Comments and Suggestions for Authors

This paper describes a broad spectral photodetector by using organic bisindolo

quinoxaline on ZnO Nanorods. I think it can be accepted by Chemosensors after
major revision.

Q1.I can't see any new ideas in the introduction, the author should emphasize the
advantage of BIQ over BIQ-TPs.

Ans: Thanks to the reviewer for the construction.

As for two previous published papers related to BIQ-TIPs, we found the thermal
instability of BIQ-TIPs/ZnO NRs during the gas sensing measurements due to the
degradation of BIQ-TIPs. In this paper, in contrast to the thermal instability of BIQ-
TIPs, BIQ has better sensing performance because there is no risk of TIP bonds
breaking. Without the TIPs moieties, the organic compound can have better stability
and performance. Originally, we expected BIQ-TIPs can have better π-π stacking
effects but the structure is too bulky and can not form π-π stacking. Deviated from our
plan, BIQ-TIPs samples behave worse than BIQ. The distorted sensing measurements
of BIQ-TIPs are shown below. The novelty of this research has been added in the
revised manuscript.

Q2. The processing of the SEM images is too rough, I can 't even see the scale bar of
the picture.

Ans: The SEM images in Figure 2 have been processed accordingly. The scale bars
have been added in the images.
 Fig. 2. (a) The top-view SEM image of BIQ on a SiO 2/Si substrate. (b) The top-view and (c)
the cross-sectional SEM image of BIQ/ZnO NRs. (d) The magnified top-view SEM image of
(c). (e) Schematical illustration of BIQ/ZnO NRs.

Q3. The photodetection test is not sufficient. More performance parameters need to be
tested, calculated, and displayed!!!!

Ans: More parameters of our experiment have been added into the experimental
section.
Comments and Suggestions for Authors

This article proposed a hybrid structure to achieve a broad spectral photodetector

with bisindolo quinoxaline (BIQ) and ZnO nanorods. Although many
characterizations were used to reveal the morphology and material properties of the
prepared BIQ/ZnO NRs, the photodetection performance was not fully examined, and
the superiority of BIQ/ZnO NRs (relative to the BIQ-TIPs/ZnO NRs composite and
pure ZnO nanorods) in the broad spectral photodetection was also not demonstrated.
Besides, the absolutely detection performances seem to be very poor. So, I do not
deem this manuscript is deserved publication.  

The following detailed issues are suggested to improve this work.

1. The authors mentioned that presumably due to the high surface energy of ZnO
NRs compared with SiO2, the BIQ/ZnO NRs exhibit less BIQ domains covered
on the ZnO NRs. Will it influence the photodetection performance of BIQ/ZnO
NRs?

Ans: We thank the comments from the reviewer. In this work, we mainly integrate
BIQ with ZnO-NRs photodetectors to enhance their photosensing capability. We don’t
focus on the BIQ/SiO2 heterojunction. The deposition of BIQ on planar SiO 2 substrate
can help us realize the difference between the deposition of BIQ on the planar SiO 2
substrate and that on the ZnO nanostructured substrate. Although the surface
morphology of BIQ on ZnO NRs is totally different to that on SiO 2, the high surface
energy of ZnO NRs could facilitate the formation of regular BIQ domain on the top of
ZnO NRs. The BIQ molecules could be well-arranged in the regular domain, which
can absorb the visible light, undergo a charge transfer from BIQ to ZnO NRs, and
extend the photosensing wavelength range of ZnO-NRs photodetector to the visible
light.

2. The two subfigures in Figure 3 can be merged into one figure. What is the point
by comparation of XRD patterns of BIQ/SiO2 and BIQ/ZnO NRs?

Ans: We have integrated two subfigures in Fig. 3 into one figure. The revised Fig. 3 is
shown below. Since the coverage of BIQ on SiO 2 substrate is higher than that of BIQ
on ZnO NRs, a high amount of BIQ on the SiO 2 substrate allows us to obtain the
characteristic peak of BIQ.
 Fig. 3. The XRD profile of BIQ deposited on (a) the SiO2 substrate and (b) the ZnO NRs.

3.      TEM images of BIQ/ZnO NRs are shown in Fig. 4(a) to further explore the
nanostructures of BIQ/ZnO NRs. But the enlarge marks are confused and not neat.
What is the structure of the highlighted part? A clearer legend should be involved in
Fig. 4(a).

Ans: The TEM images in Fig. 4(a) have been revised accordingly. The revised Fig.
4(a) is shown below, and we identify the position of ZnO NRs and organic BIQ
domain in the magnified TEM image (right subfigure of Fig. 4(a)).
 Fig. 4. (a) The TEM images of BIQ/ZnO NRs. (b) The TEM image with Si, Zn, O, and C
element mapping.

4.      Fig. 5(f) illustrates that BIQ/ZnO NRs extend the absorption compared with
ZnO NRs. It will be more convincing if a PL emission profile of ZnO NRs is added
for contrast.

Ans: The PL emission profile of ZnO NRs is measured in our previous work. We cite
the corresponding literature as a reference in the revised manuscript. The near-band-
edge PL emission of ZnO is around 375 nm and the defect PL emission is around 550
nm.
5.      In the Introduction part, the advantages and shortages of BIQ-TIPs/ZnO NRs
were expressed in detail, but in the Results and Discussions part, only the
comparation among of the BIQ/ZnO NRs, BIQ/SiO2, and ZnO NRs was conducted.

Ans: The advantages of the sample including TIPS can have better solubility but
thermal stability will become worse and the structure becomes too bulky. The
sturcutre can not form π-π stacking..

6.      The sensitivity of the detectors should be calculated, and the light intensity of
the used LEDs should also be indicated.

Ans: We have calculated the sensitivity of BIQ/ZnO NRs based photodetectors with
different drop of BIQ solution under UV light illumination. The corresponding
sensitivity is added in the following figure.
7.      The absorption spectra with a UV-vis-IR spectrometer are suggested to be
obtained.

Ans:

8.      In Figure 2-6, how many of drops of BIQ should be indicated as that in Figure 7.

Ans: In the material analysis shown in Fig. 2-6, one drop of BIQ is deposited on the
ZnO NRs. We have added description about the amount of BIQ in the revised
manuscript.

Comments and Suggestions for Authors

1. Line 17 There are some format errors, ‘abstract-’

Ans: Thank the comment from the reviewer. We have revised the format error.

2. Line42-43, ‘there are 4 TIPs moieties connected to BIQ.’ Maybe the author can
mark in the schematic diagram (like fig2(d)) of this chemical formula to give a
good understanding.

Ans: We have revised Fig. 1 as follows. In the revised figure, we highlight the TIPs
moieties that bond with BIQ via C≡C.
3. fig.1 Whether two chemical molecular characteristics need to be described more
clearly so that reader can figure out their difference.

Ans: In the revised Fig.1 below, the TIPs moieties bonding with BIQ via C≡C can be
bread under heating.

4. Line 63-69 It would be better if there was a detailed figure for the preparation
process.

Ans: Illustration for the preparation process is shown below.

5. Line 75 The format needs to be modified.

Ans: We have revised the format accordingly.

6. Line 89-90 about high surface energy of ZnO NRs, more references and
discussion are needed.

Ans: The deposition of BIQ on planar SiO 2 substrate exhibits higher surface coverage
than that on ZnO NRs. This is ascribed to low wettability of ZnO NRs due to their
high surface energy of ZnO NRs. Reference 15 has been added.

7. Line121-122 ‘These dark areas may be related to the organic materials due to their
low conductivity’, more references and discussion are needed.

Ans: We have modified the sentence to prevent the readers misleading. The following
sentences are revised in the manuscript.
“TEM image in Fig.4(a) reveals a rod-shaped ZnO NR that was overlapped with high-
contrast areas. These high-contrast areas may be related to the organic materials due to
their low density.”

8. Line 119-126 The author should further explain about the chart. the charts and
information are too much so that the author should precisely select useful chart. At
the same time, the scale and name in the chart are too small.

Ans: The TEM images in Fig. 4(a) have been revised accordingly. The revised Fig.
4(a) is shown below, and we identify the position of ZnO NRs and organic BIQ
domain in the magnified TEM image (right subfigure of Fig. 4(a)).
 Fig. 4. (a) The TEM images of BIQ/ZnO NRs. (b) The TEM image with Si, Zn, O, and C
element mapping.

9. Fig 5 the author needs to redesign the order of the pictures.

Ans: We have redesigned the order of subfigures in Fig. 5 as seen below.

 Fig. 5. The CLSM images of (a) BIQ/SiO2 and (b) BIQ/ZnO NRs samples. The PL
receiving wavelength range is from 510 to 810 nm. The subfigure in (a) and (b) are
the CLSM image by receiving the PL wavelength range from 350 to 510 nm. The PL
image of BIQ/ZnO NRs sample at different position of (c) P1, (d) P2, and (e) P3. (f)
The corresponding PL emission spectrum at P1-P3.

10. Fig 5(c)(d)(e) The three graphs can be combined with the f graph. The 123
marked in the graph (f) is not clear, it should indicate which PL curve is obtained
from the different location.

Ans: We have revised Fig. 5(c)-5(f) to correlate the PL image at difference location
with the corresponding PL emission profile.
 Fig. 5. The CLSM images of (a) BIQ/SiO2 and (b) BIQ/ZnO NRs samples. The PL
receiving wavelength range is from 510 to 810 nm. The subfigure in (a) and (b) are
the CLSM image by receiving the PL wavelength range from 350 to 510 nm. The PL
image of BIQ/ZnO NRs sample at different position of (c) P1, (d) P2, and (e) P3. (f)
The corresponding PL emission spectrum at P1-P3.

11. Line 139-141 the sentences are need to modified more concisely.

Ans: We have modified the sentences as follow.

“Figure 5(c)-5(e) shows the PL image of BIQ/ZnO NRs probed at different position,
and the corresponding PL emission profile is revealed in Fig. 5(f). The results indicate
that the main emission wavelength of BIQ/ZnO NRs is within 450-800 nm with a PL
emission peak at around 600 nm. The PL emission peak of ZnO NRs defect state is at
around 550 nm. The shifted PL emission peak of BIQ/ZnO NRs also suggest the
charge transfer from ZnO NRs to BIQ.”
12. Fig7 The title in the chart should be marked in detail, the author should indicate
clearly about the meaning of 1,3,5 in the figure.

Fig. 7. The photoresponse of ZnO-NRs photodetector with various drops (0, 1, 3, and 5 drops)
of BIQ solution under (a) UV, (b) white, (c) green, and (d) red light illumination.

Comments and Suggestions for Authors

The manuscript describes a photodetector using ZnO nanorods covered with bisindolo
quinoxaline. The morphology of photodetector is studied well, but there needs more
investigation about current-voltage characteristics. I think it is acceptable for
publication with major revisions. 

 1. It is more informative to readers by providing essential photodetector

characteristics such as current-voltage characteristics of the photodetector with and
without illumination, spectral response, and so on.

 Ans:

2. The caption of Figure 5(f) is missing. 

Ans: The figure caption of Fig. 5(f) has been added.  

 Fig. 5. The CLSM images of (a) BIQ/SiO2 and (b) BIQ/ZnO NRs samples. The PL
receiving wavelength range is from 510 to 810 nm. The subfigure in (a) and (b) are
the CLSM image by receiving the PL wavelength range from 350 to 510 nm. The PL
image of BIQ/ZnO NRs sample at different position of (c) P1, (d) P2, and (e) P3. (f)
The corresponding PL emission spectrum at P1-P3.

3. The experimental details need to be supplemented. A detailed device fabrication

condition, such as solution concentration, spin coating RPM, etc., and measurement
instrument information, such as model and fabrication company, need to be provided. 

 Ans:

4. The SEM and TEM image in Figure 2, 4, and 6 has unclear scale bar. 

 Ans: Scale bar in Fig. 2, and 4 has been added.

5. The optimized device performance had three drops of BIQ solution. However, to
correlate the device results, it needs to be clarified what the specific fabrication
condition is for the morphology analysis.

Ans: To characterize the presence and clearly view the regular BIQ domain, we chose
the sample of ZnO NRs with one drop of BIQ for the morphology analysis.