Abstract

The optical absorption coefficient at room temperature has been measured for cerium-doped Y2O3 and Y1.4Gd0.6O3 samples from 1500 to 45000 wave numbers. Diffuse reflectivity has been measured on cerium-doped powders of Y2O3, Lu2O3, Sc2O3, Ba2GdTaO6, and ThO2 over the same range. A number of 4f − 4f and 4f − 5d transitions of trivalent Ce have been seen, and some experimental values for their oscillator strengths have been determined. A tentative assignment of particular transitions to either C2 or C3i sites in the Y2O3 structure has been made. Some of the transitions have also been seen by use of Raman scattering. Several phonon replicas of the 4f − 4f transitions have been identified. The charge-transfer band of tetravalent cerium in Y1.4Gd0.6O3 has been identified.

© 1994 Optical Society of America

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H. T. Hintzen and H. M. VanNoort, J. Phys. Chem. Solids 49, 873 (1988).
[CrossRef]

T. Schleid and G. Meyer, J. Less-Common Met. 149, 73 (1988).
[CrossRef]

1987 (1)

X. Liu, X. Wang, and W. Shun, Phys. Status Solidi A 101, K161 (1987).
[CrossRef]

1986 (5)

C. A. Hogarth and Z. T. Al-Dhhan, Phys. Status Solidi B 137, K157 (1986).
[CrossRef]

T. Tomiki, J. Tamashiro, Y. Tanahara, A. Yamada, H. Fukutani, T. Miyahara, H. Kato, S. Shin, and M. Ishigame, J. Phys. Soc. Jpn. 55, 4543 (1986).
[CrossRef]

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R. W. Mires and G. L. Walker, Phys. Rev. B 33, 3516 (1986).
[CrossRef]

B. F. Aull and H. P. Jensen, Phys. Rev. B 34, 6647 (1986).
[CrossRef]

1985 (3)

J. B. Gruber, R. P. Leavitt, C. A. Morrison, and N. C. Chang, J. Chem. Phys. 82, 5373 (1985).
[CrossRef]

J. B. Gruber, R. P. Leavitt, C. A. Morrison, and N. C. Chang, J. Chem. Phys. 82, 5373 (1985).
[CrossRef]

S. Mroczkowski and P. Dorain, J. Less-Common Met. 110, 259 (1985).
[CrossRef]

1984 (2)

Kh. S. Bagdasarov, V. P. Zhuze, M. G. Karin, K. K. Sidorin, and A. I. Shelykh, Fiz, Tverd. Tela 26, 1134 (1984) [Sov. Phys. Solid State 26, 687 (1984)].

N. V. Porotnikov, O. I. Kondratov, L. L. Kochergina, and K. I. Petrov, Zh. Neorg. Khim. 29, 1664 (1984) [Russ. J. Inorg. Chem. 29, 954 (1984)].

1983 (1)

R. C. Buchanan and S. Pope, J. Electrochem. Soc. 130, 962 (1983).
[CrossRef]

1982 (4)

N. C. Chang, J. B. Gruber, R. P. Leavitt, and C. A. Morrison, J. Chem. Phys. 76, 3877 (1982).
[CrossRef]

R. P. Leavitt, J. Chem. Phys. 77, 1661 (1982).
[CrossRef]

E. Antic-Fidancev, M. LeMaitre-Blaise, and P. Caro, J. Chem. Phys. 76, 2906 (1982).
[CrossRef]

R. P. Leavitt, J. B. Gruber, N. C. Chang, and C. A. Morrison, J. Chem. Phys. 76, 4755 (1982).
[CrossRef]

1981 (1)

S. Yokono, T. Abe, and T. Hoshina, J. Lumin. 24/25, 309 (1981).
[CrossRef]

1980 (4)

G. L. Walker and R. W. Mires, Phys. Rev. B 21, 1876 (1980).
[CrossRef]

T. Hoshina, J. Phys. Soc. Jpn. 48, 1261 (1980).
[CrossRef]

M. Faucher and J. Pannetier, Acta Cryst. B 36, 3209 (1980).
[CrossRef]

C. A. Morrison, R. P. Leavitt, and D. E. Wortman, J. Chem. Phys. 73, 2580 (1980).
[CrossRef]

1979 (2)

J. Gouteron, J. Zarembowitch, and A. M. Lejus, C. R. Acad. Sci. 289C, 243 (1979).

D. J. Robbins, J. Electrochem. Soc. 126, 1550 (1979).
[CrossRef]

1978 (3)

J. M. Badie, Rev. Int. Hautes Temp. Refract. 15, 183 (1978).

V. S. Stubican, R. C. Hink, and S. P. Ray, J. Am. Ceram. Soc. 61, 17 (1978).
[CrossRef]

G. Rauser and S. Kemmler-Sack, Z. Anorg. Allg. Chem. 439, 237 (1978).
[CrossRef]

1976 (4)

N. Karayianis, D. E. Wortman, and C. A. Morrison, Solid State Commun. 18, 1299 (1976).
[CrossRef]

T. R. Griffiths, M. J. Davies, and H. V. S. Hubbard, J. Chem. Soc. Faraday Trans. II,  72, 765 (1976).
[CrossRef]

A. Paul, M. Mulholland, and M. S. Zaman, J. Mater. Sci. 11, 2082 (1976).
[CrossRef]

H. D. Amberger, G. G. Rosenbauer, and R. D. Fischer, Mol. Phys. 32, 1291 (1976).
[CrossRef]

1975 (2)

J. M. Badie, C. R. Acad. Sci. 277C, 1365 (1975).

R. Diehl and G. Brandt, Mat. Res. Bull. 10, 85 (1975).
[CrossRef]

1973 (6)

N. VanVugt, T. Wigmans, and G. Blasse, J. Inorg. Nucl. Chem. 35, 2601 (1973).
[CrossRef]

M. J. Weber, J. Appl. Phys. 44, 3205 (1973).
[CrossRef]

D. B. Faithful, S. M. Johnson, and I. J. McColm, Rev. Chim. Mineral. 10, 291 (1973).

N. V. Starostin, P. F. Gruzdev, V. A. Ganin, and T. A. Chebotareva, Opt. Spektrosk. 35, 476 (1973) [Opt. Spectrosc. (USSR) 35, 277 (1973)].

R. W. Schwartz and P. N. Schatz, Phys. Rev. B 8, 3229 (1973).
[CrossRef]

W. J. Manthey, Phys. Rev. B 8, 4086 (1973).
[CrossRef]

1972 (3)

T. Hoshina and S. Kuboniwa, J. Phys. Soc. Jpn. 32, 771 (1972).
[CrossRef]

W. B. White and V. G. Keramidas, Spectrochim. Acta 28A, 501 (1972).

D. Bloor and J. R. Dean, J. Phys. C5, 1237 (1972).

1971 (2)

B. Iwasaki and T. Katsura, Bull. Chem. Soc. Jpn. 44, 1297 (1971).
[CrossRef]

Y. Nigara, M. Ishigame, and T. Sakurai, J. Phys. Soc. Jpn. 30, 453 (1971).
[CrossRef]

1970 (1)

G. Schaack and J. A. Koningstein, J. Opt. Soc. Am 60, 1110 (1970).
[CrossRef]

1969 (4)

G. Schäfer, Phys. Kondens. Mater. 9, 359 (1969).

R. D. Shannon and C. T. Prewitt, Acta Cryst. B 25, 925 (1969).
[CrossRef]

F. M. Spiridonov, L. N. Komissarova, A. G. Kocharov, and V. I. Spitsyn, Zh. Neorg. Khim. 14, 2535 (1969) [Russ. J. Inorg. Chem. 14, 1332 (1969)].

W. W. Holloway and M. Kestigian, J. Opt. Soc. Am. 59, 60 (1969).
[CrossRef]

1968 (1)

Y. Nigara, Jpn. J. Appl. Phys. 7, 404 (1968).
[CrossRef]

1967 (5)

G. Blasse and A. Bril, J. Chem. Phys. 47, 5139 (1967).
[CrossRef]

R. C. Linares, J. Phys. Chem. Solids 28, 1285 (1967).
[CrossRef]

G. Blasse and A. Bril, Appl. Phys. Letters 11, 53 (1967).
[CrossRef]

E. D. Ruchkin, M. N. Sokolova, and S. S. Batsanov, Zh. Strukt. Khim. 8, 465 (1967) [J. Struct. Chem. USSR 8, 410 (1967)].

S. S. Derbeneva and S. S. Batsanov, Dokl. Akad. Nauk SSSR 175, 1062 (1967) [Dokl. Chem. Proc. Acad. Sci. USSR 175–177, 710 (1967)].

1966 (4)

H. H. Tippins, J. Phys. Chem. Solids 27, 1069 (1966).
[CrossRef]

G. F. Herrmann, J. J. Pearson, K. A. Wickersheim, and R. A. Buchanan, J. Appl. Phys. 37, 1312 (1966).
[CrossRef]

F. S. Galasso, G. K. Layden, and D. E. Flinchbaugh, J. Chem. Phys. 44, 2703 (1966).
[CrossRef]

N. T. McDevitt and A. D. Davidson, J. Opt. Soc. Am. 56, 636 (1966).
[CrossRef]

1964 (1)

N. T. McDevitt and W. L. Baun, Spectrochim. Acta 20, 799 (1964).
[CrossRef]

1962 (3)

K. R. Lea, M. J. M. Leask, and W. P. Wolf, J. Phys. Chem. Solids 23, 1381 (1962).
[CrossRef]

H. Witzmann and G. Herzog, Z. Phys. Chem. (Leipzig) 219, 369 (1962).

Z. J. Kiss, Phys. Rev. 127, 718 (1962).
[CrossRef]

1961 (3)

J. D. Axe, H. J. Stapleton, and C. D. Jeffries, Phys. Rev. 121, 1630 (1961); also, J. C. Krupa, Inorgan. Chem. Acta 139, 223 (1987).
[CrossRef]

J. S. Stround, J. Chem. Phys. 35, 844 (1961).
[CrossRef]

K. A. Wickersheim and R. A. Lefever, J. Opt. Soc. Am. 51, 1147 (1961).
[CrossRef]

1960 (1)

R. Pappalardo and D. L. Wood, J. Chem. Phys. 33, 1734 (1960).
[CrossRef]

1959 (1)

V. V. Vargin and G. O. Karapetyan, Glastech. Ber. 32, 443 (1959).

1958 (1)

1948 (1)

C. Kittel and J. M. Luttinger, Phys. Rev. 73, 162 (1948).
[CrossRef]

1936 (1)

R. J. Lang, Can. J. Res. 14A, 127 (1936).
[CrossRef]

Abe, T.

S. Yokono, T. Abe, and T. Hoshina, J. Lumin. 24/25, 309 (1981).
[CrossRef]

Al-Dhhan, Z. T.

C. A. Hogarth and Z. T. Al-Dhhan, Phys. Status Solidi B 137, K157 (1986).
[CrossRef]

Amberger, H. D.

H. D. Amberger, G. G. Rosenbauer, and R. D. Fischer, Mol. Phys. 32, 1291 (1976).
[CrossRef]

Antic-Fidancev, E.

E. Antic-Fidancev, M. LeMaitre-Blaise, and P. Caro, J. Chem. Phys. 76, 2906 (1982).
[CrossRef]

Aull, B. F.

B. F. Aull and H. P. Jensen, Phys. Rev. B 34, 6647 (1986).
[CrossRef]

Axe, J. D.

J. D. Axe, H. J. Stapleton, and C. D. Jeffries, Phys. Rev. 121, 1630 (1961); also, J. C. Krupa, Inorgan. Chem. Acta 139, 223 (1987).
[CrossRef]

Badie, J. M.

J. M. Badie, Rev. Int. Hautes Temp. Refract. 15, 183 (1978).

J. M. Badie, C. R. Acad. Sci. 277C, 1365 (1975).

Bagdasarov, Kh. S.

Kh. S. Bagdasarov, V. P. Zhuze, M. G. Karin, K. K. Sidorin, and A. I. Shelykh, Fiz, Tverd. Tela 26, 1134 (1984) [Sov. Phys. Solid State 26, 687 (1984)].

Batsanov, S. S.

S. S. Derbeneva and S. S. Batsanov, Dokl. Akad. Nauk SSSR 175, 1062 (1967) [Dokl. Chem. Proc. Acad. Sci. USSR 175–177, 710 (1967)].

E. D. Ruchkin, M. N. Sokolova, and S. S. Batsanov, Zh. Strukt. Khim. 8, 465 (1967) [J. Struct. Chem. USSR 8, 410 (1967)].

Baun, W. L.

N. T. McDevitt and W. L. Baun, Spectrochim. Acta 20, 799 (1964).
[CrossRef]

Blasse, G.

N. VanVugt, T. Wigmans, and G. Blasse, J. Inorg. Nucl. Chem. 35, 2601 (1973).
[CrossRef]

G. Blasse and A. Bril, Appl. Phys. Letters 11, 53 (1967).
[CrossRef]

G. Blasse and A. Bril, J. Chem. Phys. 47, 5139 (1967).
[CrossRef]

Bloor, D.

D. Bloor and J. R. Dean, J. Phys. C5, 1237 (1972).

Brandt, G.

R. Diehl and G. Brandt, Mat. Res. Bull. 10, 85 (1975).
[CrossRef]

Bril, A.

G. Blasse and A. Bril, Appl. Phys. Letters 11, 53 (1967).
[CrossRef]

G. Blasse and A. Bril, J. Chem. Phys. 47, 5139 (1967).
[CrossRef]

Buchanan, R. A.

G. F. Herrmann, J. J. Pearson, K. A. Wickersheim, and R. A. Buchanan, J. Appl. Phys. 37, 1312 (1966).
[CrossRef]

Buchanan, R. C.

R. C. Buchanan and S. Pope, J. Electrochem. Soc. 130, 962 (1983).
[CrossRef]

Caro, P.

E. Antic-Fidancev, M. LeMaitre-Blaise, and P. Caro, J. Chem. Phys. 76, 2906 (1982).
[CrossRef]

Chang, N. C.

J. B. Gruber, R. P. Leavitt, C. A. Morrison, and N. C. Chang, J. Chem. Phys. 82, 5373 (1985).
[CrossRef]

J. B. Gruber, R. P. Leavitt, C. A. Morrison, and N. C. Chang, J. Chem. Phys. 82, 5373 (1985).
[CrossRef]

N. C. Chang, J. B. Gruber, R. P. Leavitt, and C. A. Morrison, J. Chem. Phys. 76, 3877 (1982).
[CrossRef]

R. P. Leavitt, J. B. Gruber, N. C. Chang, and C. A. Morrison, J. Chem. Phys. 76, 4755 (1982).
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Figures (11)

Fig. 1
Fig. 1

Optical absorption coefficient versus photon wave number in the infrared at room temperature for sample YGC of Y1.4 Gd0.6O3 doped with trivalent cerium. The main Ce3+ lines are given in wave numbers. The peaks labeled R1, R2, and R4 are phonon replicas of these peaks.

Fig. 2
Fig. 2

Diffuse reflectivity versus photon wave number in the infrared at room temperature for sample YB of Y2O3 doped with trivalent cerium. The main Ce3+ lines are given in wave numbers. R1 and R2 are phonon replicas. A hydroxy-carbonate band is indicated.

Fig. 3
Fig. 3

Diffuse reflectivity versus photon wave number in the infrared at room temperature for Ba2GdTaO6 doped with trivalent cerium.

Fig. 4
Fig. 4

Diffuse reflectivity versus photon wave number in the infrared at room temperature for Sc2O3 doped with trivalent cerium.

Fig. 5
Fig. 5

Diffuse reflectivity versus photon wave number in the infrared at room temperature for ThO2 doped with trivalent cerium.

Fig. 6
Fig. 6

Optical absorption coefficient versus photon wave number in the infrared for the 2127-cm−1 line of Ce3+ in sample YA of Y2O3 at room temperature. The half-width is W = 3.1 cm−1; resolution is 0.2 cm−1.

Fig. 7
Fig. 7

Optical absorption coefficient versus photon wave number in the visible and the ultraviolet regions at room temperature for samples YGA and YGB of Y1.4 Gd0.6O3. The ultraviolet edge for Y2O3 from Ref. 6 is also shown. The absorption coefficient curve for YGB has had the gadolinium peaks between 31000 and 41000 cm−1 subtracted to show the trivalent cerium behavior. The dashed curve is part of the YGB curve multiplied by 5.

Fig. 8
Fig. 8

Diffuse reflectivity versus phonon wave number in the visible and the ultraviolet of sample YB of Y2O3 doped with trivalent cerium.

Fig. 9
Fig. 9

Energy levels of eight-coordinated trivalent cerium ions in several compounds. The C2-sites in Sc2O3 and Y2O3, although they are six coordinated, are included for comparison. The compounds are YAG, Y3Al5O12; YAP, YAlO3; SCO, Sc2O3; YGG, Y3Ga5O12; THO, ThO2; and YTO, Y2O3. The rightmost column shows the calculated Y2O3 levels from Ref. 1.

Fig. 10
Fig. 10

Energy levels of six-coordinated trivalent cerium ions in several compounds. The compounds are LUB, LuBO3; CNC, Cs2NaCeCl6; BGT, Ba2GdTaO6; and YTO, Y2O3 in C3i sites.

Fig. 11
Fig. 11

Optical absorption coefficient versus photon wave number for (mainly) tetravalent cerium in sample YGD of Y1.4 Gdo0.6O3 at room temperature. The solid curve is for a Ce4+ concentration of 6.3 × 1018 cm−3 and a Ce3+ concentration of ~3.2 × 1017 cm−3. The dashed curve shows the a values for sample YGB in Fig. 4 divided by 20. Both curves have had the gadolinium Gd3+ absorption peaks subtracted from them. The ultraviolet edge of CeO2 is indicated by an arrow.

Tables (11)

Tables Icon

Table 1 Samples Studied

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Table 2 Observed Infrared Absorption Peaks of Ce3+ in C2 Sites

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Table 3 Observed Infrared Absorption Peaks of Ce3+ in C3 or Octahedral Sites

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Table 4 Phonon Sideband Replicas of Cerium Lines in the Infrared Region

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Table 5 Visible and Ultraviolet Absorption Bands of Ce3+ from Transmission or Diffuse-Reflection Spectra

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Table 6 Band Parameters for Sample YGB for Transitions from the Ground State

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Table 7 4f Energy Levels of Ce3+ in Cubal Sites in ThO2a

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Table 8 4f Energy Levels of Ce3+ in the C3i Site in Y2O3a

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Table 9 4f Energy Levels of Ce3+ in the Gadolinium Sites in Ba2GdTaO6a

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Table 10 Crystal Field Strength Values for the 4f Levels of Ce3+ in Several Hosts

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Table 11 Comparison of the Energy Levels (cm−1) of Ce3+ in Octahedral Sites in Several Double Perovskites with those in Y2O3 on C3i Sitesa

Equations (19)

Equations on this page are rendered with MathJax. Learn more.

I = 0 α d ν ¯
α PK α ( ν ¯ ) = exp ( ν ¯ - ν ¯ 0 σ 2 ) 2 , W = σ 8 ln 2 ,
I = ( π 4 ln 2 ) 1 / 2 ( α PK W ) = 1.0645 α PK W .
α PK α ( ν ¯ ) = 1 + ( ν ¯ 2 - ν ¯ 0 2 W ν ¯ ) 2 .
α PK α ( ν ¯ ) = 1 + ( 2 ( ν ¯ - ν ¯ 0 ) W ) 2 .
I = π 2 ( α PK W ) = 1.5708 α PK W .
1.0645 I α PK W 1.5708.
f = n π r e [ 3 ( n 2 + 2 ) ] 2 I N = Q [ 3 ( n 2 + 2 ) ] 2 .
I α PK W ,
f = 2.7 × 10 - 3 .
f 7 × 10 - 3 .
B 60 13 35 B 40
S 2 = 1 3 k 1 ( 2 k + 1 ) [ B k 0 2 + 2 m > 0 ( R B k m ) 2 + ( I B k m ) 2 ] ,
B 40 , B 60 , B 44 , B 64 ,
B 44 = B 40 5 / 14 ,
B 64 = - B 60 7 / 2 .
Δ c = 2575 cm - 1 ,
σ = α / N = 0.0047 nm 2
α = 4 π ν ¯ k .

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