Skip to main content
SpringerLink
Log in

From Cu2S nanocrystals to Cu doped CdS nanocrystals through cation exchange: controlled synthesis, optical properties and their p-type conductivity research

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Heterovalent doping represents an effective method to control the optical and electronic properties of semiconductor nanocrystals (NCs), such as the luminescence and electronic impurities (p-, n-type doping). Considering the phase structure diversity, coordination varieties of Cu atoms in Cu2S NCs, and complexity of Cu doping in II-VI NCs, monodisperse Cu2S NCs with pure hexagonal phase were synthesized firstly. Then through cation exchange reaction between Cd ions and well-defined Cu2S NCs, dominant Cu(I) doped CdS NCs were produced successfully. The substitutional Cu(I) dopants with controllable concentrations were confirmed by local atom-specific fine structure from X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS) spectroscopy, elemental analysis characterizations from X-ray photoelectron spectroscopy (XPS) and the electron spin resonance (ESR) measurement. The dominant and strong Cu(I) dopant fluorescence was verified by their absorption and photoluminescence (PL) spectra, and PL lifetime. Finally, the band positions and the p-type conductivities of the as-prepared Cu2S and Cu(I) doped CdS NCs were identified by ultraviolet photoelectron spectroscopy (UPS) measurements. The high monodispersity of NCs enables their strong film-scale self-assembly and will hasten their subsequent applications in devices.

中文摘要

异价掺杂, 能有效调控半导体纳米晶的电学及光学性能, 实现高效掺杂发光及n型、p型导电类型的调控. 因为Cu2S晶型多 变、Cu原子配位繁杂以及Cu掺杂II-VI纳米晶的体系复杂等问题, 本文提出一种全新的方法, 首先可控制备了单分散的高纯度六方相 Cu2S纳米晶, 然后通过可控的离子交换反应, 合成了单分散Cu(I)掺杂的CdS纳米晶. 通过X射线近边吸收谱(XANES)、扩展X射线吸收 精细结构(EXAFS)、X射线光电子能谱(XPS)及电子顺磁共振波谱(EPR)等精确表征手段证实了可控浓度的取代型的异价Cu掺杂. 其紫 外-可见吸收光谱、荧光光谱、荧光寿命光谱等表征证实了以Cu(I)掺杂为主导的掺杂发光, 绝对量子产率可达28.9%. 紫外光电子能谱 (UPS)确认了Cu(I)掺杂的CdS为p型半导体. 高度单分散的CdS掺杂纳米晶可以形成大规模的自组装, 将会加速其在光电器件上的应用.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Erwin SC, Zu LJ, Haftel MI, et al. Doping semiconductor nanocrystals. Nature, 2005, 436: 91–94

    Article  Google Scholar 

  2. Norris DJ, Efros AL, Erwin SC. Doped nanocrystals. Science, 2008, 319: 1776–1779

    Article  Google Scholar 

  3. Beaulac R, Schneider L, Archer PI, Bacher G, Gamelin DR. Light-induced spontaneous magnetization in doped colloidal quantum dots. Science, 2009, 325: 973–976

    Article  Google Scholar 

  4. Mocatta D, Cohen G, Schattner J, et al. Heavily doped semiconductor nanocrystal quantum dots. Science, 2011, 332: 77–81

    Article  Google Scholar 

  5. Viswanatha R, Battaglia DM, Curtis ME, et al. Shape control of doped semiconductor nanocrystals (d-Dots). Nano Res, 2008, 1: 138–144

    Article  Google Scholar 

  6. Viswanatha R, Brovelli S, Pandey A, Crooker SA, Klimov VI. Copper- doped inverted core/shell nanocrystals with “permanent” optically active holes. Nano Lett, 2011, 11: 4753–4758

    Article  Google Scholar 

  7. Sahu A, Kang MS, Kompch A, et al. Electronic impurity doping in CdSe nanocrystals. Nano Lett, 2012, 12: 2587–2594

    Article  Google Scholar 

  8. Jana S, Srivastava BB, Acharya S, et al. Prevention of photooxidation in blue-green emitting Cu doped ZnSe nanocrystals. Chem Commun, 2010, 46: 2853–2855

    Article  Google Scholar 

  9. Xie Y, Carbone L, Nobile C, et al. Metallic-like stoichiometric copper sulfide nanocrystals: phase- and shape-selective synthesis, near-infrared surface plasmon resonance properties, and their modeling. ACS Nano, 2013, 7: 7352–7369

    Article  Google Scholar 

  10. Bekenstein Y, Vinokurov K, Keren-Zur S, et al. Thermal doping by vacancy formation in copper sulfide nanocrystal arrays. Nano Lett, 2014, 14: 1349–1353

    Article  Google Scholar 

  11. Cooper JK, Gul S, Lindley SA, Yano J, Zhang JZ. Tunable photoluminescent core/shell Cu+-doped ZnSe/ZnS quantum dots codoped with Al3+, Ga3+, or In3+. ACS Appl Mater Interfaces, 2015, 7: 10055–10066

    Article  Google Scholar 

  12. Brovelli S, Galland C, Viswanatha R, Klimov VI. Tuning radiative recombination in Cu-doped nanocrystals via electrochemical control of surface trapping. Nano Lett, 2012, 12: 4372–4379

    Article  Google Scholar 

  13. Srivastava BB, Jana S, Pradhan N. Doping Cu in semiconductor nanocrystals: some old and some new physical insights. J Am Chem Soc, 2011, 133: 1007–1015

    Article  Google Scholar 

  14. Isarov AV, Chrysochoos J. Optical and photochemical properties of nonstoichiometric cadmium sulfide nanoparticles: surface modification with copper(II) ions. Langmuir, 1997, 13: 3142–3149

    Article  Google Scholar 

  15. Sambasivam S, Sathyaseelan B, Raja Reddy D, Reddy BK, Jayasankar CK. ESR and photoluminescence properties of Cu doped ZnS nanoparticles. Spectrochim Acta Part A, 2008, 71A: 1503–1506

    Article  Google Scholar 

  16. Zheng HM, Rivest JB, Miller TA, et al. Observation of transient structural-transformation dynamics in a Cu2S nanorod. Science, 2011, 333: 207–209

    Article  Google Scholar 

  17. Leidinger P, Popescu R, Gerthsen D, Lunsdorf H, Feldmann C. Nanoscale copper sulfide hollow spheres with phase-engineered composition: covellite (CuS), digenite (Cu1.8S), chalcocite (Cu2S). Nanoscale, 2011, 3: 2544–2551

    Article  Google Scholar 

  18. Riha SC, Jin S, Baryshev SV, et al. Stabilizing Cu2S for photovoltaics one atomic layer at a time. ACS Appl Mater Interfaces, 2013, 5: 10302–10309

    Article  Google Scholar 

  19. Zhuang ZB, Peng Q, Zhang BC, Li YD. Controllable synthesis of Cu2S nanocrystals and their assembly into a superlattice. J Am Chem Soc, 2008, 130: 10482–10483

    Article  Google Scholar 

  20. Desnica UV. Doping limits in II-VI compounds—challenges, problems and solutions. Prog Cryst Growth Charact Mater, 1998, 36: 291–357

    Article  Google Scholar 

  21. Kashiwaba Y, Kanno I, Ikeda T. p-type characteristics of Cudoped CdS thin films. Jpn J Appl Phys, 1992, 31: 1170–1175

    Article  Google Scholar 

  22. Huang Q, Li Q, Xiao XD. Hydrogen evolution from Pt nanoparticles covered p-type CdS:Cu photocathode in scavenger-free electrolyte. J Phys Chem C, 2014, 118: 2306–2311

    Article  Google Scholar 

  23. Son DH, Hughes SM, Yin Y, Alivisatos AP. Cation exchange reactions- in ionic nanocrystals. Science, 2004, 306, 1009–1012

    Article  Google Scholar 

  24. Gui J, Ji MW, Liu JJ, Xu M, Zhang JT. Phosphine-initiated cation exchange for precisely tailoring composition and properties of semiconductor nanostructures: old concept, new applications. Angew Chem Int Ed, 2015, 127, 3754–3758

    Article  Google Scholar 

  25. Qian HM, Zhao Q, Dai B S, et al. Oriented attachment of nanoparticles to form micrometer-sized nanosheets/nanobelts by topotactic reaction on rigid/flexible substrates with improved electronic properties. NPG Asia Mater, 2015, 7: e152

    Article  Google Scholar 

  26. Deng ML, Wang LY. Unexpected luminescence enhancement of upconverting nanocrystals by cation exchange with well retained small particle size. Nano Res, 2014, 7: 782–793

    Article  Google Scholar 

  27. Beberwyck BJ, Surendranath Y, Alivisatos AP. Cation exchange: a versatile tool for nanomaterials synthesis. J Phys Chem C, 2013, 117: 19759–19770

    Article  Google Scholar 

  28. Kang MS, Sahu A, Frisbie CD, Norris DJ. Influence of silver doping on electron transport in thin films of PbSe nanocrystals. Adv Mater, 2013, 25: 725–731

    Article  Google Scholar 

  29. Liu J, Zhao Q, Liu JL, et al. Heterovalent-doping-enabled efficient dopant luminescence and controllable electronic impurity via a new strategy of preparing II-VI nanocrystals. Adv Mater, 2015, 27: 2753–2761

    Article  Google Scholar 

  30. Li S, Wang HZ, Xu WW, et al. Synthesis and assembly of monodisperse spherical Cu2S nanocrystals. J Colloid Interface Sci, 2009, 330: 483–487

    Article  Google Scholar 

  31. Rivest JB, Fong LK, Jain PK, Toney MF, Alivisatos AP. Size dependence of a temperature-induced-solid phase transition in copper(I) sulfide. J Phys Chem Lett, 2011, 2: 2402

    Article  Google Scholar 

  32. Wang PP, Yang Y, Zhuang J, Wang X. Self-adjustable crystalline inorganic nanocoils. J Am Chem Soc, 2013, 135: 6834–6837

    Article  Google Scholar 

  33. Zhu Y, Li Z, Chen M, et al. One-pot preparation of highly fluorescent cadmium telluride/cadmium sulfide quantum dots under neutral- pH condition for biological applications. J Colloid Interface Sci, 2013, 390: 3–10

    Article  Google Scholar 

  34. Pan D, Wang Q, Pang J, et al. Semiconductor “nano-onions” with multifold alternating CdS/CdSe or CdSe/CdS structure. Chem Mater, 2006, 18: 4253–4258

    Article  Google Scholar 

  35. Xuan T, Wang S, Wang X, et al. Single-step noninjection synthesis of highly luminescent water soluble Cu+ doped CdS quantum dots: application as bio-imaging agents. Chem Commun, 2013, 49: 9045–9047

    Article  Google Scholar 

  36. Rockenberger J, Troger L, Kornowski A, et al. EXAFS studies on the size dependence of structural and dynamic properties of CdS nanoparticles. J Phys Chem B, 1997, 101: 2691–2701

    Article  Google Scholar 

  37. Gul S, Cooper JK, Glans P, et al. Effect of Al3+ co-doping on the dopant local structure, optical properties, and exciton dynamics in Cu+-doped ZnSe nanocrystals. ACS Nano, 2013, 7: 8680–8692

    Article  Google Scholar 

  38. Sun ZH, Liu QH, Yao T, Yan WS, Wei SQ. X-ray absorption fine structure spectroscopy in nanomaterials. Sci China Mater, 2015, 58: 313–341

    Article  Google Scholar 

  39. Grandhi GK, Viswanatha R. Tunable infrared phosphors using Cu doping in semiconductor nanocrystals: surface electronic structure evaluation. J Phys Chem Lett, 2013, 4: 409–415

    Article  Google Scholar 

  40. Wang XB, Yan XS, Li WW, Sun K. Doped quantum dots for whitelight-emitting diodes without reabsorption of multiphase phosphors. Adv Mater, 2012, 24: 2742–2747

    Article  Google Scholar 

  41. Meinardi F, Colombo A, Velizhanin KA, et al. Large-area luminescent solar concentrators based on ‘stokes-shift-engineered’ nanocrystals in a mass-polymerized PMMA matrix. Nat photonics, 2014, 8: 392–399

    Article  Google Scholar 

  42. Krumer Z, Pera SJ, van Dijk-Moes RJA, et al. Tackling self-absorption in luminescent solar concentrators with type-II colloidal quantum dots. Sol Energ Mater Sol Cell, 2013, 111: 57–65

    Article  Google Scholar 

  43. Chun WJ, Ishikawa A, Fujisawa H, et al. Conduction and valence band positions of Ta2O5, TaON, and Ta3N5 by UPS and electrochemical methods. J Phys Chem B, 2003, 107: 1798–1803

    Article  Google Scholar 

  44. Cho KS, Lee EK, Joo WJ, et al. High-performance crosslinked colloidal quantum-dot light-emitting diodes. Nat Photonics, 2009, 3: 341–345

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Jian Liu, Yuheng Zhao, Muwei Ji, Yuanmin Zhou, Meng Xu & Jiatao Zhang

  2. Department of Physics, Beihang University, Beijing, 100191, China

    Jialong Liu & Weichang Hao

  3. Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing, 100083, China

    Shouguo Wang

  4. Laboratory of Chemical Biology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, 130022, China

    Yan Cheng

Authors
  1. Jian Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yuheng Zhao
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Jialong Liu
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Shouguo Wang
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Yan Cheng
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Muwei Ji
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yuanmin Zhou
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Meng Xu
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Weichang Hao
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Jiatao Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Jiatao Zhang.

Additional information

Jian Liu was born in Jiangsu, China, in 1991. He received his BSc degree in 2013 from the University of Shanghai for Science and Technology, and is now studying at Beijing institute of technology for his MSc degree. His research interest includes doping semiconductor nanocrystals.

Jiatao Zhang was born in 1975. He received his PhD degree in 2006 from the Department of Chemistry, Tsinghua University, China. Currently he is Xu Teli Professor in the School of Materials and Engineering, Beijing Institute of Technology. He was awarded Excellent Young Scientist foundation of NSFC in 2013. He also serves as the director of Beijing Key Laboratory of Construction-Tailorable Advanced Functional Materials and Green Applications. His current research interest is inorganic chemistry of semiconductor based hybrid nanostructures to possess novel optical, electronic properties for applications in energy conversion and storage, catalysis, optoelectronics and biology.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Liu, J., Zhao, Y., Liu, J. et al. From Cu2S nanocrystals to Cu doped CdS nanocrystals through cation exchange: controlled synthesis, optical properties and their p-type conductivity research. Sci. China Mater. 58, 693–703 (2015). https://doi.org/10.1007/s40843-015-0080-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-015-0080-z

Keywords

Search

Navigation