Sulfur-free synthesis of size tunable rickardite (Cu3−xTe2) spheroids and planar squares

We report a novel synthesis of monodisperse samples of copper telluride with crystallinity and stoichiometry corresponding to forms of rickardite, Cu3−xTe2 (x < 1). This synthesis makes use of a ligand balanced reaction to allow control over shape and size by varying the relative and absolute concentration of oleylamine to stearic acid. The rickardite samples presented here display size dependent plasmon peaks in the near infrared and direct energy band gaps between 1.7 and 2.3 eV. As such they may find utility in photovoltaic, thermoelectric or as novel optical materials for study of surface plasmons.


Recommendation? Accept with minor revision (please list in comments)
Comments to the Author(s) Semiconductor nanocrystal (NC) plays important roles in solar cells. In this paper, the authors synthesized monodisperse copper telluride and changed the ratio of oleylamine to stearic acid to study the morphology of final products. Various characterizations were executed to study the structure and composition, and the results could be interest in the readers of Royal Society Open Science. The manuscript can be accepted after a minor revision. Below are my comments: 1. The specific graph order (like a, b…) should be provided in every Figure, to make reading convenient for the readers. 2. In Page 2, Line 48, "The stoichiometric ratio of the particles in this sample was observed to be Cu2.26Te2 by EDX measurements", the corresponding EDX pattern needs to be offered.

Review form: Reviewer 2
Is the manuscript scientifically sound in its present form? No

Do you have any ethical concerns with this paper? No
Have you any concerns about statistical analyses in this paper? No

Recommendation? Reject
Comments to the Author(s) Dear editor, The manuscript "Sulfur-Free Synthesis of Size Tunable Rickardite (Cu3-xTe2) Spheroids and Planar Squares" has reported a method to synthesize Cu3-xTe2 nanoparticles in shapes of Spheroids and Planar Squares. It is claimed tuning the amount of oleylamine as the coordinating ligand is the key to tune the nanoparticle shapes from spheroids to planar squares. The pros of this work is that the TEM images have proved such evaluation process, however, the presented method cannot considered as novel method, since it is slightly different than the methods from previous literature (Inorg. Chem. 2018, 57, 10241−10248; Nature Comm. volume 8, Article number: 14925 (2017)) and show not much improvement. And the resulted nanoparticles are hardly considered as monodispersed especially for the ones in shape of planar squares (in Figure  4). Adding oleylamine seems to be able to cause the shape evolution, however, loss control of nanoparticle monidispersity and uniformity. Further study to find a better coordinating ligand is recommended. The editor assigned to your manuscript has now received comments from reviewers. We would like you to revise your paper in accordance with the referee and Subject Editor suggestions which can be found below (not including confidential reports to the Editor). Please note this decision does not guarantee eventual acceptance.
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Reviewer: 2
Comments to the Author(s) Dear editor, The manuscript "Sulfur-Free Synthesis of Size Tunable Rickardite (Cu3-xTe2) Spheroids and Planar Squares" has reported a method to synthesize Cu3-xTe2 nanoparticles in shapes of Spheroids and Planar Squares. It is claimed tuning the amount of oleylamine as the coordinating ligand is the key to tune the nanoparticle shapes from spheroids to planar squares. The pros of this work is that the TEM images have proved such evaluation process, however, the presented method cannot considered as novel method, since it is slightly different than the methods from previous literature (Inorg. Chem. 2018, 57, 10241−10248;Nature Comm. volume 8, Article number: 14925 (2017)) and show not much improvement. And the resulted nanoparticles are hardly considered as monodispersed especially for the ones in shape of planar squares (in Figure  4). Adding oleylamine seems to be able to cause the shape evolution, however, loss control of nanoparticle monidispersity and uniformity. Further study to find a better coordinating ligand is recommended.

Response to Referees
Thank you very much for your professional comments. All advices are very important to our studies. These suggestions have great guiding significance for our academic writing and scientific research. We have modified the manuscript accordingly, and the detailed corrections are listed below point by point for the reviewers' comments as following:

Reviewer: 1
Semiconductor nanocrystal (NC) plays important roles in solar cells. In this paper, the authors synthesized monodisperse copper telluride and changed the ratio of oleylamine to stearic acid to study the morphology of final products.
Various characterizations were executed to study the structure and composition, and the results could be interest in the readers of Royal Society Open Science.
The manuscript can be accepted after a minor revision. Below are my comments: 1. The specific graph order (like a, b…) should be provided in every Figure, to make reading convenient for the readers.

Response:
The graph order has been provided and revised in every Figure in the manuscript.
2. In Page 2, Line 48, "The stoichiometric ratio of the particles in this sample was observed to be Cu 2.26 Te 2 by EDX measurements", the corresponding EDX pattern needs to be offered.

Response:
The stoichiometric ratio of the particles in this sample is added and demonstrated in Table 1.  (2017)) and show not much improvement. And the resulted nanoparticles are hardly considered as monodispersed especially for the ones in shape of planar squares (in Figure 4). Adding oleylamine seems to be able to cause the shape evolution, however, loss control of nanoparticle monidispersity and uniformity. Further study to find a better coordinating ligand is recommended.