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Optics Express

Optics Express

  • Editor: C. Martijn de Sterke
  • Vol. 18, Iss. 9 — Apr. 26, 2010
  • pp: 9671–9676
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Efficient broadband near-infrared quantum cutting for solar cells

Yu Teng, Jiajia Zhou, Xiaofeng Liu, Song Ye, and Jianrong Qiu  »View Author Affiliations


Optics Express, Vol. 18, Issue 9, pp. 9671-9676 (2010)
http://dx.doi.org/10.1364/OE.18.009671


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Abstract

Yb2+ and Yb3+ co-activated luminescent material that can cut one photon in ultraviolet and visible region into multi NIR photons could be used as a downconversion luminescent convertor in front of crystalline silicon solar cell panels to reduce thermalization loss of the solar cell. After a direct excitation of Yb2+ ions, an intense Yb3+ luminescence is observed based on a cooperative energy transfer process. The energy transfer process is discussed according to the dependence of Yb3+ luminescence intensity on the excitation power and the ambient temperature.

© 2010 OSA

1. Introduction

However, the present studied DC materials are still far from practical application, because the transitions between 4f levels of trivalent lanthanide ions are forbidden transitions. The oscillator strengths of 4f–4f transitions are typically on the order of 10−6; dipole allowed transitions, by comparison, may have oscillator strength of up to unity. Thus, the absorption strength of lanthanide 4f–4f transitions is very weak [14

14. B. M. van der Ende, L. Aarts, and A. Meijerink, “Lanthanide ions as spectral converters for solar cells,” Phys. Chem. Chem. Phys. 11(47), 11081–11095 (2009). [CrossRef] [PubMed]

]. To solve the absorption problem a new ion is required to work as a donor which absorbs efficiently in the UV and visible part and transfers the energy to Yb3+ ions. In this paper, we demonstrate the efficient broadband energy transfer from Yb2+ to Yb3+ ions in CaAl2O4 phosphors for the first time. The photoluminescence (PL) and photoluminescence excitation (PLE) spectra show that energy transfer happened between Yb2+ and Yb3+ ions. Through the study of the dependence of luminescence intensity on the excitation power and the ambient temperature, the mechanism of energy transfer involving a two or three photon cutting process is discussed.

2. Experiments

CaAl2O4: Yb2+, Yb3+ samples were prepared using high-temperature solid-state reaction method. High purity (99.99%) CaCO3, Al2O3, and Yb2O3 were used as raw materials. Reactant samples after mixed thoroughly in an agate mortar were presintered in air at 900 °C for 6 h. The samples were ground again and sintered under two different ambiences, reducing atmosphere (8 vol% H2 + 92 vol% N2) and air, at 1300 °C for 2 hours. Samples doped with 0 and 4 mol% Yb3+ ions were labeled as sample A0 (B0) and A (B); respectively (A/A0 stands for the samples sintered under reducing atmosphere while B/B0 represents the samples sintered in air). The crystalline phase and crystallinity of the synthesized phosphors were investigated by powder XRD using Rigaku D/MAX-RA diffractometer. The absorption spectra were obtained with a spectrophotometer (Hitachi-4100). The PL and PLE spectra in the infrared region were recorded with a FLS920 fluorescence spectrophotometer.

3. Results and discussion

The XRD patterns of sample A and A0 are shown in Fig. 1
Fig. 1 Powder XRD pattern of sample A and A0. (“*” belong to Ca3Al2O6 impure phase, other diffraction peaks belong to CaAl2O4 phase).
. From the XRD pattern, all the diffraction peaks except for two small ones (shown in Fig. 1 with a “*” in sample A), can be indexed to the pure monoclinic phase (space group: P21/n) of CaAl2O4. Calculated lattice parameters are as follows: a = 8.702 Å, b = 8.092 Å, c = 15.18 Å and Z = 12. The XRD pattern matched perfectly with that reported for CaAl2O4 (JCPDS (23-1036)) [15

15. W. Hörkner, “Zur kristallstruktur von CaAl2O4,” J. Inorg. Nucl. Chem. 38(5), 983 (1976). [CrossRef]

]. The XRD patterns of sample B and B0 are the same as that of sample A and A0, which can be indexed to the pure monoclinic phase (space group: P21/n) of CaAl2O4. The crystal structure of CaAl2O4 is derivative of the stuffed tridymite structure. In this structure, all atoms are on the general site, with C1 site symmetry. Two of the Ca ions sit in distorted octahedra, the third Ca is housed in a lopsided pentagonal pyramid, whereas Al is in six distorted tetrahedral sites that are corner linked in three dimensions [16

16. S. Iftekhar, J. Grins, G. Svensson, J. Loof, T. Jarmar, G. A. Botton, C. M. Andrei, and H. Engqvist, “Phase formation of CaAl2O4 from CaCO3-Al2O3 powder mixtures,” J. Eur. Ceram. Soc. 28(4), 747–756 (2008). [CrossRef]

]. When Yb2+ and Yb3+ ions are introduced into CaAl2O4 crystal, they will take the place of Ca2+ ions on the same site due to the similar ionic radius of Ca2+, Yb2+ and Yb3+ ions (both 0.099 nm for Ca2+ and Yb3+, and 0.102 nm for Yb2+) [17

17. R. D. Shannon, “Revised effective ionic radii and systematic studies of interatomicdistances in halides and chalcogenides,” Acta Crystallogr. 32(5), 751–767 (1976). [CrossRef]

].

Figure 2
Fig. 2 Absorption spectra for sample A0, A, B0 and B. Inset: Curves 1 and 2 are the difference absorption spectra between sample B and B0, and between sample A and A0, respectively. Curve 3 is the difference absorption spectrum between curve 2 and curve 1.
shows the absorption spectra for sample A0, A, B0 and B, respectively. The peak centered at 950 nm in the near infrared region is due to the absorption of Yb3+ ions. The intensity of the absorption peak in sample B is much stronger than that of sample A due to the reduction of Yb3+ ions sintered under reducing atmosphere [18

18. J. Oliva, E. De la Rosa, L. A. Diaz-Torres, P. Salas, and C. Ángeles-Chavez, “Annealing effect on the luminescence properties of BaZrO3: Yb3+ microcrystals,” J. Appl. Phys. 104(2), 023505 (2008). [CrossRef]

]. We calculated the integral area of the absorption peak at 950 nm in sample A and B, and estimate the extent of Yb2+ ions. The result shows that about 42 percents of Yb3+ ions were reduced to Yb2+ in a reducing atmosphere. We calculated the difference between the absorption spectra of sample A and A0, and also the difference between the absorption spectra of sample B and B0 (shown in the inset of Fig. 1, curve 2 and 1). For curve 1, in the ultraviolet region, the peak located at 265 nm is due to the charge transfer (CT) transition of Yb3+ ions that involves the transfer of an electron from the ligand anion O2− to the central cation Yb3+ ion [19

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

]. It is known that configurational 4fN –4fN−15d transitions are in general composed of very broad peaks due to a displacement of the vibrational equilibrium position between the ground and excited states [20

20. C. Duan and P. A. Tanner, “Simulation of 4f-5d transitions of Yb2+ in potassium and sodium halides,” J. Phys. Condens. Matter 20(21), 215228 (2008). [CrossRef]

]. The new absorption peak in the curve 2, which centered at 310 nm, is caused by the 4f-5d transitions of Yb2+ ions [21

21. M. Engholm, L. Norin, and D. Åberg, “Strong UV absorption and visible luminescence in ytterbium-doped aluminosilicate glass under UV excitation,” Opt. Lett. 32(22), 3352–3354 (2007). [CrossRef] [PubMed]

]. Curve 3 is the calculated difference between curve 1 and curve 2. From the absorption spectra and the difference curves, we can conclude that some Yb3+ ions were reduced to Yb2+ ions during the sintering process in sample A, and this difference in concentration of Yb2+ and Yb3+ ions between samples A and A0, and B and B0 affects their luminescence properties.

In Fig. 3
Fig. 3 Emission spectra in the near infrared region under excitation at 310 nm for sample A and A0, and under excitation at 275 nm for sample B (solid lines in red, blue and magenta). Excitation spectra of Yb3+ monitored at 978 nm of sample A (red dashed line) and B (blue dashed line).
, PL spectra in the near infrared region and PLE spectra in the ultraviolet and visible region of Yb3+ monitored at 978 nm of three samples (A, A0 and B) are shown. In the Yb3+-free sample, there is no detectable emission peaks in the near infrared region for both samples A0 and B0 (the emission curve of B0 is not shown). For sample B sintered in air, the near infrared region emission peaks correspond to an excitation peak located at 275 nm which is due to the CT transition of Yb3+ ions, as discussed above. For sample A, when excited with a 310 nm UV light, there is an intense emission peak located at 978 nm accompanied by several weak shoulders owing to transitions among different Stark levels of 2FJ (J=5/2, 7/2) of Yb3+ ions. The excitation spectra monitoring the Yb3+ emission of sample A contains two peaks located at 275 and 310 nm, respectively. The 275 nm excitation peak has been discussed above. The 310 nm excitation peak is caused by the energy transfer (ET) from Yb2+to Yb3+ [21

21. M. Engholm, L. Norin, and D. Åberg, “Strong UV absorption and visible luminescence in ytterbium-doped aluminosilicate glass under UV excitation,” Opt. Lett. 32(22), 3352–3354 (2007). [CrossRef] [PubMed]

]. When irradiated with a 310 nm UV light, the Yb2+ ions were excited from the 4f14 energy level to the 4f135d energy level. The excited Yb2+ ions can transfer their energy to Yb3+ ions, and result in the near infrared emission originated from the 2F5/22F7/2 transition of Yb3+ ions. In the visible region, no Yb2+ ions emission is observed. Similar phenomenon has been reported by Meijerink et al in 1997 in the same phosphors matrix [22

22. S. Lizzo, E. P. Klein Nagelvoort, R. Ersens, A. Meijerink, and G. Blasse, “On the quenching of the Yb2+ luminescence in different host lattices,” J. Phys. Chem. Solids 58(6), 963–968 (1997). [CrossRef]

]. It is known that the host lattice (composition and structure) has a large influence on the quenching temperature of the f-d luminescence. In this system, the Yb2+ luminescence cannot be detected until down to 4.2 K caused by thermally activated photoionization at relatively low temperature.

4. Conclusions

In summary, CaAl2O4 phosphors doped with 0 and 4 mol% Yb3+ ions were successfully synthesized using solid-state reaction method under two different ambiences. The quantity of Yb2+ sintered in reducing atmosphere is far larger than that sintered in air. Strong infrared emission originated from Yb3+ 2F5/22F7/2 transition is observed in Yb3+ ions doped powder samples sintered in reducing atmosphere, which is due to the energy transfer from Yb2+ ions to Yb3+ ions. These Yb2+ ions correspond to a broad excitation band in the near-ultraviolet and visible region of 250-450 nm. From the PL and PLE spectra of powder sample sintered under reducing atmosphere, we can conclude that this kind of materials would have potential use in the modification and application of solar spectral through a downconversion process achieved by energy transfer from Yb2+ to Yb3+ ions and may increase the conversion efficiency of c-Si solar cells.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (Grant Nos. 50672807, 50872123 and 50802083), National Basic Research Program of China (2006CB8060007), and the Program for Changjiang Scholars and Innovative Research Team in University (IRT0651).

References and links

1.

D. Timmerman, I. Izeddin, P. Stallinga, I. N. Yassievich, and T. Gregorkiewicz, “Space-separated quantum cutting with silicon nanocrystals for photovoltaic applications,” Nat. Photonics 2(2), 105–109 (2008). [CrossRef]

2.

B. van der Zwaan and A. Rabl, “Prospects for PV: a learning curve analysis,” Sol. Energy 74(1), 19–31 (2003). [CrossRef]

3.

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

4.

B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-Infrared Quantum Cutting for Photovoltaics,” Adv. Mater. 21(30), 1 (2009). [CrossRef]

5.

L. Aarts, B. M. van der Ende, and A. Meijerink, “Downconversion for solar cells in NaYF4:Er,Yb,” J. Appl. Phys. 106(2), 023522 (2009). [CrossRef]

6.

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]

7.

X. Liu, Y. Qiao, G. Dong, S. Ye, B. Zhu, G. Lakshminarayana, D. Chen, and J. Qiu, “Cooperative downconversion in Yb3+/-RE3+ (RE=Tm or Pr) codoped lanthanum borogermanate glasses,” Opt. Lett. 33(23), 2858–2860 (2008). [CrossRef] [PubMed]

8.

Q. Zhang, G. Yang, and Z. Jiang, “Cooperative downconversion in GdAl3(BO3)4:RE3+, Yb3+ (RE=Pr, Tb, and Tm),” Appl. Phys. Lett. 91(5), 051903 (2007). [CrossRef]

9.

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]

10.

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]

11.

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]

12.

D. Chen, Y. Yu, Y. Wang, P. Huang, and F. Weng, “Cooperative Energy Transfer Up-Conversion and Quantum Cutting Down-Conversion in Yb3+:TbF3 Nanocrystals Embedded Glass Ceramics,” J. Phys. Chem. C 113(16), 6406–6410 (2009). [CrossRef]

13.

S. Ye, B. Zhu, J. X. Chen, J. Luo, and J. Qiu, “Infrared quantum cutting in Tb3+, Yb3+ codoped transparent glass ceramics containing CaF2 nanocrystals,” Appl. Phys. Lett. 92(14), 141112 (2008). [CrossRef]

14.

B. M. van der Ende, L. Aarts, and A. Meijerink, “Lanthanide ions as spectral converters for solar cells,” Phys. Chem. Chem. Phys. 11(47), 11081–11095 (2009). [CrossRef] [PubMed]

15.

W. Hörkner, “Zur kristallstruktur von CaAl2O4,” J. Inorg. Nucl. Chem. 38(5), 983 (1976). [CrossRef]

16.

S. Iftekhar, J. Grins, G. Svensson, J. Loof, T. Jarmar, G. A. Botton, C. M. Andrei, and H. Engqvist, “Phase formation of CaAl2O4 from CaCO3-Al2O3 powder mixtures,” J. Eur. Ceram. Soc. 28(4), 747–756 (2008). [CrossRef]

17.

R. D. Shannon, “Revised effective ionic radii and systematic studies of interatomicdistances in halides and chalcogenides,” Acta Crystallogr. 32(5), 751–767 (1976). [CrossRef]

18.

J. Oliva, E. De la Rosa, L. A. Diaz-Torres, P. Salas, and C. Ángeles-Chavez, “Annealing effect on the luminescence properties of BaZrO3: Yb3+ microcrystals,” J. Appl. Phys. 104(2), 023505 (2008). [CrossRef]

19.

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

20.

C. Duan and P. A. Tanner, “Simulation of 4f-5d transitions of Yb2+ in potassium and sodium halides,” J. Phys. Condens. Matter 20(21), 215228 (2008). [CrossRef]

21.

M. Engholm, L. Norin, and D. Åberg, “Strong UV absorption and visible luminescence in ytterbium-doped aluminosilicate glass under UV excitation,” Opt. Lett. 32(22), 3352–3354 (2007). [CrossRef] [PubMed]

22.

S. Lizzo, E. P. Klein Nagelvoort, R. Ersens, A. Meijerink, and G. Blasse, “On the quenching of the Yb2+ luminescence in different host lattices,” J. Phys. Chem. Solids 58(6), 963–968 (1997). [CrossRef]

23.

T. Miyakawa and D. L. Dexter, “Phonon sidebands, multiphonon relaxation of excited states, and phonon-assisted energy transfer between ions in solids,” Phys. Rev. B 1(7), 2961–2969 (1970). [CrossRef]

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

ToC Category:
Solar Energy

History
Original Manuscript: March 5, 2010
Revised Manuscript: April 8, 2010
Manuscript Accepted: April 13, 2010
Published: April 23, 2010

Virtual Issues
Focus Issue: Solar Concentrators (2010) Optics Express

Citation
Yu Teng, Jiajia Zhou, Xiaofeng Liu, Song Ye, and Jianrong Qiu, "Efficient broadband near-infrared quantum cutting for solar cells," Opt. Express 18, 9671-9676 (2010)
http://www.opticsinfobase.org/oe/abstract.cfm?URI=oe-18-9-9671


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References

  1. D. Timmerman, I. Izeddin, P. Stallinga, I. N. Yassievich, and T. Gregorkiewicz, “Space-separated quantum cutting with silicon nanocrystals for photovoltaic applications,” Nat. Photonics 2(2), 105–109 (2008). [CrossRef]
  2. B. van der Zwaan and A. Rabl, “Prospects for PV: a learning curve analysis,” Sol. Energy 74(1), 19–31 (2003). [CrossRef]
  3. C. Strumpel, M. McCann, G. Beaucarne, V. Arkhipov, A. Slaouic, V. Svrcek, C. del Canizo, and I. Tobias, “Modifying the solar spectrum to enhance silicon solar cell efficiency - An overview of available materials,” Solar Energy Solar Cells. 91(4), 238–249 (2007). [CrossRef]
  4. B. M. van der Ende, L. Aarts, and A. Meijerink, “Near-Infrared Quantum Cutting for Photovoltaics,” Adv. Mater. 21(30), 1 (2009). [CrossRef]
  5. L. Aarts, B. M. van der Ende, and A. Meijerink, “Downconversion for solar cells in NaYF4:Er,Yb,” J. Appl. Phys. 106(2), 023522 (2009). [CrossRef]
  6. 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]
  7. X. Liu, Y. Qiao, G. Dong, S. Ye, B. Zhu, G. Lakshminarayana, D. Chen, and J. Qiu, “Cooperative downconversion in Yb3+/-RE3+ (RE=Tm or Pr) codoped lanthanum borogermanate glasses,” Opt. Lett. 33(23), 2858–2860 (2008). [CrossRef] [PubMed]
  8. Q. Zhang, G. Yang, and Z. Jiang, “Cooperative downconversion in GdAl3(BO3)4:RE3+, Yb3+ (RE=Pr, Tb, and Tm),” Appl. Phys. Lett. 91(5), 051903 (2007). [CrossRef]
  9. 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]
  10. 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]
  11. 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]
  12. D. Chen, Y. Yu, Y. Wang, P. Huang, and F. Weng, “Cooperative Energy Transfer Up-Conversion and Quantum Cutting Down-Conversion in Yb3+:TbF3 Nanocrystals Embedded Glass Ceramics,” J. Phys. Chem. C 113(16), 6406–6410 (2009). [CrossRef]
  13. S. Ye, B. Zhu, J. X. Chen, J. Luo, and J. Qiu, “Infrared quantum cutting in Tb3+, Yb3+ codoped transparent glass ceramics containing CaF2 nanocrystals,” Appl. Phys. Lett. 92(14), 141112 (2008). [CrossRef]
  14. B. M. van der Ende, L. Aarts, and A. Meijerink, “Lanthanide ions as spectral converters for solar cells,” Phys. Chem. Chem. Phys. 11(47), 11081–11095 (2009). [CrossRef] [PubMed]
  15. W. Hörkner, “Zur kristallstruktur von CaAl2O4,” J. Inorg. Nucl. Chem. 38(5), 983 (1976). [CrossRef]
  16. S. Iftekhar, J. Grins, G. Svensson, J. Loof, T. Jarmar, G. A. Botton, C. M. Andrei, and H. Engqvist, “Phase formation of CaAl2O4 from CaCO3-Al2O3 powder mixtures,” J. Eur. Ceram. Soc. 28(4), 747–756 (2008). [CrossRef]
  17. R. D. Shannon, “Revised effective ionic radii and systematic studies of interatomicdistances in halides and chalcogenides,” Acta Crystallogr. 32(5), 751–767 (1976). [CrossRef]
  18. J. Oliva, E. De la Rosa, L. A. Diaz-Torres, P. Salas, and C. Ángeles-Chavez, “Annealing effect on the luminescence properties of BaZrO3: Yb3+ microcrystals,” J. Appl. Phys. 104(2), 023505 (2008). [CrossRef]
  19. G. Blasse, and B. Grabmaier, Luminescent Materials, Springer-Verlag, 1994.
  20. C. Duan and P. A. Tanner, “Simulation of 4f-5d transitions of Yb2+ in potassium and sodium halides,” J. Phys. Condens. Matter 20(21), 215228 (2008). [CrossRef]
  21. M. Engholm, L. Norin, and D. Åberg, “Strong UV absorption and visible luminescence in ytterbium-doped aluminosilicate glass under UV excitation,” Opt. Lett. 32(22), 3352–3354 (2007). [CrossRef] [PubMed]
  22. S. Lizzo, E. P. Klein Nagelvoort, R. Ersens, A. Meijerink, and G. Blasse, “On the quenching of the Yb2+ luminescence in different host lattices,” J. Phys. Chem. Solids 58(6), 963–968 (1997). [CrossRef]
  23. T. Miyakawa and D. L. Dexter, “Phonon sidebands, multiphonon relaxation of excited states, and phonon-assisted energy transfer between ions in solids,” Phys. Rev. B 1(7), 2961–2969 (1970). [CrossRef]

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