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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 19, Iss. 3 — Jan. 31, 2011
  • pp: 1749–1754
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Efficient near-infrared quantum cutting in NaYF4: Ho3+, Yb3+ for solar photovoltaics

Kaimo Deng, Tao Gong, Lingxun Hu, Xiantao Wei, Yonghu Chen, and Min Yin  »View Author Affiliations


Optics Express, Vol. 19, Issue 3, pp. 1749-1754 (2011)
http://dx.doi.org/10.1364/OE.19.001749


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Abstract

Quantum cutting converting a ultraviolet photon into two near-infrared photons has been demonstrated by spectroscopic measurements in NaYF4:Ho3+,Yb3+ synthesized by hydrothermal method. Evidence is provided to confirm the occurrence of quantum cutting. Upon excitation of Ho3+ 5G4 level, near-infrared quantum cutting could occur through a two-step resonance energy transfer from Ho3+ to Yb3+ by cross relaxation, with a maximum quantum efficiency of 155.2%. This result reveals the possibility of violet to near-infrared quantum cutting with a quantum efficiency larger than 100% in Ho3+/Yb3+ codoped fluorides, suggesting the possible application in modifying the solar spectrum to enhance the efficiency of silicon solar cells.

© 2011 OSA

1. Introduction

Effective spectral modification can be obtained by combination of different rare earth ions thanks to the unique and rich energy levels of lanthanide rare earth ions covering a wide spectral range from ultraviolet to infrared. Near-infrared quantum cutting was first achieved in YPO4:Tb3+,Yb3+ [5

5. P. Vergeer, T. J. H. Vlugt, M. H. F. Kox, M. I. den Hertog, J. P. J. M. van der Eerden, and A. Meijerink, “Quantum cutting by cooperative energy transfer in YbxY1-xPO4:Tb3+,” Phys. Rev. B 71(1), 014119 (2005). [CrossRef]

] where a visible photon was converted into two near infrared photons through cooperative energy transfer from Tb3+ to Yb3+. Yb3+ ion possesses only two manifolds: the 2F7/2 ground state and the 2F5/2 excited state, which are separated by about 10000cm−1 in the energy level scheme. Photons emitted by Yb3+ ions is around 1000nm, just above the band gap of crystalline silicon, where the silicon solar cells show an excellent spectral response. Similar phenomena have also been observed in RE3+/Yb3+ (RE = Bi, Tm, and Ce) codoped phosphors and glasses [10

10. X. Wei, J. Zhao, Y. Chen, M. Yin, and Y. Li, “Quantum cutting downconversion by cooperative energy transfer from Bi3+ to Yb3+ in Y2O3 phosphor,” Chin. Phys. B 19(7), 077804 (2010). [CrossRef]

12

12. D. Chen, Y. Wang, Y. Yu, P. Huang, and F. Weng, “Quantum cutting downconversion by cooperative energy transfer from Ce3+ to Yb3+ in borate glasses,” J. Appl. Phys. 104(11), 116105 (2008). [CrossRef]

]. Nevertheless, due to the second order nature of the transfer process, such a cooperative energy transfer is not as efficient as resonance energy transfer, and a high transfer efficiency will only be possible at relatively heavy Yb3+ doping where Yb3+ emission is largely depressed by concentration quenching [13

13. B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-Infrared Quantum Cutting for Photovoltaics,” Adv. Mater. (Deerfield Beach Fla.) 21(30), 3073–3077 (2009). [CrossRef]

]. Therefore resonance energy transfer between rare earth ions is more favorable in order to get a higher quantum efficiency. However, until now, there have been few reports of near-infrared quantum cutting through resonance energy transfer [13

13. B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-Infrared Quantum Cutting for Photovoltaics,” Adv. Mater. (Deerfield Beach Fla.) 21(30), 3073–3077 (2009). [CrossRef]

,14

14. J. J. Eilers, D. Biner, J. T. van Wijngaarden, K. Krämer, H.-U. Güdel, and A. Meijerink, “Efficient visible to infrared quantum cutting through downconversion with the Er3+–Yb3+ couple in Cs3Y2Br9,” Appl. Phys. Lett. 96(15), 151106 (2010). [CrossRef]

].

Ho3+/Yb3+ codoped NaYF4, a host with phonon energy about 400cm−1 [15

15. J. F. Suyver, J. Grimm, M. K. van Veen, D. Biner, K. W. Krämer, and H. U. Güdel, “Upconversion spectroscopy and properties of NaYF4 doped with Er3+, Tm3+ and/or Yb3+,” J. Lumin. 117(1), 1–12 (2006). [CrossRef]

], is well-known as a high-efficiency upconversion phosphor due to efficient energy transfer from Yb3+ to Ho3+. Figure 1
Fig. 1 Energy levels diagram of Ho3+ and Yb3+ showing possible mechanisms for a near-infrared quantum cutting. One ultraviolet photon absorbed by Ho3+ is converted into two Yb3+ near infrared photons through two-step sequential cross relaxations. Solid, dotted, curly arrows represent optical transition, cross relaxation, and multiphonon relaxation, respectively.
presents a schematic diagram of the energy levels of Ho3+ and Yb3+ that are of interest. Close inspection shows that the energy gap of 5G4 and 5F5, 5F5 and 5I7 are resonant with the energy for the transition from 2F5/2 to 2F7/2 on Yb3+. As a result, resonance energy transfer by cross relaxation can be expected to realize quantum cutting. In this paper we investigate the spectroscopic properties of Ho3+ single doped and Ho3+/Yb3+ codoped NaYF4, and demonstrate the existence of near infrared quantum cutting as well as the quantum cutting mechanism for the first time.

2. Experiments

The powder samples of NaYF4 doped with Ho3+(0.5mol%) and Yb3+(0,5,10,20mol%) were synthesized by hydrothermal method. All the chemicals are of analytical grade reagents and used without further purification. The RE(NO3)3 standard solutions(Y/Ho/Yb, 2 mmol in total) with desired stoichiometric ratio were added into 35ml aqueous solution containing 16 mmol NaF by dropwise under magnetic stirring. Then the resulting suspension was transferred into a 50 ml Teflon bottle held in a stainless steel autoclave, sealed, and maintained at 180°C for 24h. After cooling to room temperature, the precipitates were separated by filtration, washed with ethanol for several times and then dried in air. The crystalline phases of the synthesized samples were characterized by XRD(MAC Science Co. Ltd. MXP18AHF), using nickel-filtered Cu Kα radiation in the2θrange from 10° to 70°. Luminescent spectra were measured with a Jobin Yvon Fluorolog-3 system equipped with a 450W Xe-lamp as excitation source and a 50W flash lamp for time resolved measurements, where the visible and infrared emission were detected with a Hamamatsu R928 photomultiplier tube and a liquid nitrogen-cooled DSS-IGA020L InGaAs detector, respectively. To compare the emission intensities of samples with different Yb3+ doping, the emission spectra were recorded at identical experimental conditions. All the measurements were carried out at room temperature.

3. Results and discussion

The XRD patterns for NaYF4 samples with 0.5mol% Ho3+ and different Yb3+ doping concentrations are shown in Fig. 2
Fig. 2 XRD patterns of the NaYF4:Ho3+,Yb3+ samples with different Yb3+ doping concentration compared with NaYF4 standard data JCPDS No.16-0334.
. The little change of the lanthanide ions in their atomic radii facilitates the substitution for Ho3+ and Yb3+ within the NaYF4 matrix. Compared with standard data(JCPDS No.16-0334), all the samples exhibit the peaks of pure hexagonal phase. No second phase is detected in the XRD pattern, revealing the successful doping of Ho3+ and Yb3+ ions in NaYF4. Additionally, the fairly narrow full width at half maximum and intense diffraction peaks indicate the well crystallization of the sample. However, due to the preferential growth effect in the hydrothermal process [16

16. C. Li, Z. Quan, J. Yang, P. Yang, and J. Lin, “Highly Uniform and Monodisperse α-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) Hexagonal Microprism Crystals: Hydrothermal Synthesis and Luminescent Properties,” Inorg. Chem. 46(16), 6329–6337 (2007). [CrossRef] [PubMed]

], the relative intensities of the peaks are a little different from those in standard data.

The cross relaxation depopulates the 5G4 level but simultaneously populates the 5F5 level. Thus an increase of the 5F5 emission intensity is expected in NaYF4:Ho3+,Yb3+ compared with that in NaYF4:Ho3+. On the contrary, the 5F5 emission intensity drops with increasing Yb3+ concentration according to Fig. 3. Figure 5
Fig. 5 Decay curves of (a) Ho3+ 5S2 emission at 540nm and (b) 5F5 emission at 650nm under 359nm excitation in NaYF4:Ho3+,Yb3+ with different Yb3+ concentration. Insets show the lifetime(τ) of 5S2 and 5F5 level, respectively.
presents the decay curves of Ho3+ 5S2 emission at 540nm as well as 5F5 emission at 650nm. It is noted that both the Ho3+ emissions in all the samples show a nearly exponential decay and the lifetime, fitted by a single exponential, decreases rapidly with the increase of Yb3+ concentration as can be seen in the insets of Fig. 4. Since the Ho3+ concentration was maintained constant in all the samples, the decline of the lifetime should not be attributed to the concentration quenching of Ho3+ but to extra decay pathway introduced by Yb3+ doping: resonance energy transfer from Ho3+ to Yb3+ by cross relaxation from Ho3+(5S25I6) to Yb3+(2F7/22F5/2) and Ho3+(5F55I7) to Yb3+(2F7/22F5/2), which accelerates the depopulation of 5F4(5S2) and 5F5 level, respectively, and leads to a shorter lifetime and weaker intensity for both emission. The presence of the former cross relaxation can also be confirmed by the pronounced increase of 5I6 emission in Ho3+/Yb3+ codoped sample. The 5I6 emission around 1200nm, however, is beyond the spectral response of Si solar cells. From the decay curves the energy transfer efficiency can be determined using the following equation [5

5. P. Vergeer, T. J. H. Vlugt, M. H. F. Kox, M. I. den Hertog, J. P. J. M. van der Eerden, and A. Meijerink, “Quantum cutting by cooperative energy transfer in YbxY1-xPO4:Tb3+,” Phys. Rev. B 71(1), 014119 (2005). [CrossRef]

]:
ηTR=1Ix%YbdtI0%Ybdt,
(2)
where I denotes intensity and x%Yb stands for the Yb3+ concentration. The efficiency for the energy transfer from 5S2, 5F5 level to Yb3+ is 92.6% and 94.9%, respectively, in the sample with 20mol% Yb3+ doping. This result means that energy transfer from Ho3+ to Yb3+ is extremely efficient.

4. Conclusions

In summary, an efficient near-infrared quantum cutting through two sequential resonant energy transfer from Ho3+ to Yb3+ has been demonstrated in Ho3+/Yb3+ codoped NaYF4. A maximum quantum efficiency of 155.2% can be determined from excitation spectra and decay curves. The high quantum efficiency and the intense Yb3+ near-infrared emission indicate the potential application in realizing a high energy efficiency of crystalline silicon based solar cells.

Acknowledgments

This work was supported by National Nature Science Foundation of China (10774140, 11011120083, 11074245, and 10904139), Knowledge Innovation Project of the Chinese Academy of Sciences (KJCX2-YW-M11), and Special Foundation for Talents of Anhui Province, China (2007Z021).

References and links

1.

T. Trupke, M. A. Green, and P. Würfel, “Improving solar cell efficiencies by down-conversion of high-energy photons,” J. Appl. Phys. 92(3), 1668 (2002). [CrossRef]

2.

T. Ameri, G. Dennler, C. Lungenschmied, and C. J. Brabec, “Organic tandem solar cells: A review,” Energy Environ. Sci. 2(4), 347–363 (2009). [CrossRef]

3.

B. S. Richards, “Luminescent layers for enhanced silicon solar cell performance: Down-conversion,” Sol. Energy Mater. Sol. Cells 90(9), 1189–1207 (2006). [CrossRef]

4.

C. Strumpel, M. McCann, G. Beaucarne, V. Arkhipov, A. Slaoui, V. Svrcek, C. del Canizo, and I. Tobias, “Modifying the solar spectrum to enhance silicon solar cell efficiency - An overview of available materials,” Sol. Energy Mater. Sol. Cells 91(4), 238–249 (2007). [CrossRef]

5.

P. Vergeer, T. J. H. Vlugt, M. H. F. Kox, M. I. den Hertog, J. P. J. M. van der Eerden, and A. Meijerink, “Quantum cutting by cooperative energy transfer in YbxY1-xPO4:Tb3+,” Phys. Rev. B 71(1), 014119 (2005). [CrossRef]

6.

X. Wei, S. Huang, Y. Chen, C. Guo, M. Yin, and W. Xu, “Energy transfer mechanism in Yb3+ doped YVO4 near-infrared downconversion phosphor,” J. Appl. Phys. 107(10), 103107 (2010). [CrossRef]

7.

Y. Teng, J. Zhou, X. Liu, S. Ye, and J. Qiu, “Efficient broadband near-infrared quantum cutting for solar cells,” Opt. Express 18(9), 9671–9676 (2010). [CrossRef] [PubMed]

8.

D. Chen, Y. Yu, H. Lin, P. Huang, Z. Shan, and Y. Wang, “Ultraviolet-blue to near-infrared downconversion of Nd(3+)-Yb(3+) couple,” Opt. Lett. 35(2), 220–222 (2010). [CrossRef] [PubMed]

9.

D. Chen, Y. Wang, Y. Yu, P. Huang, and F. Weng, “Near-infrared quantum cutting in transparent nanostructured glass ceramics,” Opt. Lett. 33(16), 1884–1886 (2008). [CrossRef] [PubMed]

10.

X. Wei, J. Zhao, Y. Chen, M. Yin, and Y. Li, “Quantum cutting downconversion by cooperative energy transfer from Bi3+ to Yb3+ in Y2O3 phosphor,” Chin. Phys. B 19(7), 077804 (2010). [CrossRef]

11.

S. Ye, B. Zhu, J. Luo, J. Chen, G. Lakshminarayana, and J. Qiu, “Enhanced cooperative quantum cutting in Tm3+- Yb3+ codoped glass ceramics containing LaF3 nanocrystals,” Opt. Express 16(12), 8989–8994 (2008). [CrossRef] [PubMed]

12.

D. Chen, Y. Wang, Y. Yu, P. Huang, and F. Weng, “Quantum cutting downconversion by cooperative energy transfer from Ce3+ to Yb3+ in borate glasses,” J. Appl. Phys. 104(11), 116105 (2008). [CrossRef]

13.

B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-Infrared Quantum Cutting for Photovoltaics,” Adv. Mater. (Deerfield Beach Fla.) 21(30), 3073–3077 (2009). [CrossRef]

14.

J. J. Eilers, D. Biner, J. T. van Wijngaarden, K. Krämer, H.-U. Güdel, and A. Meijerink, “Efficient visible to infrared quantum cutting through downconversion with the Er3+–Yb3+ couple in Cs3Y2Br9,” Appl. Phys. Lett. 96(15), 151106 (2010). [CrossRef]

15.

J. F. Suyver, J. Grimm, M. K. van Veen, D. Biner, K. W. Krämer, and H. U. Güdel, “Upconversion spectroscopy and properties of NaYF4 doped with Er3+, Tm3+ and/or Yb3+,” J. Lumin. 117(1), 1–12 (2006). [CrossRef]

16.

C. Li, Z. Quan, J. Yang, P. Yang, and J. Lin, “Highly Uniform and Monodisperse α-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) Hexagonal Microprism Crystals: Hydrothermal Synthesis and Luminescent Properties,” Inorg. Chem. 46(16), 6329–6337 (2007). [CrossRef] [PubMed]

17.

G. Blasse, and B. Grabmaier, Luminescent Materials, (Springer-Verlag, 1994).

18.

J. M. Meijer, L. Aarts, B. M. van der Ende, T. J. H. Vlugt, and A. Meijerink, “Downconversion for solar cells in YF3:Nd3+, Yb3+,” Phys. Rev. B 81(3), 035107 (2010). [CrossRef]

OCIS Codes
(160.2540) Materials : Fluorescent and luminescent materials
(160.5690) Materials : Rare-earth-doped materials
(300.6340) Spectroscopy : Spectroscopy, infrared

ToC Category:
Materials

History
Original Manuscript: November 16, 2010
Revised Manuscript: January 13, 2011
Manuscript Accepted: January 13, 2011
Published: January 14, 2011

Citation
Kaimo Deng, Tao Gong, Lingxun Hu, Xiantao Wei, Yonghu Chen, and Min Yin, "Efficient near-infrared quantum cutting in NaYF4: Ho3+, Yb3+ for solar photovoltaics," Opt. Express 19, 1749-1754 (2011)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-19-3-1749


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References

  1. T. Trupke, M. A. Green, and P. Würfel, “Improving solar cell efficiencies by down-conversion of high-energy photons,” J. Appl. Phys. 92(3), 1668 (2002). [CrossRef]
  2. T. Ameri, G. Dennler, C. Lungenschmied, and C. J. Brabec, “Organic tandem solar cells: A review,” Energy Environ. Sci. 2(4), 347–363 (2009). [CrossRef]
  3. B. S. Richards, “Luminescent layers for enhanced silicon solar cell performance: Down-conversion,” Sol. Energy Mater. Sol. Cells 90(9), 1189–1207 (2006). [CrossRef]
  4. C. Strumpel, M. McCann, G. Beaucarne, V. Arkhipov, A. Slaoui, V. Svrcek, C. del Canizo, and I. Tobias, “Modifying the solar spectrum to enhance silicon solar cell efficiency - An overview of available materials,” Sol. Energy Mater. Sol. Cells 91(4), 238–249 (2007). [CrossRef]
  5. P. Vergeer, T. J. H. Vlugt, M. H. F. Kox, M. I. den Hertog, J. P. J. M. van der Eerden, and A. Meijerink, “Quantum cutting by cooperative energy transfer in YbxY1-xPO4:Tb3+,” Phys. Rev. B 71(1), 014119 (2005). [CrossRef]
  6. X. Wei, S. Huang, Y. Chen, C. Guo, M. Yin, and W. Xu, “Energy transfer mechanism in Yb3+ doped YVO4 near-infrared downconversion phosphor,” J. Appl. Phys. 107(10), 103107 (2010). [CrossRef]
  7. Y. Teng, J. Zhou, X. Liu, S. Ye, and J. Qiu, “Efficient broadband near-infrared quantum cutting for solar cells,” Opt. Express 18(9), 9671–9676 (2010). [CrossRef] [PubMed]
  8. D. Chen, Y. Yu, H. Lin, P. Huang, Z. Shan, and Y. Wang, “Ultraviolet-blue to near-infrared downconversion of Nd(3+)-Yb(3+) couple,” Opt. Lett. 35(2), 220–222 (2010). [CrossRef] [PubMed]
  9. D. Chen, Y. Wang, Y. Yu, P. Huang, and F. Weng, “Near-infrared quantum cutting in transparent nanostructured glass ceramics,” Opt. Lett. 33(16), 1884–1886 (2008). [CrossRef] [PubMed]
  10. X. Wei, J. Zhao, Y. Chen, M. Yin, and Y. Li, “Quantum cutting downconversion by cooperative energy transfer from Bi3+ to Yb3+ in Y2O3 phosphor,” Chin. Phys. B 19(7), 077804 (2010). [CrossRef]
  11. S. Ye, B. Zhu, J. Luo, J. Chen, G. Lakshminarayana, and J. Qiu, “Enhanced cooperative quantum cutting in Tm3+- Yb3+ codoped glass ceramics containing LaF3 nanocrystals,” Opt. Express 16(12), 8989–8994 (2008). [CrossRef] [PubMed]
  12. D. Chen, Y. Wang, Y. Yu, P. Huang, and F. Weng, “Quantum cutting downconversion by cooperative energy transfer from Ce3+ to Yb3+ in borate glasses,” J. Appl. Phys. 104(11), 116105 (2008). [CrossRef]
  13. B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-Infrared Quantum Cutting for Photovoltaics,” Adv. Mater. (Deerfield Beach Fla.) 21(30), 3073–3077 (2009). [CrossRef]
  14. J. J. Eilers, D. Biner, J. T. van Wijngaarden, K. Krämer, H.-U. Güdel, and A. Meijerink, “Efficient visible to infrared quantum cutting through downconversion with the Er3+–Yb3+ couple in Cs3Y2Br9,” Appl. Phys. Lett. 96(15), 151106 (2010). [CrossRef]
  15. J. F. Suyver, J. Grimm, M. K. van Veen, D. Biner, K. W. Krämer, and H. U. Güdel, “Upconversion spectroscopy and properties of NaYF4 doped with Er3+, Tm3+ and/or Yb3+,” J. Lumin. 117(1), 1–12 (2006). [CrossRef]
  16. C. Li, Z. Quan, J. Yang, P. Yang, and J. Lin, “Highly Uniform and Monodisperse α-NaYF4:Ln3+ (Ln = Eu, Tb, Yb/Er, and Yb/Tm) Hexagonal Microprism Crystals: Hydrothermal Synthesis and Luminescent Properties,” Inorg. Chem. 46(16), 6329–6337 (2007). [CrossRef] [PubMed]
  17. G. Blasse, and B. Grabmaier, Luminescent Materials, (Springer-Verlag, 1994).
  18. J. M. Meijer, L. Aarts, B. M. van der Ende, T. J. H. Vlugt, and A. Meijerink, “Downconversion for solar cells in YF3:Nd3+, Yb3+,” Phys. Rev. B 81(3), 035107 (2010). [CrossRef]

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