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Precursors for Inorganic MaterialsALD and
Sol-gel (Spin Coating)
Morten Frøseth Centre for Materials Science and
Nanotechnology
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Precursors for Inorganic MaterialsALD and
Sol-gel (Spin Coating)

• Introduction
• Precursors in general
• Single source precursors
• Case study

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Chemistry for Physicists
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Making of Thin Films
Further processing
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Requirements for Precursors

• In General
• Purity
• High yield synthesis
• Soluble and/or volatile
• Good control of hydrolysis
• Providing the perfect properties of the product
• Chemical Composition
• Metal
• Ligands

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Mixing of Precursors
Further processing
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The Precursors

• Inorganic salts, oxides
• Bi2O3, Fe2O3, PbO
• Organometallic complexes
• Bi(OtBu)3, Fe(OtBu)3, Pb(OtBu)2

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ß-diketonates

• Most metals available (in different oxidation
  states)
• A lot of possible variations in the ß-diketonates

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Alkoxides
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Alkoxides
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Carboxylates
Thurston, J. H., et al., Inorg. Chem. 2002, 41,
4194.
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Reaction Between Precursors
Mixture
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Reaction Between Precursors

• ß-diketonates and alkoxides

Seisenbaeva, G. A., et al., J. Mater. Chem.,
2004, 14, 3177.
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Reaction Between Precursors
Bi2(Hsal)6?Al(acac)3

• Carboxylates and ß-diketonates

Bi2(Hsal)6?Al(acac)3
Thurston, J. H., et al., Inorg. Chem. 2004, 43,
3299.
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Reaction Between Precursors

• Carboxylates and alkoxides

Bi2Nb2(sal)4(Hsal)4(OR)4
Bi2Nb2(sal)4(Hsal)4(OR)4
Thurston, J. H., et al., Inorg. Chem. 2002, 41,
4194.
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Precursors for BiFeO3 Thin Films
MOE
H2O
2 H2O
- 2 ROH
- 2 ROH
Chandler C. D. et al., Chem. Rev. 1993, 93,
1205-1241
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Precursors for BiFeO3 Thin Films and Dopants
MOE
H2O
MOE
H2O
Pb(X)2
Pb(X)2
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BiFeO3 Thin Films Doped with Pb
Pb(X)2
Pb(OAc)2?3H2O
Bi1-nPbnFeO3 3 layers, 700C/600s
Pb(NO3)2
Pb(tBuO)2
Pb(BF4)2
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AFM of Pb Doped BiFeO3 Films
Pb(OAc)2?3H2O Rq 16.8 nm
Pb(NO3)2 Rq 25.3 nm
Pb(tBuO)2 Rq 23.9 nm
Pb(BF4)2 Rq 76.6 nm
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Bi1-nPbnFeO3 vs. BiFeO3 Thin Films

• Bi1-nPbnFeO3, 2 layers
• Bi1-nPbnFeO3 , 3 layers
• BiFeO3 , 3 layers
• BiFeO3, 2 layers

Annealed at 700C/600s
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Bi1-nPbnFeO3 vs. BiFeO3 Thin Films
BiFeO3, 2 layers, 700C/600s Rrms 11.0 nm
BiFeO3, 3 layers, 700C/600s Rrms 6.25 nm
Bi1-nPbnFeO3, 2 layers, 700C/600s Rrms 9.44 nm
Bi1-nPbnFeO3, 3 layers, 700C/600s Rrms 13.9 nm
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Acknowledgments

• Prof. Helemer Fjellvåg, UiO/SMN
• The Research Council of Norway