Comparison of Self-Assembled Monolayers Using 3-Aminopropyltrimethoxysilane and Decyltrimethoxysilane in Vapor Phase for Porous SiOCH Dielectrics
Aruna Kumar Barick
Round 1
Reviewer 1 Report
The authors reported their work on Self-Assembled Monolayers comparison with different precursors on porous SiOCH films. Electrical characteristics and reliability of obtained p-SiOCH films were characterized and compared. The authors described the target of the paper, along with the practical applications of it in a clear manner.
Introduction:
1. As feedstock for the experiments, self-assembled monolayer processing was used. One of my initial concerns was whether it would be possible to accurately identify and pinpoint advantages of self-assembled monolayer processing in comparison with other technologies. Does technology have disadvantages? Scalability? The authors do not address this point in a sufficient manner in the Introduction, although they discuss about this in the Results and Discussion chapter. This will make the motivation for this experiment easier to understand in my opinion and introduce the reader better into the topic.
- M&M. The authors stated: The dielectric constant of the p-SiOCH film was 2.56 ± 0.05, and the porosity and pore diameter of the p-SiOCH film were 15.5 % and 1.35 nm, respectively. How does this parameters were measured?
- The authors should briefly describe the suggested chemical-vapor-deposition (PE-CVD) methodology for readers. Please provide an experimental illustration scheme to describe suggested methodology.
- Section 2 should be separated in to the 2.1 Samples preparation and 2.2 Samples characterization sections.
- What about statistical analysis in suggested manuscript?
- Further in R&D section the authors discussed I-V measurements, fig 3 illustrate I-E curves. The gap was similar foe each curves (pristine, O2 plasma-irradiated, APTMS-SAMs, and DTMOS-SAMs p-SiOCH films)?
- Page 5. The authors stated: The accumulation capacitance can be used to determine the k value of a dielectric film by using the expression of k = Cd/ε0A. What is ε0 in this equation?
- Page 6. The authors stated: This indicates that the O2 plasma-induced damage is repaired and the formation SAMs provides another resistance to against breakdown….Please explain in details the mechanism of such behavior.
- Fig 5, 7, and 9 are not introduced in a M&M section as well as the stud-pull tape tests for the pristine, APTMS-SAMs, and DTMOS-SAMs p-SiOCH films.
Some additional general comments:
1. The manuscript looks like it was written in a hurry. There is no holistic perception of information.
2. The overall English of the text can be improved further. In particular, the usage of articles (a, an, the) is very commonly omitted. The authors are invited to make further re-reads and improve the structure of the manuscript.
Based on the above points, I would propose a major revision of the manuscript and I would be very interested to have a second revision once they are addressed by the authors.
Author Response
- As feedstock for the experiments, self-assembled monolayer processing was used. One of my initial concerns was whether it would be possible to accurately identify and pinpoint advantages of self-assembled monolayer processing in comparison with other technologies. Does technology have disadvantages? Scalability? The authors do not address this point in a sufficient manner in the Introduction, although they discuss about this in the Results and Discussion This will make the motivation for this experiment easier to understand in my opinion and introduce the reader better into the topic.
[Reply] We had added advantages of self-assembled monolayer processing in the introduction part in the revised manuscript.
- M&M. The authors stated: The dielectric constant of the p-SiOCH film was 2.56 ± 0.05, and the porosity and pore diameter of the p-SiOCH film were 15.5 % and 1.35 nm, respectively. How does this parameters were measured?
[Reply] The measured method for the porosity and pore diameter of the p-SiOCH film had been added in the revised manuscript.
- The authors should briefly describe the suggested chemical-vapor-deposition (PE-CVD) methodology for readers. Please provide an experimental illustration scheme to describe suggested methodology.
[Reply] The deposition conditions for the p-SiOCH film had been added in the revised manuscript.
- Section 2 should be separated in to the 2.1 Samples preparation and 2.2 Samples characterization sections.
[Reply] Experimental part had been separated to the (a) Samples preparation and (b) Samples characterization sections.
- What about statistical analysis in suggested manuscript?
[Reply] The measurement points had been mentioned in the revised manuscript. Additionally, the error had been shown for the measurement result.
- Further in R&D section the authors discussed I-V measurements, fig 3 illustrate I-E curves. The gap was similar foe each curves (pristine, O2 plasma-irradiated, APTMS-SAMs, and DTMOS-SAMs p-SiOCH films)?
[Reply] We had added the description about I-V and I-E. “ The applied voltage was transformed to the electric field (E) by dividing by the film’s thickness.”
- Page 5. The authors stated: The accumulation capacitance can be used to determine the k value of a dielectric film by using the expression of k = Cd/ε0A. What is ε0 in this equation?
[Reply] These parameters had been defined in the revised manuscript.
- Page 6. The authors stated: This indicates that the O2 plasma-induced damage is repaired and the formation SAMs provides another resistance to against breakdown….Please explain in details the mechanism of such behavior.
[Reply] We had explained the detailed mechanism in the revised manuscript.
- Fig 5, 7, and 9 are not introduced in a M&M section as well as the stud-pull tape tests for the pristine, APTMS-SAMs, and DTMOS-SAMs p-SiOCH films.
[Reply] Experimental part had been revised. All tests had been described in details.
Some additional general comments:
- The manuscript looks like it was written in a hurry. There is no holistic perception of information.
[Reply] This paper had been revised according to reviewer’s comment. Holistic perception had been added in the revised manuscript.
- The overall English of the text can be improved further. In particular, the usage of articles (a, an, the) is very commonly omitted. The authors are invited to make further re-reads and improve the structure of the manuscript.
[Reply] Grammatical and writing style errors in the original version had been corrected again by our colleague who is a native English speaker. In addition, the figures had been re-plotted and revised in order to improve the quality and make it clearer.
Reviewer 2 Report
The manuscript may be accepted for publication in current form.
Author Response
The manuscript may be accepted for publication in current form.
[Reply] : Thanks for reviewer's positive comment!!
Reviewer 3 Report
1. It is established that the results of two methods with different precursors (DTMOS and APTMS) are compared; however, it is not possible to know what benefit or originality is obtained with the research. The improvement of the breakdown field and time-dependent-dielectric-breakdown, Cu barrier capacity, and promote the adhesion is established in the Abstract, but it is not established that it contributes to the impacts or scope of scientific and/or technological applications
2. The experimental methods are not complete and are scattered throughout the manuscript (eg, the deposition parameters by PE-CVD and to do the TDDB test are not established, and the voltage profile is not described, respectively )
3. In the equation k=Cd/ε0A, only d and A are defined.
4. Define FT-IR spectrum (Fourier Transformation- InfraRed) (it is necessary to understand that it must be entirely understandable for anyone who reads it and is not familiar)
5. In the manuscript, there must be a discussion and cite the sources or show the results of the assertions (e.g. After O2 plasma radiation, Si dangling bonds…)
6. Figure 4. Correct DTMOD… Figure 5. Correct SMAs, completely revise the manuscript and correct these errors.
7. There is no discussion or citations that show the characteristics of the comparison between APTMS-DTMOS
8. The writing leaves much to be desired (e.g. the Abstract says, "..., but a larger increase in the dielectric constant was a cost"...); the ideas are not understood.
9. The quality of the figures must improve a lot…
10. The manuscript is not numbered…
Author Response
- It is established that the results of two methods with different precursors (DTMOS and APTMS) are compared; however, it is not possible to know what benefit or originality is obtained with the research. The improvement of the breakdown field and time-dependent-dielectric-breakdown, Cu barrier capacity, and promote the adhesion is established in the Abstract, but it is not established that it contributes to the impacts or scope of scientific and/or technological applications
[Reply] The abstract had been revised. Scientific and/or technological applications had been added in the revised manuscript. “Therefore, SAMs derived from APTMS is a promising candidate for sub-nanometer barrier application for advanced interconnects.”
- The experimental methods are not complete and are scattered throughout the manuscript (eg, the deposition parameters by PE-CVD and to do the TDDB test are not established, and the voltage profile is not described, respectively )
[Reply] Experimental part had been revised. All tests had been described in details.
- In the equation k=Cd/ε0A, only d and A are defined.
[Reply] These parameters had been defined in the revised manuscript.
- Define FT-IR spectrum (Fourier Transformation- InfraRed) (it is necessary to understand that it must be entirely understandable for anyone who reads it and is not familiar)
[Reply] We had defined FT-IR spectrum in the revised manuscript.
- In the manuscript, there must be a discussion and cite the sources or show the results of the assertions (e.g. After O2 plasma radiation, Si dangling bonds…)
[Reply] We had explained the detailed mechanism in the revised manuscript.
- Figure 4. Correct DTMOD… Figure 5. Correct SMAs, completely revise the manuscript and correct these errors.
[Reply] All figures had been re-checked and re-plotted.
- There is no discussion or citations that show the characteristics of the comparison between APTMS-DTMOS
[Reply] The comparison between APTMS-DTMOS SAMs had been discussed in the revised manuscript.
- The writing leaves much to be desired (e.g. the Abstract says, "..., but a larger increase in the dielectric constant was a cost"...); the ideas are not understood.
[Reply] The manuscript had been revised and grammatical and writing style errors in the original version had been corrected.
- The quality of the figures must improve a lot…
[Reply] The figures had been re-plotted and revised in order to improve the quality and make it clearer.
- The manuscript is not numbered…
[Reply] The revised manuscript had been numbered.
Reviewer 4 Report
The manuscript provides interesting data on SAMs formation on low K dielectrics. It can be accepted after incorporating the following comments:
1. Please modify the usage ‘but a larger increase in the dielectric constant was a cost’ in the abstract…also ‘and promoted the adhesion’ = which adhesion.
2. ‘The WCA values recovered to 82.6° and 73.2° for APTMS and DTMOS treatments, respectively’. This statement is not matching with table 1.
3. Is there any role of the surface roughness on the higher WCA of DTMOS. A few recent reviews on surface wettability shall be cited for further reading (10.1021/cr400083y, 10.1002/asia.202001425)
4. The conclusion section shall be expanded by mentioning more characterization and evaluation studies results.
Author Response
The manuscript provides interesting data on SAMs formation on low K dielectrics. It can be accepted after incorporating the following comments:
- Please modify the usage ‘but a larger increase in the dielectric constant was a cost’ in the abstract…also ‘and promoted the adhesion’ = which adhesion.
[Reply] Abstract had been revised and grammatical and writing style errors in the original version had been corrected.
- ‘The WCA values recovered to 82.6° and 73.2° for APTMS and DTMOS treatments, respectively’. This statement is not matching with table 1.
[Reply] This mismatch had been corrected.
- Is there any role of the surface roughness on the higher WCA of DTMOS. A few recent reviews on surface wettability shall be cited for further reading (10.1021/cr400083y, 10.1002/asia.202001425)
[Reply] The surface roughness is less related to WCA.
- The conclusion section shall be expanded by mentioning more characterization and evaluation studies results.
[Reply] The conclusion had been revised
Round 2
Reviewer 1 Report
I felt that this paper is important and of benefit to researchers in this particular field . I recommend to accept the manuscript.
Reviewer 3 Report
Without comments
