Investigation on Solar Absorption and Thermal Emittance of Al Films Deposited by Magnetron Sputtering

Round 1

Reviewer 1 Report

The article is devoted to the study of the optical and structural properties of thin films used as intelligent radiation devices used in the aerospace industry. The presented results have scientific novelty and practical significance, and can also be used in the future to create prototypes of these devices. However, before accepting the article for publication, the authors should answer all the questions posed when reading it.
1. What is the reason for the amorphousness of the synthesized structures of the films shown in Figure 2, as a rule, thermal annealing should lead to crystallization processes, but this effect was not detected. The authors need to be explained.
2. How roughness affects the reflective and absorptive capacity of films, the authors should give a more detailed description of this effect.
3. How were the thicknesses of the obtained films determined, were any additional methods used besides scanning electron microscopy?
4. Is there a correlation of data between the results of morphological changes obtained using scanning electron microscopy and atomic force microscopy.
5. The conclusion requires substantial revision; it should reflect new data obtained as a result of the research carried out, as well as the prospects for further research.

Author Response

Comments from Reviewer 1 and Reply from the authors

Recommendation: The article is devoted to the study of the optical and structural properties of thin films used as intelligent radiation devices used in the aerospace industry. The presented results have scientific novelty and practical significance, and can also be used in the future to create prototypes of these devices. However, before accepting the article for publication, the authors should answer all the questions posed when reading it.

Comments:

1) What is the reason for the amorphousness of the synthesized structures of the films shown in Figure 2, as a rule, thermal annealing should lead to crystallization processes, but this effect was not detected. The authors need to be explained.

Response:  Thanks for your careful reading of our manuscript and instructive suggestions. The peak at 17 ^o – 27 ^o corresponds to the quartz substrate, which is the amorphous SiO₂. To better observe the diffraction peak of the Al films, we have put the partially enlarged view in Figure R1, which is removed the background. Although the intensity of the diffraction peak is small, Al film is still crystalline. Meanwhile, the 38.5^o peak corresponds to (111) crystal planes of the Al films (JCPDS: 99-0005).

Thanks to your professional comments, we have replaced the Figure 1 in the manuscript with the following “Figure R1”, and made some revises in the manuscript to address the comment, which is highlighted in yellow:

“As shown in Figure 2, the 38.5 ^o peak corresponds to (111) crystal planes of the Al films (JCPDS: 99-0005). As the lowest energy plane, (111) plane in growing films easily aligns parallel to the substrate.¹¹ In the partially enlarged view in Figure 2, the intensity of the (111) plane is very low at the deposition temperature of the RT. The intensity of the diffraction peak of (111) enhances when the deposition temperature is above 100 ^oC. However, the change of diffraction peak is unobvious with increasing temperature from 100 to 400 ^oC. It is mainly due to the short deposition time, which leads to the thin thickness.”

Figure R1. XRD pattern of the Al film at different deposition temperatures.

2) How roughness affects the reflective and absorptive capacity of films, the authors should give a more detailed description of this effect.

Response: We thank the reviewer for pointing out the need to explain the relationship between the roughness and the spectrum for investigation. According to the previous studies, the increase of the surface roughness could lead the reflectance decrease, especially in the wavelength of the UV-VIS-IR region.^1-4 Khachatryan et al studied the effect of the surface roughness on the reflection spectrum of Al films on the steel substrate at 200 – 1000 nm. As estimated, the 30 nm thick film had the highest reflection due to the lowest roughness and very smooth surface.³ And a similar phenomenon was observed by Kim et al., who reported that increasing surface roughness led to a decrease in reflectivity.⁴ The reflectance change of the metal films can be attributed to several effects. In the solar wavelengths, the high absorptance arises from the plasmon resonances of the metal nanoparticles.⁵ The spectral absorbance is broader than that of bulk metal, likely due to resonance-broadening arising from electron scattering at the boundaries of and defects within the polycrystalline nanoparticles.^5-8 Besides, the forward Trunc ellipse cone structure is easy to achieve impedance matching and reduce reflection, and the higher the height, the more obvious the anti-reflection effect.^9-10

In this experiment, the reflectance spectrum of the Al films is obtained by the integrating sphere, that is, the loss of diffuse reflection is considered. Therefore, for an opaque material, the spectral absorption or emittance can be expressed as α=ε=1-R. Combing our simulation and experimental results, it can be found that the surface particles further aggregate, and larger particles and deep grooves among the hill-like tops have formed with the deposition temperature and deposition time continually increasing. The particle coarsening contributes to enhancing the particle size and the film roughness, resulting in the volume for both light–matter interactions and near-field coupling between neighboring nano-particles increases, which could strengthen and broaden the absorption, respectively.^5,11 As shown in Figure R2, the width and the height of the Al particles increase with the deposition temperature increasing from RT to 400 ^oC. According to the simulated results, the height of the Al particles has more influence on the absorption. The height of the Al particles increases obviously form ~ 13 nm to ~ 180 nm, resulting in the increase of the absorption in the visible light range. For the IR band, the size of the Al particles is less than the mid-far infrared wavelength, therefore, the size of the Al particles has little influence on the IR reflectance of the Al films in the wavelength of 2.5 – 25 μm.

Figure R2. AFM image of Al films and height profiles in the directions of i and ii (guided by white lines). a. Deposition temperature at RT, b. Deposition temperature at 400 ^oC.

But we realized that the statement may be not logically coherent thanks to your professional comments, we made some revises in the manuscript to address the comment, which is highlighted in yellow:

“3.2 Morphology of the Ag films

The nanoparticles range from ~ 11 to ~ 180 nm in height and range from ~ 100 to ~ 900 nm in width (Figure S2), when the deposition temperature increases from RT to 400 ^oC.….. About the influence of the deposition time on the morphological characteristics, it can be noted that Rq of the Al films also gradually becomes larger from 4.4 nm to 29.8 nm (Figure S3), and the nanoparticles range from ~ 14 to ~ 53 nm in height and range from ~ 140 to ~ 340 nm in width (Figure S4), as the deposition time increases from 5 min to 25 min.

3.3.1 Effect of deposition temperature on reflectance spectrum

At low temperatures, the surface of the Al film consists of tiny particles with needle-like structure and the surface roughness is small. As the temperature reaches 200 ^oC, the hill-like structure is formed. With the deposition temperature continually increasing, the surface particles further aggregate. Therefore, larger particles with the size of hundreds of nanometers have formed and the film roughness has enhanced, resulting in the volume for both light–matter interactions and near-field coupling between neighboring nano-particles increases, which could strengthen and broaden the absorption, respectively.^21-23 Besides, it’s easier to achieve impedance matching and reduce reflection due to the increased size of the Al particles.¹⁴ Thus, the reflectance of the Al films decreased, and the absorption increased. The solar absorption of the Al films has increased from 0.09 to 0.44 with the deposition temperature increasing (Table S2). For the IR reflectance at 2.5 – 25 μm, the size of the Al particles is less than the mid-far infrared wavelength, and the difference of the Al film thickness is little. Therefore, all the samples show high IR reflectance (Figure 5b).”

1. Schmitt, P.; Stempfhuber, S.; Felda, N.; Szeghalmi, A.V.; Kaiser, N.; Tünnermann, A.; Schwinde, S. Influence of seed layers on the reflectance of sputtered aluminum thin films. Opt. Express. 2021, 29, 19472.
2. Huang, M.; Du, N.; Zhao, J.F.; Liu, H.B. Effect of Metal Surface Roughness On Properties Of Selective Absorption Coating of Solar Energy. Acta Energiae Solaris Sinica, 2021, 42(6), 243-246.
3. Khachatryan, H.; Lee, S.N.; Kim, K.B.; Kim, M. Deposition of Al Thin Film on Steel Substrate: The Role of Thickness on Crystallization and Grain Growth. Metals, 2019, 9 (12), 1-8.
4. Kim, S.D.; Rhee, J.K.; Hwang, I.S.; Park, H.M.; Park, H.C. Surface Condition Effects of the Inter-Metal Dielectrics on Interconnect Aluminum Film Properties. Thin Solid Film. 2001, 401, 273–278.
5. Mandal, J.; Wang, D.; Overvig, A.C., Shi, N.N.;, Paley, D.; Zangiabadi, A.; Cheng, Q.; Barmak, K.; Yu, N.F.; Yang, Y. Scalable, “Dip-and-Dry” Fabrication of a Wide-Angle Plasmonic Selective Absorber for High-Efficiency Solar–Thermal Energy Conversion. Adv. Mater. 2017, 29, 1702156.
6. K. Boer, Advances in Solar Energy, Vol. 3, Plenum Press, New York, USA, 1986.
7. Xu, K.; Hao L.; Du M.; Mi J.; Yu Q.H.; Li S.; Wang J.N.; Li S.J. Thermal emittance of Ag films deposited by magnetron sputtering. Vacuum. 2020, 174, 109200.
8. Ma, S.B; Liu, Q.; Qian, X.C,; Hong, R.J.; Tao, C.X. Controllability study of surface plasmon resonance spectra of aluminium nanoparticles. Acta Optica Sin. 2017, 37(9):0931001.
9. Zhang, X.; Wu, Y; Tong, X. Study of surface plasmon polaritons waveguide of silver nanowire. Acta Optica, 2016, 36 (1), 0124001.
10. Fan, P.X.; Bai, B.F.; Long, J.Y.; Jiang, D.F.; Jin, G.F.; Zhang, H.J.; Zhong, M.L.. Broadband High-Performance Infrared Antireflection Nanowires Facilely Grown on Ultrafast Laser Structured Cu Surface. Nano Lett. 2015, 15, 5988−5994.
11. Vu, T.C.; Cao, X.; Hu, H.B; A universal robust bottom-up approach to engineer Greta-oto-inspired anti-reflective structure. Cell Reports Physical Science. 2021, 2, 100479.
12. P. K. Jain, M. A. El-Sayed, Chem. Phys. Lett. 2010, 487, 153.

3) How were the thicknesses of the obtained films determined, were any additional methods used besides scanning electron microscopy?

Response: We thank the reviewer for the valuable and thoughtful comments. Besides SEM, we also have Profilm3D profiler to obtain the film’s thickness. However, the thicknesses of the Al films are relatively thin and no obvious step exists in the samples, thus the measurement error using 3D profiler is relatively large. In contrast, the thinner thickness measured by SEM is more accurate

4) Is there a correlation of data between the results of morphological changes obtained using scanning electron microscopy and atomic force microscopy.

Response: We thank the reviewer for the helpful comment about the need for understanding the correlation of the data obtained using scanning electron microscopy and atomic force microscopy. The basic morphology of the Al film surface, such as uniformity and particle size, can be observed by SEM. Whereas, the AFM test can further obtain the surface roughness of the Al films, as well as the particle width and height, and can be fed back to the SEM test results. Take the surface morphology at the deposition temperature of 400 °C as an example (Figure R3), it can be seen in the SEM image that Al particles on the surface are uniform and the size of the large particles are distributed between 500 and 1000 nm. From the AFM image and the height profiles, a similar morphology can be observed, and the height profiles show that the sizes of particles are around 460 – 900 nm.

Figure R3. SEM image and AFM image of Al films deposition temperature of 400 ^oC. ( The height profiles in the directions of i and ii).

5) The conclusion requires substantial revision; it should reflect new data obtained as a result of the research carried out, as well as the prospects for further research.

Response: We thank the reviewer for the forward-thinking comment about the conclusion. According to your constructive comments, we have made a lot of changes to the conclusion. And to address the comment, this part is highlighted in yellow:

“4. Conclusions

The Al films were successfully fabricated on the fused silica substrate by DCMS. With the increase of the deposition temperature and time, the Al particles will grow and coarsen, resulting in the increase of surface roughness. Therefore, the reflectance of the Al films decreases obviously, and then the solar absorption increases. Furthermore, the simulation results by FDTD have further confirmed that the decrease in the height of the particle on the Al surface could reduce the solar absorption of the Al film. Besides, all the samples show high IR reflectance in the 2.5- 25 μm. For the practical application, it’s an effective way to reduce solar absorption of the Al films by decreasing the deposition temperature and time, which could reduce the particle size and surface roughness. Based on the optimized condition with the deposition temperature of 100 ^oC and deposition time of 10 min, the Al film exhibits small solar absorption of 0.14 and low emittance of 0.02, which is conducive to its application in smart radiation devices and solar reflectors.”

Author Response File: Author Response.pdf

Reviewer 2 Report

The authors present a study on the solar absorption of sputtered films of aluminum. I suggest a major revision as detailed below:

1. For the grazing incicence XRD the incidence angle should be given.
2. The contrast of the SEM images (Fig. 2) and SI should to be improved. 
3. There is a repeated typo in Fig. 4 and Fig. 5. "wavalength".
4. Most imortant: the connection between experimental results and simulated reflectance spectra is weak. One could use the simulated spectra as motivation to aim for a certain morphology. And of course one should compare simulation and experimental results. But this is done only scarcely with the final sentence 3.3.3.
5. References should be checked. For some references the first and family names are confused (ref. 9, 15, 23). 

Author Response

Comments from Reviewer 2 and Reply from the authors

Recommendation: The authors present a study on the solar absorption of sputtered films of aluminum. I suggest a major revision as detailed below:

Comments:

1) For the grazing incicence XRD the incidence angle should be given.

Response: We thank the editor for the valuable and thoughtful comments. According to your comments, we have added the incidence angle of the XRD, and the we made the revise in the manuscript, which is highlighted in yellow:

“Crystalline structures of the Al films were determined by X-ray diffraction using Cu Kα radiation (λ = 0.15406 nm) at an X-ray grazing angle of 5 °.”

2) The contrast of the SEM images (Fig. 2) and SI should to be improved. 

Response: We thank the reviewer for pointing out the contrast of the SEM images. We have adjusted the contrast of the picture with drawing software. Meanwhile, we are sorry for the mistake of the picture number, Fig.2 is the Fig.3. Then We have checked this content, and made corrections to the paper. And it had been highlighted in yellow.

3) There is a repeated typo in Fig. 4 and Fig. 5. "wavalength".

Response: We thank the reviewer for the kind comment and pointing out the mistake. We have checked the content and Figures, and made the revise in the manuscript.

Figure 4. (a) UV-VIS-IR reflectance spectra and (b) NIR/MIR-IR reflectance spectra of the Al films at different deposition temperatures. (c) UV-VIS-IR reflectance spectra and (d) NIR/MIR-IR reflectance spectra of the Al films at different deposition time

Figure 5. (a) Schematic representation of the Al films with nano-particles on the surface. (b) The simulated reflectance spectra of the planar Al films with no nano-particles. The simulated reflectance spectra of the Al films with the nano-particles: (c) particle height is 30 nm, width is from 150 nm to 800 nm, (d) particle height is from 30 nm to 150 nm, width is 200nm.

4) Most imortant: the connection between experimental results and simulated reflectance spectra is weak. One could use the simulated spectra as motivation to aim for a certain morphology. And of course one should compare simulation and experimental results. But this is done only scarcely with the final sentence 3.3.3.

Response: We thank the reviewer for the kind and constructive comments. We should indeed strengthen the analysis of the connection between experimental and simulation results. According to your comments, we have made revisions in the section 3.3.3, which are highlighted in yellow:

“Figure 6c shows the reflectance for the Al nanoparticle height h of 30 nm, with width w varying from 150 nm to 800 nm, which is set according to the actual particle width in Figure S2 and Figure S4”

“The reflectance has decreased obviously at 0.25-1.25 μm as the height increases from 30 nm to 150 nm, which is similar to the experimental results and has proved the influence of particle height on reflectance spectrum in theory. Whereas, the actual solar absorption of the Al films is larger due to the uneven particle size and disordered distribution on the surface of the prepared Al films.”

5) References should be checked. For some references the first and family names are

confused (ref. 9, 15, 23). 

Response: We are grateful to the reviewer for the kind comment and nicely summarizing. To address this comment, we have checked the first and family names, and now corrected the corresponding references in the manuscript. The number of refs 23 has become refs 26 due to the three references added in the manuscript.

9. Schmitt, P.; Stempfhuber, S.; Felda, N.; Szeghalmi, A.V.; Kaiser, N.; Tünnermann, A.; Schwinde, S. Influence of seed layers on the reflectance of sputtered aluminum thin films. Opt. Express. 2021, 29, 19472.
10. Rincón-Llorente, G.; Heras, I; Rincón-Llorente, Elena.; Schumann, E.; Krause, M.; Escobar-Galindo, R. On the effect of thin film growth mechanisms on the specular reflectance of aluminium thin films deposited via filtered cathodic vacuum Arc. Coatings. 2018, 8, 321.
11. Kaune, G.; Metwalli, E.; Meier, R.; Körstgens, V.; Schlage, K.; Couet, S.; Röhlsberger, R.; V.Roth, S.; Müller-Buschbaum, P. Growth and morphology of sputtered aluminum thin films on P3HT surfaces. ACS Applied Material Interfaces. ACS Appl. Mater. Interfaces 2011, 3, 1055–1062.

Author Response File: Author Response.pdf

Reviewer 3 Report

The authors submitted a manuscript dealing with sputtered aluminium thin films. Even though I like this style of fully applied research, there are several major issues that prohibit manuscript acceptance.

(1) Unknown film composition: the authors provided the x-ray diffractogram where is observable single peak only (and very low intensity). If there is (a polycrystalline) film with a thickness of 100 nm (or more), the diffraction should be greatly more significant. As a result, the data supporting the film composition are not credible and reliable.

(2) optical properties: the authors suggested presence of localized surface plasmon resonance (SPR) on aluminium nanoparticles for the wavelength of about 860 nm. However, the SPR conditions for aluminium (dielectric constant equal minus two) is satisfied in the UV spectrum and not for the IR spectrum. Hence, the observed phenomenon cannot be associated with aluminium thin films.

In conclusion, the experimental results do not support the Authors' conclusions and I have no other option but to reject the submitted manusript. 

Author Response

Comments from Reviewer 3 and Reply from the authors

Recommendation: The authors submitted a manuscript dealing with sputtered aluminium thin films. Even though I like this style of fully applied research, there are several major issues that prohibit manuscript acceptance. In conclusion, the experimental results do not support the Authors' conclusions and I have no other option but to reject the submitted manuscript. 

Comments:

1) Unknown film composition: the authors provided the x-ray diffractogram where is observable single peak only (and very low intensity). If there is (a polycrystalline) film with a thickness of 100 nm (or more), the diffraction should be greatly more significant. As a result, the data supporting the film composition are not credible and reliable.

Response: We thank the reviewer for this comment about the x-ray diffractogram. Firstly, we have ensured the credibility and reliability of data. In the previous studies, Khachatryan et al deposited the Al films of different thicknesses on steel substrate and examined their phase, microstructure. Summarizing the XRD data (Figure R4), they concluded that 10 nm films on steel substrate have a mainly amorphous structure and could not be detected by XRD. When film thickness exceeded 10 nm, the crystallization process was triggered. Thus, in films with thicknesses of > 30 nm, well-developed crystallites were observed. Thus, to better observe the diffraction peak of the Al films, we have put the partially enlarged view in Figure R1, which is removed the background. Although the intensity of the diffraction peak is small, Al film is still crystalline. Meanwhile, the 38.5^o peak corresponds to (111) crystal planes of the Al films (JCPDS: 99-0005).

Figure R1. XRD pattern of the Al film at different deposition temperatures.

Figure R4 X-ray diffraction (XRD) patterns of Al film with different thicknesses deposited on steel substrates.¹

1. Khachatryan, H.; Lee, S.N.; Kim, K.B.; Kim, M. Deposition of Al Thin Film on Steel Substrate: The Role of Thickness on Crystallization and Grain Growth. Metals, 2019, 9 (12), 1-8.

2) optical properties: the authors suggested presence of localized surface plasmon resonance (SPR) on aluminium nanoparticles for the wavelength of about 860 nm. However, the SPR conditions for aluminium (dielectric constant equal minus two) is satisfied in the UV spectrum and not for the IR spectrum. Hence, the observed phenomenon cannot be associated with aluminium thin films.

Response: We thank the reviewer for the professional and constructive suggestions about the spectrum. Firstly, we have mentioned that the absorption peak at ~ 860 nm is related to the interband transition due to the free electron-like behavior of the Al in the manuscript.^1-2 Secondly, according to the simulated results, the absorption observed in 0.25-0.4 μm for the Al particles with a width of 200 nm is attributed to the localized surface plasmon resonance (Figure R4).

Mandal et al fabricate a class of plasmonic-metal-nanoparticle as a wide-angle plasmonic selective absorber, and studied the influence of the metal nanoparticle size on the reflectance spectrum.³ It’s demonstrated the high absorptance in the solar wavelengths arises from the plasmon resonances of the Cu nanoparticles. And the spectral absorbance of the metal-nanoparticles is broader than that of bulk copper, likely due to resonance-broadening arising from electron scattering at the boundaries of and defects within the polycrystalline nanoparticles. Min et al found that the arrays of subwavelength nipples generate a graded transition of refractive index, leading to minimized reflection over a broad range of wavelengths and angles of incidence.⁴ In addition, the forward Trunc ellipse cone structure is easy to achieve impedance matching and reduce reflection, and the higher the height, the more obvious the anti-reflection effect.^5-6 Therefore, the increase of the Al particle height could decrease the reflectance at 0.25-1.25 μm in this study.

But we realized that the statement may be not logically coherent thanks to your professional comments, we made some revises in the manuscript to address the comment, which is highlighted in yellow:

“3.3.1 Effect of deposition temperature on reflectance spectrum

An obvious absorption peak appears at 840 – 860 nm and is slightly red-shifted accompanied by the widened bandwidth and the strengthened intensity (Figure 5a). According to the previous reports, the absorption peak at ~ 800 nm is related to the interband transition due to the free electron-like behavior of the Al.^14,20”

“3.3.1 Effect of deposition temperature on reflectance spectrum

With the deposition temperature continually increasing, the surface particles further aggregate. Therefore, larger particles with the size of hundreds of nanometers have formed and the film roughness has enhanced, resulting in the volume for both light–matter interactions and near-field coupling between neighboring nano-particles increases, which could strengthen and broaden the absorption, respectively.^21-23 Besides, it’s easier to achieve impedance matching and reduce reflection due to the increased size of the Al particles.¹⁴ Thus, the reflectance of the Al films decreased, and the absorption increased. The solar absorption of the Al films has increased from 0.09 to 0.44 with the deposition temperature increasing (Table S2).

“3.3.3 Effect of particle size on reflectance spectrum

As shown in Figure 6b, the typical absorption peak at 867 nm is also observed due to the interband transition of the Al.

In Figure 6d, the plasmon resonance absorption is observed in 0.25-0.4 μm for the Al particles with a width of 200 nm. As reported, the forward Trunc ellipse cone structure is easy to achieve impedance matching and reduce reflection, and the higher the height, the more obvious the anti-reflection effect.²⁵ The reflectance has decreased obviously at 0.25-1.25 μm as the height increases from 30 nm to 150 nm, which is similar to the experimental results and has proved the influence of particle height on reflectance spectrum in theory.”

Figure R4. The simulated reflectance spectra of the Al films with the nano-particles: article height is from 30 nm to 150 nm, width is 200nm.

1. Ma, S.B; Liu, Q.; Qian, X.C.; Hong, R.J.; Tao, C.X. Controllability study of surface plasmon resonance spectra of aluminium nanoparticles. Acta Optica Sin. 2017, 37(9):0931001.
2. Yu, H. Controlled-Synthesis, optical properties and biological applications of aluminum nanoparticles. JiLin University, 2020:11-12.
3. Mandal, J.; Wang, D.; Overvig, A.C., Shi, N.N.;, Paley, D.; Zangiabadi, A.; Cheng, Q.; Barmak, K.; Yu, N.F.; Yang, Y. Scalable, “Dip-and-Dry” Fabrication of a Wide-Angle Plasmonic Selective Absorber for High-Efficiency Solar–Thermal Energy Conversion. Adv. Mater. 2017, 29, 1702156.
4. Min, L.W.; Jiang, B.; Jiang, P.. Bioinspired Self-Cleaning Antireflection Coatings. Adv. Mater. 2008, 20, 3914–3918.
5. Fan, P.X.; Bai, B.F.; Long, J.Y.; Jiang, D.F.; Jin, G.F.; Zhang, H.J.; Zhong, M.L.. Broadband High-Performance Infrared Antireflection Nanowires Facilely Grown on Ultrafast Laser Structured Cu Surface. Nano Lett. 2015, 15, 5988−5994.
6. Vu, T.C.; Cao, X.; Hu, H.B; A universal robust bottom-up approach to engineer Greta-oto-inspired anti-reflective structure. Cell Reports Physical Science. 2021, 2, 100479.

Author Response File: Author Response.pdf

Round 2

Reviewer 1 Report

The authors answered all the questions posed, the article can be accepted for publication.

Reviewer 2 Report

ok

Reviewer 3 Report

The authors revised the manuscript and included responses to the Reviewers'. Even though the authors responded and fixed the worst part of the manuscript, I cannot say that I am satisfied. I will have no further objections to the manuscript acceptance; however, I need to mention that the experimental results are doubtful and the manuscript has therefore very limited chance to be cited.