Summary

AI TPBiLiF

8.5 Summary

Over the past decade, CQDs have attracted worldwide interest. CQDs have optoelectronic applications owing to desirable electronic and optical properties,

(A) (B)

(C) (D)

5 kW/cm² 80 kW/cm² 195 kW/cm² 210 kW/cm² 258 kW/cm² 320 kW/cm²

Front mirror (reflactance 95%)

Back mirror (reflactance 99%)

Focused pumping laser

Output laser

Detector 450 500 550 600 650 700 750

Wavelength / nm

Normalized Intensity

Figure 8.17 (A) Normalized green lasing emission of CQDs ethanol aqueous solution under various optically pumped pulse densities. (B) The corresponding schematic of optical pumping and output of the CQDs-based laser. The green lasing emission from CQDs-based laser pumped by 355 nm laser at (C) 30 kW/cm²and (D) 190 kW/cm².

Source: Reproduced with permission from S. Qu, et al., Amplified spontaneous green emission and lasing emission from carbon nanoparticles.Advanced Functional Materials, 24 (18) (2014) 2689 2695.

cost-effectiveness, and biocompatibility. The wavelength-tunable fluorescence across the entire visible spectrum makes CQDs promising materials for a wide range of optoelectronic devices. Especially, full-color fluorescent CQDs have been demonstrated as excellent materials to develop multicolor LEDs that are valuable for lighting technology. Thus, it is of great scientific effort to study the optical properties of the CQDs for various device applications. This chapter presents a review of the recent research achievements in synthesis and optical properties of CQDs, focusing on stable full-color fluorescence emissions arising from the quan- tum confinement and surface functionalization effects. First, the conventional top- down and bottom-up approaches are commonly applied to synthesize CQDs. These methods consist of electrochemical synthesis, arc discharge, pulsed laser ablation/

passivation, microwave-assisted synthesis, and hydrothermal and solvothermal pro- cesses that have been presented in the chapter. Then, the optical properties of CQDs were studied and discussed. The CQDs device applications as recent achieve- ments in using the CQDs in LEDs and lasers have been evaluated. We hope that the present chapter will stimulate interest for further investigations on carbon nanoparticles-based LEDs.

References

[1] J. Liu, R. Li, B. Yang, Carbon dots: a new type of carbon-based nanomaterial with wide applications, ACS Central Science 6 (12) (2020) 2179 2195.

[2] P. He, et al., Recent advances in white light-emitting diodes of carbon quantum dots, Nanoscale 12 (8) (2020) 4826 4832.

[3] L. Wang, et al., Full-color fluorescent carbon quantum dots, Science Advances 6 (40) (2020) eabb6772.

[4] M.J. Molaei, The optical properties and solar energy conversion applications of carbon quantum dots: a review, Solar Energy 196 (2020) 549 566.

[5] L. Tian, et al., Carbon quantum dots for advanced electrocatalysis, Journal of Energy Chemistry 55 (1) (2020) 279 294.

[6] A. Nair, et al., Natural carbon-based quantum dots and their applications in drug deliv- ery: a review, Biomedicine & Pharmacotherapy 132 (2020) 110834.

[7] P. Das, et al., Acoustic cavitation assisted synthesis and characterization of photolumi- nescent carbon quantum dots for biological applications and their future prospective, Nano-Structures & Nano-Objects 25 (2021) 100641.

[8] T. Yuan, et al., Carbon quantum dots: an emerging material for optoelectronic applica- tions, Journal of Materials Chemistry C 7 (23) (2019) 6820 6835.

[9] K.J. Mintz, Y. Zhou, R.M. Leblanc, Recent development of carbon quantum dots regarding their optical properties, photoluminescence mechanism, and core structure, Nanoscale 11 (11) (2019) 4634 4652.

[10] H. Luo, et al., Manipulating the optical properties of carbon dots by fine-tuning their structural features, ChemSusChem 12 (19) (2019) 4432 4441.

[11] L. Tian, et al., The influence of inorganic electrolyte on the properties of carbon quan- tum dots in electrochemical exfoliation, Journal of Electroanalytical Chemistry 878 (2020) 114673.

[12] M. Liu, et al., Carbon quantum dots directly generated from electrochemical oxidation of graphite electrodes in alkaline alcohols and the applications for specific ferric ion detection and cell imaging, Analyst 141 (9) (2016) 2657 2664.

[13] X. Li, Z. Zhao, Facile ionic-liquid-assisted electrochemical synthesis of size-controlled carbon quantum dots by tuning applied voltages, RSC Advances 4 (101) (2014) 57615 57619.

[14] J. Deng, et al., Electrochemical synthesis of carbon nanodots directly from alcohols, Chemistry A European Journal 20 (17) (2014) 4993 4999.

[15] F. Chao-Mujica, et al., Carbon quantum dots by submerged arc discharge in water: syn- thesis, characterization, and mechanism of formation, Journal of Applied Physics 129 (16) (2021) 163301.

[16] A. Nevar, et al., Carbon nanodots with tunable luminescence properties synthesized by electrical discharge in octane, Carbon Letters 31 (1) (2021) 39 46.

[17] I.F. Andhika, S. Hastuti, T.E. Saraswati, The surface characteristics of carbon nanopar- ticles produced via submerged arc discharge in ethanol/water, AIP Conference Proceedings 2296 (1) (2020) 020069.

[18] D. Reyes, et al., Laser ablated carbon nanodots for light emission, Nanoscale Research Letters 11 (1) (2016) 1 11.

[19] L. Cui, et al., Synthesis of homogeneous carbon quantum dots by ultrafast dual-beam pulsed laser ablation for bioimaging, Materials Today Nano 12 (2020) 100091.

[20] V. Nguyen, et al., Double-pulse femtosecond laser ablation for synthesis of ultrasmall carbon nanodots, Materials Research Express 7 (1) (2020) 015606.

[21] C. Don˜ate-Buendia, et al., Fabrication by laser irradiation in a continuous flow jet of carbon quantum dots for fluorescence imaging, ACS Omega 3 (3) (2018) 2735 2742.

[22] X. Li, et al., Preparation of carbon quantum dots with tunable photoluminescence by rapid laser passivation in ordinary organic solvents, Chemical Communications 47 (3) (2010) 932 934.

[23] G. Jeong, et al., Microwave-assisted synthesis of multifunctional fluorescent carbon quantum dots from A4/B2 polyamidation monomer sets, Applied Surface Science 542 (2021) 148471.

[24] A. Dager, et al., Ultrafast synthesis of carbon quantum dots from fenugreek seeds using microwave plasma enhanced decomposition: application of C-QDs to grow fluorescent protein crystals, Scientific Reports 10 (1) (2020) 1 15.

[25] K.M. Omer, et al., Photoluminescence enhancement via microwave irradiation of car- bon quantum dots derived from solvothermal synthesis of L-arginine, New Journal of Chemistry 43 (2) (2019) 689 695.

[26] T. Yu, et al., A rapid microwave synthesis of green-emissive carbon dots with solid- state fluorescence and pH-sensitive properties, Royal Society Open Science 5 (7) (2018) 180245.

[27] H. Behboudi, et al., Carbon quantum dots in nanobiotechnology, Nanomaterials for advanced biological applications, Springer, 2019, pp. 145 179.

[28] J. Wang, et al., Large-scale green synthesis of fluorescent carbon nanodots and their use in optics applications, Advanced Optical Materials 3 (1) (2015) 103 111.

[29] N. Papaioannou, M.-M. Titirici, A. Sapelkin, Investigating the effect of reaction time on carbon dot formation, structure, and optical properties, ACS Omega 4 (26) (2019) 21658 21665.

[30] Z. Han, et al., Hydrothermal synthesis of carbon dots and their application for detection of chlorogenic acid, Luminescence: The Journal of Biological and Chemical Luminescence 35 (7) (2020) 989 997.

[31] Y. Xie, et al., One-step hydrothermal synthesis of fluorescence carbon quantum dots with high product yield and quantum yield, Nanotechnology 30 (8) (2019) 085406.

[32] Y. Yang, et al., Dual-emission ratiometric fluorescent detection of dinotefuran based on sulfur-doped carbon quantum dots and copper nanocluster hybrid, Sensors and Actuators B: Chemical 321 (2020) 128534.

[33] L. Li, T. Dong, Photoluminescence tuning in carbon dots: surface passivation or/and functionalization, heteroatom doping, Journal of Materials Chemistry C 6 (30) (2018) 7944 7970.

[34] Y. Wang, Y. Li, L. Feng, Exploring solvent-related reactions and corresponding band gap tuning strategies for carbon nanodots based on solvothermal synthesis, The Journal of Physical Chemistry Letters 11 (2020) 10439 10445.

[35] H. Ding, et al., Solvent-controlled synthesis of highly luminescent carbon dots with a wide color gamut and narrowed emission peak widths, Small (Weinheim an der Bergstrasse, Germany) 14 (22) (2018) 1800612.

[36] M. Shao, et al., Continuous synthesis of carbon dots with full spectrum fluorescence and the mechanism of their multiple color emission, Lab on a Chip 19 (23) (2019) 3974 3978.

[37] K. Jiang, et al., Preparation of multicolor photoluminescent carbon dots by tuning sur- face states, Nanomaterials (Basel, Switzerland) 9 (4) (2019) 529.

[38] X. Xu, et al., Red, orange, yellow and green luminescence by carbon dots: hydrogen- bond-induced solvation effects, Nanoscale 13 (14) (2021) 6846 6855.

[39] S.Y. Lim, W. Shen, Z. Gao, Carbon quantum dots and their applications, Chemical Society Reviews 44 (1) (2015) 362 381.

[40] P. Zhu, et al., Origins of efficient multiemission luminescence in carbon dots, Chemistry of Materials 31 (13) (2019) 4732 4742.

[41] L. Ai, et al., Insights into photoluminescence mechanisms of carbon dots: advances and perspectives, Science Bulletin 66 (8) (2021) 839 856.

[42] H. Ding, et al., Surface states of carbon dots and their influences on luminescence, Journal of Applied Physics 127 (23) (2020) 231101.

[43] W. Liang, et al., Evaluation of commercial “carbon quantum dots” sample on origins of red absorption and emission features, C 5 (4) (2019) 70.

[44] L. Bao, et al., Photoluminescence-tunable carbon nanodots: surface-state energy-gap tuning, Advanced Materials 27 (10) (2015) 1663 1667.

[45] H. Ding, et al., Full-color light-emitting carbon dots with a surface-state-controlled luminescence mechanism, ACS Nano 10 (1) (2016) 484 491.

[46] B. Zhi, et al., Synthesis, applications and potential photoluminescence mechanism of spectrally tunable carbon dots, Nanoscale 11 (43) (2019) 20411 20428.

[47] M.S. Ghamsari, et al., Wavelength-tunable visible to near-infrared photoluminescence of carbon dots: the role of quantum confinement and surface states, Journal of Nanophotonics 10 (2) (2016) 026028.

[48] F. Wang, et al., White light-emitting devices based on carbon dots’ electrolumines- cence, Chemical Communications 47 (12) (2011) 3502 3504.

[49] C. Qi, et al., Toward near-white electroluminescence with enhanced blue emission from carbon dots in PEDOT: PSS/ZnO organic/inorganic hybrid heterojunctions, Journal of Luminescence 224 (2020) 117230.

[50] X. Zhang, et al., Color-switchable electroluminescence of carbon dot light-emitting diodes, ACS Nano 7 (12) (2013) 11234 11241.

[51] X. Mo, et al., Low-voltage multicolor electroluminescence from all-inorganic carbon dots/Si-heterostructured light-emitting diodes, Journal of Materials Science 54 (11) (2019) 8492 8503.

[52] Y. Ding, et al., Synthesis of short-chain passivated carbon quantum dots as the light emitting layer towards electroluminescence, RSC Advances 7 (46) (2017) 28754 28762.

[53] L.M. Veca, et al., Electroluminescence of carbon ‘quantum’ dots from materials to devices, Chemical Physics Letters 613 (2014) 40 44.

[54] B. Zhao, Za Tan, Fluorescent carbon dots: fantastic electroluminescent materials for light-emitting diodes, Advanced Science 8 (7) (2021) 2001977.

[55] P. Lagonegro, U. Giovanella, M. Pasini, Carbon dots as a sustainable new platform for organic light emitting diode, Coatings 11 (1) (2021) 5.

[56] X. Wang, et al., Carbon-dot-based white-light-emitting diodes with adjustable correlated color temperature guided by machine learning, Angewandte Chemie International Edition 60 (22) (2021) 12585 12590.

[57] S. Paulo-Mirasol, E. Martı´nez-Ferrero, E. Palomares, Direct white light emission from carbon nanodots (C-dots) in solution processed light emitting diodes, Nanoscale 11 (23) (2019) 11315 11321.

[58] H. Jia, et al., Electroluminescent warm white light-emitting diodes based on passivation enabled bright red bandgap emission carbon quantum dots, Advanced Science 6 (13) (2019) 1900397.

[59] T. Feng, et al., Color-tunable carbon dots possessing solid-state emission for full-color light-emitting diodes applications, ACS Photonics 5 (2) (2018) 502 510.

[60] F. Yuan, et al., Bright high-colour-purity deep-blue carbon dot light-emitting diodes via efficient edge amination, Nature Photonics 14 (3) (2020) 171 176.

[61] X. Wang, et al., Ultra-bright and stable pure blue light-emitting diode from O, N Co- doped carbon dots, Laser & Photonics Reviews 15 (3) (2021) 2000412.

[62] F. Chen, et al., Blue quantum dot-based electroluminescent light-emitting diodes, Materials Chemistry Frontiers 4 (5) (2020) 1340 1365.

[63] J. Xu, et al., Ultrahigh brightness carbon dot based blue electroluminescent LEDs by host guest energy transfer emission mechanism, Advanced Optical Materials 6 (14) (2018) 1800181.

[64] T.H. Kim, et al., Yellow-emitting carbon nanodots and their flexible and transparent films for white LEDs, ACS Applied Materials & Interfaces 8 (48) (2016) 33102 33111.

[65] R. Guo, T. Li, S. Shi, Aggregation-induced emission enhancement of carbon quantum dots and applications in light emitting devices, Journal of Materials Chemistry C 7 (17) (2019) 5148 5154.

[66] Y.R. Park, et al., Quantum-dot light-emitting diodes with nitrogen-doped carbon nano- dot hole transport and electronic energy transfer layer, Scientific Reports 7 (1) (2017) 1 13.

[67] M.B. Alam, et al., Carbon quantum dot as electron transporting layer in organic light emitting diode, ChemistrySelect 4 (25) (2019) 7450 7454.

[68] Z. Wang, et al., Multifunctional p-type carbon quantum dots: a novel hole injection layer for high-performance perovskite light-emitting diodes with significantly enhanced stability, Advanced Optical Materials 7 (24) (2019) 1901299.

[69] X. Chen, et al., Blue and green double band luminescent carbon quantum dots: synthe- sis, origin of photoluminescence, and application in white light-emitting devices, Applied Physics Letters 118 (15) (2021) 153102.

[70] E. Liu, et al., Highly emissive carbon dots in solid state and their applications in light- emitting devices and visible light communication, ACS Sustainable Chemistry &

Engineering 7 (10) (2019) 9301 9308.

[71] X. Lan, et al., A facile microwave-assisted synthesis of highly crystalline red carbon dots by adjusting the reaction solvent for white light-emitting diodes, Nanotechnology 31 (21) (2020) 215704.

[72] Y. Liu, et al., Multicolor tunable highly luminescent carbon dots for remote force mea- surement and white light emitting diodes, Chemical Communications 55 (81) (2019) 12164 12167.

[73] Q. Li, Y. Li, S. Meng, J. Yang, Y. Qin, J. Tan, et al., Achieving 46% efficient white- light emissive carbon dot-based materials by enhancing phosphorescence for single- component white-light-emitting diodes, Journal of Materials Chemistry C 9 (21) (2021) 6796 6801.

[74] W. Zhang, et al., Observation of lasing emission from carbon nanodots in organic sol- vents, Advanced Materials 24 (17) (2012) 2263 2267.

[75] S. Qu, et al., Amplified spontaneous green emission and lasing emission from carbon nanoparticles, Advanced Functional Materials 24 (18) (2014) 2689 2695.

[76] Z. Han, et al., Highly efficient and ultra-narrow bandwidth orange emissive carbon dots for microcavity lasers, Nanoscale 11 (24) (2019) 11577 11583.

[77] Z. Xi, et al., Highly efficient and stable full-color random lasing emission based on car- bon quantum dots, Acta Chim Sin 76 (6) (2018) 460.

[78] F. Yuan, et al., Ultrastable and low-threshold random lasing from narrow-bandwidth- emission triangular carbon quantum dots, Advanced Optical Materials 7 (2) (2019) 1801202.

[79] W. Zhang, et al., Realization of multiphoton lasing from carbon nanodot microcavities, Nanoscale 9 (18) (2017) 5957 5963.

[80] A. Yadav, et al., Lasing behavior of surface functionalized carbon quantum dot/RhB composites, Nanoscale 9 (16) (2017) 5049 5054.

[81] S. Prakash, et al., Carbon dot-NaCl crystals for white-light generation and fabry-perot lasing, Chemistry An Asian Journal 16 (7) (2021) 783 792.

[82] Y. Ni, et al., Transformation of random lasing to Fabry Perot lasing: observation of high temperature lasing from carbon dots, Nanoscale 13 (16) (2021) 7566 7573.

[83] Y.-P. Sun, et al., Quantum-sized carbon dots for bright and colorful photoluminescence, Journal of the American Chemical Society 128 (24) (2006) 7756 7757.

[84] F. Yuan, et al., Bright multicolor bandgap fluorescent carbon quantum dots for electro- luminescent light-emitting diodes, Advanced Materials 29 (3) (2017) 1604436.

[85] F. Yuan, et al., Engineering triangular carbon quantum dots with unprecedented narrow bandwidth emission for multicolored LEDs, Nature Communications 9 (1) (2018) 1 11.

[86] J. Ren, et al., Precisely controlled up/down-conversion liquid and solid state photolumi- nescence of carbon dots, Advanced Optical Materials 6 (14) (2018) 1800115.

[87] X. Zhang, et al., Carbon quantum dots serving as spectral converters through broadband upconversion of near-infrared photons for photoelectrochemical hydrogen generation, Journal of Materials Chemistry A 1 (38) (2013) 11529 11533.

[88] Y.H. Chien, et al., NIR-responsive nanomaterials and their applications; upconversion nanoparticles and carbon dots: a perspective, Journal of Chemical Technology &

Biotechnology 93 (6) (2018) 1519 1528.

[89] D. Li, et al., Thermally activated upconversion near-infrared photoluminescence from carbon dots synthesized via microwave assisted exfoliation, Small (Weinheim an der Bergstrasse, Germany) 15 (50) (2019) 1905050.

[90] K.K. Liu, et al., Efficient red/near infrared emissive carbon nanodots with multiphoton excited upconversion fluorescence, Advanced Science 6 (17) (2019) 1900766.

[91] Y. Hu, et al., Visible-light upconversion carbon quantum dots decorated TiO2for the photodegradation of flowing gaseous acetaldehyde, Applied Surface Science 440 (2018) 266 274.

[92] Y. Deng, et al., Visible ultraviolet upconversion carbon quantum dots for enhance- ment of the photocatalytic activity of titanium dioxide, ACS Omega 6 (6) (2021) 4247 4254.

[93] K.M. Omer, N.N. Mohammad, S.O. Baban, Up-conversion fluorescence of phospho- rous and nitrogen co-doped carbon quantum dots (CDs) coupled with weak LED light source for full-spectrum driven photocatalytic degradation via ZnO-CDs nanocompo- sites, Catalysis Letters 148 (9) (2018) 2746 2755.

[94] J. Wang, Y. Zhu, L. Wang, Synthesis and applications of red-emissive carbon dots, The Chemical Record 19 (10) (2019) 2083 2094.

[95] X. Wen, et al., On the upconversion fluorescence in carbon nanodots and graphene quantum dots, Chemical Communications 50 (36) (2014) 4703 4706.

9

Nanoelectronic applications of carbon quantum dots

M. Shiva Subramani¹, Soumyo Chatterjee²and Kallol Mohanta¹

1Nanotech Research Innovation and Incubation Centre (NRIIC), PSG Institute of Advanced Studies (PSG IAS), Peelamedu, Coimbatore, Tamil Nadu, India,²School of Physical Sciences (SPS), Indian Association for the Cultivation of Science (IACS), Jadavpur, Kolkata, West Bengal, India

TOC picture