BaWO4:Ce Single Crystals Codoped with Na Ions
, Tomasz Bodziony 1, Hubert Fuks 1, Zbigniew Kowalski 1, Winicjusz Drozdowski 2, Marek Berkowski 3, Michal Głowacki 3, Marcin E. Witkowski 2 and Michal Makowski 2Round 1
Reviewer 1 Report
Referee report on the paper "BaWO4:Ce Single Crystals Codoped with Sodium Ions" S.M. Kaczmarek, G. Leniec, T. Bodziony, H. Fuks, Z. Kowalski, W. Drozdowski, M. Berkowski, M. Glowacki, M. Witkowski and M. Makowski
The paper describes the characterization and properties of several doped crystals of BaWO4, growned by Czochralski's method. The results are interesting.
The authors list a good number of information about the properties of these crystals, but some information is missing:
- Synthesis and processing of BaWO4 powders and/or its reference are missing.
- The information about the experimental set-up/configuration, used to perform the radioluminescence spectra and the light yield investigations, are totally missing.
- All the captions are too synthetic and sometime not enough clear.
- There are several misprints, for example, too much free space as in this case: "BaWO4: Ce" or in the lines: 68 and 69; etc.
- In several sections, more references are needed.
Some more items are detailed below (the * indicates major corrections).
line 24: "sheelite" --> scheelite
line 36*: "Good quality BaWO4 crystals can be grown by Czochralski technique and doped with rare-earth ions." I suggest to put a relative reference as, for example, the articles reported in [A].
line 57: "Obtained crystals" --> better to adding "boule": "Obtained crystal boules".
lines 57, 58*: The 60 mm in length of the crystal boules seem not compatible with the measures read from fig 1a and 1b. Can you explain why? See, also, comments about line 60.
line 59: "Co-doping of BaWO4:Ce with Na leads to some cracks of the crystal": How can you support the claim that the cracks are (surely) due to the co-doping? It might be better to replace line 59 with "BaWO4:Ce crystals co-doped with Na shows some cracks."? Would it be possible to show a picture of these cracks?
line 60*: The caption of figure 1 is not very clear.
In particular:
- the cube c come from the boule a?
- the cube d come from the boule b?
- the cube d is a codoping of BaWO4:Ce with Na?
- what is the dimension of cubes c and d?
- the bottom part of the crystal boules is not shown: why (a) and (b) don't show the entire crystal boules?
- are the markers of the ruler in the (a) and (b) in mm? In any case is necessary to write these units in the caption.
line 70*: A reference about the structure of the BaWO4 crystal would be good.
line 70: "tatrahedral" --> tetrahedral
line 73: "3-300 K" --> "(3 - 300) K". I suggest to put spaces and parentheses as shown.
line 75*: figure 2 is not referenced into the text.
line 75*: Reference [1] (see the caption of fig 2) does not seem to contain picture 2 or any information to build it, please add a reference about the structure of the BaWO4 crystal or, eventually, a reference of the fig 2.
line 77: "Oxford flow cryostat" --> this needs a reference.
line 80*: "the angular dependences of Ce3+ have been drawn" --> please add a cross-reference to the corresponding figure.
line 86: "X-ray measurements data are ..." --> "The X-ray diffraction patterns, for all the crystals investigated, are ..."
line 86*: It could be useful to report the crystal temperature (working temperature) during the x-ray diffraction measurements.
line 89-91*: It would be better to list these lattice parameters in a table.
line 100*: It would be better to report the working temperature.
line 101: I suggest to add: "The red diffractogram indicates the position and relative intensity of JCPDS card no.: 43-0646."
line 118: "liguid" --> liquid.
line 127: Please explain that the a,b,c axis labels are referred to the laboratory axes (within the caption).
line 175: If possible, it would be better to enlarge the two pictures on fig 8 to better resolve the coloured curves.
line >178*: No information about the radiation used to perform the radioluminescence measurement is reported. It is necessary to integrate paragraph 5 with such information.
line 184: It is advisable to re-bin the spectrum in fig 9 (decreasing the binnig) in order to emphasize the band structure described into the text.
line 194*: It would be interesting to report if the PL structures are (or are not) in line with the results obtained by other authors for BaWO crystals as in [reference needs].
line >196*: No information about the experimental setups and the devices used for that investigation is reported. It is necessary to integrate the paragraph number 6 with this information, for example: photosensor(s) used, setup location (underground or sea-level?), how was the crystal coupled with the photosensor(s)? digitizer used? has a guide light been used? pulse shape analysis? etc.
line 201*: In the caption of figure 10 there is no information about some technical parameters written directly into the picture boxes; for example, what does SK1804 mean? etc. Moreover, are the spectra normalized in time? have some gamma sources used to perform the spectra? if yes which one? if no, why?
line 203*: "There is not observed light yield, as compare to, e.g., ZnWO4 or ZnWO4:Ca or ZnWO4:Ca, Eu single crystals [9], so the crystals cannot be applied as scintillating materials."
To demonstrate this claim some more studies are needed. A way could be to compare different pulses spectra: spectra obtained by gamma-quanta sources vs background spectrum.
line 220*: It is not clear to which authors the sentence "Authors have concluded" referens. The authors of reference 10 or the authors of the present article?
line 222: To claim: "The luminescence is strongly temperature quenched" it would be necessary some quantitative information in addition to the simple comparison of spectra as in fig 9.
line 224*: The sentence: "It was observed that in crystals doped with Ce3+ exciton emission intensity is higher than in pure crystals." these sentence does not seem supported by specific information/investigation/reference(s) into the text. It is necessary to support such a claim.
[A] https://doi.org/10.1016/j.nima.2018.06.005,
https://www.sciencedirect.com/science/article/pii/S0022024807001996,
https://doi.org/10.1016/j.jallcom.2017.11.357 .
Author Response
Referee report on the paper "BaWO4:Ce Single Crystals Codoped with Sodium Ions" S.M. Kaczmarek, G. Leniec, T. Bodziony, H. Fuks, Z. Kowalski, W. Drozdowski, M. Berkowski, M. Glowacki, M.E. Witkowski and M. Makowski
The paper describes the characterization and properties of several doped crystals of BaWO4, growned by Czochralski's method. The results are interesting.
The authors list a good number of information about the properties of these crystals, but some information is missing:
- Synthesis and processing of BaWO4 powders and/or its reference are missing.
The powders were gained from Aldrich or Fluka
- The information about the experimental set-up/configuration, used to perform the radioluminescence spectra and the light yield investigations, are totally missing.
We have added an extra paragraph describing these setups in detail
- All the captions are too synthetic and sometime not enough clear.
They have been corrected according to your expectation
- There are several misprints, for example, too much free space as in this case: "BaWO4: Ce" or in the lines: 68 and 69; etc.
It has been corrected
- In several sections, more references are needed.
It has been corrected. Some new references were added. E.g. :
Oliveria et al., Ceramics International, 42, 10913 (2016), Apllied Surafce Science, 463, 907 (2019)
Ke et la., Naono-Micro Letters, 10:69 (2018)
Shi et al., Ceramics International, 43, 16356 (2018)
Liu et al., Crystal Growth and Design, 18, 1367 (2018)
Leniec, applied Magnetic Resonance, 1-15 (2018)
Some more items are detailed below (the * indicates major corrections).
line 24: "sheelite" --> scheelite
Corercted
line 36*: "Good quality BaWO4 crystals can be grown by Czochralski technique and doped with rare-earth ions." I suggest to put a relative reference as, for example, the articles reported in [A].
Three new references have been added as [3-5]:
J.C. Brice and P.A.C. Whiffin, Br. J. Appl. Phys., 18 (1967) 581
F.G. Yang, C.Y. Tu, H.Y. Wang, Y.P. Wei, Z.Y. You, G.H. Jia, J.F. Li, Z.J. Zhu, X.A. Lu and Y. Wang, J. Alloys Comp., 455 (208) 269
D. Errandonea, C.Y. Tu, G.H. Ha, I.R. Martin, U.R. Rodriguez-Mendoza, F. Lahoz, M.E. Torres and V. Lavin, J. Alloys Compd., 451 (2008) 212
line 57: "Obtained crystals" --> better to adding "boule": "Obtained crystal boules".
It has been corrected
lines 57, 58*: The 60 mm in length of the crystal boules seem not compatible with the measures read from fig 1a and 1b. Can you explain why? See, also, comments about line 60.
We have obtained several single crystals, among them also 60 mm in length. In Fig. 1 there are presented crystals with less length, 40 mm. So it was corrected in the text.
line 59: "Co-doping of BaWO4:Ce with Na leads to some cracks of the crystal": How can you support the claim that the cracks are (surely) due to the co-doping? It might be better to replace line 59 with "BaWO4:Ce crystals co-doped with Na shows some cracks."? Would it be possible to show a picture of these cracks?
It has been corrected according to your suggestion.
line 60*: The caption of figure 1 is not very clear.
In particular:
- the cube c come from the boule a?
- the cube d come from the boule b?
- the cube d is a codoping of BaWO4:Ce with Na?
- what is the dimension of cubes c and d?
- the bottom part of the crystal boules is not shown: why (a) and (b) don't show the entire crystal boules?
- are the markers of the ruler in the (a) and (b) in mm? In any case is necessary to write these units in the caption.
It has been explained in the corrected figure caption
line 70*: A reference about the structure of the BaWO4 crystal would be good.
It has been added:
[4] A.W. Sleight, Acta Crystallogr. B, 28 (1972) 2899
line 70: "tatrahedral" --> tetrahedral
It has been corrected
line 73: "3-300 K" --> "(3 - 300) K". I suggest to put spaces and parentheses as shown.
It has been corrected
line 75*: figure 2 is not referenced into the text.
It is not true. See line 67.
line 75*: Reference [1] (see the caption of fig 2) does not seem to contain picture 2 or any information to build it, please add a reference about the structure of the BaWO4 crystal or, eventually, a reference of the fig 2.
It has been added as [4]
line 77: "Oxford flow cryostat" --> this needs a reference.
It has been corrected “Oxford Instruments flowing liquid He cryostat”, nevertheless previously used by us description is more often met.
line 80*: "the angular dependences of Ce3+ have been drawn" --> please add a cross-reference to the corresponding figure.
(Figs 5, 7-8) has been added
line 86: "X-ray measurements data are ..." --> "The X-ray diffraction patterns, for all the crystals investigated, are ..."
It has been corrected
line 86*: It could be useful to report the crystal temperature (working temperature) during the x-ray diffraction measurements.
It has been done
line 89-91*: It would be better to list these lattice parameters in a table.
Single crystal | a [Å] | c [Å] |
BaWO4:Ce 0.5 at.% | 5.6149(1) | 12.7201(2) |
BaWO4:Ce 1 at.% | 5.6152(1) | 12.7209(3) |
BaWO4:Ce 0.5 at.%, Na 1 at.% | 5.6180(1) | 12.7141(2) |
BaWO4:Ce 1 at.%, Na 2 at.% | 5.619(1) | 12.717(2) |
Pure BaWO4 | 5.61 | 12.71 |
Table. Lattice constants of the investigated single crystals
line 100*: It would be better to report the working temperature.
It has been done.
line 101: I suggest to add: "The red diffractogram indicates the position and relative intensity of JCPDS card no.: 43-0646."
It has been done
line 118: "liguid" --> liquid.
It has been corrected
line 127: Please explain that the a,b,c axis labels are referred to the laboratory axes (within the caption).
It has been done
line 175: If possible, it would be better to enlarge the two pictures on fig 8 to better resolve the coloured curves.
The color of the lines in both figures 8a, b corresponds to each other, concerning lattice positions of cerium ions. Additional color lines in Fig. 8b show additional positions of cerium ions while sodium ions are codoped
line >178*: No information about the radiation used to perform the radioluminescence measurement is reported. It is necessary to integrate paragraph 5 with such information.
It has been corrected
line 184: It is advisable to re-bin the spectrum in fig 9 (decreasing the binnig) in order to emphasize the band structure described into the text.
It has been done
line 194*: It would be interesting to report if the PL structures are (or are not) in line with the results obtained by other authors for BaWO crystals as in [reference needs].
It has been corrected. More details in: D. Wlodarczyk, L.I. Bulyk, M. Berkowski, M. Głowacki, S.M. Kaczmarek, Z. Kowalski, A. Wittlin, Przybylinska, S. Zhydachevskii, A. Suchocki, "High pressure and low temperature studies of BaWO4:Ce, Na", J. Mat. Chem C, under review
line >196*: No information about the experimental setups and the devices used for that investigation is reported. It is necessary to integrate the paragraph number 6 with this information, for example: photosensor(s) used, setup location (underground or sea-level?), how was the crystal coupled with the photosensor(s)? digitizer used? has a guide light been used? pulse shape analysis? etc.
It has been corrected
line 201*: In the caption of figure 10 there is no information about some technical parameters written directly into the picture boxes; for example, what does SK1804 mean? etc. Moreover, are the spectra normalized in time? have some gamma sources used to perform the spectra? if yes which one? if no, why?
The figures have been corrected and exchanged
line 203*: "There is not observed light yield, as compare to, e.g., ZnWO4 or ZnWO4:Ca or ZnWO4:Ca, Eu single crystals [9], so the crystals cannot be applied as scintillating materials."
To demonstrate this claim some more studies are needed. A way could be to compare different pulses spectra: spectra obtained by gamma-quanta sources vs background spectrum.
It is discussed in actual version of this section
line 220*: It is not clear to which authors the sentence "Authors have concluded" referens. The authors of reference 10 or the authors of the present article?
The authors of reference 10 (19)
line 222: To claim: "The luminescence is strongly temperature quenched" it would be necessary some quantitative information in addition to the simple comparison of spectra as in fig 9.
This conclusion is derived from a reference 10 (19). More detail information you are interested in one can find in a paper: D. Wlodarczyk, L.I. Bulyk, M. Berkowski, M. Głowacki, S.M. Kaczmarek, Z. Kowalski, A. Wittlin, Przybylinska, S. Zhydachevskii, A. Suchocki, "High pressure and low temperature studies of BaWO4:Ce, Na", J. Mat. Chem C, under review
line 224*: The sentence: "It was observed that in crystals doped with Ce3+ exciton emission intensity is higher than in pure crystals." these sentence does not seem supported by specific information/investigation/reference(s) into the text. It is necessary to support such a claim.
This conclusion is derived from a reference 10 (19). More detail information you are interested in one can find in a paper: D. Wlodarczyk, L.I. Bulyk, M. Berkowski, M. Głowacki, S.M. Kaczmarek, Z. Kowalski, A. Wittlin, Przybylinska, S. Zhydachevskii, A. Suchocki, "High pressure and low temperature studies of BaWO4:Ce, Na", J. Mat. Chem C, under review
Reviewer 2 Report
I found the manuscript very interesting and clearly written. The methodology is well adapted to this subject.
However, my major difficulty is with the references. More recent publications on BaWO4 need to be cited along the appropriate sentences in the revised versions.
They are:
Oliveria et al., Ceramics International, 42, 10913 (2016), Apllied Surafce Science, 463, 907 (2019)
Ke et la., Naono-Micro Letters, 10:69 (2018)
Shi et al., Ceramics International, 43, 16356 (2018)
Liu et al., Crystal Growth and Design, 18, 1367 (2018)
Leniec, applied Magnetic Resonance, 1-15 (2018)
Therefore I recommend the publication with this minor revision.
Author Response
I found the manuscript very interesting and clearly written. The methodology is well adapted to this subject.
However, my major difficulty is with the references. More recent publications on BaWO4 need to be cited along the appropriate sentences in the revised versions.
They are:
Oliveria et al., Ceramics International, 42, 10913 (2016), Apllied Surafce Science, 463, 907 (2019)
Ke et la., Naono-Micro Letters, 10:69 (2018)
Shi et al., Ceramics International, 43, 16356 (2018)
Liu et al., Crystal Growth and Design, 18, 1367 (2018)
Leniec, applied Magnetic Resonance, 1-15 (2018)
All the above papers have been introduced to the Introduction of the paper. Moreover some more papers:
J.C. Brice and P.A.C. Whiffin, Br. J. Appl. Phys., 18 (1967) 581
F.G. Yang, C.Y. Tu, H.Y. Wang, Y.P. Wei, Z.Y. You, G.H. Jia, J.F. Li, Z.J. Zhu, X.A. Lu and Y. Wang, J. Alloys Comp., 455 (208) 269
D, Errandonea, C.Y. Tu, G.H. Ha, I.R. Martin, U.R. Rodriguez-Mendoza, F. Lahoz, M.E. Torres and V. Lavin, J. Alloys Compd., 451 (2008) 212
A.W. Sleight, Acta Crystallogr. B, 28 (1972) 2899
Author Response File: 
Author Response.pdf
Round 2
Reviewer 1 Report
The concerns raised about this work do not seem to have been addressed to a satisfactory level and in fact, despite the modifications introduced, several parts of the manuscript continue to be very unclear or superficial.
All the captions (for example, the caption of figs 1, 8, 9) are still too concise and often not clear.
The question as to whether the PL structures are (or are not) in line with
the results obtained by other authors for BaWO crystals has been not
discussed. Paragraph 6 is not very informative.
Relevant references about related work are still missing.
Unfortunately, the paper is not ready to be published.
