Ag Behavior on TiN Thin Films for Decorative Coatings

Round 1

Reviewer 1 Report

Comments and Suggestions for Authors

Title: Ag behavior on TiN thin films for decorative coatings

I reviewed the manuscript entitled “Ag behavior on TiN thin films for decorative coatings”. The work carried out in the manuscript is interesting and aims to investigate the influence of the different silver concentrations on the morphological and structural behavior of the deposited films, as well as their influence and applicability in the aesthetic aspect, for decorative coatings. However, in my opinion, several aspects should be modified or detailed more in-depth prior to publication, thus major modifications are advised. Here is a list of main comments:

Please consider all the comments below and highlight the changes.

-The writing and grammar of the manuscript should be carefully checked to resolve some existing errors and provide smooth text. for example in the abstract line 15 and 16:’When the increase in Ag content was high, however, this, reflected in a significant and decreasing reduction in L* values and also in the change in red reflectance.’ This should be changed to: When the Ag content experienced a substantial increase, it was evident in a notable and consistent decrease in L* values, as well as a corresponding shift in red reflectance.

In line 17, the word ‘also’ was repeated. (were also also 17 analyzed,...)

-The term "matte characteristic" is mentioned in the abstract without a detailed explanation. It would be beneficial to clarify what specific characteristics contribute to the matte appearance and how this impacts the film's performance. Authors could consider expanding on this point for better clarity.

-While the literature review touches on the antibacterial properties of TiN/Ag coatings, there's a potential gap in the discussion of previous research on decorative coatings specifically. Authors may consider incorporating more references related to TiN coatings in decorative applications to provide a comprehensive background. you may use the following references:

https://doi.org/10.3389/fmats.2019.00188

https://doi.org/10.1016/j.ceramint.2020.06.207

https://doi.org/10.1016/j.matdes.2018.05.025

- The introduction mentions the need for surfaces with functional characteristics, especially related to preventing bacterial adhesion. It would be constructive for the authors to discuss specific surface modification techniques considered in the literature for achieving antibacterial properties and how their approach differs or aligns with those methods.

- The abstract discusses the agglomeration of particulates and increased roughness in films with higher Ag concentrations. Authors should consider addressing the composition of these particulates, whether they are purely silver or a combination with TiN, and how this composition might influence the film's mechanical and aesthetic properties.

- The paper discusses the competition between the evaporation of Ti and Ag elements, leading to a reduction in the Ti/Ag ratio. A more in-depth discussion of the implications of this competition and how it affects the properties of the TiN-Ag films could add value.

- While the paper mentions an almost linear relationship between roughness and the incorporation of silver, further quantitative analysis or modeling could strengthen this claim. Discussing potential reasons for this linear relationship would enhance the paper's scientific rigor.

- The XRD patterns are briefly discussed, but a more comprehensive discussion on how changes in Ag concentration influence crystallographic orientation, especially the shift and reduction in intensity of TiN peaks, could improve the depth of the analysis.

- The conclusion briefly touches upon the findings but could be strengthened by suggesting potential areas for future research and discussing practical applications of the TiN-Ag coatings beyond decorative purposes.

- The paper briefly mentions variations in color (L*, a*, b*) but does not elaborate on the stability of these color parameters over time. Discussing color changes over an extended period could provide additional valuable insights for practical applications.

Comments on the Quality of English Language

has been mentioned in the above comments in detail.

Author Response

Dear Reviewer, Thank you for your contribution to our publication. Your notes were very
constructive for this and subsequent work. We made the proposed corrections. We accepted your suggestion to change the
text and include references.

We detail the process of silver evaporation in a little more detail
(in fact, this was missing in the first version). We seek to further improve discussions about results and RX. Regarding the evaluation of L* a* and b* behavior, we think your suggestion
is pertinent, however we have not evaluated this item and are suggesting it
as future work. In time, the group is carrying out an experiment with copper, and we will
carry out this study in parallel in the next work. Thank you in advance for your attention and we remain at your disposal  

Author Response File: Author Response.pdf

Reviewer 2 Report

Comments and Suggestions for Authors

The manuscript, Ag behavior on TiN thin films for decorative coatings, by Arruda and co-workers demonstrates very interesting work in the direction of decorative coatings application. The abstract and introduction are appropriate, the motivation part at the end has been clearly stated. The following remarks need to be considered for its improvement:

1. What is the reason to use p-type and not n-type silicon?

 

2   2. Are the targets rotated during magnetron sputtering, to ensure high homogeneity of the deposits?

3   3. XRD patterns, authors affirm that ‘A reduction in intensity and a shift of the TiN peaks (111) and (200) can be observed as the Ag concentration is increased intensity’. What is the reason underpinning the observed shift? Authors should detail it in the text. Also, the intensity unit should be indicated in a.u. and not u.a., please correct.

     4. Authors are suggested to provide higher magnification of SEM, 9000x is not sufficient to me to properly discriminate the surface and size of Ag particles.

           5. Authors are suggested to refer in the introduction to other chemical methods of deposition of Ag, for example Dalton Trans., 2017,46, 10986-10995 (https://doi.org/10.1039/C7DT01647F), Materials Science & Engineering C 119 (2021) 111496 (https://doi.org/10.1016/j.msec.2020.111496), and others.

 

 

 

Author Response

Dear Reviewer, Thank you for your contribution to our publication. Your notes were very
constructive for this and subsequent work. We made the proposed corrections. We accepted your suggestion to change the
text and include references.

About your questions, follow:

1 What is the reason to use p-type and not n-type silicon?
No specific reason. The p-type silicon wafers were available for use in
an acceptable quantity. However, we understand that n-type silicon wafers
could be used. Its use was largely due to its surface quality and
the possibility and ease of using it in analyzes during the
characterization of the film.

 2. Are the targets rotated during magnetron sputtering, to ensure high homogeneity of the deposits?
It remained fixed. To guarantee the homogeneity of the deposited film, we use a
specific sample holder, which guarantees a thickness uniformity of 95%
in a certain region of the equipment

Question3 -
As suggested, we modified the text and provided more detail


4. Authors are suggested to provide higher magnification of SEM, 9000x is not sufficient to me to properly discriminate the surface and size of Ag particles
We agree, however at the moment we only had low resolution equipment available,
which provided us with an estimate, but in the future we will evaluate
with higher resolutions.

5. We include suggested references. We made some adjustments and adjustments
to the text, according to the considerations made by the reviewers.

Thank you in advance and I remain at your disposal
 

Author Response File: Author Response.pdf

Reviewer 3 Report

Comments and Suggestions for Authors

In this study, the authors investigate the influence of different silver concentrations on the morphological and structural behavior of the deposited films. While the results of this work are intriguing, there is a need for improved explanations of the mechanism and more comprehensive references. Therefore, I recommend accepting this manuscript following a minor revision.

1.    Elaborate on the novelty of the work in the introduction section. Clarify the unique properties of the proposed structures compared to existing literature.

2.    Improve the quality of Fig. 1 by enlarging the words in the inset to ensure clarity. Similarly, enhance the clarity of Fig. 5 by enlarging the text.

3.    Since silver is prone to oxidation in the surroundings, briefly discuss whether the sample silver could be replaced by gold in the proposed structure.

4.    In the conclusion section, elaborate further on the statement "The presence of silver in the concentrations used in this work made it impossible to measure the surface energy." Include necessary references in the main text to support this statement.

5.    Provide a detailed explanation in the text regarding the mechanism behind the observation that "a hydrophobic coating (θ > 90°) was observed for samples with a silver concentration above (8.3 ± 0.5) at %, whereas a hydrophilic behavior (θ < 90°) was observed for coatings with Ag concentrations lower than (6.3 ± 1.2) at %."

6.    Ensure to check and correct any typos and grammatical errors throughout the manuscript.

Author Response

Dear reviewer, we thank you for your notes and suggestions. We make adjustments according to the recommended suggestions We changed the introduction and summary to provide more clarity and details and included
new references to expand the scope of application.

about your question:

We will improve de quality of figure 1. We send in the separated file.

We are planning to use other materials (as future work), such as copper,
as it is more economically viable, as it would have a smaller impact on
the manufacturing cost.

In a future step, we will use another non-polar component, in order to evaluate the surface energy. We consider this as a future activity and intend to compare it with the results obtained with copper in the next work. We believe that this way we would have more information to detail the results obtained in wettability. Thank you in advance for your attention and I remain at your disposal for further clarification.

Author Response File: Author Response.pdf

Round 2

Reviewer 1 Report

Comments and Suggestions for Authors

I regret to inform you that I couldn't locate the response file containing the reviewer's comments, which address each comment individually. Please prepare this file accordingly. Moreover, in addition to highlighting the changes made in the manuscript, it is imperative that some questions receive clear and concise answers within the same document.

Furthermore, I requested a native English speaker to thoroughly check the manuscript, but there are still numerous typos and grammatical errors, such as "stailess stell" in line 123, which should be "stainless steel," and in line 31, "The use of different TiN, CrN, and other multilayer films is reported in the literature [5,6]," where the verb "is" should be changed to "are." There are many more errors like these. Once these issues are addressed, I will review it again. It is compulsory to attach the certificate of English proofreading.

Comments on the Quality of English Language

there are still numerous typos and grammatical errors, such as "stailess stell" in line 123, which should be "stainless steel," and in line 31, "The use of different TiN, CrN, and other multilayer films is reported in the literature [5,6]," where the verb "is" should be changed to "are." There are many more errors like these. Once these issues are addressed, I will review it again. It is compulsory to attach the certificate of English proofreading.

Author Response

Dear reviewer, thank you for the given notes. Please see the attachment.

We apologize for the earlier mistakes; the text has now been corrected by a native speaker.

Attached are our point-by-point comments on the recommended changes.


- Specifically, in the sentence discussed in the second round, our native colleague made the following note: The supposed correction of the sentence: "The use of different TiN,.......is reported in the literature.", where it is requested to use "are"  (not is) is incorrect. The use of..." requires a singular verb. For example, "The use of such-and-such films is reported" is correct.       Another doubt from the group. Do we need to send a letter from the reviewer attesting to the review? And this is your request? Thank you in advance and I remain at your disposal  

Author Response File: Author Response.pdf