MAPLE deposition of Mn(III) metalloporphyrin thin films: Structural, topographical and...

Accepted Manuscript

Title: MAPLE DEPOSITION OF Mn(III)METALLOPORPHYRIN THIN FILMS: STRUCTURAL;TOPOGRAPHICAL AND ELECTROCHEMICALINVESTIGATIONS

Authors: R. Cristescu, C. Popescu, A.C. Popescu, S.Grigorescu, I.N. Mihailescu, A.A. Ciucu, S. Iordache, A.Andronie, I. Stamatin, E. Fagadar-Cosma, D.B. Chrisey

PII: S0169-4332(10)01814-3DOI: doi:10.1016/j.apsusc.2010.12.085Reference: APSUSC 21151

To appear in: APSUSC

Received date: 12-6-2010Revised date: 14-12-2010Accepted date: 15-12-2010

Please cite this article as: R. Cristescu, C. Popescu, A.C. Popescu, S.Grigorescu, I.N. Mihailescu, A.A. Ciucu, S. Iordache, A. Andronie, I.Stamatin, E. Fagadar-Cosma, D.B. Chrisey, MAPLE DEPOSITION OF Mn(III)METALLOPORPHYRIN THIN FILMS: STRUCTURAL; TOPOGRAPHICALAND ELECTROCHEMICAL INVESTIGATIONS, Applied Surface Science (2010),doi:10.1016/j.apsusc.2010.12.085

This is a PDF file of an unedited manuscript that has been accepted for publication.As a service to our customers we are providing this early version of the manuscript.The manuscript will undergo copyediting, typesetting, and review of the resulting proofbefore it is published in its final form. Please note that during the production processerrors may be discovered which could affect the content, and all legal disclaimers thatapply to the journal pertain.

dx.doi.org/doi:10.1016/j.apsusc.2010.12.085

dx.doi.org/10.1016/j.apsusc.2010.12.085

of 22

Accep

ted

Man

uscr

ipt

We deposited (5,10,15,20-tetraphenyl)porphinato manganese (III) chloride (MnTPP)Cl)

thin films by MAPLE.

Globular structures with average diameters decreasing with laser fluence.

Surface enhanced Raman effect was noticed on MAPLE-deposited thin films at 300

mJ/cm2.

(MnTPP)Cl-coated Au-SPE is appropriate as a single mediator for dopamine sensing in

the specific case of gold screen-printed electrodes.

*Research Highlights

of 22

Accep

ted

Man

uscr

ipt

REVISED III MANUSCRIPT: APSUSC_D-10-01835

1

MAPLE DEPOSITION OF Mn(III) METALLOPORPHYRIN THIN FILMS:

STRUCTURAL, TOPOGRAPHICAL AND ELECTROCHEMICAL

INVESTIGATIONS

R. Cristescu1, C. Popescu

1, A.C. Popescu

1, S. Grigorescu

1, I.N. Mihailescu

1, A.A. Ciucu

2,

S. Iordache3, A. Andronie

3, I. Stamatin

3, E. Fagadar-Cosma

4, and D.B. Chrisey

5

1National Institute for Lasers, Plasma & Radiation Physics, Lasers Department, P.O.

Box MG-36, Bucharest-Magurele, Romania, [email protected]

2University of Bucharest, Faculty of Chemistry, Bucharest, Romania

3University of Bucharest, 3Nano-SAE Research Center, PO Box MG-38, Bucharest-

Magurele, Romania

4Institute of Chemistry Timisoara of Romanian Academy, Department of Organic

Chemistry, 300223, Timisoara, Romania

5Rensselaer Polytechnic Institute, Department of Materials Science & Engineering, Troy,

12180-3590, NY USA

Abstract

We report the deposition by MAPLE of metallized nanostructured (5,10,15,20-

*Corresponding Author: Tel: +40-21-4574491; Fax: +40-21-4574243; E-mail:

[email protected]; [email protected]

mailto:[email protected]

mailto:[email protected];%[email protected]

of 22

Accep

ted

Man

uscr

ipt


2

tetraphenyl)porphinato manganese (III) chloride thin films onto gold screen-printed

electrodes, or <111> Si substrates. The deposited nanostructures were characterized by

atomic force microscopy and exhibited globular structures with average diameters

decreasing with laser fluence. Raman spectroscopy showed that no major decomposition

appeared. We have investigated the Mn(III)-metalloporphyrin thin films by cyclic

voltammetry in order to evaluate the potential bio/chemosensing activity on dopamine

neurotransmitter analyte. We have found that the manganese(III)-porphyrin is appropriate

as a single mediator for dopamine sensing in the specific case of gold screen-printed

electrodes.

Keywords: Metalloporphyrins; Dopamine; Thin films; Matrix assisted pulsed laser

evaporation

of 22

Accep

ted

Man

uscr

ipt


3

1. Introduction

Porphyrins have been used in many applications ranging from fuel cells to drug

development and chemical/biological sensors. The interaction of porphyrins with many

compounds has been studied including, but not limited to: metals (atoms) [1-2], small

molecules [3], amines [4], amino acids and amino acid derivatives [5], alcohols [6],

carbohydrates [7], quinones [8], proteins [9], DNA [10], nucleobases, and nucleic acids

[11], surfactants [12], volatile organic compounds [13], and a variety of other cyclic

and/or aromatic compounds [14]. The metalloporphyrin nanostructures with unoccupied

orbitals in metals having symmetries as eg(d(π))dxz and dyz were designed for new

efficient catalysts mimicking natural enzymatic systems [15], and electrochemical [16]

and biological sensors [17].

(5,10,15,20-tetraphenyl)porphinato manganese (III) chloride, (MnTPP)Cl and its

derivatives, generally named Mn(III)-metalloporphyrins, are intensively used in current

research as catalysts in oxidative cleavage of plasmid bluescript [18] and as ionophores in

novel potentiometric, piezoelectric, or fluorimetric sensor devices for the detection of

hydrazine [19], thiocyanate [20], dioxins [21], and salicylate [22]. Each Mn(III)

porphyrin complex might be oxidized or reduced to derivatives containing either Mn(II),

Mn(IV) or Mn(V) valence states depending upon the axial ligands on the macrocycle,

type of solution, environmental conditions. The increasing demand for catalysts in

oxidation reactions under mild conditions is the motivation for research concerning the

photoactivity of TiO2 anatase [23] impregnated with Mn-porphyrins.

The major pitfall faced for these applications is the selection of the porphyrin structure

and its deposition on the sensor substrate. Traditional solvent-based deposition

https://www.researchgate.net/publication/230195492_Chemistry_of_Water-Soluble_Porphyrins?el=1_x_8&enrichId=rgreq-3a562fb9-883e-4a8f-b22b-668a0d74d1ba&enrichSource=Y292ZXJQYWdlOzIyODA5MDc0NDtBUzoyMjI3OTgxMjQ0NTc5ODRAMTQzMDEzMDYyMDM0Mg==

of 22

Accep

ted

Man

uscr

ipt


4

techniques (e.g., drop-casting, spin-casting, Langmuir–Blodgett, etc.) require a solution

of the material in a solvent to physically coat the surface of the substrate. Such techniques

limit the substrate choices to materials that do not dissolve in solvent. The uneven and

unpredictable wetting, distribution, and evaporation of the solvent molecules result in

non-uniform coatings. To avoid these difficulties, the necessity for accurate deposition of

the sensitive element onto support/substrate has emerged. A proven solution to similar

problems is to use matrix assisted pulsed laser evaporation (MAPLE) [24]. The MAPLE

technique has demonstrated it's capability for obtaining high quality thin films and

structures in many solvent-material combinations that have applications in optical data

storage, optical communications, gene therapy, medical implants, microfluidic

biosensors, and biochips, etc. [25-37]. In this work, we demonstrate that MAPLE is

capable of growing uniform thin films of (MnTPP)Cl. The evaluation of the response to

dopamine was performed on gold screen-printed electrodes.

2. Experimental

2.1. Materials

The synthesis methods of (MnTPP)Cl (Fig. 1) and its full physico-chemical

characterization were described [38-42]. (MnTPP)Cl is soluble and stable (within a wide

range of pH (6 - 13.5)) in acetonitrile, N,N-dimethylformamide, dimethylsulfoxide,

dichloromethane, dichloroethane, THF, and chloroform. In order to get a suitable

MAPLE target, (MnTPP)Cl was solvated into a 1% solution with chloroform.

2.2. Experimental conditions

A copper target holder was filled with ~5 ml (MnTPP)Cl dissolved in chloroform and

frozen by immersing in liquid nitrogen. The frozen target was mounted on a refrigerated

https://www.researchgate.net/publication/229790161_Deposition_of_Polymers_and_Biomaterials_Using_the_Matrix-Assisted_Pulsed_Laser_Evaporation_MAPLE_Process?el=1_x_8&enrichId=rgreq-3a562fb9-883e-4a8f-b22b-668a0d74d1ba&enrichSource=Y292ZXJQYWdlOzIyODA5MDc0NDtBUzoyMjI3OTgxMjQ0NTc5ODRAMTQzMDEzMDYyMDM0Mg==

of 22

Accep

ted

Man

uscr

ipt


5

assembly which was cooled down to 173 K. MAPLE depositions of (MnTPP)Cl were

performed using a pulsed excimer KrF* laser ( = 248 nm, tFWHM = 25 ns, pulse

repetition rate = 10 Hz, laser fluence = 200–500 mJ/cm2). The threshold fluence for

MAPLE deposition of (MnTPP)Cl was about 200 mJ/cm2. The incident angle of the laser

beam was 45º and the target–substrate distance was set at 4 cm. The laser spot size was ~

8 mm2 and the beam was scanned over the entire surface of the 3 cm diameter target

rotating at 5 Hz for 10,000 pulses. During deposition the residual pressure inside chamber

was stabilized at a value between ~ 9.3 - 11.5 Pa. The evaporated material was collected

on <111> Si wafers or gold screen-printed electrodes (Au-SPE) and kept at room

temperature for post-deposition analyses. All the Si substrates have been cleaned prior to

deposition by immersion in an Elma Transsonic T 310 ultrasonic bath filled with ethanol

and then dried in air under UV exposure from a VL-115 MVilber Lourmat UV lamp.

2.3 Characterization methods

(MnTPP)Cl thin films were characterized by Raman spectroscopy, Atomic Force

Microscopy (AFM) and cyclic voltammetry. Raman spectra of thin films were recorded

by Jasco NRS 3100 with dual laser beams, 532 nm and 785 nm, respectively. AFM phase

contrast micrographs were made with an Integrated Platform SPM-NTegra model Prima

in tapping mode. Cyclic voltammetry tests were performed with a Voltalb 40 system

(Radiometer Analytical) adapted for screen-printed electrodes (SPE). SPE, model DS—

220-AT (Drop Sense) is designed with 3 separate electrodes: i. auxiliary electrode

(counter), ii. working electrode (4 mm diameter) and iii. silver reference electrode.

Dopamine (Sigma Aldrich) was dissolved in ultrapure water (18 MOhm) to a

concentration of 10-2

M and used for cyclic voltammetry. Both oxidation and reduction

of 22

Accep

ted

Man

uscr

ipt


6

potentials were recorded within the range (−0.8-1.2) V. Cyclic voltammetry is currently

used for the monitoring of the redox reaction between analytes (dopamine) and sensing

elements (MnTPP)Cl). In a cyclic voltammetry experiment, the working electrode

potential is ramped linearly versus time and the current density is directly related to the

electron transfer that takes place within the oxidation-reduction reactions. For each

progress of oxidation or reduction reaction, both voltage and associated current density

values were assigned.

3. Results and discussion

3.1. AFM investigations

AFM micrograph of (MnTPP)Cl thin films obtained by MAPLE at the fluence of 200 (a),

300 (b), and 500 mJ/cm2 (c) are given in Fig. 2. Globular structures with average

diameters that decrease for higher fluence values were noticed. Both a uniform surface

morphology (62.07 nm average RMS) and a preferential orientation were observed in the

case of 200 mJ/cm2 laser fluence. At 300 mJ/cm

2, both alignment and globular/columnar

tendency were observed. The average diameter was 100 nm with a RMS of 139.48 nm.

At 500 mJ/cm2, the globular structures stack into a more columnar shape. In this case, a

RMS value of 80.58 nm was inferred.

3.2. Raman spectroscopy

Typical Raman spectra of (MnTPP)Cl drop cast (a-(MnTPP)Cl symbol) and MAPLE-

deposited thin films on a Si substrate at 200 mJ/cm2 (b-(MnTPP)Cl-200-Si symbol), 300

mJ/cm2 (c-(MnTPP)Cl-300-Si symbol), 500 mJ/cm

2 (d-(MnTPP)Cl-500-Si symbol) and

Au-SPE at 300 mJ/cm2 (e-(MnTPP)Cl-300-SPE-Au symbol) are presented in Fig. 3.

Raman spectra for porphyrins and metalloporphyrins are complicated because of their

of 22

Accep

ted

Man

uscr

ipt


7

complex structures. For pristine porphyrins, the vibration reference data calculated by

DFT-SQM (density functional theory−scaled quantum mechanical) analysis [43] have a

complex spectrum. For metalloporphyrins the vibration spectra depend on nature of

metallic ion core. It was identified that the wavenumber positions are sensitive to both

central metallic ion and type of constituents grafted on the phenyl rings [44-48]. Among

the metalloporphyrins, the most studied have a metallic core: Ni, Co, Mg, Zn, Cu where

bivalent and zero-valent oxidation states are dominant. The wavenumber position of

vibration bands within the high-frequency region (1,600-900 cm-1

) are sensitive to the

core size, axial ligands, and electron density of the central metal ion. In this respect,

(MnTPP)Cl has a similar behavior. The assignment of Raman bands for the (MnTPP)Cl

complex are briefly discussed on the basis of band shifts of (MnTPP)Cl thin films vs.

drop cast at higher wavenumbers (1,550-1,600) cm-1

. A first observation is the role of the

substrate on which porphyrins are deposited. In drop cast form, (MnTPP)Cl shows a

Raman spectrum with less resolved bands. Deposited by MAPLE on electronic grade Si

substrates and Au-SPE, the Raman spectra show an enhanced resolution and

amplification of the band intensities. Within the fluence range of 200-500 mJ/cm2,

Raman spectra were very similar to drop cast (MnTPP)Cl; he only difference being in

their morphology and topography of the films (Fig. 2).

In Table I we give the bands for the different laser fluences (200, 300 and 500 mJ/cm2)

and substrates (Si, and Au-SPE) in comparison with the pristine (MnTPP)Cl (Fig. 3)

indexing different carbons: a-carbon in the pyrrole ring which connects to the phenyl-

mesocarbon (m) and b-the carbon in the pyrrole rings. Cb-Cb symmetric (1,570 cm-1

) and

asymmetric (1,583 cm-1

) stretching vibrations attributed to Ca-Cm are dominant in the

of 22

Accep

ted

Man

uscr

ipt


8

upper wavenumber region. The porphyrin ligand band centered at about 1,495 cm-1

is

appointed to phenyl ring vibration. It has a little shift to 1,501-1,503 cm-1

in complexes

that confirmed the fact that the metal ion has a small effect on the phenyls at meso-

positions.

The surface enhanced Raman effect is clearly observed for the band centered at 1,444 cm-

1 which can be attributed to phenyl vibration. These bands were not observed in either

drop cast (MnTPP)Cl nor thin films deposited at 500 mJ/cm2, because of the layer

thickness. The porphyrin ligands were assigned to both 1,371 and 1,343 cm-1

. They were

usually associated with symmetric stretch pyrrole half-ring vibrations (C-N). The bands

group 1,272 and 1,236 cm-1

was assigned to Cm-Phenyl. The band of 1,016 cm-1

belonging to porphyrin ligands was ascribed to both vibration of pyrrole breathing and

phenyl stretching that do not shift in Mn complexes. The bands within the range 1,000-

450 cm-1

were assigned to rotations, wagging and out of plane vibrations of TPP structure

[46-48]. The bands centered at 438, 436 and 328 cm-1

, were associated to Mn-N

vibrations.

These results imply that no major decomposition or rearrangement occurred. In case of

MAPLE-deposited thin films at 200 mJ/cm2, the Raman investigations evidenced that the

spectra were very close to the drop cast. The typical thickness of one film deposited at

200 mJ/cm2 is about 2 μm. When increasing the laser fluence (over 300 mJ/cm

2), the

conformational modifications started to appear as is evident from the changing

vibrational groups (symmetric/antisymmetric groups). The films deposited at 300 and

500 mJ/cm2 have 7 and 8 μm thickness, respectively. Under these conditions we decided

to continue our further investigations with a 300 mJ/cm2 fluence.

of 22

Accep

ted

Man

uscr

ipt


9

None of the features of the recorded Raman spectra indicated residual solvent in the

MAPLE deposited films.

3.3. Cyclic voltammetry

The voltammetric behavior of dopamine was compared for Au-SPE, and Au-SPE with

(MnTPP)Cl deposited on the electrode by MAPLE and is shown in Fig. 4. The response

of dopamine at Au-SPE electrode displayed a well-defined oxidation peak at 104 mV and

a larger reduction peak centered around 50 mV (Fig. 4, long dashed curve). The

difference between the anodic and cathodic peak potentials is (Epa–Epc)=54 mV,

indicating a quasi-reversible process. The Au-SPE covered with MAPLE-deposited

(MnTPP)Cl has a strong oxidation peak centered at 980 mV and the reduction peak

centered at 142 mV (Fig. 4, short dashed curve). The difference (Epa–Epc) is 838 mV.

The first two oxidation peaks centered at 300 and 500 mV are minor and could be

assigned to the interference with OH groups, the metastable oxidation states, and

porphyrinic ring oxidation reaction [49]. The dopamine potential estimated from the

average value of anodic (Epa) and cathodic (Epc) peak potentials, (Epa + Epc)/2, were of

77 and 561 mV vs. silver reference electrode at the Au-SPE and Au-SPE with

(MnTPP)Cl, respectively. This result showed that there is no difference in the

reversibility behavior. As the last peak corresponds to a high voltage value, a weak

interference with other analytes (present in the body fluids such as uric and ascorbic

acids) permitted the identification of dopamine with reasonable accuracy. The anodic

peak of (MnTPP)Cl-coated Au-SPE was shifted to higher potentials. This is the reason

why the MnTPP)Cl-coated Au-SPE can be considered appropriate as a single mediator

of 22

Accep

ted

Man

uscr

ipt


10

for dopamine oxidation. The oxidation potential at 980 mV is associated with the

formation of the porphyrin cation (-cation radical) in a higher oxidation state.

The high oxidation potential is not usually convenient for the sensor development

(analyte detection) because the mediators (in our case (MnTPP)Cl) reduce the oxidation

potential to rather small values (less than 200 mV). In case of oxidation potentials of

(200-500) mV significant interferences come out from the other analytes present in body

fluids (uric and ascorbic acids). Because the dopamine concentration in body fluids is

very small, its detection is therefore quite difficult. However, for high oxidation

potentials (980 mV) the answer (the current density) reaches ~108 μA/cm2. The

dopamine detection becomes accordingly possible for very small concentrations (less

than 10-2

M). This demonstrates that the (MnTPP)Cl coated gold screen-printed electrode

could be considered as a potential candidate for biosensor development.

Conclusions

We have demonstrated that matrix assisted pulsed laser evaporation (MAPLE) is suitable

for the deposition of (5,10,15,20-tetraphenyl)porphinato manganese (III) chloride

(MnTPP)Cl) thin films. AFM micrographs reveal globular structures with average

diameters decreasing with laser fluence. Typical characteristic group fingerprints of

(MnTPP)Cl starting material were identified by Raman investigations for the case of

MAPLE-deposited thin films with laser fluence within the range (200-500) mJ/cm2.

Surface enhanced Raman effect was noticed on MAPLE-deposited thin films at 300

mJ/cm2. Increasing the laser fluence over 300 mJ/cm

2 caused conformational

modifications appearing as was observed from the changing vibrational groups

(symmetric/antisymmetric groups). By cyclic voltammetry of (MnTPP)Cl MAPLE-

of 22

Accep

ted

Man

uscr

ipt


11

deposited onto screen-printed gold at 300 mJ/cm2

using dopamine neurotransmitter as

analyte it was observed that the anodic peak of (MnTPP)Cl-coated Au-SPE was shifted

towards higher potentials Under these conditions, we can state that (MnTPP)Cl-coated

Au-SPE is appropriate as a single mediator for dopamine sensing in the specific case of

gold screen-printed electrodes.

Acknowledgments

R.C., C.P., A.P., S.G., and I.N.M. thank the financial support of this work under the

contract 22-079/2008. A.A.C., S.I., A.A., and I.S. would like to thank both Bios-ADN

81-028/2007 and MINASEP 11-024/2007 programs.

References

[1] M. Biesaga, K. Pyrzynska, M. Trojanowicz, Talanta 51 (2000) 209-24.

[2] S. Hamai, J. Nanosci. Nanotech. 1 (2001) 177-184.

[3] M.C. Drain, T.H. Joeseph, K.S. Suslick, M.R. Wasielewski, X. Chen, J. Porph. Phtal. 6

(2002) 243-273.

[4] O.Q. Munro, S.C. Shabalala, N.J. Brown, Inorg. Chem. 40 (2001) 3303-3317.

[5] H. Tamiaki, N. Matsumoto, S. Unno, S. Shinoda, H. Tsukube, Inorg. Chim. Acta 300-

302 (2000) 243-249.

[6] P. Hambright, Chemistry of Water Soluble Porphyrins, in: K.M. Kadish, K.M. Smith,

R. Guilard (Eds), The Porphyrin Handbook, vol. 3,.: Academic Press, 2000, pp. 129-

210.

[7] N.A. Rakow, K.S. Suslick, Nature 406 (2000) 710-713.

[8] H. Ogoshi, T. Mizutani, T. Hayashi, Y. Kuroda, Porphyrins and Metalloporphyrins as

Receptor Models in Molecular Recognition, in: K.M. Kadish, K.M. Smith, R.

of 22

Accep

ted

Man

uscr

ipt


12

Guilard (Eds.), The Porphyrin Handbook, Vol. 6, Academic Press, San Diego, 2000,

pp 279−340.

[9] B.J. White, J.A. Legako, H.J. Harmon, Sensors and Actuators B Chemical 91 (2003)

138-142.

[10] S. Mohammadi, M. Perree-Fauvet, N. Gresh, K. Hillairet, E. Taillandier,

Biochemistry 37 (1998) 6165-6178.

[11] H.J. Harmon, J. Porph. Phthal. 6, (2002) 73-77.

[12] S.C.M. Gandini, V.E. Yushmanov, M. Tabak, Journal of Inorganic Biochemistry 85

(2001) 263-277.

[13] M.P. Jensen, D.P. Riley, Inorg. Chem. 41 (2002) 4788-4797.

[14] X.B. Zhang, Z.Z. Li, C.C. Guo, S.H. Chen, G.L. Shen, R.Q. Yu, Anal. Chim. Acta

439 (2001) 65-71.

[15] J.A.A.W. Elemans, R. Van Hameren, R.J.M. Nolte, A.E. Rowan, Adv. Mater. 18

(2006) 1251.

[16] M. Yuasa, K. Oyaizu, A. Yamaguchi, M. Ishikawa, K. Eguchi, T. Kobayashi, Y.

Toyoda, S. Tsutsui, Polymers for Advanced Technologies 6(4) (2005) 287-292.

[17] S.J. Kwon, A.L. de Boer, R. Petri, C. Schmidt-Dannert, Appl. Environ. Microbiology

69(8) (2003) 4875–4883.

[18] S. Banfi, E. Cassani; E. Caruso, M. Cazzaro, Bioorg. Med. Chem. 11(17) (2003)

3595-3605.

[19] M.S.M. Quintino, K. Araki, H.E. Toma, L. Angnes, Talanta 74(4) (2008) 730-735.

[20] J.H. Khorasani, M.K. Amini, H. Motaghi, S. Tangestaninejad, M. Moghadam,

Sensors and Actuators B: Chemical 87(3) (2002) 448-456.

of 22

Accep

ted

Man

uscr

ipt


13

[21] M. Mascini, A. Macagnano, D. Monti, M.D. R. Carlo Paolesse, B. Chen, P. Warner,

A. D’Amico, C. Di Natale, D. Compagnone, Biosensors and Bioelectronics 20(6)

(2004) 1203-1210.

[22] N.A. Chaniotakis, A.M. Chasser, M.E. Meyerhoff, J.T. Groves, Anal. Chem. 60

(1988) 185–188.

[23] G. Mele, R. Del Sole, G. Vasapollo, E. García-López, L. Palmisano, Jun Li, R. Słota

G. Dyrda, Res. Chem. Intermed. 33(3–5) (2007) 433–448]

[24] R.A. McGill, D.B. Chrisey, Method of producing a film coating by matrix assisted

pulsed laser deposition, Patent number 6,025,036 (2000).

[25] D.B. Chrisey, R.A. McGill, J.S. Horwitz, A. Pique, B.R. Ringeisen, D.M. Bubb,

P.K. Wu, Chem. Rev. 103 (2003) 553–576.

[26] A. Piqué, Deposition of Polymers and Biomaterials Using the Matrix-Assisted

Pulsed Laser Evaporation (MAPLE) Process, in: R. Eason (Ed.), Pulsed Laser

Deposition of Thin Films: Applications-Led Growth of Functional Materials,

Wiley-Interscience, Hoboken, USA, 2006, pp. 705.

[27] Gutierrez-Llorente, Horowitz G., Perez-Casero R., Perriere J., Fave J.L., Yassar A.,

Sant C., Organic Electronics 5 (2004) 29-34.

[28] R. Cristescu, D. Mihaiescu, I. Stamatin, G. Socol, I.N. Mihailescu, D.B. Chrisey,

Appl. Phys. A – Mater. Sci. & Process. 79(4-6) (2004) 1023-1026.

[29] G. S. Edwards, S. J. Allen, R.F. Haglund, R.J. Nemanich, B. Redlich, J. D. Simon,

and W-C. Yang, Photochem. Photobiol. 81 (4) (2005) 711-735.

[30] R. Fryček, M Jelínek, T. Kocourek, P. Fitl, M. Vrňata, V. Myslík, M. Vrbová, Thin

Solid Films 495(1-2) (2006) 308-311.

of 22

Accep

ted

Man

uscr

ipt


14

[31] D.M. Bubb, M. Papantonakis, Brian Collins, Elijah Brookes, Joshua Wood, Ullas

Gurudas, Chem. Phys. Lett. 448 (2007) 194-197.

[32] Andreea Purice, Jørgen Schou, Peter Kingshott, Maria Dinescu, Chem. Phys. Lett.

435 (2007) 350-353.

[33] A. Sellinger, E. Leveugle, J. M. Fitz-Gerald, L. V. Zhigilei, Appl. Phys. A 92 (2008)

821-829.

[34] A.P. Caricato, M. Lomascolo, A. Luches, F. Mandoj, M.G. Manera, M. Mastroianni,

M. Martino, R. Paolesse, R. Rella, F. Romano, T. Tunno and D. Valerini, Applied

Physics A-Materials Science & Processing 93(3) (2008) 651-654.

[35] R. Pate and A.D. Stiff-Roberts, Chem. Phys. Lett. 477 (2009) 406–410.

[36] Califano V, Bloisi F, Vicari LRM, Colombi P, Bontempi E, Depero LE, Appl. Surf.

Sci. 254(22) (2008) 7143-7148.

[37] A. Rotaru, A. Kropidlowska, C. Constantinescu, N. Scarisoreanu, M. Dumitru, M.

Strankowski, P. Rotaru, V. Ion, C. Vasiliu, B. Becker, M. Dinescu, Appl. Surf. Sci.

255(15) (2009) 6786-6789.

[38] E. Fagadar-Cosma, M.C. Mirica, I. Balcu, C. Bucovicean, C. Cretu, I. Armeanu, Gh.

Fagadar-Cosma, Molecules 14 (2009) 1370-1388.

[39] J.H. Khorasani, M.K. Amini, H. Motaghi, S. Tangestaninejad, M. Moghadam,

Sensors and Actuators B 87 (2002) 448–456

[40] M.C. Curet-Arana, R.Q. Snurr, L.J. Broadbelt, Quantum Chemical Analysis of the

Reaction Pathway for Styrene Epoxidation Catalyzed by Mn-Porphyrins, in T.

Oyama Ed.) Mechanisms in Homogeneous and Heterogeneous Epoxidation

Catalysis, Elsevier, Amsterdam (2008); pp. 471-486.

of 22

Accep

ted

Man

uscr

ipt


15

[41] F. Bedioui, J. Devynck, C. Bied-Charreton, J. Mol. Catal. A: Chemical, (1996) 113

(1-2) 3-11.

[42] S. Banfi, E. Cassani, E. Caruso, M. Cazzaro, Bioorg & Med. Chem.(2003) 11 3595–

3605.

[43] T.S. Rush III, P.M. Kozlowski, C.A. Piffat, R. Kumble, M.Z. Zgierski, T.G.Spiro, J.

Phys. Chem. B 104 (2000) 5020–5034.

[44] T.G. Spiro, X.Y. Li, Resonance Raman spectroscopy of metalloporphyrins, in T.G.

Spiro (Ed.), Biological Applications of Raman Spectroscopy, Wiley-Interscience,

New York, 1988, Vol. 3.

[45] T. Kitagawa, Y. Ozaki,, Infrared and Raman spectra of metalloporphyrins, in Metal

Complexes with Tetrapyrrole Ligands I, Book Series, Structure & Bond, Springer,

1987, Vol 64.

[46] G.S.S. Saini, Spectrochim. Acta Part A 64 (2006) 981-986.

[47] E. Sun, Y. Shi, P. Zhang, M. Zhou, Y. Zhang, X. Tang, T. Shi, J. Mol. Struct. 889

(2008) 28–34.

[48] J. Odo, M. Mifune, A. Iwado, T. Karasudani, H. Hashimoto, N. Motohashi,Y.

Tanaka, Y. Saito, Anal. Sci. 7 (1991) 555-559.

[49] K.M. Kadish, Z. Ou, J. Shao, C.P. Gros, J.-M. Barbe, F. Jerome, F. Bolze, F. Burdet,

R. Guilard, Inorg. Chem. 41 (2002) 3990-4005.

of 22

Accep

ted

Man

uscr

ipt


16

Tables

Table I. Resonance Raman assignments for (MnTPP)Cl pristine (a-(MnTPP)Cl, Raman

spectra symbol according to Fig. 3) and MAPLE-deposited thin films on i. Si

substrate at 200 mJ/cm2 (b-(MnTPP)Cl-200-Si, Raman spectra symbol according

to Fig. 3), 300 mJ/cm2 (c-(MnTPP)Cl-300-Si, Raman spectra symbol according to

Fig. 3), 500 mJ/cm2 (d-(MnTPP)Cl-500-Si, Raman spectra symbol according to

Fig. 3) and ii. Au-SPE at 300 mJ/cm2 (e-(MnTPP)Cl-300-SPE-Au, Raman spectra

symbol according to Fig. 3).

a-

(MnTPP)Cl

[cm-1

]

b-

(MnTPP)Cl-

200-Si

[cm-1

]

c-

(MnTPP)Cl-

300-Si

[cm-1

]

d-

(MnTPP)Cl-

500-Si

[cm-1

]

e-

(MnTPP)Cl-

300-SPE-Au

[cm-1

]

Band

assignement

[43-46]

- 1,654 1,654 1,656 Phenyl

1,584 1,582 1,580 1,583 as Ca-Cm

1,569 1,572 1,560 1,555 1,570 s Cb-Cb

1,495 1,501 1,503 1,500 1,501 Phenyl, as Cb-Cb

- 1,444 1,442 - 1,444 Phenyl, νs Ca -Cm

1,364 1,372 1,370 1,369 1,371 s Ca-N

- 1,345 1,340 1,340 1,343 s Ca-N

1,265 1,270 1,272 1,269 1,272 Cm-Cph

1,232 1,238 1,237 1,235 1,236 Cm-Cph

1,187 1,193 - 1,193 1,193 as (Cb-H)

1,083 1,090 1,080 1,088 1,086 s (Cb-H)

1,016 1,012 1,015 1,011 1,016 s Ca-Cm

- 443 443 438 s1 (Mn-N)

391 408 412 408 409 s2 (Mn-N)

- 336 331 333 328 as (Mn-N)

of 22

Accep

ted

Man

uscr

ipt


17

Figure Caption

Fig. 1. The structure of (5,10,15,20-tetraphenyl)porphinato manganese (III) chloride

((MnTPP)Cl) is shown.

Fig. 2. AFM-tapping phase contrast images of (MnTPP)Cl MAPLE-deposited thin films

on Si wafers at 200 (a), 300 (b) and 500 mJ/cm2 (c).

Fig. 3. Typical Raman spectra of (MnTPP)Cl drop cast (a-(MnTPP)Cl symbol) and

MAPLE-deposited thin films on: i. Si substrate at 200 mJ/cm2 (b-(MnTPP)Cl-

200-Si symbol), 300 mJ/cm2 (c-(MnTPP)Cl-300-Si symbol), 500 mJ/cm

2 (d-

(MnTPP)Cl-500-Si symbol) and ii. SPE-220AT at 300 mJ/cm2 (e-(MnTPP)Cl-

300-SPE-Au symbol).

Fig. 4. Typical cyclic voltammograms of water blank (solid curve), SPE-220AT (long

dashed curve), and MAPLE-deposited thin films on SPE-220AT at 300 mJ/cm2

(short dashed curve).

of 22

Accep

ted

Man

uscr

ipt


18

N N

NN

Mn

Cl

Fig. 1.

of 22

Accep

ted

Man

uscr

ipt


19

Fig. 2.

of 22

Accep

ted

Man

uscr

ipt


20

Fig. 3.

of 22

Accep

ted

Man

uscr

ipt


21

Fig. 4.

MAPLE deposition of Mn(III) metalloporphyrin thin films: Structural, topographical and...

Documents

Transcript of MAPLE deposition of Mn(III) metalloporphyrin thin films: Structural, topographical and...