Project name: Fabrication of photofunctional guest/layered double hydroxide host hybrid thin films

Acronym: PHOTOLAY

Contract no. 271/ 2015-10-01

Project code: PN-II-RU-TE-2014-4-1550

Program: Human Resources

Project type: Research projects for the stimulation of the forming of young independent research teams

Project director: Alexandra Angela Vlad

Coordinator: National Institute for Lasers, Plasma, and Radiation Physics (INFLPR)

Financing Authority: Executive Unit for Financing Higher Education, Research, Development and Innovation (UEFISCDI)
 

Project summary:

The preparation of a highly photofunctional hybrid thin films of intercalated chromophores in Layered double hydroxides (LDH) matrix by pulsed laser deposition (PLD) is investigated, and the functionality of the films will be examined through the optical properties  introduced by the chromophore. The use of composite of organic chromophores offers a number of advantages. An interesting class of chromophores is coumarins and coumarins derivates. Two systems will be studied: coumarin intercalated in MgAl-LDH and coumarin and dodecyl sulfate (DS) co-intercalated in MgAl-LDH.  Layered double hydroxides are materials of a growing interest in the field of material chemistry due to their structural anisotropy which allow an easy functionalization by intercalation of some species with specific properties. Finding proper conditions for the deposition of the photofunctional guest/layered double hydroxide host hybrid thin films would be the difficulty and the challenge of the project. The project is of scientific impact because for a large number of optically functional materials, both for passive (absorption) as well as active (emission) materials the incorporation into a matrix is an inevitable necessity for their further applications. The functionality of coumarins is exploited mostly in the solution phase therefore confined them between two “hard” layers and next, fixing them on a substrate as thin films is a first step to fulfill in order to extent their applicability.

Value of the project: 550,000 lei

Duration: 26 months

First stage - 31.12.2015 (click for the scientific report)

Value of first stage: 90.000 lei

Establishing the Mg-Al layered double hydroxides (LDHs) and dodecylsulfate (DS) modified LDHs powder preparation method and their characterization.

Second stage - 31.12.2016

Value of second stage: 284,391 lei

Coumarin modified LDHs powders preparation and coumarin modified LDH thin film deposition using pulsed laser deposition (PLD)
Objectives:
- Establishing the protocol for coumarin- LDH synthesis method
Activity 1. Selection of powder preparation method
Activity 2. Powder characterization by XRD, SEM
Activity 3. Thermogravimetric measurements on powders
- Selection of the appropriate PLD deposition conditions
Activity 1. LDH thin film deposition
Activity 2. Structural, morphological characterization of the deposited layers
Activity 3. Optical characterization of the deposited layers

Dissemination:
1. "Nanocomposite dodecyl sulfate-modified Mg-Al layered double hydroxide thin films deposited via laser technique", A. Vlad, R. Birjega, A. Matei, I. Tirca, M. Dinescu, R. Zavoianu, O.D. Pavel, M.C. Corobea, TechConnect World 2016, Washington DC, USA, 22-25.05.2017 (POSTER)
2. "Comparison of different routes for the manufacture of intercalated dodecyl sulfate Mg,Al-layered double hydroxides composite thin films using laser techniques", I. Tirca, A. Vlad, R. Birjega, A. Matei, M. Dumitru, M. Dinescu, R. Zavoianu, M.C. Corobea, 10TH INTERNATIONAL CONFERENCE ON PHOTOEXCITED PROCESSES AND APPLICATIONS, Brasov, Romania, 29.08-02.09.2016 (POSTER)
3. "Conditions for the deposition of organo-layered double hydroxides hybrid thin films by laser techniques", A. Vlad, R. Birjega, A. Matei, I. Tirca, M. Dinescu, 11th International Conference On Physics Of Advanced Materials, Cluj-Napoca, Romania, 08.09.2016-14.10.2016 (ORAL PRESENTATION)
4. Research stage Linz-JKU Austria, 28.06-03.07.2016
 

Third stage - 30.11.2017

Value of third stage: 175,609 lei

Coumarin and dodecyl sulfat (DS) modified LDHs powders preparation and photofunctional LDH thin film preparation to construct host–guest hybrid materials
Objectives
- Establishing the protocol for coumarin& dodecyl sulfate - LDH synthesis method. Influence of DS on the coumarin intercalation
Activity 1. LDH powder preparation using reconstruction and ion exchange methods
Activity 2. Powder characterization by XRD, SEM, thermogravimetry methods, FTIR
Activity 3. Coumarin& dodecyl sulfat LDH thin film deposition
Activity 4. Optical and structural characterization of thin films
Activity 5. Dissemination

Dissemination:
1. "Photoluminescent Layered Double Hydroxides thin films", A. Vlad, I. Tirca, M. Secu, R. Birjega, R. Zavoianu, A. Matei, A. Marinescu, M. Dinescu, EMRS Fall meeting 2017, Warsaw-Poland, 18-20.09.2017 (POSTER)
2. " Chromophore intercalated layered double hydroxides thin films with photoluminescence response", A. Vlad, I. Tirca, M. Secu, R. Birjega, R. Zavoianu, A. Matei, M. Dinescu, ROCAM, Bucharest-Romania, 11-14.07.2017 (ORAL PRESENTATION)
3. "Layered Double Hydroxides thin films deposited by pulsed laser deposition: optical and structural characterization", I. Tirca, A. Vlad, M. Secu, R. Birjega, R. Zavoianu, A. Matei, M. Dinescu, ROCAM, Bucharest-Romania, 11-14.07.2017 (POSTER)
4. "The fabrication of organic-inorganic thin films based on layered double hydroxides materials using laser techniques", A. Vlad, R. Birjega, I. Tirca, M. Secu, A. Matei, A. Rotaru, R. Zavoianu, CC. MArdare, A. W. Hassel, M. Dinescu, EMRS Spring meeting, Strasbourg-France, 22-25.05.2017 (ORAL PRESENTATION)
5. "Coumarin intercalated layered double hydroxides thin films prepared by laser techniques", I. Tirca, A. Vlad, A. Rotaru, M. Secu, R. Birjega, A. Matei R. Zavoianu, Central and Eastern European Committee for Thermal Analysis and Calorimetry CEEC-TAC 4, Chisinau-Moldova, 28-31.08.2017(ORAL PRESENTATION)
6. "Properties of Layered Double Hydroxides (LDHs) thin films deposited by laser techniques", I. Tirca, A. Vlad, M. Secu, R. Birjega, R. Zavoianu, V. Marascu, A. Marinescu, M. Dinescu, Central and Eastern European Committee for Thermal Analysis and Calorimetry CEEC-TAC 4, Chisinau-Moldova, 28-31.08.2017(POSTER)
7. "Organic Chromophore Modified Layered Double Hydroxides and its functional mixed oxides thin films obtained by PLD", I. Tirca, A. Vlad, M. Secu, R. Birjega, R. Zavoianu, A. Matei, A. Marinescu, M. Dinescu


Conclusions:

The optimal conditions for coumarin and coumarin& dodecyl sulfate LDH thin film deposition by PLD have been identified. Thin films based on coumarin and coumarin&dodecyl sulfate with photoluminescence properties have been obtained. The method described provides an alternative, a simple way to fabricate functional layered double hydroxides thin films with special optical properties.