Formation of Quantum-Size Semiconductor Particles in a Layered Metal Phosphonate Host Lattice

Guang Cao, L.K. Rabenberg; Christine M. Nunn; Thomas E. Mallouk

doi:10.1021/cm00013a032

Formation of Quantum-Size Semiconductor Particles in a Layered Metal Phosphonate Host Lattice

Guang Cao, L.K. Rabenberg, Christine M. Nunn, Thomas E. Mallouk

Chemistry

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Abstract

Quantum-size ZnSe, PbS, CdS, and CdSe particles 30-50 A in diameter were grown in the interlamellar region of the layered host material Zr(O₃PCH₂CH₂CO₂H)₂ by reaction of H₂S or H₂Se with M^II[Zr-(O₃PCH₂CH₂CO₂)₂]. Diffraction from the PbS particles indicated the rocksalt structure, whereas CdSe adopts the zincblende structure and grows with the [111] zone axis parallel to the host layering direction. CdSe crystallites within a single host platelet are oriented relative to each other, even though the crystallinity of the host is destroyed during particle growth. Little or no reaction was found under similar conditions with M^II[Zr(PO₄)₂]. It is postulated that M^II[Zr(O₃PCH₂CH₂CO₂)₂], prepared by dehydration of M^II-[Zr(O₃PCH₂CH₂CO₂)₂]-xH₂O (x ~ 1.4) has an open structure that allows for interlamellar diffusion of H₂S and H₂Se. Contraction of the layer axis upon dehydration is significantly smaller for M^II[Zr-(O₃PCH₂CH₂CO₂)₂]-xH₂O than for M^II[Zr(PO₄)₂]•yH₂O. For comparison, an analogously layered compound, Zn[Zn(O₃PCH₂CH₂CO₂)]₂•3H₂O, was prepared and structurally characterized. This compound crystallizes in orthorhombic space group Pbcn (No. 60) with a = 5.126 (1), b = 10.837 (2), c = 28.596 (9) Å, V = 1588.5 Å³, Z = 4, R = 0.028, R_w = 0.033 for 1567 unique reflections with F_o > 3σ(F_o). The structure contains one set of zinc atoms four-coordinated by oxygen atoms of the phosphonate groups and another set five-coordinated by oxygen atoms of the carboxyl groups and lattice water molecules. The repeating unit is Zn/O₃PCH₂CH₂CO₂/Zn(H₂O)₃/O₂CCH₂CH₂PO₃/Zn… along the layering (c axis) direction. Complete dehydration of this compound causes a relatively small decrease in the layer spacing, from 28.6 to 28.0 Å.

Original language	English (US)
Pages (from-to)	149-156
Number of pages	8
Journal	Chemistry of Materials
Volume	3
Issue number	1
DOIs	https://doi.org/10.1021/cm00013a032
State	Published - Jan 1 1991

All Science Journal Classification (ASJC) codes

General Chemistry
General Chemical Engineering
Materials Chemistry

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@article{30488bf7f93c4f7290cbb28dd7a2c2ba,

title = "Formation of Quantum-Size Semiconductor Particles in a Layered Metal Phosphonate Host Lattice",

abstract = "Quantum-size ZnSe, PbS, CdS, and CdSe particles 30-50 A in diameter were grown in the interlamellar region of the layered host material Zr(O3PCH2CH2CO2H)2 by reaction of H2S or H2Se with MII[Zr-(O3PCH2CH2CO2)2]. Diffraction from the PbS particles indicated the rocksalt structure, whereas CdSe adopts the zincblende structure and grows with the [111] zone axis parallel to the host layering direction. CdSe crystallites within a single host platelet are oriented relative to each other, even though the crystallinity of the host is destroyed during particle growth. Little or no reaction was found under similar conditions with MII[Zr(PO4)2]. It is postulated that MII[Zr(O3PCH2CH2CO2)2], prepared by dehydration of MII-[Zr(O3PCH2CH2CO2)2]-xH2O (x ~ 1.4) has an open structure that allows for interlamellar diffusion of H2S and H2Se. Contraction of the layer axis upon dehydration is significantly smaller for MII[Zr-(O3PCH2CH2CO2)2]-xH2O than for MII[Zr(PO4)2]•yH2O. For comparison, an analogously layered compound, Zn[Zn(O3PCH2CH2CO2)]2•3H2O, was prepared and structurally characterized. This compound crystallizes in orthorhombic space group Pbcn (No. 60) with a = 5.126 (1), b = 10.837 (2), c = 28.596 (9) {\AA}, V = 1588.5 {\AA}3, Z = 4, R = 0.028, Rw = 0.033 for 1567 unique reflections with Fo > 3σ(Fo). The structure contains one set of zinc atoms four-coordinated by oxygen atoms of the phosphonate groups and another set five-coordinated by oxygen atoms of the carboxyl groups and lattice water molecules. The repeating unit is Zn/O3PCH2CH2CO2/Zn(H2O)3/O2CCH2CH2PO3/Zn… along the layering (c axis) direction. Complete dehydration of this compound causes a relatively small decrease in the layer spacing, from 28.6 to 28.0 {\AA}.",

author = "Rabenberg, {Guang Cao, L.K.} and Nunn, {Christine M.} and Mallouk, {Thomas E.}",

year = "1991",

month = jan,

day = "1",

doi = "10.1021/cm00013a032",

language = "English (US)",

volume = "3",

pages = "149--156",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "1",

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TY - JOUR

T1 - Formation of Quantum-Size Semiconductor Particles in a Layered Metal Phosphonate Host Lattice

AU - Rabenberg, Guang Cao, L.K.

AU - Nunn, Christine M.

AU - Mallouk, Thomas E.

PY - 1991/1/1

Y1 - 1991/1/1

N2 - Quantum-size ZnSe, PbS, CdS, and CdSe particles 30-50 A in diameter were grown in the interlamellar region of the layered host material Zr(O3PCH2CH2CO2H)2 by reaction of H2S or H2Se with MII[Zr-(O3PCH2CH2CO2)2]. Diffraction from the PbS particles indicated the rocksalt structure, whereas CdSe adopts the zincblende structure and grows with the [111] zone axis parallel to the host layering direction. CdSe crystallites within a single host platelet are oriented relative to each other, even though the crystallinity of the host is destroyed during particle growth. Little or no reaction was found under similar conditions with MII[Zr(PO4)2]. It is postulated that MII[Zr(O3PCH2CH2CO2)2], prepared by dehydration of MII-[Zr(O3PCH2CH2CO2)2]-xH2O (x ~ 1.4) has an open structure that allows for interlamellar diffusion of H2S and H2Se. Contraction of the layer axis upon dehydration is significantly smaller for MII[Zr-(O3PCH2CH2CO2)2]-xH2O than for MII[Zr(PO4)2]•yH2O. For comparison, an analogously layered compound, Zn[Zn(O3PCH2CH2CO2)]2•3H2O, was prepared and structurally characterized. This compound crystallizes in orthorhombic space group Pbcn (No. 60) with a = 5.126 (1), b = 10.837 (2), c = 28.596 (9) Å, V = 1588.5 Å3, Z = 4, R = 0.028, Rw = 0.033 for 1567 unique reflections with Fo > 3σ(Fo). The structure contains one set of zinc atoms four-coordinated by oxygen atoms of the phosphonate groups and another set five-coordinated by oxygen atoms of the carboxyl groups and lattice water molecules. The repeating unit is Zn/O3PCH2CH2CO2/Zn(H2O)3/O2CCH2CH2PO3/Zn… along the layering (c axis) direction. Complete dehydration of this compound causes a relatively small decrease in the layer spacing, from 28.6 to 28.0 Å.

AB - Quantum-size ZnSe, PbS, CdS, and CdSe particles 30-50 A in diameter were grown in the interlamellar region of the layered host material Zr(O3PCH2CH2CO2H)2 by reaction of H2S or H2Se with MII[Zr-(O3PCH2CH2CO2)2]. Diffraction from the PbS particles indicated the rocksalt structure, whereas CdSe adopts the zincblende structure and grows with the [111] zone axis parallel to the host layering direction. CdSe crystallites within a single host platelet are oriented relative to each other, even though the crystallinity of the host is destroyed during particle growth. Little or no reaction was found under similar conditions with MII[Zr(PO4)2]. It is postulated that MII[Zr(O3PCH2CH2CO2)2], prepared by dehydration of MII-[Zr(O3PCH2CH2CO2)2]-xH2O (x ~ 1.4) has an open structure that allows for interlamellar diffusion of H2S and H2Se. Contraction of the layer axis upon dehydration is significantly smaller for MII[Zr-(O3PCH2CH2CO2)2]-xH2O than for MII[Zr(PO4)2]•yH2O. For comparison, an analogously layered compound, Zn[Zn(O3PCH2CH2CO2)]2•3H2O, was prepared and structurally characterized. This compound crystallizes in orthorhombic space group Pbcn (No. 60) with a = 5.126 (1), b = 10.837 (2), c = 28.596 (9) Å, V = 1588.5 Å3, Z = 4, R = 0.028, Rw = 0.033 for 1567 unique reflections with Fo > 3σ(Fo). The structure contains one set of zinc atoms four-coordinated by oxygen atoms of the phosphonate groups and another set five-coordinated by oxygen atoms of the carboxyl groups and lattice water molecules. The repeating unit is Zn/O3PCH2CH2CO2/Zn(H2O)3/O2CCH2CH2PO3/Zn… along the layering (c axis) direction. Complete dehydration of this compound causes a relatively small decrease in the layer spacing, from 28.6 to 28.0 Å.

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Formation of Quantum-Size Semiconductor Particles in a Layered Metal Phosphonate Host Lattice

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