Luminescence Properties of Tetrahedral Coordinated Mn²⁺; Genthelvite and Willemite Examples

Round 1

Reviewer 1 Report

The paper deals with the luminescence of tetrahedral Mn²⁺ in genthelvite and willemite. From the experimental data, deep consideration of Mn²⁺ transitions has been investigated. This paper also provides numerical approaches based on the theoretical backgrounds. In my opinion, this paper could be considered to publish after serving additional corrections.

1. Please check the following minor corrections.
   - Dq Line 11,
   - On page 3, At the beginning of paragraph d), I guess there is a missing character in “… also verified whether the ___ value”.
   - On page 4, please break the line in front of paragraph f)
2. In figure 7, the shape of Mn emission is often considered as “Pekarian curve”, which is non-symmetrical shape due to electron-phonon coupling e.g. ZnS:Mn. Such “Pekarian curve” would limit the deconvolution process. How is it to be excluded?

Author Response

Dear reviewer #1,

thank you kindly for any critical (and kind) comments regarding our work.

Fulfilling the comment of Reviewer # 2, I rewrote the introduction, trying to show that the study of Mn2 + luminescent properties is still an important and current topic. Following the recommendation of reviewer # 2, I added a table to chapter 3.3 with the Raman band positions of the tested samples. This resulted in the renumbering of tables 4-8 to tables 5-9. Changes to the text in the introduction and chapter 3.3 have been underlined in yellow.

Rewriting the introduction chapter also made it necessary to add 9 new references - these are references 1-7 and 15 and 16. This was also underlined in yellow in the manuscript.

Remarks 1:

- „Dq Line 11, „

Sorry, I don't know what to make this point to. I always write Dq in italics. Can it stay that way?

-I fixed the other 2 bugs, I hope they will not change after the conversion

Remark 2:

“In figure 7, the shape of Mn emission is often considered as “Pekarian curve”, which is non-symmetrical shape due to electron-phonon coupling e.g. ZnS:Mn. Such “Pekarian curve” would limit the deconvolution process. How is it to be excluded?”

My answer is as follow:

I highly agree with Reviewer that this type of emission shape may disturb the deconvolution processes. Regardless, for our samples the shape of Mn emission

depends on different peculiarities of electron-phonon coupling and the luminescent centers may interplay with various host phonons. We can point that these shapes of emission curves have not impeded the suitable analysis.

 

 

 

Author Response File: Author Response.docx

Reviewer 2 Report

Referee report on “Luminescence properties of tetrahedral coordinated Mn2+; genthelvite and willemite examples” by Maria Czaja et al.

This is a quite good and useful article, which is undoubtedly suitable for publication, but nevertheless requires some serious improvements.

1. The introduction requires a very serious revision. Where it is necessary to reveal the main essence of the work, explain the motivation and objects of research. There is nothing of this, but on the contrary, we see a very special chapter, which is not understandable to many readers. Here it is necessary to give basic references, which will and should be useful for beginners in this field of research.
2. Among the first 25 references, all of them are over 10 years old. This does not at all confirm both the relevance of the work and the fact how closely the authors follow the development of science. New references must be added, which is only to confirm that this direction is still living and developing. Some of them could be:
3. Qiang Zhou, Leonid Dolgov, Alok M. Srivastava, Lei Zhou, Zhengliang Wang, Jianxin Shi, Miroslav D. Dramićanin, Mikhail G. Brik and Mingmei Wu, "Mn2+ and Mn4+ red phosphors: synthesis, luminescence and applications in WLEDs. A review", Journal of Materials Chemistry C 6 (2018) 2652-2671
4. Antuzevics, A., Rogulis, U., Fedotovs, A., & Popov, A. I. (2018). Crystalline phase detection in glass ceramics by EPR spectroscopy. Low Temperature Physics, 44(4), 341-345.
5. l’Alzit, F. R., Bazin, T., Poulon-Quintin, A., Champion, E., Bertrand, C., Cardinal, T., & Gaudon, M. (2020). Thermochromoluminescent Mn2+-Doped oxides as thermal sensor for selective laser sintering. Optical Materials, 110, 110542.

and many others…

3. Is Fig.1 really original? Such figure with a diagram (Tanabe-Sugano) requires reference. Note that many sentences in the Introduction s require exact referencing, especially when it comes to factual material.
4. Paragraph 3.3. It will be great if the data of the Raman spectra are given in the table for both minerals and the corresponding interpretation.
5. References:

10 – must be “Optoelectron”

28 – no volume number

31, 32 and 34 -  no volume and pages numbers

Author Response

Dear Reviewer,

thank you kindly for any critical (and kind) comments regarding our work.

Fulfilling Yours’s comment, I rewrote the introduction, trying to show that the study of Mn2 + luminescent properties is still an important and current topic. Following the recommendation of reviewer # 2, I added a table to chapter 3.3 with the Raman band positions of the tested samples. This resulted in the renumbering of tables 4-8 to tables 5-9. Changes to the text in the introduction and chapter 3.3 have been underlined in yellow.

Rewriting the introduction chapter also made it necessary to add 9 new references - these are references 1-7 and 15 and 16. This was also underlined in yellow in the manuscript.

 

 

As I mentioned at the beginning - I changed the introduction and added some references.

In the earlier version of the work, I did not really emphasize that the research on Mn2 + phosphors is still very intensive. Basically, I have limited myself only to the literature on the problem of calculating Mn2 + energy levels, especially for minerals. And these works are really old. This could discourage potential readers. I will bear this remark in mind when preparing possible future publications. I also tried to rewrite the introduction in such a way as to refer the reader to source works for a more complete set of information.

-I have added a note to Fig 1 about the reference for the Tanabe-Sugano diagram

-I made a table with the vibration bands - Table 4 in chapter 3.3

-I corrected the bugs in the references.

 

Author Response File: Author Response.docx

Round 2

Reviewer 2 Report

The revised version is OK, so manuscript can be recommended  for publication.