Graziella Malandrino and Guglielmo G. Condorelli

Italian-French seminar on

nanotechnology and advanced

materials

Dipartimento di Scienze Chimiche, Università di

Catania, and INSTM, UdR Catania, Viale A. Doria 6,

95125 Catania, Italy

1. Synthesis of functional binary oxides in form of thin films and/or

nanostructure (NiO, ZnO, CuO, CeO2,Co3O4, Fe3O4, Mn3O4)

Semiconducting, Magnetic, Gas sensing, Catalysis

2. Synthesis of complex oxides (perovskites, spinels)

Multiferroic, SOFC

3. Synthesis of metallic complexes as precursors for MOCVD

Alkaline earth, lanthanides, transition metals

4. Synthesis of fluoride phases as luminescent ions

Know how and skills of the group

MOCVD precursors and processes

1. Sensing and biosensing on silicon

2. Multifunctional Fe3O4 based Magnetic Nanoparticles (MNPs)

3. Semiconductor oxides (TiO2, and ZnO) functionalization for Dye sensitized

Solar Cells (DSSC)

Surface functionalization

Metal organic chemical vapor deposition represents a bottom

up approach to the nanostructures

ZnO

Oxide nanotubes through an hybrid MOCVD/template

approach

CuO

1 m1 m

Co3O4

1. G. Malandrino, S. T. Finocchiaro, R. Lo Nigro, C. Bongiorno, C. Spinella, and I. L. Fragala’ Free-Standing Copper(II) Oxide Nanotube

Arrays through an MOCVD TemplateProcessChem. Mater. 2004, 16, 5559-5561.

G. Malandrino, L. M. S. Perdicaro, I. L. Fragala`, R. Lo Nigro, M. Losurdo, G. Bruno, MOCVD Template Approach to the Fabrication of Free-Standing

Nickel(II) Oxide Nanotube Arrays: Structural, Morphological, and Optical Properties Characterization, J. Phys. Chem. C, 2007,111,,3211-3215.

L. M. S. Perdicaro,R. G. Toro, M. E. Fragalà,G. Malandrino, R. Lo Nigro, C. Bongiorno, M. Losurdo, M. M. Giangregorio,G. Bruno, A Template Metal-Organic

Chemical Vapour Deposition Route to the Fabrication of Free Standing Co3O4 Nanotube ArraysNanoscience and Nanotechnology Letters Vol. 1, 87–92,

2009.

Template = Anodic Aluminum oxide

NiO

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1. Synthesis of functional binary oxides in form of thin films and/or

nanostructure

1 m

20 nm

(a)

50 nm

(d)

(b)

(c)

2 m

20 nm

(e)

1 m1 m

20 nm20 nm

(a)

50 nm

(d)

50 nm50 nm

(d)

(b)

(c)

2 m2 m

20 nm20 nm

(e)

Nanostructures growth of Pt and CeO2 nanorods driven by process

parameter control

Pt

CeO2

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M. E. Fragalà, R. G. Toro, P. Rossi, P. Dapporto and G. Malandrino, Template-Free and Seedless Growth of Pt Nanocolumns: Imaging

and Probing, Their Nanoelectrical Properties, ACS Nano, 1, 183-190, 2007.

P.Fiorenza, G. Greco, G. Fisichella, G. F. Roccaforte, G. Malandrino, R.Lo Nigro, High permittivity cerium oxide thin films on

AlGaN/GaN heterostructures, Appl. Phys. Lett. (2013), 103(11), 112905/1-112905/5.

R. Lo Nigro, R.G. Toro, G. Malandrino, I. L. Fragala, Morphological and structural control of nanostructured <100> oriented CeO2

films grown on random metallic substrates, J. Phys. Chem. B (2004), 108(42), 16357-16364

1. Synthesis of functional binary oxides in form of thin films and/or

nanostructure

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1. Synthesis of functional binary oxides in form of thin films and/or

nanostructure

Films of ZnO oxides for PV applications

ZnO films grown on quartz at a)

400°C; b) 500C, c) 600°C and d)

750°C.

G. Malandrino, M. Blandino ,M. E. Fragalà, M. Losurdo, G. Bruno, Relationship between nanostructure and optical properties of

ZnO thin films, J. Phys. Chem. C, 2008, 112, 9595–9599.

A.A. Scalisi, R.G.Toro, G. Malandrino, M.E. Fragala, G.Pezzotti, Growth of ZnO nanostructures produced by MOCVD. A study of

the effect of the substrate, Chem. Vap. Deposition (2008), 14,, 115-122.

3

La1-x

(Sr)xMnO

3 films as cathode

for IT micro SOFC

MOLTEN MULTIMETAL

SOURCE AT 130°C

Tdep = 850-950°C

Ar = 200sccm

O2/H2O= 900 sccm

R. G. Toro, G. Malandrino, L. M.S. Perdicaro, D. M.R. Fiorito, A. Andreone, G. Lamura, I. L. Fragala, In-Situ Growth and Characterization of Highly

Textured La0.9Sr0.1MnO3 Films on LaAlO3(100) Substrates, Chem. Vap. Deposition, 2010, 16, 143–150.

R. G. Toro, D. M.R. Fiorito, M. E. Fragalà, A. Barbucci, M. P. Carpanese, G. Malandrino, A novel MOCVD strategy for the fabrication of cathode in a

solid oxide fuel cell: Synthesis of La0.8Sr0.2MnO3 films on YSZ electrolyte pellets, Mat. Chem. Phys. 2010, 124, 1015–1021.

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2. Synthesis of complex oxides (perovskites, spinels)

La1-x

SrxMnO

3 films on YSZ

electrolyte

R. G. Toro, G. Malandrino, L. M.S. Perdicaro, D. M.R. Fiorito, A. Andreone, G. Lamura, I. L. Fragala, In-Situ Growth and Characterization of Highly

Textured La0.9Sr0.1MnO3 Films on LaAlO3(100) Substrates, Chem. Vap. Deposition, 2010, 16, 143–150.

R. G. Toro, D. M.R. Fiorito, M. E. Fragalà, A. Barbucci, M. P. Carpanese, G. Malandrino, A novel MOCVD strategy for the fabrication of cathode in a

solid oxide fuel cell: Synthesis of La0.8Sr0.2MnO3 films on YSZ electrolyte pellets, Mat. Chem. Phys. 2010, 124, 1015–1021.

2. Synthesis of complex oxides (perovskites, spinels)

M. R. Catalano, R. G. Toro, A. Gulino, G. MalandrinoG. Perovskite LaCoO3 thin films on single crystal substrates: MOCVD growth and

characterization Surf. Coat. Technology 230 (2013) 174–179.

G. G. Condorelli a, M. R. Catalano, E. Smecca,R. Lo Nigro, G. Malandrino. Piezoelectric domains in BiFeO3 films grown via MOCVD: Structure/

property relationship Surf. Coat. Technology 230 (2013) 168–173.

2. Synthesis of complex oxides (perovskites, spinels)

Multiferroic BiFeO3 films on SrTiO

3:Nb substrate Perovskite LaCoO

3 films on MgO substrate

Precursor chemistry of transition metals M(tta)2tmeda (M = Cd, Ni, Zn)

1 2

3

1. G. Malandrino, S. T. Finocchiaro, P. Rossi, P. Dapporto, I. L. Fragala, Multifunctional cadmium single source precursor for the selective deposition of

CdO or CdS by a solution route, Chem. Comm., 2005, 5681–5683.

2. G. Malandrino, M. Blandino, L. M. S. Perdicaro, I. L. Fragala`, P. Rossi, P. Dapporto A Novel Diamine Adduct of Zinc Bis(2-thenoyl-

trifluoroacetonate) as a Promising Precursor for MOCVD of Zinc Oxide FilmsInorg. Chem., 44, 2005, 9684-9689.

3. G. Malandrino, L. M. S. Perdicaro, G. Condorelli, I. L. Fragalà, P. Rossi, P. Dapporto, Synthesis, characterization and application of Ni(tta)2·tmeda to

MOCVD of nickel oxide thin films, Dalton Trans., 2006, 1101–1106.

(Htta = 2-thenoyltri-

fluoroacetone, tmeda =

N,N,N,N-tetramethyl-

ethylendiamine),

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3. Synthesis of metallic complexes as precursors for MOCVD

Precursor chemistry of transition metals Mn(hfa)2tmeda

(Hhfa= hexafluoroacetyl-acetone; tmeda = N,N,N,N-tetramethylethylendiamine)

1. G. Malandrino, R. G. Toro, M. R. Catalano, M. E. Fragalà,P. Rossi, P. Paoli, Pompon-Like MnF2 Nanostructures from a Single-Source Precursor

through Atmospheric Pressure Chemical Vapor Deposition, Eur. J. Inorg. Chem. 2012, 1021–1024.

2. Z. Lipani, M. R. Catalano, P. Rossi, P. Paoli, G. Malandrino, A Novel Manganese(II) MOCVD Precursor: Synthesis,Characterization, and Mass

Transport Properties of Mn(hfa)2tmeda ,Chem. Vap. Deposition 2013, 19, 22–28

High surface area Mn3O4

films

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3. Synthesis of metallic complexes as precursors for MOCVD

254nm

Silicon and porous silicon functionalization

T= 200 °C

E. Biavardi, M. Favazza, A. Motta, I. L. Fragalà, C. Massera, L. Prodi, M. Montalti, M. Melegari, G. G. Condorelli, E. Dalcanale “Molecular

recognition on a cavitand functionalized silicon surface” J. Am. Chem. Soc. 2009, 131, 7447-7455

C. Tudisco, P. Betti, A. Motta, R. Pinalli, L. Bombaci, E. Dalcanale, G. G. Condorelli, “Cavitand-Functionalited Porous Silicon as Active Surface for

Organophosphorus Vapors Detection” Langmuir 2012, 28, 1782–1789.

Surf

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380 400 420 440 460 480 500

rela

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inte

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(nm)

Sarc

1 mM – 0.1 mM

Before urine exposure

After dipping for 5 min in urine

After dipping in 0.1 mM sarcosine-added-urine for 5 min

After dipping in 1 mM sarcosine-added-urine for 5 min

E. Biavardi, C. Tudisco, F. Maffei, A. Motta, C. Massera, G. G. Condorelli, E. Dalcanale ”Methylation leads to complexation: Exclusive recognition of

sarcosine in water and urine by a cavitand-functionalized silicon surface” PNAS, 2012, 109, 2263-2268.

1) Sensing and biosensing on silicon

Sarcosine recognition in urine: fluorescence detection

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1) Sensing and biosensing on silicon

Selective complexation/decomplexation process monitored by XPS: (a) pristine receptor functionalised Si

surface before complexation; (b) competition experiment of triclorotoluene (TCT ) versus 1,2-

dibromocyclohexane and 1-bromononane complexation; (c) thermal decomplexation of cavity included TCT

Gas phase sensing: recognition of aromatic Volatile

Organic Compounds (VOC)

G. G. Condorelli, A. Motta, M. Favazza, E. Gurrieri, P. Betti, E. Dalcanale “Molecular recognition of halogen-tagged aromatic VOCs at

the air–silicon interface” Chem. Commun., 2010, 46, 288-290

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Cavitand grafting on Pegylated MNPs

C. Tudisco, F. Bertani, M. T. Cambria, F. Sinatra, E. Fantechi, C. Innocenti, C. Sangregorio, E. Dalcanale and G. G. Condorelli

Functionalization of Pegylated Fe3O4 Magnetic Nanoparticles with Tetraphosphonate Cavitand for Biomedical Application Nanoscale, 2013,

DOI: 10.1039/C3NR02188B

2) Multifunctional Fe3O4 based Magnetic Nanoparticles

(MNPs) Su

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Both nanocarriers resulted biocompatible with hMSCs at all concentrations, while they showed a lower biocompatibility on LoVo cells to which they caused a slowdown in proliferative activity.

Cytotoxicity Tests

The release profile of PCZ is much faster than EPN,

Drug loading and release Study

2) Multifunctional Fe3O4 based Magnetic Nanoparticles

(MNPs)

C. Tudisco, F. Bertani, M. T. Cambria, F. Sinatra, E. Fantechi, C. Innocenti, C. Sangregorio, E. Dalcanale and G. G. Condorelli

Functionalization of Pegylated Fe3O4 Magnetic Nanoparticles with Tetraphosphonate Cavitand for Biomedical Application Nanoscale, 2013,

DOI: 10.1039/C3NR02188B

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Cyclodextrin (b-CD) functionalization of MNPs

C. Tudisco, M. Cantarella, V. Oliveri, G. Vecchio, G. G. Condorelli “Cyclodextrin Anchoring on Magnetic Fe3O4 Nanoparticles modified with

Phosphonic Linkers” Eur.J. Inorg. Chem. 2012, 5223-5331

2) Multifunctional Fe3O4 based Magnetic Nanoparticles

(MNPs) Su

rfac

e fu

ncti

onal

izat

ion

Giovanna Pellegrino, Guglielmo G. Condorelli, Vittorio Privitera, Brunella Cafra, Silvia Di Marco and Alessandra Alberti, Dye-Sensitizing of Self-

Nanostructured Ti(:Zn)O2/AZO Transparent Electrodes by Self-Assembly of 5,10,15,20-Tetrakis(4-carboxyphenyl)porphyrin J. Phys. Chem. C 2011,

115, 7760–7767

Porphyrin and phthalocyanine dyes anchoring on

nanostructured metal oxides through phosphonic

and/or carboxylic tethering groups

E. Smecca , A. Motta , M. E. Fragalà , Y. Aleeva , G. G. Condorelli «Spectroscopic and Theoretical Study of the Grafting Modes of

Phosphonic Acids on ZnO Nanorods” J. Phys. Chem. C, 2013, 117, 5364–5372

G. Pellegrino, A. Alberti, G. G. Condorelli, F. Giannazzo, A. La Magna, A. M. Paoletti, G. Pennesi, G. Rossi, G. Zanotti «Study of the Anchoring Process

of Tethered Unsymmetrical Zn-Phthalocyanines on TiO2 Nanostructured Thin Films” J. Phys. Chem. C, 2013, 117, 11176–11185

3) Semiconductor oxides (TiO2, and ZnO) functionalization for

Dye sensitized Solar Cells (DSSC)

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Contact person for Surface functionalization

Prof. Guglielmo G. Condorelli

E-mail: guido.condorelli@unict.it

Contact person for MOCVD precursors and processes

Prof. Graziella Malandrino

E-mail: gmalandrino@dipchi.unict.it