Robust flow synthesis of defect-incorporated ZnO quantum dots and investigation of

their structure-property interlink

Sayoni Sarkar1, Rohit Srivastava2, and Ajit R. Kulkarni3*
1
Centre for Research in Nanotechnology and Science, 2Department of Biosciences and Bioengineering, 3Department of
Metallurgical Engineering and Materials Science, Indian Institute of Technology Bombay, Mumbai, 400076, India
*Corresponding author: ajit.kulkarni@iitb.ac.in

Introduction:
In recent years, colloidal zinc oxide quantum dots (ZnO QDs) with dominant defect chemistry have befitting
utility in the emerging areas of agriculture, energy, and health care. The novel characteristics of ZnO QDs are
primarily accredited to the singly ionized oxygen vacancies (V O•) that render them unique size-controlled
optical, physiochemical, and biological properties. These intriguing features of ZnO QDs are accomplished
through the fabrication methods and process variables adopted. However, recent studies involving conventional
batch synthesis of nanomaterials have revealed flawed process control, the discrepancy in scale-up, poor
reproducibility and yield, leading to unnecessary energy consumption and material wastage. To combat these
challenges, rapidly evolving quantum dots production technologies that tend toward sustainable development
have ushered in newer strategies which, in the long run, will be beneficial to meet the increased demand for
high-quality ZnO QDs [1] [2]. Thus, in this study, the structure-property interlink has been explored for
defective ZnO QDs synthesized by a sustainable continuous flow synthesis platform by certain sophisticated
characterization and analytical techniques, including high-angle annular dark field scanning transmission
electron microscopy (HAADF-STEM), Fourier transform infrared (FTIR), electron paramagnetic resonance
(EPR), and UV-visible spectroscopy. This will promulgate the idea of enhanced functionality of the QDs
induced by the confluence of “green chemistry” and flow synthesis, which has the potency to accelerate
application based-pristine-quantum dots development.

Experimental section:
Zinc acetate ((Zn(CH3COO)2) and lithium hydroxide (LiOH) were procured from Sigma Aldrich (USA). The as-
purchased precursors were dissolved in absolute ethanol (99.99%). Synthesis of defect-enriched colloidal ZnO
quantum dots (Zd-QDs) was performed in the constructed continuous flow platform. This in-house platform
consists of a stainless-steel helically coiled reactor positioned inside a water bath held at 75°C and a T-mixer to
aid fast mixing and efficient heat transfer essential for accelerated nucleation-growth kinetics that eventually
leads to monodispersed QDs. Ethanolic solutions of the raw precursors were fed by the peristaltic pumps into
the mixing junction via the two separate inlets of the T-mixer. The pumps were calibrated to assure a constant
flowrate of 2.4 ml/min. The strategies for process intensification also involved heating the Zn(CH 3COO)2
solution (0.1M) to 75°C and maintaining this temperature throughout the synthesis by placing the round bottom
flask containing the solution in a heating mantle. However, the LiOH solution (0.1 M) in the beaker was held at
room temperature. These ambient synthesis conditions were aimed to enhance the defect-mediated luminescent
properties of Zd-QDs as well as other properties of nanosystems that rely on homogenous particle sizes. The
competency of this designed sustainable flow assembly was validated by HAADF-STEM, HR-TEM, FTIR,
EPR and UV-visible spectroscopy for transmittance studies. The HAADF-STEM and HR-TEM images were
captured by the Tecnai G2, F30 transmission electron microscope (acceleration voltage of 300 kV). FTIR, UV-
visible, and EPR spectroscopic measurements were done in JASCO FT/IR-600, Carry 100 UV-Vis, and JES -
FA200, JEOL, Japan, respectively.

Results and discussion:

The uniform particle size distribution and crystalline nature of quasi-spheroid-shaped Zd-QDs were analysed
systematically by HAADF-STEM and HR-TEM. Fig. 1a demonstrates the HAADF-STEM image of
homogenous sized Zd-QDs revealing an average size of 5 nm determined from the narrow particle size
histogram, denoting enhanced structural attributes. Coupled with this imaging technique, HR-TEM was
performed to investigate the phase-purity and the internal features of nanostructured Z d-QDs. It is apparent from
the corresponding image (shown in the inset of Fig. 1a) that the estimated lattice fringe spacing of 2.6 Å can be
well correlated to the (101) plane of the wurtzite structure of ZnO. Further, the HR-TEM image corroborated
that the “green” continuous flow approach could precisely synthesize phase-pure Z d-QDs on a large-scale.
Besides, to gain an in-depth understanding of the surface functionality of Z d-QDs, FTIR spectroscopy was
employed to identify the active functional groups with respect to the peak value in the IR region, as shown in
Fig. 1b. The results elucidate the presence of a number of absorption peaks from 1000-4000 cm- 1. The
symmetric and asymmetric stretches of ʋC=O (carbonyl group) at 1588 and 1421 cm −1 identified the acetate
groups attached to the surface of the Z d-QDs. The peak in the range of 3000- 3700 cm −1 and 1012 cm−1 is
typically due to ʋO-H stretching and bending modes of hydroxyl groups. FTIR spectra suggest that these
functional groups are present only at the surface of Z d-QDs. The absorption peaks due to the interatomic
vibrations of Zd-QDs are usually present below 1000 cm−1 (fingerprint region). The Zn-O vibrational modes
were identified in the near-infrared (NIR) region at 665 cm −1, designated to the polar stretching and deformation
present in the sample, which is evident from Fig. 1b.

The presence of rich intrinsic VO• density in Zd-QDs was investigated by EPR spectroscopy (Fig. 1c). EPR is a
powerful non-destructive analytical method for determining the defects that serve as the origin for
photoluminescence characteristics in ZnO nanoparticles. Thus, the room temperature measurements recorded
the EPR signal related to VO• at approximately g~2.003 in the as-synthesized Z d-QDs [3]. This observation
evinced that the reactor’s micro-environment heavily supported the promotion of an increased density of surface
VO• in Zd-QDs. Hence, these VO•- rich Zd-QDs have a flair for attracting immense attention in biomedicine,
optoelectronics, photonics, and beyond. The UV-visible transmittance spectrum of colloidal Z d-QDs was
measured within the spectral range (300-700 nm) as depicted in Fig. 1d. that substantiates an intriguing aspect of
the optical properties of the synthesized samples. It was discernible from the recorded spectrum that Z d-QDs
exhibited an optical transmittance of ~ 98.2% in the visible regime 450-700 nm. Further, a distinct increase in
the transmittance from 98.2% to almost 100% was observed within the region of 459-365 nm. These UV-visible
transmittance studies suggest that Zd-QDs can be a desirable candidate as a transparent active ingredient for
healthcare (mainly cosmetics) and in flexible sensor applications.

In summary, the defective ZnO QDs synthesized by the in-house fabricated continuous flow platform exhibited
superior structural and optical features driven by the anomalous surface chemistry. The designed synthesis
protocol is sustainable and easily scalable with convenient downstream processes. Thus, this continuous flow
assembly can be extrapolated to facilitate the production of colloidal quantum dot systems that harmoniously
adapts to the “green chemistry” ideologies and successfully tailor the processing conditions for pilot-scale
synthesis. The fabricated Zd-QDs additionally display remarkable transmittance that fuels the potency of these
QDs for ubiquitous widespread application in the age of “Industry 4.0”.

Fig 1. a) HAADF-STEM images of as-synthesized Zd-QDs, with bottom inset showing the particle size distribution
histogram and the top inset displaying the lattice fringe spacing estimated from HR-TEM image. b) FTIR spectra of Zd-QDs
indicating the presence of surface functional groups. c) EPR spectra of Zd-QDs, the inset depicts the as-fabricated colloidal
QDs under UV-irradiation. d) UV-vis transmittance spectra of Zd-QDs and the absorption spectra shown at the inset.

Acknowledgement:
The authors are thankful to CRNTS, SAIF and the Department of MEMS, IIT Bombay, for the central
instrumentation support. SS thanks Mr. Nilesh Marle, technical superintendent, CRNTS, IIT Bombay, for his
assistance in EPR studies. SS is grateful for the funding support from the Prime Minister’s Research Fellowship
scheme (PMRF), the Ministry of Higher Education, Government of India to conduct the detailed measurements.

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