the end, the authors also concluded that ‘Thus, the theoretical and experimental results coincide to each other ... ’, the referee was confused where the authors showed the experimental data of penetration depth?

There are also numerous grammar errors in the text.

Given these, the referees cannot recommend the manuscript for publication.

Author Response

Reply to referee 2.

Dear Referee!

Thank you for your useful remarks and recommendation. I hope that the paper can be improved. Please see my answers to your questions. All added parts are colored with yellow.

1). Kamanina et al. showed a study of ‘Semiconductors ZnSe and ZnS materials nanostructuring via laser oriented deposition technique (LOD)’. The topic is interesting. LOD approach seems quite perspective in the surface treatment of semiconductor materials. However, the results that the authors presented in this article lack enough details to demonstrate the respective experimental data, which stops the reviewer from doing a positive review. 

For instance,   the authors mentioned that electrical fields were applied to orient the nanotubes vertically during the deposition process. However, it is difficult to justify from the optical image in Figure 1.  The authors should show SEM or TEM images to prove that instead of optical images.

Thank you! I have added the laser-vacuum scheme, which explain in detail our orienting process, when we have varied the distance between network (grid) and upper substrates with the materials.

Please see novel Figure. It is now Figure 1.

2). The authors showed the mechanical properties of the studied materials in Table 1 and Table 2.  Why is there no microhardness data from ZnS materials shown in Table 1, no surface hardness data from ZnSe shown in Table 2?

Yes, thanks! Good remarks. I have added an additional data in Table 1 and Table 2. These Tables are now corrected. The novel data are colored with yellow.

3). Wetting data from ZnS is shown in Figure 3. How about wetting behavior from ZnSe?

I have added the data on wetting angle for the ZnSe as well. Now it is Fig.4.

4). The MD simulation data is shown in Figure4 and Figure 5 but without any discussion. In the end, the authors also concluded that ‘Thus, the theoretical and experimental results coincide to each other ... ’, the referee was confused where the authors showed the experimental data of penetration depth?

Sorry, it maybe not correct sentence. Indeed, simulation is only partially supported the experimental results.

5). There are also numerous grammar errors in the text.

I have checked the mistakes. The corrected words are collared with yellow.

Thank you once again for your job to read the paper and to make the referee’s remarks.

Best Regards,

Natalia Kamanina

=======================================

Natalia V. Kamanina (Prof., Dr.Sci., PhD)

Head of the lab for Photophysics of media with nanoobjects

Vavilov State Optical Institute

Kadetskaya Liniya V.O., dom.5, korpus 2,

St.- Petersburg, 199053, Russia

Professor of the St.-Petersburg Electrotechnical University (“LETI”),

Part-time Leading Researcher at Nuclear Physics Institute (Gatchina)

Job phone: +7 (812) 327-00-95

Fax: +7 (812) 331-75-58 (for N.V.Kamanina)

e-mail:  [email protected]

http://www.photophysics-lab.org/ 

https://publons.com/researcher/1696479/natalia-kamanina/

https://sciprofiles.com/news-feed

http://rusnor.org/network/webinars/10203.htm

http://www.npkgoi.ru/?module=articles&c=profil&b=7

http://www.nanometer.ru/2007/08/09/liquid_crystal_3905.html

http://www.eltech.ru/ru/fakultety/fakultet-elektroniki/sostav-fakulteta/kafedra-kvantovoy-elektroniki-i-optiko-elektronnyh-priborov/sostav-kafedry

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Author Response File: Author Response.pdf

Reviewer 3 Report

In this work, authors study the process of ZnSe and ZnS substrates surface modification in presence of carbon nanotubes. For it, laser oriented deposition technique which authors have successfully used with other substrates, has been used. The final purpoise of this materials is to be used in optoelectronic devices.

In order to investigate the improvement of the modified materials transmittance in IR range, micro-hardness and contact angle of the modified substrates, have been selected as control properties.

Results indicate a decrease of the IR range light absorption and increase in the number of revolutions which generate a distinct ring and the contact angle.

However, although I don’t have any important criticism about the structure, the presentation or the experimental approach, I have the following comments/disagreement which must be revised to accept the manuscript for publication.

1. Although nanostructured materials are studied for the final objective of manufacturing optoelectronic devices, the relationship between the materials and their specific application is not clear. Will they be used to make solar cells? Spectral detectors? Optical limiters?. It would be convenient for the authors to relate the measured properties (transmittance, hardness, contact angle) with the future application of the studied materials.
2. In line 110, authors say “LOD procedure indicates some advantage of the modified properties of such materials”. Modified properties must be specified. What properties?
3. Figure 2. Figure caption should include a complete information of the figure not only a vague description. Is transmittance the same magnitude than transmission? If yes Please, change one of the figure axis. If not, specify

4. Figure 5 shows the calculated penetration depth of CNT in ZnS surface, however data referred to ZnSe are not shown. What is the reason?
5. Finally, in line 172, authors argue the “the theoretical and experimental results are coincided to each other ". I think the is not comparable theoretical and experimental results. Is it possible to obtain an electronic microscopy image of the modified surface? I think that the image could experimentally prove the theoretical results and I also think that it is necessary to include it in the corrected version of the manuscript.

Author Response

Reply to referee 3.

Dear Referee!

Thank you for your useful remarks and recommendation. I hope that the paper can be improved. Please see my answers to your questions. All added parts are colored with yellow.

In this work, authors study the process of ZnSe and ZnS substrates surface modification in presence of carbon nanotubes. For it, laser oriented deposition technique which authors have successfully used with other substrates, has been used. The final purpoise of this materials is to be used in optoelectronic devices. In order to investigate the improvement of the modified materials transmittance in IR range, micro-hardness and contact angle of the modified substrates, have been selected as control properties. Results indicate a decrease of the IR range light absorption and increase in the number of revolutions which generate a distinct ring and the contact angle.

However, although I don’t have any important criticism about the structure, the presentation or the experimental approach, I have the following comments/disagreement which must be revised to accept the manuscript for publication.

1. Although nanostructured materials are studied for the final objective of manufacturing optoelectronic devices, the relationship between the materials and their specific application is not clear. Will they be used to make solar cells? Spectral detectors? Optical limiters?. It would be convenient for the authors to relate the measured properties (transmittance, hardness, contact angle) with the future application of the studied materials.

Good remarks, thanks! I have added some explanation in the Introduction section. This paragraph is colored by yellow.

Furthermore, it should be remarked that ZnSe and ZnS materials are widely used to make the electrically- and optically-addressed spatial light modulators (SLM), operated in the blue and visible spectral range. This specific application is connected with the high carrier mobility of these types of the materials. Thus, the response (switch-on and switch-off time) can be revealed with good speed. Indeed, the resolution of the SLM with photo layers based on ZnSe and ZnS structure is not so good. But the compromise between resolution and speed can be found via specific pulsed regime of the laser operations, when the delay between the electric pulse and light one can be varied.

1. In line 110, authors say “LOD procedure indicates some advantage of the modified properties of such materials”. Modified properties must be specified. What properties?

I have added some explanation in the Introduction section. This paragraph is colored by yellow.

Why? It is connected with the fact, that the refractive index of the CNTs is so small and close to 1,1; but the Young modulus is so large and it is placed in the range of some teraPascale’s. Thus, the Fresnel losses can be decreased, transparency can be increased and mechanical parameters can be improved.

 

1. Figure 2. Figure caption should include a complete information of the figure not only a vague description. Is transmittance the same magnitude than transmission? If yes Please, change one of the figure axis. If not, specify

I have corrected this paragraph. The included parts in this paragraph is colored by yellow. Now it is Fig.3.

Some change of the spectral characteristics of the ZnSe and ZnS substrate in the range of 1,4 microns to 2,4 microns is shown in Fig.3. It is shown the influence of the CNTs structuration on the spectral parameters. Really, Fig.3,a (curve 1) presents the transmission of the pure ZnSe substrate on the indicated above wavelength range. In the Fig.3,a (curve 2 and curve 3) shows spectral characteristics after the treatment of the ZnSe surface from one side (Fig.3,a; curve 2) and from both sides (Fig.3,a; curve 3), respectively. The spectral parameters change for the ZnS with one side treatment is presented in Fig.3,b. Green curve shows the transmittance for the pure substrate; the blue curve presents the transmittance for the ZnS covered with CNTs. It is important that surface treatment of samples with CNTs can increase the transparency of both materials. It can be coincided with the fact, that  should be remarked once again, that the CNTs refractive index is close to 1.1 [21,22], that is less than the refractive index of the ZnSe or ZnS materials, thus the Fresnel losses can be decreased dramatically, that can predict the increase of the transparency.

1. Figure 5 shows the calculated penetration depth of CNT in ZnS surface, however data referred to ZnSe are not shown. What is the reason?

You are right! But, sorry, this additional simulation will require an additional time, which I have to ask for my colleagues from other Institutes. With your kind permission I would like to put the following sentence in the paper:

We can plan to make the analogous simulation for the ZnSe materials and will show the results in future publications.

1. Finally, in line 172, authors argue the “the theoretical and experimental results are coincided to each other ". I think the is not comparable theoretical and experimental results. Is it possible to obtain an electronic microscopy image of the modified surface? I think that the image could experimentally prove the theoretical results and I also think that it is necessary to include it in the corrected version of the manuscript.

I am agreeing with your remark, it is good! Please see my sentence, added and corrected this paragraph.

Thus, the experimental results are partially can be added by this simulation; it supports the fact of the effective application of the LOD technique in order to improve the basic properties of such materials with good advantage.

 

Thank you once again for your job to read the paper and to make the referee’s remarks.

Best Regards,

Natalia Kamanina

=======================================

Natalia V. Kamanina (Prof., Dr.Sci., PhD)

Head of the lab for Photophysics of media with nanoobjects

Vavilov State Optical Institute

Kadetskaya Liniya V.O., dom.5, korpus 2,

St.- Petersburg, 199053, Russia

Professor of the St.-Petersburg Electrotechnical University (“LETI”),

Part-time Leading Researcher at Nuclear Physics Institute (Gatchina)

Job phone: +7 (812) 327-00-95

Fax: +7 (812) 331-75-58 (for N.V.Kamanina)

e-mail:  [email protected]

http://www.photophysics-lab.org/ 

https://publons.com/researcher/1696479/natalia-kamanina/

https://sciprofiles.com/news-feed

http://rusnor.org/network/webinars/10203.htm

http://www.npkgoi.ru/?module=articles&c=profil&b=7

http://www.nanometer.ru/2007/08/09/liquid_crystal_3905.html

http://www.eltech.ru/ru/fakultety/fakultet-elektroniki/sostav-fakulteta/kafedra-kvantovoy-elektroniki-i-optiko-elektronnyh-priborov/sostav-kafedry

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Author Response File: Author Response.pdf

Round 2

Reviewer 1 Report

The slightly updated manuscript does still lack fundamentally necessary information. Also, a specific application is not shown and the literature context of the work remains unclear.

I thus have to suggest that this work should not be published in the Journal of Carbon Research

Specifically I criticize the following points:

1. All results: A comparison of the results to literature is missing. How significant are the detected changes? Are the described materials outperforming existing ones?
2. All results: How about the reproducibility of the sown results? Why are there no error bars reported?
3. How significant are these changes? Could this also be a result of missing normalizations?
4. Table 1 + 2: The shown results are completely out of context. A reference value through a standardized material has to be provided.

Author Response

Reply to referee 1.

Thank you for your useful remarks and recommendation in the framework of the second round. I hope that the paper can be improved once again. Please see added parts, which are colored with blue.

 

I would like to answer to your comments (Specifically I criticize the following points).

1. All results: A comparison of the results to literature is missing. How significant are the detected changes? Are the described materials outperforming existing ones?

Thank you! I have added in the conclusion section that It should be noticed that all results are repeatedly checked with a multiplicity of checks once a month. The error is plus or minus 0,5 % and less. Moreover, all results of the modified ZnS and ZnSe have testified the better data than shown, for example, in the classical books [38,39] for the pure materials.

1. All results: How about the reproducibility of the sown results? Why are there no error bars reported?

All results are repeatedly checked with a multiplicity of checks once a month. The error is plus or minus 0,5 % and less. I have added this sentence in the conclusion section and colored with blue.

1. How significant are these changes? Could this also be a result of missing normalizations?

The results for these materials are significant, because achieving even 1% improvement in properties with different methods of testing parameters is important. For example, if these materials are used both as photosensitive sensors and as protection against dynamic dust, then, naturally, both transmission and mechanical strength, improved even by 1%, will increase the sensitivity of the sensor as a whole.

1. Table 1 + 2: The shown results are completely out of context. A reference value through a standardized material has to be provided.

I'm sorry, but I don't agree with this comment. The results of the modified composite are compared with the unmodified (pure) one. Comparison with the glass crown K8 is given in the description directly after the Table 1. I have colored this part in blue in order to draw your attention.

Thank you once again for your job to read the paper and to make the referee’s remarks.

Best Regards,

Natalia Kamanina

=======================================

Natalia V. Kamanina (Prof., Dr.Sci., PhD)

Head of the lab for Photophysics of media with nanoobjects

Vavilov State Optical Institute

Kadetskaya Liniya V.O., dom.5, korpus 2,

St.- Petersburg, 199053, Russia

Professor of the St.-Petersburg Electrotechnical University (“LETI”),

Part-time Leading Researcher at Nuclear Physics Institute (Gatchina)

Job phone: +7 (812) 327-00-95

Fax: +7 (812) 331-75-58 (for N.V.Kamanina)

e-mail:  [email protected]

http://www.photophysics-lab.org/ 

https://publons.com/researcher/1696479/natalia-kamanina/

https://sciprofiles.com/news-feed

http://rusnor.org/network/webinars/10203.htm

http://www.npkgoi.ru/?module=articles&c=profil&b=7

http://www.nanometer.ru/2007/08/09/liquid_crystal_3905.html

http://www.eltech.ru/ru/fakultety/fakultet-elektroniki/sostav-fakulteta/kafedra-kvantovoy-elektroniki-i-optiko-elektronnyh-priborov/sostav-kafedry

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Author Response File: Author Response.pdf

Reviewer 2 Report

The authors have added some missing mechanical data and revised the manuscript accordingly. This clearly improves the quality of the manuscript.

Page 7, Line 206, correct the sentence.    

Page 8, Line 221, correct the sentence.

Author Response

Reply to referee 2.

Thank you for your useful remarks and recommendation in the framework of the second round. I hope that the paper can be improved once again. Please see added parts, which are colored with blue.

 

I corrected the articles on page 7 and 8. These ones are collared with blue.

All mistakes and sentence with not good English I have controlled and colored in blue.

Thank you once again for your job to read the paper and to make the referee’s remarks.

Best Regards,

Natalia Kamanina

=======================================

Natalia V. Kamanina (Prof., Dr.Sci., PhD)

Head of the lab for Photophysics of media with nanoobjects

Vavilov State Optical Institute

Kadetskaya Liniya V.O., dom.5, korpus 2,

St.- Petersburg, 199053, Russia

Professor of the St.-Petersburg Electrotechnical University (“LETI”),

Part-time Leading Researcher at Nuclear Physics Institute (Gatchina)

Job phone: +7 (812) 327-00-95

Fax: +7 (812) 331-75-58 (for N.V.Kamanina)

e-mail:  [email protected]

http://www.photophysics-lab.org/ 

https://publons.com/researcher/1696479/natalia-kamanina/

https://sciprofiles.com/news-feed

http://rusnor.org/network/webinars/10203.htm

http://www.npkgoi.ru/?module=articles&c=profil&b=7

http://www.nanometer.ru/2007/08/09/liquid_crystal_3905.html

http://www.eltech.ru/ru/fakultety/fakultet-elektroniki/sostav-fakulteta/kafedra-kvantovoy-elektroniki-i-optiko-elektronnyh-priborov/sostav-kafedry

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Author Response File: Author Response.pdf

Reviewer 3 Report

It would be desirable for them to show electron microscopy images of the materials.

Author Response

Reply to referee 3.

Thank you for your useful remarks and recommendation in the framework of the second round. I hope that the paper can be improved once again. Please see added parts, which are colored with blue.

 

It would be desirable for them to show electron microscopy images of the materials.

Sorry, at the present time I have no electron microscope in my Lab. In order to make the image required, I have to ask my colleagues from the other research Centre, but now, by the end of year it is so complicated. I will remember your recommendation and will make these experiments on 2022 year. Maybe we will present the novel results for these types or extended types of the semiconductor materials, including, for example, Ge and Si.

All mistakes and sentence with not good English I have controlled and colored in blue.

Thank you once again for your job to read the paper and to make the referee’s remarks.

Best Regards,

Natalia Kamanina

=======================================

Natalia V. Kamanina (Prof., Dr.Sci., PhD)

Head of the lab for Photophysics of media with nanoobjects

Vavilov State Optical Institute

Kadetskaya Liniya V.O., dom.5, korpus 2,

St.- Petersburg, 199053, Russia

Professor of the St.-Petersburg Electrotechnical University (“LETI”),

Part-time Leading Researcher at Nuclear Physics Institute (Gatchina)

Job phone: +7 (812) 327-00-95

Fax: +7 (812) 331-75-58 (for N.V.Kamanina)

e-mail:  [email protected]

http://www.photophysics-lab.org/ 

https://publons.com/researcher/1696479/natalia-kamanina/

https://sciprofiles.com/news-feed

http://rusnor.org/network/webinars/10203.htm

http://www.npkgoi.ru/?module=articles&c=profil&b=7

http://www.nanometer.ru/2007/08/09/liquid_crystal_3905.html

http://www.eltech.ru/ru/fakultety/fakultet-elektroniki/sostav-fakulteta/kafedra-kvantovoy-elektroniki-i-optiko-elektronnyh-priborov/sostav-kafedry

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Author Response File: Author Response.pdf