Investigation on Mechanism of Enhanced Luminescence Efficiency of Carbon Quantum Dots Through Thiol-ene Cross-linking

ZHANG Pei; CHAI Xinyi; LI Shaojun; REN Linjiao; ZHENG Yibo; QIN Zirui; ZHANG Jitao; ZHANG Qingfang; JIANG Liying

doi:10.37188/CJL.20230173

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Investigation on Mechanism of Enhanced Luminescence Efficiency of Carbon Quantum Dots Through Thiol-ene Cross-linking

Synthesis and Properties of Materials | 更新时间：2023-11-27

- Investigation on Mechanism of Enhanced Luminescence Efficiency of Carbon Quantum Dots Through Thiol-ene Cross-linking
  增强出版
- Chinese Journal of Luminescence Vol. 44, Issue 11, Pages: 1990-2001(2023)
- 作者机构：
  
  1.郑州轻工业大学电气信息工程学院，河南郑州　450002
  2.郑州轻工业大学电子信息学院，河南郑州　450002
  3.郑州轻工业大学量子科技研究院，河南郑州　450002
- 作者简介：
- 基金信息：
  
  National Natural Science Foundation of China(12004348;62073299;61801436);Project of Central Plains Science and Technology Innovation Leading Talents(224200510026);Henan Province Science and Technology Plan Project(212102210002;232102220008;212102210196;212102210278)
- DOI：10.37188/CJL.20230173
  CLC： O482.31
- Published：05 November 2023，
  
  Received：27 July 2023，
  
  Revised：13 August 2023，
- 稿件说明：
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张培,柴鑫毅,李少君等.硫醇⁃烯交联增强碳量子点发光效率机理研究[J].发光学报,2023,44(11):1990-2001.

ZHANG Pei,CHAI Xinyi,LI Shaojun,et al.Investigation on Mechanism of Enhanced Luminescence Efficiency of Carbon Quantum Dots Through Thiol-ene Cross-linking[J].Chinese Journal of Luminescence,2023,44(11):1990-2001.
张培,柴鑫毅,李少君等.硫醇⁃烯交联增强碳量子点发光效率机理研究[J].发光学报,2023,44(11):1990-2001. DOI： 10.37188/CJL.20230173.

ZHANG Pei,CHAI Xinyi,LI Shaojun,et al.Investigation on Mechanism of Enhanced Luminescence Efficiency of Carbon Quantum Dots Through Thiol-ene Cross-linking[J].Chinese Journal of Luminescence,2023,44(11):1990-2001. DOI： 10.37188/CJL.20230173.

摘要

通过溶剂热反应法制备了N和O含量不同的碳量子点（CQDs）溶液，利用“点击”化学反应将CQDs与非计量硫醇⁃烯（OSTE）聚合物交联固化，形成CQDs/OSTE复合材料。固化后，O⁃CQDs的荧光量子产率从液态下的2.6%提高到16.5%，增大倍数约为6倍；N，O⁃CQDs的荧光量子产率从液态下的4.5%提高到17.6%，增大倍数约为4倍。通过微结构和光学特性分析，我们认为交联固化后与氧相关的非辐射复合中心减少、非辐射跃迁过程抑制以及N和S的协同效应是提高CQDs材料发光效率的主要原因。本文的研究成果有望为CQDs的固态转化、表面功能化以及荧光增强提供一种有效、便捷的方法，从而促进CQDs在发光二极管、激光器和发光太阳能聚光器等领域的应用。

Abstract

The carbon quantum dots（CQDs） containing different N， O contents were prepared by using solvothermal reaction， and the CQDs/OSTE composites were obtained quickly through cross-linking and curing the CQDs with the off-stoichiometric thiol-ene （OSTE） polymer

via

the reaction of “click” chemistry. It is found the fluorescence quantum yield（QY）of O-CQDs and N，O-CQDs were increased to 16.5% and 17.6%， respectively. Compared with their QYs（2.6% and 4.5%）in the liquid environment， the enhancement of about 6 and 4 times was achieved， respectively. By analyzing the changes of microstructure and optical properties of CQDs materials before and after curing， we suggested that the enhanced PL QY might originate mainly from the reduction of the oxygen-related non-radiative recombination center， the suppression of the non-radiative transition probability and the synergistic effect of N and S. Our results provide a convenient and efficient method for solid state transformation， surface functionalization and fluorescence enhancement of CQDs， which will promote the application of CQDs in light-emitting diodes， lasers and luminescent solar concentrators.

关键词

碳量子点非计量硫醇-烯聚合物交联增强荧光表面态与氧相关的发光中心

Keywords

carbon quantum dotsoff-stoichiometric thiol-ene polymercross-linking enhanced emissionsurface stateluminescence center related to oxygen

references

AUBERT T， GOLOVATENKO A A， SAMOLI M， et al. General expression for the size-dependent optical properties of quantum dots ［J］. Nano Lett.， 2022， 22（4）： 1778-1785. doi: 10.1021/acs.nanolett.2c00056http://dx.doi.org/10.1021/acs.nanolett.2c00056

LIU J J， ZHANG X J， JI Y， et al. Rational energy band alignment and Au nanoparticles in surface plasmon enhanced Si‐based perovskite quantum dot light‐emitting diodes ［J］. Adv. Opt. Mater.， 2018， 6（19）： 1800693. doi: 10.1002/adom.201800693http://dx.doi.org/10.1002/adom.201800693

ZHANG P， LI S J， LI D K， et al. Quantum size-dependent luminescence and nonlinear optical properties of silicon quantum dots/SiO2 multilayer ［J］. Opt. Laser Technol.， 2023， 157： 108706. doi: 10.1016/j.optlastec.2022.108706http://dx.doi.org/10.1016/j.optlastec.2022.108706

WANG B Y， CAI H J， WATERHOUSE G I N， et al. Carbon dots in bioimaging， biosensing and therapeutics： a comprehensive review ［J］. Small Sci.， 2022， 2（6）： 2200012. doi: 10.1002/smsc.202200012http://dx.doi.org/10.1002/smsc.202200012

张艺，邢晶晶，孙思佳，等. 绿色方法合成纳米碳点及对Fe3+的特异性荧光检测［J］. 发光学报， 2020， 41（10）： 1249-1254. doi: 10.37188/cjl.20200174http://dx.doi.org/10.37188/cjl.20200174

ZHANG Y， XING J J， SUN S J， et al. Green synthesis of carbon nanodots and their application in specific fluorescence detection of Fe3+ ［J］. Chin. J. Lumin.， 2020， 41（10）： 1249-1254. （in Chinese）. doi: 10.37188/cjl.20200174http://dx.doi.org/10.37188/cjl.20200174

YAO Y， ZHANG H Y， HU K S， et al. Carbon dots based photocatalysis for environmental applications ［J］. J. Environ. Chem. Eng.， 2022， 10（2）： 107336. doi: 10.1016/j.jece.2022.107336http://dx.doi.org/10.1016/j.jece.2022.107336

孟维雪，杨柏，卢思宇. 从碳点到碳化聚合物点：发展和挑战［J］. 发光学报， 2021， 42（8）： 1075-1094. doi: 10.37188/cjl.20210155http://dx.doi.org/10.37188/cjl.20210155

MENG W X， YANG B， LU S Y. From carbon dots to carbonized polymer dots： development and challenges ［J］. Chin. J. Lumin.， 2021， 42（8）： 1075-1094. （in Chinese）. doi: 10.37188/cjl.20210155http://dx.doi.org/10.37188/cjl.20210155

王琴，杨雯，庄镜儒，等. 生物基碳点制备及其在LED器件上的应用［J］. 发光学报， 2021， 42（8）： 1314-1322. doi: 10.37188/CJL.20210159http://dx.doi.org/10.37188/CJL.20210159

WANG Q， YANG W， ZHUANG J R， et al. Preparation and application of bio-based carbon dots for LED chips ［J］. Chin. J. Lumin.， 2021， 42（8）： 1314-1322. （in Chinese）. doi: 10.37188/CJL.20210159http://dx.doi.org/10.37188/CJL.20210159

ZHAO H G， LIU G J， YOU S J， et al. Gram-scale synthesis of carbon quantum dots with a large Stokes shift for the fabrication of eco-friendly and high-efficiency luminescent solar concentrators ［J］. Energy Environ. Sci.， 2021， 14（1）： 396-406. doi: 10.1039/d0ee02235ghttp://dx.doi.org/10.1039/d0ee02235g

GHOSH D， SARKAR K， DEVI P， et al. Current and future perspectives of carbon and graphene quantum dots： from synthesis to strategy for building optoelectronic and energy devices ［J］. Renewable Sustain. Energy Rev.， 2021， 135： 110391. doi: 10.1016/j.rser.2020.110391http://dx.doi.org/10.1016/j.rser.2020.110391

GUO J Z， LU Y S， XIE A Q， et al. Yellow‐emissive carbon dots with high solid‐state photoluminescence ［J］. Adv. Funct. Mater.， 2022， 32（20）： 2110393. doi: 10.1002/adfm.202110393http://dx.doi.org/10.1002/adfm.202110393

TIAN Z， ZHANG X T， LI D， et al. Full‐color inorganic carbon dot phosphors for white‐light‐emitting diodes ［J］. Adv. Opt. Mater.， 2017， 5（19）： 1700416. doi: 10.1002/adom.201700416http://dx.doi.org/10.1002/adom.201700416

WANG Z F， YUAN F L， LI X H， et al. 53% efficient red emissive carbon quantum dots for high color rendering and stable warm white‐light‐emitting diodes ［J］. Adv. Mater.， 2017， 29（37）： 1702910. doi: 10.1002/adma.201702910http://dx.doi.org/10.1002/adma.201702910

ZDRAŽIL L， KALYTCHUK S， HOLÁ K， et al. A carbon dot-based tandem luminescent solar concentrator ［J］. Nanoscale， 2020， 12（12）： 6664-6672. doi: 10.1039/c9nr10029fhttp://dx.doi.org/10.1039/c9nr10029f

SHIN S， KANG K， JANG H， et al. Ligand-crosslinking strategy for efficient quantum dot light‐emitting diodes via thiol‐ene click chemistry ［J］. Small Methods， 2023， 7（9）： 2300206. doi: 10.1002/smtd.202300206http://dx.doi.org/10.1002/smtd.202300206

NAZIM M， KIM J H. Fluorescent N-doped graphene quantum dots embedded in transparent polymer films for photon-downconversion applications ［J］. ACS Appl. Nano Mater.， 2020， 3（3）： 2322-2335. doi: 10.1021/acsanm.9b02436http://dx.doi.org/10.1021/acsanm.9b02436

MARININS A， ZANDI SHAFAGH R， VAN DER WIJNGAART W， et al. Light-converting polymer/Si nanocrystal composites with stable 60%-70% quantum efficiency and their glass laminates ［J］. ACS Appl. Mater. Interfaces， 2017， 9（36）： 30267-30272. doi: 10.1021/acsami.7b09265http://dx.doi.org/10.1021/acsami.7b09265

HUANG J， ZHOU J J， HARALDSSON T， et al. Triplex glass laminates with silicon quantum dots for luminescent solar concentrators ［J］. Sol. RRL， 2020， 4（9）： 2000195. doi: 10.1002/solr.202000195http://dx.doi.org/10.1002/solr.202000195

GU G W， ZHENG Z D， ZHANG H H， et al. Re-absorption-free perovskite quantum dots for boosting the efficiency of luminescent solar concentrator ［J］. J. Lumin.， 2022， 248： 118963. doi: 10.1016/j.jlumin.2022.118963http://dx.doi.org/10.1016/j.jlumin.2022.118963

SONG Z H， ZHENG Z D， ZHANG Y， et al. The trade-off between optical efficiency and aesthetic properties of InP/ZnS quantum dots based luminescent solar concentrators ［J］. J. Lumin.， 2023， 256： 119622. doi: 10.1016/j.jlumin.2022.119622http://dx.doi.org/10.1016/j.jlumin.2022.119622

RAVEENDRAN P T V， RENUKA N K. Hydrothermal synthesis of biomass-derived carbon nanodots： characterization and applications ［J］. Mater. Chem. Phys.， 2022， 288： 126236. doi: 10.1016/j.matchemphys.2022.126236http://dx.doi.org/10.1016/j.matchemphys.2022.126236

REN J， WEBER F， WEIGERT F， et al. Influence of surface chemistry on optical， chemical and electronic properties of blue luminescent carbon dots ［J］. Nanoscale， 2019， 11（4）： 2056-2064. doi: 10.1039/c8nr08595ahttp://dx.doi.org/10.1039/c8nr08595a

LIU C， BAO L， YANG M L， et al. Surface sensitive photoluminescence of carbon nanodots： coupling between the carbonyl group and π-electron system ［J］. J. Phys. Chem. Lett.， 2019， 10（13）： 3621-3629. doi: 10.1021/acs.jpclett.9b01339http://dx.doi.org/10.1021/acs.jpclett.9b01339

QI B P， HU H， BAO L， et al. An efficient edge-functionalization method to tune the photoluminescence of graphene quantum dots ［J］. Nanoscale， 2015， 7（14）： 5969-5973. doi: 10.1039/c5nr00842ehttp://dx.doi.org/10.1039/c5nr00842e

LADDHA H， YADAV P， AGARWAL M， et al. Quick and hassle-free smartphone's RGB-based color to photocatalytic degradation rate assessment of malachite green dye in water by fluorescent Zr⁃N⁃S co-doped carbon dots ［J］. Environ. Sci. Pollut. Res.， 2022， 29（37）： 56684-56695. doi: 10.1007/s11356-022-19808-5http://dx.doi.org/10.1007/s11356-022-19808-5

ZHAN Y， GENG T， LIU Y L， et al. Near-ultraviolet to near-infrared fluorescent nitrogen-doped carbon dots with two-photon and piezochromic luminescence ［J］. ACS Appl. Mater. Interfaces， 2018， 10（33）： 27920-27927. doi: 10.1021/acsami.8b07498http://dx.doi.org/10.1021/acsami.8b07498

JIANG K， SUN S， ZHANG L， et al. Red， green， and blue luminescence by carbon dots： full‐color emission tuning and multicolor cellular imaging ［J］. Angew. Chem.， 2015， 127（18）： 5450-5453. doi: 10.1002/ange.201501193http://dx.doi.org/10.1002/ange.201501193

WEI S Q， YIN X H， LI H Y， et al. Multi‐color fluorescent carbon dots： graphitized sp2 conjugated domains and surface state energy level Co‐modulate band gap rather than size effects ［J］. Chem. Eur. J.， 2020， 26（36）： 8129-8136. doi: 10.1002/chem.202000763http://dx.doi.org/10.1002/chem.202000763

LI D， JING P T， SUN L H， et al. Near‐infrared excitation/emission and multiphoton‐induced fluorescence of carbon dots ［J］. Adv. Mater.， 2018， 30（13）： 1705913. doi: 10.1002/adma.201870092http://dx.doi.org/10.1002/adma.201870092

WANG W P， LU Y C， HUANG H， et al. Facile synthesis of water-soluble and biocompatible fluorescent nitrogen-doped carbon dots for cell imaging ［J］. Analyst， 2014， 139（7）： 1692-1696. doi: 10.1039/c3an02098chttp://dx.doi.org/10.1039/c3an02098c

BAO L， LIU C， ZHANG Z L， et al. Photoluminescence‐tunable carbon nanodots： surface‐state energy‐gap tuning ［J］. Adv. Mater.， 2015， 27（10）： 1663-1667. doi: 10.1002/adma.201405070http://dx.doi.org/10.1002/adma.201405070

LI Y， HU Y， ZHAO Y， et al. An electrochemical avenue to green‐luminescent graphene quantum dots as potential electron‐acceptors for photovoltaics ［J］. Adv. Mater.， 2011， 23（6）： 776-780. doi: 10.1002/adma.201003819http://dx.doi.org/10.1002/adma.201003819

XU Q， PU P， ZHAO J G， et al. Preparation of highly photoluminescent sulfur-doped carbon dots for Fe （III） detection ［J］. J. Mater. Chem. A， 2015， 3（2）： 542-546. doi: 10.1039/c4ta05483khttp://dx.doi.org/10.1039/c4ta05483k

LIU S， TIAN J Q， WANG L， et al. Hydrothermal treatment of grass： a low‐cost， green route to nitrogen‐doped， carbon‐rich， photoluminescent polymer nanodots as an effective fluorescent sensing platform for label‐free detection of Cu （II） ions ［J］. Adv. Mater.， 2012， 24（15）： 2037-2041. doi: 10.1002/adma.201200164http://dx.doi.org/10.1002/adma.201200164

GAN Z X， XU H， HAO Y L. Mechanism for excitation-dependent photoluminescence from graphene quantum dots and other graphene oxide derivates： consensus， debates and challenges ［J］. Nanoscale， 2016， 8（15）： 7794-7807. doi: 10.1039/c6nr00605ahttp://dx.doi.org/10.1039/c6nr00605a

GAN Z X， XIONG S J， WU X L， et al. Mechanism of photoluminescence from chemically derived graphene oxide： role of chemical reduction ［J］. Adv. Opt. Mater.， 2013， 1（12）： 926-932. doi: 10.1002/adom.201300368http://dx.doi.org/10.1002/adom.201300368

YU J J， LIU C， YUAN K， et al. Luminescence mechanism of carbon dots by tailoring functional groups for sensing Fe3+ ions ［J］. Nanomaterials， 2018， 8（4）： 233. doi: 10.3390/nano8040233http://dx.doi.org/10.3390/nano8040233

DONG Y Q， PANG H C， YANG H B， et al. Carbon‐based dots Co‐doped with nitrogen and sulfur for high quantum yield and excitation‐independent emission ［J］. Angew. Chem.， 2013， 125（30）： 7954-7958. doi: 10.1002/ange.201301114http://dx.doi.org/10.1002/ange.201301114

ZHENG H Z， WANG Q L， LONG Y J， et al. Enhancing the luminescence of carbon dots with a reduction pathway ［J］. Chem. Commun.， 2011， 47（38）： 10650-10652. doi: 10.1039/c1cc14741bhttp://dx.doi.org/10.1039/c1cc14741b

GAN Z X， XU H， FU Y. Photon reabsorption and nonradiative energy-transfer-induced quenching of blue photoluminescence from aggregated graphene quantum dots ［J］. J. Phys. Chem. C， 2016， 120（51）： 29432-29438. doi: 10.1021/acs.jpcc.6b10704http://dx.doi.org/10.1021/acs.jpcc.6b10704

GAN Z X， LIU L Z， WANG L， et al. Bright， stable， and tunable solid-state luminescence of carbon nanodot organogels ［J］. Phys. Chem. Chem. Phys.， 2018， 20（26）： 18089-18096. doi: 10.1039/c8cp02069hhttp://dx.doi.org/10.1039/c8cp02069h

GENC R， ALAS M O， HARPUTLU E， et al. High-capacitance hybrid supercapacitor based on multi-colored fluorescent carbon-dots ［J］. Sci. Rep.， 2017， 7（1）： 11222. doi: 10.1038/s41598-017-11347-1http://dx.doi.org/10.1038/s41598-017-11347-1

LAKOWICZ J R. Principles of Fluorescence Spectroscopy ［M］. New York： Springer Press， 2006. doi: 10.1007/978-0-387-46312-4_18http://dx.doi.org/10.1007/978-0-387-46312-4_18

GAO F， MA S Y， LI J， et al. Rational design of high quality citric acid-derived carbon dots by selecting efficient chemical structure motifs ［J］. Carbon， 2017， 112： 131-141. doi: 10.1016/j.carbon.2016.10.089http://dx.doi.org/10.1016/j.carbon.2016.10.089

LIU F， JANG M H， HA H D， et al. Facile synthetic method for pristine graphene quantum dots and graphene oxide quantum dots： origin of blue and green luminescence ［J］. Adv. Mater.， 2013， 25（27）： 3657-3662. doi: 10.1002/adma.201300233http://dx.doi.org/10.1002/adma.201300233

NIE H， LI M J， LI Q S， et al. Carbon dots with continuously tunable full-color emission and their application in ratiometric pH sensing ［J］. Chem. Mater.， 2014， 26（10）： 3104-3112. doi: 10.1021/cm5003669http://dx.doi.org/10.1021/cm5003669

BAO L， ZHANG Z L， TIAN Z Q， et al. Electrochemical tuning of luminescent carbon nanodots： from preparation to luminescence mechanism ［J］. Adv. Mater.， 2011， 23（48）： 5801-5806. doi: 10.1002/adma.201102866http://dx.doi.org/10.1002/adma.201102866

TAO S Y， ZHU S J， FENG T L， et al. Crosslink‐enhanced emission effect on luminescence in polymers： advances and perspectives ［J］. Angew. Chem.， 2020， 132（25）： 9910-9924. doi: 10.1002/ange.201916591http://dx.doi.org/10.1002/ange.201916591

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