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	Institute of Chemical Process Fundamentals ASCR, v.v.i. Prague

Laser Chemistry Group

Research staff: J. Pola, V. Drinek, R. Fajgar, A. Galik, A.Galikova, J. Kupcik, D. Pokorna, M. Urbanova, K. Vacek

• IR laser induced chemistry
• IR and UV laser induced chemical vapour deposition of novel polymeric and Si-based materials
• UV laser-induced polymerization in the gas phase
• UV laser-induced photolysis of organosilicon, organoselenium and organotellurium compounds

Laser photolysis and thermolysis of organic and organometallic compounds for fabrication of nano-structures of metals in polymer matrices

(J. Pola, supported by GAAV CR, grant No. 4072107)

IR laser gas-phase co-pyrolysis of iron pentacarbonyl with silacyclobutane, silacyclopent-3-ene and 1,3-disilacyclobutane results in novel polymerisation of the silacycles, which affords Fe clusters enveloped by organosilicon polymer. The mechanism of this reaction involves Fe(CO) species-assisted dehydrogenation and polymerisation of the silacycle [Ref. 1]. IR laser thermolysis of dimethyl selenium, dimethyl tellurium, selenophene and tellurophene was studied to elucidate mechanisms of these reactions and explain formation of solid materials deposited from the gas phase [Refs. 5, 12, 14, 17]. UV laser gas phase photolysis of some disiloxanes and alkoxysilanes affords chemical vapour deposition of polymers possessing superior thermal stability [Ref. 3, 4, 7].

Laser induced deposition of naked and polymer-embedded metal clusters

(J. Pola, supported by MEYS CR, Program COST, grant No. OC 523.60)

UV and IR laser gas-phase co-photolysis and co-pyrolysis of tetramethylgermane and tetramethyltin in the presence of carbon disulfide affords polymeric films containing nanoparticles of germanium and tin sulfides. Examination of solid products from IR laser-induced co-pyrolysis of ferrocene (or iron pentacarbonyl) and disiloxanes revealed that these materials are iron nanoparticles embedded in polyoxacarbosilane and that they have superparamagnetic behaviour. [Ref. 13]

Laser deposition of novel polymers and composites

(J. Pola, supported by MEYS CR, Program KONTAKT No. ME 612)

N2 laser-induced gas-phase co-photolysis of tetraethenylgermane (TEG) and carbon disulfide yields polymeric aerosol particles and represents a unique incorporation of TEG into polymerizing CS species [Ref. 10]. IR laser irradiation of gaseous CS2/1,3-disilacyclobutane affords chemical vapour deposition of solid polythiasilacarbosilane films whose formation takes place via co-polymerization of silene and CS2 [Ref. 16]. UV laser photolysis of CS2-C2H4 mixtures in the gaseous phase represents the first example of copolymerization of carbon disulfide with common monomer and yields novel polymers in which (CS2)n moieties are interlinked with ethylene units [Ref. 15].[Refs. 15, 22, 24]

Laser control of photochemical reactions for deposition of polymeric nano structures

(J. Pola, supported by MEYS CR, Program KONTAKT, grant No. ME 611)

UV laser photolysis of dimethylselenium affords thin films of elemental selenium that react with metallic substrates at room temperature to produce metal selenide interlayer. Reaction between bulk metal and selenium phases has been up to now regarded to proceed only at very high temperatures and this finding reveales high reactivity of selenium films [Ref. 11]. UV laser photolysis of gaseous butadiyne yields polymeric films with high content of sp2 hybridized carbon, which are promising candidate materials for EPR oximetry.

Laser- and Cl atom induced chemical vapour deposition of novel polycarbosilazanes

(J. Pola, supported by MEYS CR, Program KONTAKT, grant No. ME 684)

UV laser photolysis and IR laser pyrolysis of tetramethyldisilazane and hexamethyldisilazane in the gas phase affords chemical deposition of polycarbosilazane films that undergo hydrolysis in air. Different reaction conditions have been tested to obtain polymeric films possessing different reactivity towards hydrolysis.

Laser ablative and non-ablative treatment of polymers

(J. Pola, unsupported project)

IR laser ablation of poly(ethylene-alt-maleic anhydride) affords deposition of structurally identical films and is entirely different from the conventional pyrolysis of this polymer, wherein the anhydride group gets completely lost. IR laser ablation of poly(ethylene-alt-maleic anhydride) in the presence of sodium silicate affords deposition of novel polymeric films containing COONa groups. [Ref. 2]

Laser-induced decomposition of four-membered silicon heterocycles

(R. Fajgar, supported by ICPF)

The project has started by syntheses of several model compounds as silacyclobutene and 1,1-dialkyl-silacyclobutenes.

Laser ablation of the silicon based materials at low and cryogenic temperatures

(V. Drinek, supported by ICPF)

IR laser ablation of SiO and SiO2 in Kr yielded deposits with increased defect density. Reactions of the deposits with H2, ammonia, methylamine and dimethylamine have been examined.

Dynamics of the system aliphatic amines - alumina

(A. Galikova, A. Galik, supported by ICPF)

The rate of propylene adsorption on alumina using the Cahn recording microbalances has been examined. The effect of several propylene concentrations on the rate of isothermal adsorption and desorption was investigated at 180 and at 320 oC, followed by temperature programmed desorption. The effect of the changes of temperature of isothermal part of experiment was studied in the range of 80 to 450 oC. Very interesting behaviour, in addition to that observed by us earlier, was observed around 130 oC. The modelling of the results by simulation software will follow.

Click here for explanation of abbreviations used on this page.

• Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Lodz, Poland: UV laser-induced crosslinking of polysiloxanes
• Chiba University, Chiba, Japan: Laser-induced production of novel Ge-incorporating polymers
• Instituto de Estructura de la Materia, CSIC, Madrid, Spain: Studies on IR laser deposition of polycarbosilanes and silicon carbide
• National Institute of Advanced Industrial Research and Technology, Tsukuba, Japan: Laser control of organic reactions
• University of Crete, Heraklion, Greece: Laser and Cl atom - induced chemical vapour deposition of polycarbosilazanes
• King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia: Reactive ablation for deposition of novel polymeric films

• J. Pola: Institute of Materials and Chemical Research, Tsukuba, Japan (2 months)

• H. Morita, Chiba University, Chiba, Japan
• A. Ouchi, National Institute of Materials and Chemical Research, Tsukuba, Japan
• N. Herlin, CEA-DSM-DRECAM, Service des Photons, Atomes et Molecules, Saclay, France
• L. Diaz, Institute of Structure of Materials, CSIC, Madrid, Spain
• R. Tomovska, University of St. Cyril and Methodius, Skopje, Macedonia
• J. Blazevska Gilev, University of St. Cyril and Methodius, Skopje, Macedonia
• D. Spaseska, University of St. Cyril and Methodius, Skopje, Macedonia
• H. M. Masoudi, King Fahd University of Petroleum and Minerals, Dhahran, Saudi Arabia
• A. Kowalewska, Centre of Molecular and Macromolecular Studies, Polish Academy of Sciences, Lodz, Poland
• A. Dransfeld, M. Flok, V. Cappello, G. Tekautz, Technische Universitaet, Graz, Austria

Original papers

1. Fajgar R., Bastl Z., Subrt J., Vacek K., Pola J.: IR Laser-Induced Gas-Phase Polymerization of Silacyclopent-3-ene Catalyzed by an In situ Generated Fe(CO) Species. Phys. Chem. Chem. Phys. 5, 3789-3794 (2003).

2. Pola J., Kupcik J., Durani S.M.A., Khavaja E.E., Masoudi H.M., Bastl Z., Subrt J.: Laser Ablative Structural Modification of Poly(ethylene-alt-maleic anhydride). Chem. Mater. 15(20), 3887-3893 (2003).

3. Pola J., Ouchi A., Vacek K., Galikova A., Blechta V., Bohacek J.: Megawatt UV laser Photolysis of Disiloxanes: Thermally Stable Polyoxocarbosilane Powders. Solid State Sci. 5(8), 1079-1086 (2003).

4. Pola J., Tomovska R., Bakardjieva S., Galikova A., Vacek K., Galik A.: Megawatt Laser Photolysis of Trimethyl(vinyloxy)silane: Formation of Nano-sized Cross-linked Polyoxocarbosilane with Superior Thermal Stability. J. Non-Cryst. Solids 328(1-3), 227-236 (2003).

5. Pola J., Urbanova M., Volnina E.A., Bakardjieva S., Subrt J., Bastl Z.: Polymer-Stabilized Nano-Sized Tellurium Films by Laser-Induced Chemical Vapour Co-Deposition Process. J. Mater. Chem. 13(2), 394-398 (2003).

6. Tomovska R., Bastl Z., Vorlicek V., Vacek K., Subrt J., Plzak Z., Pola J.: ArF Laser Induced Chemical Vapour Deposition of Polythiene Films from Carbon Disulfide. J. Phys. Chem. 107(36), 9793-9801 (2003).

7. Tomovska R., Bastl Z., Bohacek J., Pola J.: Laser Photolysis of Trimethoxysilane: Chemical Vapour Deposition of Nanostructured Silicone Powders with Si-H and Si-OCH3 Bonds. Appl. Organometal. Chem. 17(2), 113-119 (2003).

8. Drinek V., Bastl Z., Subrt J., Pola J.: IR Laser-Induced Ablation of Silicon Monooxide in Gaseous Methanol and Hydrocarbons: Organically-Modified Silicon Oxide. J. Anal. Appl. Pyrolysis, in press.

9. Drinek V., Vacek K., Pola J., Yuzhakov G., Solcova O., Naumov S.: Characterization of Deposits Produced by TEA CO2 Pulsed Laser Ablation of Silicon Mono- and Dioxide. J. Non-Cryst. Solids, submitted.

10. Morita H., Semba K., Bastl Z., Subrt J., Pola J.: N2 Laser-Induced Formation of Copolymeric Aerosol Particles in a Gaseous Tetraethenylgermane-Carbon Disulfide Mixture. J. Phys. Chem., submitted.

11.Ouchi A., Bastl Z., Bohacek J., Orita H., Miyazaki K., Miyashita S., Pola J.: Room-Temperature Interaction between Laser-Chemical Vapour-Deposited Seleni um and Some Metals. Appl. Surf. Sci., submitted.

12. Pokorna D., Urbanova M., Bastl Z., Subrt J., Pola J.: Laser-Induced Gas-Phase Pyrolysis of Dimethyl Selenium: Chemical Deposition of Selenium and Poly(selenoformaldehyde). J. Anal. Appl. Pyrolysis, in press.

13. Pola J., Bastl Z., Vorlicek V., Dumitrache F., Alexandrescu R., Morjan I., Sandu I., Ciupina V.: Laser-Induced Synthesis of Fe-Fe Oxide/Methylmethoxysilicone Nanocom-posite. Appl. Organometal. Chem, in press.

14. Pola J., Pokona D., Bohacek J., Bastl Z., Ouchi A.: Nano-Structured Crystalline Te Films by Laser Gas-Phase Pyrolysis of Dimethyl Tellurium. J. Anal. Appl. Pyrolysis, in press.

15. Tomovska R., Urbanova M., Fajgar R., Bastl Z., Subrt J., Pola J.: UV Laser-Induced Gas-Phase Co-Polymerization of Carbon Disulfide and Ethene. Macromol. Rapid Commun., in press.

16. Urbanova M., Pola J.: IR Laser Decomposition of 1,3-Disilacyclobutane in Presence of Carbon Disulfide: Chemical Vapour Deposition of Polythiacarbosilane. J. Anal. Appl. Pyrolysis, submitted.

17. Urbanova M., Pokorna D., Ouchi A., Pola J.: Laser Powered Homogeneous Decomposition of Selenophene and Tellurophene: Evidence on High-Energy Path from trans-Butadienediyl Diradical to Ethyne. Tetrahedron Lett., submitted.

Patents

18. Ouchi A., Pola J.: Generation of Chalcogenide Elements. Pat. No. 2002-056925. Applied: 02.03.04.

19. Ouchi A., Pola J.: Generation of Chalcogenide Elements. Pat. No. 2002-056926. Applied: 02.03.04.

20. Ouchi A., Pola J., Bastl Z., Vorlicek V., Subrt J.: Preparation Method of Metal Selenide Thin Films. Pat. No. 2003-010230. Applied: 03.01.17.

Conferences

21. Galikova A., Galik A.: The Global Approach to TPD and Isothermal Adsorption - Desorption Kinetics. 30th International Conference of Slovak Society of Chemical Engineering, Proceedings, p. 108, Tatranske Matliare, Slovakia, 26-30 May 2003.

22. Tomovska R., Fajgar R., Bastl Z., Vorlicek V., Vacek K., Subrt J., Alexandrescu R., Morjan I., Sandu I., Dumitrache F., Ciupina V., Pola J.: Laser Induced Chemical Vapor Deposition of Nanosized Polythiene and Fe/Organosilicon Nanocomposites. International Symposium on Scientific and Industrial Nanotechnology, Book of Abstracts, p. 10-11, Osaka, Japan, 08-09 December 2003.

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