Abstract

The bandgap of iron-doped ZnS has been reported by others to change significantly under the addition of a few atomic percent of iron, which would have significant implications for solar energy. Here, thin films of FexZn1-xS with x = 0 to 0.24 were made by co-deposition of Fe and ZnS using thermal evaporation. In contrast to results on nanoparticles and electrodeposited materials, all co-deposited films had optical properties consistent with a direct bandgap of ~3-3.5 eV. The absorption peak at 2.7 µm from substitutional Fe2+ in the ZnS films was well isolated up to concentrations of over 2% (~1021cm−3), despite the small crystallite size, suggesting the films may have applications as mid-infrared saturable absorbers. Increasing dopant concentration resulted in band edge softening. Density functional calculations are presented and are consistent with our observations of the Fe:ZnS films, demonstrating spin-polarized midgap states and additional states at the band edge.

© 2015 Optical Society of America

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References

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    [Crossref]
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    [Crossref]
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    [Crossref] [PubMed]
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    [Crossref]
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    [Crossref] [PubMed]
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    [Crossref]

2015 (2)

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

2014 (1)

P. C. Patel and P. C. Srivastava, “Fe doping in ZnS for realizing nanocrystalline-diluted magnetic semiconductor phase,” J. Mater. Sci. 49(17), 6012–6019 (2014).
[Crossref]

2013 (2)

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

2012 (1)

Y. A. Nitsuk, Y. A. Vaksman, V. V. Yatsun, and Y. N. Purtov, “Optical absorption and diffusion of iron in ZnS single crystals,” Funct. Mater. 19, 182–186 (2012).

2011 (1)

J. H. Zhang, J. W. Ding, J. X. Cao, and Y. L. Zhang, “Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands,” J. Solid State Chem. 184(3), 477–480 (2011).
[Crossref]

2010 (2)

F. Zhu, S. Dong, and G. Yang, “Ferromagnetic properties in Fe-doped ZnS thin films,” Optoelectron. Adv. Mater.-, Rapid Commun. 4, 2072–2075 (2010).

J. Xie, “First-principles study on the magnetism in ZnS-based diluted magnetic semiconductors,” J. Magn. Magn. Mater. 322(19), L37–L41 (2010).
[Crossref]

2008 (1)

S. H. Deulkar, C. H. Bhosale, and M. Sharon, “Optical studies on non-stiochiometric (Zn, Fe)S chalcogenide bulk pellets prepared by coprecipitation,” Mater. Chem. Phys. 111(2-3), 260–264 (2008).
[Crossref]

2007 (1)

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

2006 (3)

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

C. I. Pearce, R. A. D. Pattrick, and D. J. Vaughan, “Electrical and magnetic properties of sulfides,” Rev. Mineral. Geochem. 61(1), 127–180 (2006).
[Crossref]

H. Hu and W. Zhang, “Synthesis and properties of transition metals and rare-earth metals doped ZnS nanoparticles,” Opt. Mater. 28(5), 536–550 (2006).
[Crossref]

2005 (1)

C. Tablero, “Correlation effects and electronic properties of Cr-substituted SZn with an intermediate band,” J. Chem. Phys. 123(11), 114709 (2005).
[Crossref] [PubMed]

2001 (1)

H. C. Ong and R. P. H. Chang, “Optical constants of wurtzite ZnS thin films determined by spectroscopic ellipsometry,” Appl. Phys. Lett. 79(22), 3612–3614 (2001).
[Crossref]

1996 (1)

J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett. 77(18), 3865–3868 (1996).
[Crossref] [PubMed]

1995 (2)

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

A. Kashyout, A. Arico, N. Giordano, and V. Antonucci, “Influence of Annealing Temperature on the Crystallographic and Optical-Properties of Electrodeposited Znfes Thin-Film Semiconductors,” Mater. Chem. Phys. 41(1), 55–60 (1995).
[Crossref]

1993 (1)

D. Minkov and R. Swanepoel, “Computerization of the optical characterization of a thin dielectric film,” Opt. Eng. 32(12), 3333–3337 (1993).
[Crossref]

1991 (1)

E. J. Baerends and E. J. Baerends, “Precise density-functional method for periodic structures,” Phys. Rev. B Condens. Matter 44(15), 7888–7903 (1991).
[Crossref] [PubMed]

1983 (1)

R. Swanepoel, “Determination of the thickness and optical-constants of amorphous-silicon,” J. Phys. E Sci. Instrum. 16(12), 1214–1222 (1983).
[Crossref]

1982 (1)

K. L. Lewis, G. S. Arthur, and D. A. Edwards, “The incorporation of iron impurities in cubic ZnS,” J. Cryst. Growth 59(1-2), 201–209 (1982).
[Crossref]

1980 (1)

S. Vosko, L. Wilk, and M. Nusair, “Accurate spin-dependent electron liquid correlation energies for local spin-density calculations - a critical analysis,” Can. J. Phys. 58(8), 1200–1211 (1980).
[Crossref]

1976 (1)

J. L. Horwood, M. G. Townsend, and A. H. Webster, “Magnetic susceptibility of single-crystal Fe1−xS,” J. Solid State Chem. 17(1-2), 35–42 (1976).
[Crossref]

1972 (1)

J. D. Dow and D. Redfield, “Toward a unified theory of Urbach’s rule and exponential absorption edges,” Phys. Rev. B 5(2), 594–610 (1972).
[Crossref]

Abbad, A.

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

Ahsan, N.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Antonucci, V.

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

A. Kashyout, A. Arico, N. Giordano, and V. Antonucci, “Influence of Annealing Temperature on the Crystallographic and Optical-Properties of Electrodeposited Znfes Thin-Film Semiconductors,” Mater. Chem. Phys. 41(1), 55–60 (1995).
[Crossref]

Arico, A.

A. Kashyout, A. Arico, N. Giordano, and V. Antonucci, “Influence of Annealing Temperature on the Crystallographic and Optical-Properties of Electrodeposited Znfes Thin-Film Semiconductors,” Mater. Chem. Phys. 41(1), 55–60 (1995).
[Crossref]

Aricò, A. S.

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

Arthur, G. S.

K. L. Lewis, G. S. Arthur, and D. A. Edwards, “The incorporation of iron impurities in cubic ZnS,” J. Cryst. Growth 59(1-2), 201–209 (1982).
[Crossref]

Baerends, E. J.

E. J. Baerends and E. J. Baerends, “Precise density-functional method for periodic structures,” Phys. Rev. B Condens. Matter 44(15), 7888–7903 (1991).
[Crossref] [PubMed]

E. J. Baerends and E. J. Baerends, “Precise density-functional method for periodic structures,” Phys. Rev. B Condens. Matter 44(15), 7888–7903 (1991).
[Crossref] [PubMed]

Benstaali, W.

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

Bentata, S.

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

Bentounes, H. A.

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

Bhosale, C. H.

S. H. Deulkar, C. H. Bhosale, and M. Sharon, “Optical studies on non-stiochiometric (Zn, Fe)S chalcogenide bulk pellets prepared by coprecipitation,” Mater. Chem. Phys. 111(2-3), 260–264 (2008).
[Crossref]

Bouadjemi, B.

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

Burke, K.

J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett. 77(18), 3865–3868 (1996).
[Crossref] [PubMed]

Cao, J. X.

J. H. Zhang, J. W. Ding, J. X. Cao, and Y. L. Zhang, “Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands,” J. Solid State Chem. 184(3), 477–480 (2011).
[Crossref]

Chang, R. P. H.

H. C. Ong and R. P. H. Chang, “Optical constants of wurtzite ZnS thin films determined by spectroscopic ellipsometry,” Appl. Phys. Lett. 79(22), 3612–3614 (2001).
[Crossref]

Crea, F.

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

Deulkar, S. H.

S. H. Deulkar, C. H. Bhosale, and M. Sharon, “Optical studies on non-stiochiometric (Zn, Fe)S chalcogenide bulk pellets prepared by coprecipitation,” Mater. Chem. Phys. 111(2-3), 260–264 (2008).
[Crossref]

Ding, J. W.

J. H. Zhang, J. W. Ding, J. X. Cao, and Y. L. Zhang, “Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands,” J. Solid State Chem. 184(3), 477–480 (2011).
[Crossref]

Dong, S.

F. Zhu, S. Dong, and G. Yang, “Ferromagnetic properties in Fe-doped ZnS thin films,” Optoelectron. Adv. Mater.-, Rapid Commun. 4, 2072–2075 (2010).

Dow, J. D.

J. D. Dow and D. Redfield, “Toward a unified theory of Urbach’s rule and exponential absorption edges,” Phys. Rev. B 5(2), 594–610 (1972).
[Crossref]

Edwards, D. A.

K. L. Lewis, G. S. Arthur, and D. A. Edwards, “The incorporation of iron impurities in cubic ZnS,” J. Cryst. Growth 59(1-2), 201–209 (1982).
[Crossref]

Ekins-Daukes, N. J.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Ernzerhof, M.

J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett. 77(18), 3865–3868 (1996).
[Crossref] [PubMed]

Fan, X. W.

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Farrell, D. J.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Fedorov, V.

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

Feng, Q. J.

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Frolov, M. P.

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Ge, W. K.

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

Giordano, N.

A. Kashyout, A. Arico, N. Giordano, and V. Antonucci, “Influence of Annealing Temperature on the Crystallographic and Optical-Properties of Electrodeposited Znfes Thin-Film Semiconductors,” Mater. Chem. Phys. 41(1), 55–60 (1995).
[Crossref]

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

Guillemoles, J.-F.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Hess, O.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Horwood, J. L.

J. L. Horwood, M. G. Townsend, and A. H. Webster, “Magnetic susceptibility of single-crystal Fe1−xS,” J. Solid State Chem. 17(1-2), 35–42 (1976).
[Crossref]

Hu, H.

H. Hu and W. Zhang, “Synthesis and properties of transition metals and rare-earth metals doped ZnS nanoparticles,” Opt. Mater. 28(5), 536–550 (2006).
[Crossref]

Kashyout, A.

A. Kashyout, A. Arico, N. Giordano, and V. Antonucci, “Influence of Annealing Temperature on the Crystallographic and Optical-Properties of Electrodeposited Znfes Thin-Film Semiconductors,” Mater. Chem. Phys. 41(1), 55–60 (1995).
[Crossref]

Kashyout, A. B.

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

Kita, T.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Korostelin, Y. V.

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Kozlovsky, V. I.

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Lewis, K. L.

K. L. Lewis, G. S. Arthur, and D. A. Edwards, “The incorporation of iron impurities in cubic ZnS,” J. Cryst. Growth 59(1-2), 201–209 (1982).
[Crossref]

Li, B. K.

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

Liu, Y. C.

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Lu, Y. M.

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Martyshkin, D.

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

Minkov, D.

D. Minkov and R. Swanepoel, “Computerization of the optical characterization of a thin dielectric film,” Opt. Eng. 32(12), 3333–3337 (1993).
[Crossref]

Mirov, M.

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

Mirov, S.

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

Monforte, G.

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

Moskalev, I.

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

Nitsuk, Y. A.

Y. A. Nitsuk, Y. A. Vaksman, V. V. Yatsun, and Y. N. Purtov, “Optical absorption and diffusion of iron in ZnS single crystals,” Funct. Mater. 19, 182–186 (2012).

Nusair, M.

S. Vosko, L. Wilk, and M. Nusair, “Accurate spin-dependent electron liquid correlation energies for local spin-density calculations - a critical analysis,” Can. J. Phys. 58(8), 1200–1211 (1980).
[Crossref]

Okada, Y.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Ong, H. C.

H. C. Ong and R. P. H. Chang, “Optical constants of wurtzite ZnS thin films determined by spectroscopic ellipsometry,” Appl. Phys. Lett. 79(22), 3612–3614 (2001).
[Crossref]

Patel, P. C.

P. C. Patel and P. C. Srivastava, “Fe doping in ZnS for realizing nanocrystalline-diluted magnetic semiconductor phase,” J. Mater. Sci. 49(17), 6012–6019 (2014).
[Crossref]

Pattrick, R. A. D.

C. I. Pearce, R. A. D. Pattrick, and D. J. Vaughan, “Electrical and magnetic properties of sulfides,” Rev. Mineral. Geochem. 61(1), 127–180 (2006).
[Crossref]

Pearce, C. I.

C. I. Pearce, R. A. D. Pattrick, and D. J. Vaughan, “Electrical and magnetic properties of sulfides,” Rev. Mineral. Geochem. 61(1), 127–180 (2006).
[Crossref]

Perdew, J. P.

J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett. 77(18), 3865–3868 (1996).
[Crossref] [PubMed]

Phillips, C. C.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Podmar’kov, Y. P.

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Purtov, Y. N.

Y. A. Nitsuk, Y. A. Vaksman, V. V. Yatsun, and Y. N. Purtov, “Optical absorption and diffusion of iron in ZnS single crystals,” Funct. Mater. 19, 182–186 (2012).

Pusch, A.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Redfield, D.

J. D. Dow and D. Redfield, “Toward a unified theory of Urbach’s rule and exponential absorption edges,” Phys. Rev. B 5(2), 594–610 (1972).
[Crossref]

Savinova, S. A.

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Sharon, M.

S. H. Deulkar, C. H. Bhosale, and M. Sharon, “Optical studies on non-stiochiometric (Zn, Fe)S chalcogenide bulk pellets prepared by coprecipitation,” Mater. Chem. Phys. 111(2-3), 260–264 (2008).
[Crossref]

Shen, D. Z.

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Shoji, Y.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Skasyrsky, Y. K.

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Sogabe, T.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Sou, I. K.

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

Srivastava, P. C.

P. C. Patel and P. C. Srivastava, “Fe doping in ZnS for realizing nanocrystalline-diluted magnetic semiconductor phase,” J. Mater. Sci. 49(17), 6012–6019 (2014).
[Crossref]

Swanepoel, R.

D. Minkov and R. Swanepoel, “Computerization of the optical characterization of a thin dielectric film,” Opt. Eng. 32(12), 3333–3337 (1993).
[Crossref]

R. Swanepoel, “Determination of the thickness and optical-constants of amorphous-silicon,” J. Phys. E Sci. Instrum. 16(12), 1214–1222 (1983).
[Crossref]

Tablero, C.

C. Tablero, “Correlation effects and electronic properties of Cr-substituted SZn with an intermediate band,” J. Chem. Phys. 123(11), 114709 (2005).
[Crossref] [PubMed]

Tamaki, R.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Townsend, M. G.

J. L. Horwood, M. G. Townsend, and A. H. Webster, “Magnetic susceptibility of single-crystal Fe1−xS,” J. Solid State Chem. 17(1-2), 35–42 (1976).
[Crossref]

Vaksman, Y. A.

Y. A. Nitsuk, Y. A. Vaksman, V. V. Yatsun, and Y. N. Purtov, “Optical absorption and diffusion of iron in ZnS single crystals,” Funct. Mater. 19, 182–186 (2012).

Vaughan, D. J.

C. I. Pearce, R. A. D. Pattrick, and D. J. Vaughan, “Electrical and magnetic properties of sulfides,” Rev. Mineral. Geochem. 61(1), 127–180 (2006).
[Crossref]

Vosko, S.

S. Vosko, L. Wilk, and M. Nusair, “Accurate spin-dependent electron liquid correlation energies for local spin-density calculations - a critical analysis,” Can. J. Phys. 58(8), 1200–1211 (1980).
[Crossref]

Wang, C.

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

Wang, J. N.

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

Webster, A. H.

J. L. Horwood, M. G. Townsend, and A. H. Webster, “Magnetic susceptibility of single-crystal Fe1−xS,” J. Solid State Chem. 17(1-2), 35–42 (1976).
[Crossref]

Wilk, L.

S. Vosko, L. Wilk, and M. Nusair, “Accurate spin-dependent electron liquid correlation energies for local spin-density calculations - a critical analysis,” Can. J. Phys. 58(8), 1200–1211 (1980).
[Crossref]

Xie, J.

J. Xie, “First-principles study on the magnetism in ZnS-based diluted magnetic semiconductors,” J. Magn. Magn. Mater. 322(19), L37–L41 (2010).
[Crossref]

Yang, G.

F. Zhu, S. Dong, and G. Yang, “Ferromagnetic properties in Fe-doped ZnS thin films,” Optoelectron. Adv. Mater.-, Rapid Commun. 4, 2072–2075 (2010).

Yatsun, V. V.

Y. A. Nitsuk, Y. A. Vaksman, V. V. Yatsun, and Y. N. Purtov, “Optical absorption and diffusion of iron in ZnS single crystals,” Funct. Mater. 19, 182–186 (2012).

Yoshida, K.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Yoshida, M.

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Zhang, J. H.

J. H. Zhang, J. W. Ding, J. X. Cao, and Y. L. Zhang, “Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands,” J. Solid State Chem. 184(3), 477–480 (2011).
[Crossref]

Zhang, J. Y.

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Zhang, W.

H. Hu and W. Zhang, “Synthesis and properties of transition metals and rare-earth metals doped ZnS nanoparticles,” Opt. Mater. 28(5), 536–550 (2006).
[Crossref]

Zhang, Y. L.

J. H. Zhang, J. W. Ding, J. X. Cao, and Y. L. Zhang, “Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands,” J. Solid State Chem. 184(3), 477–480 (2011).
[Crossref]

Zhu, F.

F. Zhu, S. Dong, and G. Yang, “Ferromagnetic properties in Fe-doped ZnS thin films,” Optoelectron. Adv. Mater.-, Rapid Commun. 4, 2072–2075 (2010).

Appl. Phys. Lett. (2)

H. C. Ong and R. P. H. Chang, “Optical constants of wurtzite ZnS thin films determined by spectroscopic ellipsometry,” Appl. Phys. Lett. 79(22), 3612–3614 (2001).
[Crossref]

B. K. Li, C. Wang, I. K. Sou, W. K. Ge, and J. N. Wang, “Anomalous photocurrent observed in an Fe–ZnS:Fe Schottky diode,” Appl. Phys. Lett. 91(17), 172104 (2007).
[Crossref]

Appl. Phys. Rev. (1)

Y. Okada, N. J. Ekins-Daukes, T. Kita, R. Tamaki, M. Yoshida, A. Pusch, O. Hess, C. C. Phillips, D. J. Farrell, K. Yoshida, N. Ahsan, Y. Shoji, T. Sogabe, and J.-F. Guillemoles, “Intermediate band solar cells: Recent progress and future directions,” Appl. Phys. Rev. 2(2), 021302 (2015).
[Crossref]

Can. J. Phys. (1)

S. Vosko, L. Wilk, and M. Nusair, “Accurate spin-dependent electron liquid correlation energies for local spin-density calculations - a critical analysis,” Can. J. Phys. 58(8), 1200–1211 (1980).
[Crossref]

Funct. Mater. (1)

Y. A. Nitsuk, Y. A. Vaksman, V. V. Yatsun, and Y. N. Purtov, “Optical absorption and diffusion of iron in ZnS single crystals,” Funct. Mater. 19, 182–186 (2012).

J. Chem. Phys. (1)

C. Tablero, “Correlation effects and electronic properties of Cr-substituted SZn with an intermediate band,” J. Chem. Phys. 123(11), 114709 (2005).
[Crossref] [PubMed]

J. Cryst. Growth (1)

K. L. Lewis, G. S. Arthur, and D. A. Edwards, “The incorporation of iron impurities in cubic ZnS,” J. Cryst. Growth 59(1-2), 201–209 (1982).
[Crossref]

J. Lumin. (1)

S. Mirov, V. Fedorov, I. Moskalev, M. Mirov, and D. Martyshkin, “Frontiers of mid-infrared lasers based on transition metal doped II–VI semiconductors,” J. Lumin. 133, 268–275 (2013).
[Crossref]

J. Magn. Magn. Mater. (1)

J. Xie, “First-principles study on the magnetism in ZnS-based diluted magnetic semiconductors,” J. Magn. Magn. Mater. 322(19), L37–L41 (2010).
[Crossref]

J. Mater. Sci. (1)

P. C. Patel and P. C. Srivastava, “Fe doping in ZnS for realizing nanocrystalline-diluted magnetic semiconductor phase,” J. Mater. Sci. 49(17), 6012–6019 (2014).
[Crossref]

J. Phys. E Sci. Instrum. (1)

R. Swanepoel, “Determination of the thickness and optical-constants of amorphous-silicon,” J. Phys. E Sci. Instrum. 16(12), 1214–1222 (1983).
[Crossref]

J. Solid State Chem. (2)

J. H. Zhang, J. W. Ding, J. X. Cao, and Y. L. Zhang, “Infrared, visible and ultraviolet absorptions of transition metal doped ZnS crystals with spin-polarized bands,” J. Solid State Chem. 184(3), 477–480 (2011).
[Crossref]

J. L. Horwood, M. G. Townsend, and A. H. Webster, “Magnetic susceptibility of single-crystal Fe1−xS,” J. Solid State Chem. 17(1-2), 35–42 (1976).
[Crossref]

Laser Phys. Lett. (1)

M. P. Frolov, Y. V. Korostelin, V. I. Kozlovsky, Y. P. Podmar’kov, S. A. Savinova, and Y. K. Skasyrsky, “3 J pulsed Fe:ZnS laser tunable from 3.44 to 4.19 μm,” Laser Phys. Lett. 12(5), 055001 (2015).
[Crossref]

Mater. Chem. Phys. (3)

A. Kashyout, A. Arico, N. Giordano, and V. Antonucci, “Influence of Annealing Temperature on the Crystallographic and Optical-Properties of Electrodeposited Znfes Thin-Film Semiconductors,” Mater. Chem. Phys. 41(1), 55–60 (1995).
[Crossref]

S. H. Deulkar, C. H. Bhosale, and M. Sharon, “Optical studies on non-stiochiometric (Zn, Fe)S chalcogenide bulk pellets prepared by coprecipitation,” Mater. Chem. Phys. 111(2-3), 260–264 (2008).
[Crossref]

Q. J. Feng, D. Z. Shen, J. Y. Zhang, Y. M. Lu, Y. C. Liu, and X. W. Fan, “Influence of Fe content on the structural and optical properties of ZnFeS thin films,” Mater. Chem. Phys. 96(1), 158–162 (2006).
[Crossref]

Mater. Sci. Semicond. Process. (1)

A. Abbad, S. Bentata, H. A. Bentounes, W. Benstaali, and B. Bouadjemi, “Study of electronic and magnetic properties of binary zinc sulfide and ternary manganese- and iron-substituted alloys,” Mater. Sci. Semicond. Process. 16(3), 576–581 (2013).
[Crossref]

Opt. Eng. (1)

D. Minkov and R. Swanepoel, “Computerization of the optical characterization of a thin dielectric film,” Opt. Eng. 32(12), 3333–3337 (1993).
[Crossref]

Opt. Mater. (1)

H. Hu and W. Zhang, “Synthesis and properties of transition metals and rare-earth metals doped ZnS nanoparticles,” Opt. Mater. 28(5), 536–550 (2006).
[Crossref]

Optoelectron. Adv. Mater.-, Rapid Commun. (1)

F. Zhu, S. Dong, and G. Yang, “Ferromagnetic properties in Fe-doped ZnS thin films,” Optoelectron. Adv. Mater.-, Rapid Commun. 4, 2072–2075 (2010).

Phys. Rev. B (1)

J. D. Dow and D. Redfield, “Toward a unified theory of Urbach’s rule and exponential absorption edges,” Phys. Rev. B 5(2), 594–610 (1972).
[Crossref]

Phys. Rev. B Condens. Matter (1)

E. J. Baerends and E. J. Baerends, “Precise density-functional method for periodic structures,” Phys. Rev. B Condens. Matter 44(15), 7888–7903 (1991).
[Crossref] [PubMed]

Phys. Rev. Lett. (1)

J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized gradient approximation made simple,” Phys. Rev. Lett. 77(18), 3865–3868 (1996).
[Crossref] [PubMed]

Rev. Mineral. Geochem. (1)

C. I. Pearce, R. A. D. Pattrick, and D. J. Vaughan, “Electrical and magnetic properties of sulfides,” Rev. Mineral. Geochem. 61(1), 127–180 (2006).
[Crossref]

Sol. Energy Mater. Sol. Cells (1)

A. B. Kashyout, A. S. Aricò, G. Monforte, F. Crea, V. Antonucci, and N. Giordano, “Electrochemical deposition of ZnFeS thin film semiconductors on tin oxide substrates,” Sol. Energy Mater. Sol. Cells 37(1), 43–53 (1995).
[Crossref]

Other (3)

V. Fedorov, D. Martyshkin, M. Mirov, I. S. Moskalev, S. Vasilyev, J. Peppers, S. B. Mirov, and V. P. Gapontsev, “Fe-doped II-VI Mid-Infrared Laser Materials for the 3 to 8 μm Region,” in CLEO:2013, OSA Technical Digest (online) (Optical Society of America, 2013), p. JM4K.2.

S. S. H. Abdullah, “Optical effect of Fe doped wurtzite ZnS nanoparticles,” Proceedings of the 2nd WSEAS International Conference on Nanotechnology191–194 (2010).

M. Nematollahi, X. Yang, L. M. Aas, Z. Ghadyani, M. Kildemo, U. J. Gibson, and T. W. Reenaas, “Molecular beam and pulsed laser deposition of ZnS:Cr for intermediate band solar cells,” Sol. Energ. Mat. Sol. Cells (to be published) (2015).

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Figures (6)

Fig. 1
Fig. 1

X-ray diffraction of sample films. From top –films from the diffusion pumped system with iron content 12% (from Fe), 0%(red) and 7.4% (FeS source), a pure FeS film and a 3.5µm thick film with 1.9% Fe deposited in UHV. The amorphous quartz substrate reflection appears at ~22°.

Fig. 2
Fig. 2

TEM bright-field micrographs and diffraction images for the a) Fe:ZnS and b) FeS:ZnS films deposited onto carbon grids. Insets are Fourier transforms of the selected regions of the images.

Fig. 3
Fig. 3

Optical transmission of selected Fe-doped ZnS films. Inset shows pure ZnS and FeS films.

Fig. 4
Fig. 4

a)Absorption coefficient for pure ZnS, 6.8% and 12% Fe films, analyzed by ellipsometry (dashed lines-E) and the Swanepoel method (solid lines-S) and b) Tauc plot for these samples, showing increased absorption and softening of the band edge with the addition of iron.

Fig. 5
Fig. 5

a) derived Urbach energy and b) band gap, Eg as a function of Fe concentration, as determined from (S) Swanepoel and (E) ellipsometry analysis.

Fig. 6
Fig. 6

a) measured absorption in the mid-IR for a film with 2.1% Fe and b) density of states calculated for pure ZnS (dashed lines) and FeZn23S24 (solid lines), with green and blue for the two spin states. The energies in the pure ZnS plot are shifted by −1.8eV to allow comparison of the curve shapes. Ev and Ec indicate the valence and conduction band edges and EF denotes the position of the Fermi level for each material.

Equations (1)

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α ( E ) = α 0 e ( E / E U )

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