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Appendix 3

SUMMARY OF PROFESSIONAL

ACCOMPLISHMENTS

Anna Sobczyk-Guzenda, PhD

Institute of Materials Science and Engineering

Faculty of Mechanical Engineering

Lodz University of Technology

Łódź, May 2018

Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3

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CONTENTS

1. Name and surname ............................................................................................................ 3

2. Education, diplomas and scientific degrees ...................................................................... 3

3. Employment ...................................................................................................................... 3

4. Foreign experience ............................................................................................................ 3

5. Indication and title of scientific achievement ................................................................... 4

5.1. List of publications constituting the scientific achievement ............................................. 4

5.2. Presentation of the scientific aim of the above work and its results ............................... 6

5.2.1. Introduction and justification of the scientific subject matter selected .......................... 6

5.2.2. Scientific aim of the achievement ............................................................................. 10

5.2.3. Presentation of the results ......................................................................................... 11

5.3. Perspectives of further development .............................................................................. 33

6. Discussion of other scientific, didactic and organizational achievements. ........................ 34

6.1. Scientific activity before receiving a PhD degree ........................................................ 34

6.2. Achievements after receiving a PhD degree ................................................................ 35

6.3. Summary of scientific achievements before and after obtaining the PhD degree

with presentation of achievements in the field of

international, organizational and didactic activity .......................................................... 40


3

1. Name and surname: Anna Sobczyk-Guzenda

2. Education, diplomas and scientific degrees:

2002 Master of Science, Engineer


Faculty of Biotechnology and Food Chemistry

Field: Chemical Technology

Advisor: Dr Zbigniew Irzyniec

Grade: excellent with a distinction

2007 PhD in Technical Sciences

Dissertation: “Thin films of titanium dioxide (TiO2) and their

photocatalytic properties”


Faculty of Mechanical Engineering

Discipline: Materials Engineering

Advisor: Professor Maciej Gazicki-Lipman, PhD

3. Employment:

03.09-16.11. 2007 senior technical assistant, Institute of Materials Science and

Engineering, Faculty of Mechanical Engineering, Lodz

University of Technology

17.12.2007- now assistant professor, Institute of Materials Science and

Engineering, Faculty of Mechanical Engineering, Lodz

University of Technology

4. Foreign experience:

December 2003 Institute for Microsystem Technology – IMTEK, Albert-

Ludwigs University Freiburg, Germany, realization of a project

in the frames of Polish–German DAAD/KBN Agreement,

position – investigator

November 2004 Institute for Microsystem Technology – IMTEK, Albert-

Ludwigs University Freiburg, Germany, realization of a project

in the frames of Polish–German DAAD/KBN Agreement,

position – investigator

27.01-28.09.2014 Institute for Nanomaterials, Advanced Technologies and

Innovation, Technical University of Liberec, Czech Republic,

position - investigator


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5. Indication and title of scientific achievement

With the indication of scientific achievement resulting from the Article 16 paragraph 2 of the

Act from 14th

March 2003 on Academic Degrees and Titles and on Degrees and Title in Art

(Dz. U. 2016 r. poz. 882 ze zm. w Dz. U. z 2016 r. poz. 1311.) I present a cycle of ten related

scientific publications under a common title: „Multifunctional titanium (IV) oxide based

coatings manufactured with the plasma enhanced chemical vapour deposition method ”

5.1. List of publications constituting the scientific achievement

1. A. Sobczyk-Guzenda*, S. Owczarek, H. Szymanowski, M. Gazicki-Lipman, Amorphous

and crystalline TiO2 coatings synthesized with the RF PECVD technique from

metalorganic precursor Vacuum 117 (2015) 104-111.

IF JCR(2015): 1.558; 5-year IF JCR**

(present): 1.553 [based on webpage

https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:

25 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2015].

2. A. Sobczyk-Guzenda*, B. Pietrzyk, W. Jakubowski, H. Szymanowski, W. Szymański, J.

Kowalski, K. Oleśko, M. Gazicki-Lipman, Mechanical, photocatalytic and microbiological

properties of titanium dioxide thin films synthesized with the sol-gel and low temperature

plasma deposition techniques, Materials Research Bulletin 48 (2013) 4022-4031.

IF JCR(2013): 1.968; 5-year IF JCR(present)**

: 2.365 [based on webpage



3. J. Kowalski, A. Sobczyk-Guzenda, H. Szymanowski, M. Gazicki-Lipman, Optical

properties and morphology of PECVD deposited titanium dioxide films, Journal of

Achievements in Materials and Manufacturing Engineering 37 (2009) 298-303.

IF JCR -; 5-year IF JCR(present): -; Polish Ministry of Science and Higher Education points: 9 [based on the appendix to the Minister of Science and Higher Education communiqué of June 2009].

4. J. Kowalski, H. Szymanowski, A. Sobczyk-Guzenda, M. Gazicki-Lipman, A stack

multilayer high reflectance optical filter produced on polyester substrate with the PECVD

technique, Bulletin of the Polish Academy of Sciences-Technical Science 57 (2009) 171-

176.

IF JCR(2009) -; 5-year IF JCR**

(present): 1.238 [based on webpage https://jcr.incites.thomsonreuters.com];

Polish Ministry of Science and Higher Education points: 6 [based on the appendix to the Minister

of Science and Higher Education communiqué of June 2009].

5. A. Sobczyk-Guzenda*, S. Owczarek, H. Szymanowski, A. Wypych-Puszkarz , L. Volesky,

M. Gazicki-Lipman, Plasma enhanced chemical vapor deposition of iron doped thin

dioxide films, their structure and photowetting effect, Thin Solid Films 589 (2015) 605–

612.

https://jcr.incites.thomsonreuters.com/




5

IF JCR(2015): 1.759; 5-year IF JCR**

(present): 1.771 [based on webpage



6. A. Sobczyk-Guzenda*, S. Owczarek, D. Batory, J. Balcerzak, M. Gazicki-Lipman, H.

Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited with the

help of RF PECVD method. Part I. Chemical and phase composition, Ceramics

International 43 (2017) 3993-4004.

IF JCR*(2016): 2.986; 5-year IF JCR

**(present): 2.814 [based on webpage



7. A. Sobczyk-Guzenda*, S. Owczarek, Ł. Kołodziejczyk, W. Jakubowski, M. Gazicki-

Lipman, H. Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited

with the help of RF PECVD method. Part II. Optical and photocatalytic properties,

Ceramics International 43 (2017) 4005-4014.





8. A. Sobczyk-Guzenda*, S. Owczarek, M. Fijalkowski, D. Batory, M. Gazicki-Lipman,

Morphology, structure and photowettability of TiO2 coatings doped with copper and

fluorine, Ceramics International 44 (2018) 5076–5085.





9. A. Sobczyk-Guzenda*, S. Owczarek, A. Wojciechowska, D. Batory, M. Fijalkowski, M.

Gazicki-Lipman, Fluorine doped titanium dioxide films manufactured with the help of

plasma enhanced chemical vapour deposition technique, Thin Solid Films 650 (2018) 78–

87.





10. A. Sobczyk-Guzenda*, W. Szymanski, A. Jedrzejczak, D. Batory, W. Jakubowski, S.

Owczarek, Bactericidal and photowetting effects of titanium dioxide coatings doped with

iron and copper/fluorine deposited on stainless steel substrates, Surface & Coatings

Technology 347 (2018) 66-75.












6

IF JCR: 18.711 (according to the year of publication)

5-year IF JCR: 19.678 (present)

Polish MS&HE points: 275 (according to the year of publication)

Explanations: * corresponding author

5-year IF JCR**

(present) – data from 2016; IF JCR*(2016), Polish MNiSW points*** – the latest data available are

from 2016.

In order to facilitate a description of results and scientific achievements, the articles listed

above are later arranged in a subject order.

The described contribution to the creation of the above-mentioned publications together with

my percentage share was included in Appendix No. 6 entitled: " The list of published

scientific and creative papers and professional work and information on teaching experience,

scientific cooperation, and science communication". Statements of individual authors can be

found in Appendix No. 5.

5.2. Presentation of the scientific aim of the above work and its results

5.2.1. Introduction and justification of the scientific subject matter selected

Due to its photocatalytic activity, titanium dioxide (TiO2) is broadly described in the

scientific literature. This activity mainly comprises the ability to photo-oxidize contaminants,

of both organic [1] and inorganic [2] nature, that are present in water [1] and in air [3]. In

addition, this material exhibits bactericidal [4], virocidal [5] and fungicidal [6] properties.

Because of the superhydrophilic effect, characteristic for its surface after illumination with

UV light, TiO2 is also perceived as a self-cleaning material [7]. Due to its high index of

refraction (n) and low extinction coefficient (k), it also finds applications as a component of

optical filters [8]. Finally, titanium dioxide is characterized by good biocompatibility,

chemical stability and corrosion resistance which, altogether, makes it considered a good

biomaterial [9]. Each of the above listed applications requires, however, a strict control of the

thermodynamic state, chemical composition, surface morphology, roughness and

homogeneity of titanium dioxide.

Because of the entire spectrum of advantageous TiO2 properties presented above, it

constitutes a subject of interest of numerous researchers around the world, independent of

whether it is in the form of a powder or in that of a thin film. My interest in that material can

be dated back to 2003 when, in the beginning of my scientific career, I was looking for a

subject of my PhD dissertation. As a method of manufacture of thin TiO2 coatings, I chose the

radio frequency plasma enhanced chemical vapour deposition (RF PECVD) technique. First

of all, this method is rarely used for deposition of TiO2 films, particularly for self-cleaning

applications and, secondly, the research team that I worked with had an extensive experience

in using this technique for deposition of other semiconducting materials. In my PhD

dissertation, defended in 2007, I presented results of a study on thin TiO2 coatings

synthesized from titanium (IV) chloride (TiCl4). This graduate work of mine was devoted to

the synthesis and characterization of thin TiO2 films, deposited on flat silicon and glass

substrates, quartz Rashig rings as well as cotton and polyester fabrics. I investigated elemental

composition and chemical bonding of the films, their optical properties and photocatalytic


7

activity. As operational parameters of the process, I used the glow discharge power and the

deposition time. The resulting coatings exhibited amorphous structure, which was confirmed

by both X-ray diffraction and Raman spectroscopy. The coatings were characterized by high

index of refraction (n) equal 2.3 and low extinction coefficient (k) amounting to 10-5

-10-6

. The

coatings showed very high bactericidal effect on E. coli bacterial strain, as well as a

satisfactory ability to photo-oxidize benzene and aniline. The results of my dissertation have

been published in seven articles [pos. II.A1; II.A13; II.A14; II.E21; II.E22; II.E24; II.E25 in

Appendix No. 6], including two from the JCR list. The subsequent two articles [pos. IIA2;

IIA4 in Appendix No. 6], including three from the JCR list, published after 2007, partly

contained data acquired in my PhD dissertation, supplemented with additional results and

novel interpretations. None of the above mentioned articles has been used as a part of

scientific achievement fulfilling the requirements for higher doctoral degree. Instead, my PhD

dissertation was used as a solid base for further progress in the field of photon related

activities of both, undoped and doped, coatings of titanium dioxide.

In the subsequent phase of my scientific development, already constituting a part of the

above achievement, I designed and realized a process of deposition of thin TiO2 films

synthesized from metalorganic precursor (tetraetoxytitanium, TEOT) for photo-cleaning

applications, with an additional assessment of the effect of thermal annealing on phase

composition and the properties of the resulting materials. [A. Sobczyk-Guzenda, S. Owczarek, H.

Szymanowski, M. Gazicki-Lipman, Amorphous and crystalline TiO2 coatings synthesized with the RF PECVD

technique from metalorganic precursor, Vacuum 117 (2015) 104-111]. The aim of these investigations

comprised, among others, a selection of the appropriate precursor for deposition of TiO2

coatings, modified with different metallic and non-metallic dopants, which was described in

the subsequent sections of the present work.

A subsequent direction of the study was comprised of depositing TiO2 coatings onto

medical grade 316 LVM steel, their thermal annealing at 500oC and a comparison of the

results with those obtained for the sol-gel coatings. Thin TiO2 films synthesized with the latter

technique using different precursors and modifiers are well defined and described in the

literature. Due to its simplicity and low costs, combined with the high quality of the resulting

films, this method is a subject of a broad interest. Its undisputed disadvantage is comprised of

a necessity to use, for the purpose of material cross-linking, high annealing temperatures

severely limiting the scope of potential substrates. In contrast to that, the RF PECVD

technique proposed in this work, is able to make use of any type of substrates, including

those made of thermolabile materials. Up-to-date, however, there is a severe lack in the

literature of detailed comparative studies, performed under identical conditions, of the photo-

cleaning properties of the coatings synthesized with the RF PECVD and sol-gel methods.

Frankly speaking, only one article was published in that field before 2013. This article,

authored by Guillard et al. [10] presents a characteristics of TiO2 coatings synthesized from

tetraisopropoxytitanium (TTIP) from the point of view of the effect of their grain size and

porosity on photo-oxidation of maleic acid.

In 2013 I published two articles dealing with a comparison of the structure and

properties of TiO2 coatings deposited with the above two techniques. In one of them,

published in Ceramics International [pos. II.A2 in Appendix No. 6], I compared the coatings

deposited from inorganic precursor on glass and silicon substrates. This article has not been


8

included in the present compilation, since it contains some results obtained in my graduate

work. My next comparative work, dealing with TiO2 coatings synthesized from metalorganic

precursors onto 316LVM steel substrates, was published in 2013 in Materials Research

Bulletin [A. Sobczyk-Guzenda, B. Pietrzyk, W. Jakubowski, H. Szymanowski, W. Szymański, J. Kowalski, K.

Oleśko, M. Gazicki-Lipman, Mechanical, photocatalytic and microbiological properties of titanium dioxide thin

films synthesized with the sol-gel and low temperature plasma deposition techniques, Materials Research

Bulletin 48 (2013) 4022-4031].

The next research task, I set for myself, was to carry out detailed kinetic studies of

titanium dioxide synthesis from both precursors used. This was done in order to enable

deposition of the coating with such a high precision with regard to its thickness and optical

parameters, that it could be applied as a high refractive index component of stack multilayer

interference filters with silicon dioxide used as a low index component [J. Kowalski, A. Sobczyk-

Guzenda, H. Szymanowski, M. Gazicki-Lipman, Optical properties and morphology of PECVD deposited

titanium dioxide films, Journal of Achievements in Materials and Manufacturing Engineering 37 (2009) 298-

3012]. In this case, the most promising results were obtained for the coatings deposited from

TiCl4 and it was that precursor that was later used for the construction of the multilayer filter.

It should be stressed here that, because of low deposition temperature, the RF PECVD

method can be used to coat thermolabile substrates. And, indeed, the SiO2/TiO2 multilayer

filter was manufactured on a polymer substrate, which makes it a very advanced approach [J.

Kowalski, H. Szymanowski, A. Sobczyk-Guzenda, M. Gazicki-Lipman, A stack multilayer high reflectance optical

filter produced on polyester substrate with the PECVD technique, Bulletin of the Polish Academy of Sciences-

Technical Science 57 (2009) 171-176].

Having acquired a broad spectrum of data concerning TiO2 coatings synthesized with the

help of the RF PECVD technique, I made a decision to modify these coatings by their doping

with both metallic and non-metallic elements in order to intensify their photoactivity, to

extend its duration and to shift the absorption edge towards longer waves. My plan was to

investigate the effect of a modifier on chemical structure of the films, on their phase

composition as well as optical properties. The studies were partly performed in the frames of

a research project No N508 482638 entitled: „Thin TiO2 coatings of amorphous and

crystalline structure deposited with the plasma enhanced CVD process and exhibiting a

photocatalytic effect”, in which I was engaged as a principal investigator. Taking into account

its better performance, inorganic TiCl4 was selected as a precursor for titanium dioxide

matrix.

In the subject literature, there are numerous elements, both metallic and non-metallic,

described as additives introduced into TiO2 coatings in order to intensify the process of

photocatalysis and to prolong excitation times in that process. The following are the most

frequently used metals: copper [11], zinc [12], zircon [13], silver [14] and iron [15], while

among non-metals the most popular are: nitrogen [16], sulphur [17], phosphorus [18], boron

[19] and fluorine [20]. The principal methods of manufacture of doped TiO2 coatings are: sol-

gel [12], spray pyrolysis [21], magnetron sputtering [22], galvanic [23], hydrothermal [24],

pulsed laser deposition (PLD) [25] and metalorganic chemical vapour deposition (MOCVD)

[26]. The PECVD technique is pointed to as a means to produce bare titanium dioxide

coatings for optical and photocatalytic applications.

A modification of the structure of a TiO2 coating with foreign atoms is particularly

difficult in the case of the RF PECVD method, especially when it comes to metallic dopants.


9

A common limitation is comprised of a low availability of precursors. In the CVD processes,

the easiest way to introduce a starting material to the reaction chamber is to use one in the gas

phase, without a need to change its state of aggregation. This is a reason why the most

frequently encountered literature reports present TiO2 coatings doped with nitrogen [27] and

boron [28]. There are also coatings enriched with Si and SiO2 reported. For example, Gazal et

al. report, deposited on silicon substrates, SiO2 enriched TiO2 coatings manufactured with the

help of atmospheric pressure PECVD process from a mixture of tetraisopropoxytitanium

(TTIP) and hexamethyldisiloxane (HMDSO). In their films, the authors observed formation of

Ti-O-Si moieties, which enhanced these films photocatalytic activity [29]. Similar thin film

material, characterized by good optical properties, was obtained by Li et al. [30]. Lin et al., in

turn, have shown that oxygen vacancies play a significant role in ferromagnetic coupling

between Co2+

ions within the Ti1-xCoxO2 bond systems produced, with a plasma chemical

method, from bis(cyclopentadienyl)titanium (IV) dichloride (C10H10TiCl2) and cobalt (III)

2,4-pentandioniane (C15H21O6Co) on Si(001) substrates [31]. As it was mentioned above, a

precise introduction of metallic dopant to the structure of titanium dioxide coating in a single

RF PECVD process may appear problematic. This is a reason why such processes are often

divided into two separate steps: chemical deposition of a coating first and then its

modification. An example of such an approach is presented in the work of Hájkova et al.

where, as the first step, TiO2 coatings were deposited from TTIP precursor by means of the

RF PECVD technique and they were then enriched, using PVD method, with silver that was

later chemically reduced. The coatings obtained in such a process exhibit bactericidal effect

against a gram negative E. coli. strain [32]. Another example is given by Carraro et al. in

their work devoted to the synthesis of Fe2O3-TiO2 coatings on active carbon fibres using a

two-stage production process. The Fe2O3 coating was deposited with the PECVD method and

it was then modified by an addition of TiO2 in a RF magnetron sputtering process. The

authors have shown the application of such coatings in photocatalytic production of hydrogen

and in a process of photooxidizing organic contaminants [33].

In my work, dealing with doping of titanium dioxide, I have selected two metallic

dopants: iron and copper [A. Sobczyk-Guzenda, S. Owczarek, H. Szymanowski, A. Wypych-Puszkarz , L.

Volesky, M. Gazicki-Lipman, Plasma enhanced chemical vapor deposition of iron doped thin dioxide films, their

structure and photowetting effect, Thin Solid Films 589 (2015) 605–612; A. Sobczyk-Guzenda, S. Owczarek, D.

Batory, J. Balcerzak, M. Gazicki-Lipman, H. Szymanowski, The effect of thermal annealing on Fe/TiO2

coatings deposited with the help of RF PECVD method. Part I. Chemical and phase composition, Ceramics

International 43 (2017) 3993-4004; A. Sobczyk-Guzenda, S. Owczarek, Ł. Kołodziejczyk, W. Jakubowski, M.

Gazicki-Lipman, H. Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited with the help

of RF PECVD method. Part II. Optical and photocatalytic properties, Ceramics International 43 (2017) 4005-

4014; Anna Sobczyk-Guzenda, Sławomir Owczarek, Mateusz Fijalkowski, Damian Batory, Maciej Gazicki-

Lipman, Morphology, structure and photowettability of TiO2 coatings doped with copper and fluorine, Ceramics

International 44 (2018) 5076–5085; A. Sobczyk-Guzenda, W. Szymanski, A. Jedrzejczak, D. Batory, W.

Jakubowski, S. Owczarek, Bactericidal and photowetting effects of titanium dioxide coatings doped with iron

and copper/fluorine deposited on stainless steel substrates, Surface & Coatings Technology 347 (2018) 66-75].

The reason behind that choice was connected with a desire to answer a question how Fe3+

,

Cu2+

and Cu+ ions (of different atomic radii and electronic structures) should influence

chemical and phase composition as well as self-cleaning and optical properties of therewith

modified titanium dioxide coatings. A Fe3+

ion has its d electronic level only half-filled with

its atomic radius being very close to that of Ti4+

ion, what makes it capable of substituting


10

titanium in the crystalline structure of TiO2. Copper, in turn, and Cu2+

ion in particular, has its

atomic radius higher than titanium ion and they also substantially differ with the number of

valence electrons, which suggests that copper atoms will more likely become interstitially

incorporated in that structure. Another reason for the above choice was connected with

significant differences between bactericidity of both elements. Iron is considered a vital

element of bacterial metabolism, of similar importance as carbon, nitrogen and phosphorus. It

is an important constituent of hem, cytochromes oraz hydroperoxidase [34]. This is a reason

why bacteria like to inhabit iron-rich surfaces providing a source of this vital element.

Copper, in turn, is regarded bacteriostatic and bactericidal. Apart from iron and copper, I also

attempted to introduce silver into TiO2 coatings. Unfortunately, this element did not form any

chemical bonds with the titanium dioxide matrix and was incorporated in the coating in the

form of pure metal, which resulted in a lack of any improvement of that coating

photocatalytic and self-cleaning activity and even worsened its optical properties [pos. II.E11

in Appendix No. 6]. Therefore, these data have not been included in the content of the present

work.

In a number of newest (2015-2018) publications, there is addressed a question of the so-

called double doping, typically performed either in a metal/metal or in a metal/non-metal

arrangement. In many cases, such an approach may lead to a synergy effect comprising a shift

of the absorption edge towards visible light and an elongation of recombination times. In

order to carry out double doping, such wet methods as sol-gel or surface impregnation are

applied with the following element systems: Pd/Cu/TiO2 [35], Au/Cu/TiO2 [36], N/Cu/TiO2

[37], Cu/C/TiO2 [38], Cu/S/TiO2 [39] and Cu/F/TiO2 [40] being typically produced.

With the appropriate composition of a precursor compound, the PECVD method may be

utilized for the purpose of introducing, into a titanium dioxide matrix, several elements

simultaneously. Before the publication in 2017 of my article in this subject matter, there had

not been a single report in the literature dealing with such a modification of self-cleaning TiO2

coatings. In my studies, as a source of copper I used a precursor compound which allowed me

to introduce, in the same process, another element i.e. non-metallic fluorine [A. Sobczyk-

Guzenda, S. Owczarek, M. Fijalkowski, D. Batory, M. Gazicki-Lipman, Morphology, structure and

photowettability of TiO2 coatings doped with copper and fluorine, Ceramics International 44 (2018) 5076–5085;

A. Sobczyk-Guzenda, W. Szymanski, A. Jedrzejczak, D. Batory, W. Jakubowski, S. Owczarek, Bactericidal and

photowetting effects of titanium dioxide coatings doped with iron and copper/fluorine deposited on stainless

steel substrates, Surface & Coatings Technology, 347 (2018) 66-75]. In order to perform a comparative

study, I also carried out characterization of TiO2 coatings modified by fluorine alone [A.

Sobczyk-Guzenda, S. Owczarek, A. Wojciechowska, D. Batory, M. Fijałkowski, M. Gazicki-Lipman, Fluorine

doped titanium dioxide films manufactured with the help of plasma enhanced chemical vapour deposition

technique, Thin Solid Films 650 (2018) 78–87]. The latter studies are also meaningful by the fact that

the effect of fluorine on the photocatalytic activity of titanium dioxide is rarely discussed in

the literature.

5.2.2. Scientific aim of the achievement

The aim of my studies was a synthesis, with the help of the plasma enhanced chemical

vapour deposition technique, of thin titanium dioxide films, both unmodified and modified


11

with various metallic and/or non-metallic systems, in order to utilize them as photocleaning

and bactericidal coatings as well as in optical applications.

Attaining such a target required the formulation of a detailed scope of investigations

containing the following tasks:

Task 1. Deposition, from the organic precursor, of bactericidal TiO2 coatings on silicon and

glass substrates and the assessment of their phase composition, optical properties and

photowettability before and after thermal annealing at 500oC.

Task 2. A comparison of phase composition as well as mechanical, bactericidal and

photocleaning properties of the coatings prepared on metal substrates with the help

of PECVD and sol-gel methods.

Task 3. A selection of optimum deposition parameters for TiO2 coatings of high index of

refraction aimed at their application as the material for stack multilayer interference

filter construction.

Task 4. A selection of parameters for the manufacture of modified coatings allowing for their

precise doping with minority elements, both metallic and non-metallic. An

assessment of the effect of a type and a content of these dopants on chemical

structure, phase composition, surface topography, optical properties, water

photowettability, bactericidity and photoactivity in visible light of the TiO2 coatings

deposited on glass and silicon substrates.

Task 5. Determination of the effect of a type and a content of metallic dopants on chemical

structure, phase composition, surface topography, mechanical properties,

bactericidity and water photowettability of the TiO2 coatings deposited on metal

substrates.

A collection of ten publications indicated in this report as the scientific achievement of mine

has been divided into two parts:

- part A – concerning coatings of non-modified titanium dioxide [publications 1-4]

- part B – describing a modification of titanium dioxide coatings by an introduction to their

structure either metallic or/and non-metallic elements [publications 5-10]

5.2.3. Presentation of the results

Part A - Non-modified titanium dioxide coatings

Task 1. Deposition, from the organic precursor, of bactericidal TiO2 coatings on silicon and

glass substrates and the assessment of their phase composition, optical properties and

photowettability before and after thermal annealing at 500oC.

Despite a number of advantageous results achieved in my PhD dissertation for titanium

dioxide coatings deposited from inorganic precursor TiCl4, one serious disadvantage of this

process has also been made clear since that time. This drawback results from a presence in the


12

reaction mixture of atomic chlorine which in a contact with water vapour forms highly

corrosive hydrogen chloride. Under these circumstances, I undertook a search for another, less

aggressive precursor. My selection was tetraetoxytitanium Ti(OC2H5)4 (TEOT), a

metalorganic compound of possibly low number of carbon atoms in a molecule. [A. Sobczyk-

Guzenda, S. Owczarek, H. Szymanowski, M. Gazicki-Lipman, Amorphous and crystalline TiO2 coatings

synthesized with the RF PECVD technique from metalorganic precursor, Vacuum 117 (2015) 104-111; A.

Sobczyk-Guzenda, B. Pietrzyk, W. Jakubowski, H. Szymanowski, W. Szymański, J. Kowalski, K. Oleśko, M.

Gazicki-Lipman, Mechanical, photocatalytic and microbiological properties of titanium dioxide thin films

synthesized with the sol-gel and low temperature plasma deposition techniques, Materials Research Bulletin 48

(2013) 4022-4031; J. Kowalski, A. Sobczyk-Guzenda, H. Szymanowski, M. Gazicki-Lipman, Optical properties

and morphology of PECVD deposited titanium dioxide films, Journal of Achievements in Materials and

Manufacturing Engineering 37 (2009) 298-3012]. Another reason for this choice was the fact that

there was a limited amount of published work dealing with optical and photocatalytic

applications of TiO2 coatings deposited from this precursor with the RF PECVD technique.

Although both precursors are characterized by similar boiling point, most researchers prefer

tetraisopropoxytitanium Ti(OC3H7)4 (TTIP), a compound of a larger carbon chain.

The precursor selected – TEOT is characterized by low room temperature vapour

pressure. Therefore, evaporation at elevated temperatures was necessary. In order to select the

optimum evaporation conditions, a series of deposition processes were carried out at different

TEOT temperatures comprised within the range of 50-90oC. The resulting coatings were

characterized with regard to their index of refraction (n) and extinction coefficient (k), the

parameters already shown in my PhD dissertation to play the role of physical criteria for thin

film quality. The highest value of refractive index, namely 2.2, I received at TEOT

evaporation temperature of approximately 80oC-90

oC. In order to maintain a homogeneous

flow of TEOT vapour, its container was bubbled with a non-reactive carrier gas argon at 2

sccm [J. Kowalski, A. Sobczyk-Guzenda, H. Szymanowski, M. Gazicki-Lipman, Optical properties and

morphology of PECVD deposited titanium dioxide films, Journal of Achievements in Materials and

Manufacturing Engineering, 37 (2009) 298-3012]. Another operational parameter of the PECVD

process used in this work was the glow discharge power. In the case of the coatings deposited

from organic precursor, power was controlled within the range of 100-300W. At lower power

values, of an order of 100-200W, a non-stoichiometric composition of titanium dioxide was

obtained having an excess of oxygen. Such coatings were characterized by lower magnitudes

of refractive index, of the 2.05-2.11 range. The reason was a deficit of energy, which was too

low to carry out a complete fragmentation of the precursor molecule. As a result, larger

organic fragments of TEOT were incorporated into the structure of the growing film in which

an excess of oxygen was observed. It was only at 300W of discharge power, that TiO2

coatings of an appropriate stoichiometry and a satisfactory value of refractive index were

obtained. The value of extinction coefficient in this case amounted to 10-4

[A. Sobczyk-Guzenda,

S. Owczarek, H. Szymanowski, M. Gazicki-Lipman, Amorphous and crystalline TiO2 coatings synthesized with

the RF PECVD technique from metalorganic precursor, Vacuum 117 (2015) 104-11; J. Kowalski, A. Sobczyk-

Guzenda, H. Szymanowski, M. Gazicki-Lipman, Optical properties and morphology of PECVD deposited

titanium dioxide films, Journal of Achievements in Materials and Manufacturing Engineering, 37 (2009) 298-

3012]. For a comparison, in the case of the TiO2 coatings synthesized from the inorganic

precursor (TiCl4) this value was an order of magnitude lower. Transmission measurements of

UV-Vis radiation have shown that an application of higher discharge power results in a shift

of the absorption edge by approximately 60 nm towards visible light. Unfortunately, it was


13

still beyond the visible range of light [A. Sobczyk-Guzenda, S. Owczarek, H. Szymanowski, M. Gazicki-

Lipman, Amorphous and crystalline TiO2 coatings synthesized with the RF PECVD technique from metalorganic

precursor, Vacuum 117 (2015) 104-111].

Another operational parameter, whose effect on the quality of the coatings was

investigated was the flow rate of oxygen. This parameter was varied between 100 and 500

sccm, at the constant discharge power of 300W. The values of refractive index obtained

within this range of operational conditions remained between 2.10 and 2.23. With the flow

rate of oxygen higher than 350 sccm, these values remained already close to 2.2 [A. Sobczyk-


synthesized with the RF PECVD technique from metalorganic precursor, Vacuum 117 (2015) 104-111; J.

Kowalski, A. Sobczyk-Guzenda, H. Szymanowski, M. Gazicki-Lipman, Optical properties and morphology of

PECVD deposited titanium dioxide films, Journal of Achievements in Materials and Manufacturing Engineering

37 (2009) 298-3012]. Thickness of the coatings, determined ellipsometrically, remained between

160 and 250 nm and it increased with the increasing flow rate of oxygen at the constant

deposition time of 90 minutes. In addition, I observed an accompanying increasing

inhomogenity of the coating surfaces.

The studies of phase composition unambiguously showed that all the TiO2 coatings

deposited under glow discharge conditions from metalorganic precursor onto iced water

cooled electrode exhibited amorphous structure. It is a common understanding that, for the

photocatalytic activity of titanium dioxide only one of its polymorphs, namely anatase, should

be responsible. This is a reason why I thermally annealed the coatings at 500oC, i.e. the

temperature of this polymorph crystallization. As a result anatase reflexes appeared, but only

in the diffractograms of the films deposited at oxygen flow rates higher than 300 sccm, for

which the O:Ti elemental ratio was close to or slightly higher than two. The appearance of the

crystalline phase was accompanied by an increase of refractive index to 2.35.

Both annealed and non-annealed coatings were also subjected to the measurements of

water wettability under illumination with the UV light. They differed only with regard to the

initial value of the contact angle: while for the non-annealed (amorphous) coatings this angle

amounted to approximately 90 deg, it was equal 45-52 deg after their crystallization. As a

result of UV illumination, in both cases water contact angle was reduced to ca. 10 deg,

that is a value typical for strongly hydrophilic surfaces. In was shown, therefore, that

surfaces of both non-annealed (amorphous) and thermally annealed (crystalline) TiO2

coatings under UV illumination exhibit a shift of water wettability towards highly

hydrophilic ones. My contribution to the titanium dioxide state-of-the-art knowledge in

this case is comprised of the fact that, in contradiction to several authors’ suggestions, I

have shown that amorphous material, too, is capable of exhibiting this effect. [A. Sobczyk-


synthesized with the RF PECVD technique from metalorganic precursor, Vacuum 117 (2015) 104-111].

Task 2. A comparison of phase composition as well as mechanical, bactericidal and

photocleaning properties of the coatings prepared on metal substrates with the help

of PECVD and sol-gel methods.

A thin film deposition method most often used for a synthesis of TiO2 coatings for

photocatalytic applications is the sol-gel technique. This is a reason why I have chosen this

method as a reference for the assessment of benefits and drawbacks of the RF PECVD


14

technique. For that purpose, in order to incontestably compare the coatings synthesized with

both methods, it was necessary to conduct all the tests under identical conditions and, first of

all, to use precursors of similar chemical composition. [A. Sobczyk-Guzenda, B. Pietrzyk, W.

Jakubowski, H. Szymanwski, W. Szymański, J. Kowalski, K. Oleśko, M. Gazicki-Lipman, Mechanical,

photocatalytic and microbiological properties of titanium dioxide thin films synthesized with the sol-gel and low

temperature plasma deposition techniques, Materials Research Bulletin 48 (2013) 4022-4031].

In the above work, I presented the results of research, among others, phase

composition, surface topography, and mechanical as well as photocleaning and bactericidal

properties of the coatings before and after their illumination with the UV-B light. For the

purpose of a comparison, the coatings synthesized with the PECVD technique were

additionally thermally treated at the curing temperature of the sol-gel films. This temperature,

amounting to 500oC, is characteristic for anatase crystallization. An analysis of phase

composition has shown that non-annealed PECVD coatings, deposited at discharge power

values in the range of 100-300 W, exhibit amorphous structure. In the case of these materials,

anatase reflexes in the diffractograms appear only after thermal annealing. This result remains

in a good agreement with the properties of, earlier described, similar coatings deposited on

non-metallic substrates. Performed with the AFM microscopy, roughness measurements have

shown that the PECVD coatings, both non-annealed and thermally annealed, are somewhat

less rough than the sol-gel films. The AFM images of these coatings reveal an emergence,

with the increase of discharge power of their deposition, of an increasing amount of

cauliflower-like structures. Finally, the globules formed in the sol-gel films have smaller

dimensions than those present in the RF PECVD coatings synthesized at 300 W of discharge

power.

Adhesion measurements of the TiO2 coatings were performed for a number of samples

differing with the procedures of austenite steel substrate surface preparation: they were either

ultrasonically washed in isopropanol or washed and then etched with argon or oxygen plasma.

The following is a summary of the results of adhesion measurements. When deposited onto

non-etched surfaces, the RF PECVD coatings are characterized by substantially worse

adhesion than the sol-gel films. It was only an application of argon oxygen plasma that

brought about an improvement of adhesion. Adhesive force increased by more than 10

mN and it was 7 mN higher than that recorded for the sol-gel films. Discharge power

had no effect on adhesion forces, but the annealing had. A TiO2 coating of crystalline

structure adhered much better to a steel substrate than the amorphous one. Hardness of

the sol-gel films was similar to the value obtained for plain steel substrate, while that of

the RF PECVD coatings was somewhat higher. For the 300W sample, hardness amounted

to 6 GPa and it increased to 6.5 GPa as a result of thermal annealing.

Water photowettability tests of the investigated materials have shown that all the

coatings, whether amorphous or crystalline, are capable of activation with UV-B light

with the results being comparable for both deposition techniques. More pronounced

differences were observed between the values of bactericidal activity of the samples

illuminated with the UV radiation. For instance, following a 4 minutes long illumination,

the sol-gel film was characterized by a much lower bactericidal effect than that exhibited

by the RF PECVD coating. A presence of anatase did not improve the effect.


15

In the subsequent part of my work, I assessed the susceptibility of the non-activated

TiO2 coatings towards bacterial colonization with the Escherichia coli strain. A formation of

bacterial biofilm on a given surface depends on its chemical composition and thermodynamic

properties. The number of bacteria adhered to the PECVD coatings deposited at 100 and 200

Watt, both annealed and non-annealed, remained at the level of 60% with respect to the

control of a plain 316 LVM steel surface, with the result characteristic for the sol-gel films

being slightly higher. It was only an application of higher deposition power of 300 W and

thermal annealing of the coatings at 500oC, that resulted in a substantial reduction of that

number to 31.9%. In this case, a significant role may be played by crystalline structure as well

as by surface topography of the sample. In general, however, the closer to stoichiometric TiO2

is the elemental composition of the coating, the more toxic this coating is against Escherichia

coli cells. The results obtained in this part of my work present quite a promising perspective

of an application of titanium dioxide coatings on surgical tools, which should substantially

facilitate the process of their sterilization. [A. Sobczyk-Guzenda, B. Pietrzyk, W. Jakubowski, H.

Szymanowski, W. Szymański, J. Kowalski, K. Oleśko, M. Gazicki-Lipman, Mechanical, photocatalytic and

microbiological properties of titanium dioxide thin films synthesized with the sol-gel and low temperature

plasma deposition techniques, Materials Research Bulletin 48 (2013) 4022-4031].

Task 3. A selection of optimum deposition parameters for TiO2 coatings of high index of

refraction aimed at their application as the material for stack multilayer interference

filter construction.

Due to its high magnitude of refractive index (n), low extinction coafficient (k) and

high stability under stormy atmospheric conditions, titanium dioxide may be used as a

component of interference optical filters. In order to construct such a filter, one should deposit

a system of alternated layers of high and low index of refraction. An excellent candidate for

the low n material is silicon dioxide SiO2. For a manufacture of optical coatings, PVD

processes are most often used [41]. Even today, a utilization of the RF PECVD technique

for the construction of interference filters made of SiO2 and TiO2 layers constitutes a

rarely used approach, with an entire novelty in our case being an application of this

technique for the purpose of a production of a high reflectance filter on a flexible

polymer substrate.

Since the titanium dioxide coatings discussed above have been prepared from two

different precursors, namely TiCl4 and TEOT, it was necessary to optimize both processes

with respect to their application for the deposition of optical quality materials. The first

parameter optimized was the discharge power of deposition and its effect on the magnitude of

refractive index of the coating. For both precursors used, that index increased with an

increasing glow discharge power. It attained values attractive from the viewpoint of optical

applications in the case of that power level of 200-300W. The coatings manufactured from

TiCl4 were characterized by slightly higher values of refractive index than the ones

manufactured from organic precursor. Maximum magnitudes of that index amounted to

2.39 and to 2.25 for the materials originated from TiCl4 and TEOT, respectively.

Another parameter, determining high optical quality of materials, is extinction

coefficient k. In both cases its values were very low nearly within the entire scope of the


16

process of operational parameters used. This means that the coatings produced exhibit neither

light scattering nor radiation absorption effects. As far as the differences between both

precursors are concerned, k values of the coatings deposited from TiCl4 at higher discharge

power levels are one order of magnitude lower and amount to 10-6

as compared to 10-5

for

those obtained from TEOT. A higher value of extinction coefficient in the latter case is a

result of a substantial presence, in the coating structure, of carbon originating from the

metalorganic precursor. In general, however, very good optical properties of the TiO2 coatings

obtained in this work make them excellent candidates not only for optical filter applications,

but also in optoelectronics for a construction of thin film waveguides.

Another operational parameter being optimized in terms of optical properties of the

resulting coatings is the flow rate of oxygen at a constant supply of precursor vapours.

Detailed dependences were only studied in the case of the organic precursor TEOT, for which

the highest values of refractive index were obtained for the oxygen flow rate between 400 and

500 sccm. As far as the inorganic precursor (TiCl4) is concerned, I have already shown in my

PhD dissertation that films of good optical properties are obtained within a relatively low

range of oxygen flow rate.

For an appropriate control of a manufacturing process of an interference optical filters,

an exact knowledge of film deposition rates and their dependences on operational parameters

is extremely important. Particular component layers have to be from several nanometers to

several dozen nanometers thick, with deposition rates being as high as possible from the

economy point of view.

The results of my studies show substantial differences of deposition rates with

changing glow discharge power. Interesting enough, while the rate of film deposition from the

TiCl4 precursor increases with the discharge power, it does decrease with this parameter for

the organometallic precursor. For the discharge power of 200 W both rates are close and they

amount to approximately 3 nm/min. With an increase of the discharge power to 300 W, the

former flow rate is already five times larger than the latter one. This effect is a result of both,

differences in chamber geometry of both reactors used in this work and in the chemical nature

of both precursor compounds. At low levels of energy input (ca. 50 W), the rate of deposition

from TEOT was much larger than in the case of TiCl4 because, under these conditions, large

fragments of the former precursor were incorporated into the structure of the growing coating.

For higher power values, an extensive fragmentation of organic precursor molecules and a

subsequent oxidation of titanium took place, what lowered deposition rate on one hand but

produced stoichiometric film composition on the other. In the case of chloride precursor, in

turn, breaking titanium-chlorine bonds occurred relatively easily already at low discharge

power levels. An increase of energy input resulted in more Ti-Cl bonds broken and a growth

of deposition rate of TiO2.

Another important aspect of the coatings predestined for optical applications is their

surface morphology. With a surface that is not smooth enough, it is difficult to avoid an

uncontrolled scattering of light. All the coatings synthesized from the organometallic

precursor are characterized by a good compact structure valuable in optical applications.

Similar was the morphology of the films produced from the inorganic precursor at power

levels equal or lower than 200 W. In the case of the coatings deposited at 300 W of discharge

power, globular structures, unwanted from the viewpoint of their optical applications, began


17

to appear. As a result of a comparison of both optical parameters of the films and their

deposition rates, as the starting material for deposition of titanium dioxide coatings for

the manufacture of optical filters, titanium (IV) chloride has been selected. Because of

surface inhomogeneities observed in films deposited at higher power levels, glow

discharge power of 200 W was selected as an optimum. [J. Kowalski, A. Sobczyk-Guzenda, H.

Szymanowski, M. Gazicki-Lipman, Optical properties and morphology of PECVD deposited titanium dioxide

films, Journal of Achievements in Materials and Manufacturing Engineering 37 (2009) 298-3012].

The second component necessary for the manufacture of the optical filter was silicon

dioxide SiO2. Also in that case, an optimization of the deposition process was needed. As a

precursor compound for a deposition of SiO2, hexamethyldisiloxane (HMDSO) was used. The

results of kinetic measurements have shown an increasing dependence of deposition rate on

the discharge power up to approximately 200 W, followed by a saturation at the level of 17

nm/min. Another important parameter comprised the O2/HMDSO ratio. From the results

presented in [J. Kowalski, H. Szymanowski, A. Sobczyk-Guzenda, M. Gazicki-Lipman, A stack multilayer high

reflectance optical filter produced on polyester substrate with the PECVD technique, Bulletin of the Polish

Academy of Sciences-Technical Science 57 (2009) 171-176] it appears that increasing that ratio up to

20:1 brings about a successive lowering of the coating thickness, which remains constant for

its higher values. Surface morphology studies of the resulting coatings have shown that all

those deposited at the power of 300 W or lower are smooth, homogeneous and free of defects.

The results presented above, together with the chemical composition data, allowed to

select, as the most efficient parameters of SiO2 deposition for optical filter applications, a

glow discharge power of 200 Watt and a volume ratio O2/HMDSO of 20:1.

The optimization of both RF PECVD processes of a synthesis of high and low

refractive index materials allowed one to manufacture a high reflectance interference

optical filter consisting of five TiO2 and four SiO2 films alternately deposited on a

polyester substrate. For designing the above stack multilayer system with the thickness of

TiO2 layers equal 50 nm and that of SiO2 films amounting to 35 nm, Software Spektra Inc.

TFCalc™ program was used. With the assumed magnitudes of refractive index amounting to

2.25 and 1.4 for titanium dioxide and silicon dioxide, respectively, their quarter-wave optical

thicknesses were equal 0.84 i 1.37. For the real device, its pattern of light transmission

was very close to the designed one. In the designed system, the minimum transmittance

amounting to 5.3 % corresponded to the wavelength of 603 nm, while the maximum

transmittance equal 96.6 % was observed at the wavelength of 406 nm. In the real

device, the minimum transmittance equal 3.9 % was recorded for the wavelength of 583

nm, while the maximum transmittance amounting to 99.8 % corresponded to that of 433

nm. The differences noted above result from a slight distribution of the film thicknesses and

from a presence of additional thin protective coating, that was ignored in the design phase.

The results presented above unambiguously show that the RF PECVD technique may be

successfully used for a manufacture of interference optical filters on flexible polymer

substrates, which makes a major contribution in the field of Materials Engineering [J.

Kowalski, H. Szymanowski, A. Sobczyk-Guzenda, M. Gazicki-Lipman, A stack multilayer high reflectance optical

filter produced on polyester substrate with the PECVD technique, Bulletin of the Polish Academy of Sciences-

Technical Science 57 (2009) 171-176].

The results presented above, together with the experience gained, allowed me to

formulate a project proposal concerning a production of single layer non-homogeneous


18

optical filters deposited from organosilicon precursors. The project, entitled Manufactured

with the RF PECVD method, (SiO2)x(Si3N4)1-x coatings with a gradient of optical properties

received funding and was realized, under my supervision, in the years 2015-2018.

Part B - Titanium dioxide coatings modified with metals and non-metal

Task 4. A selection of parameters for the manufacture of modified coatings allowing for their

precise doping with minority elements, both metallic and non-metallic. An

assessment of the effect of a type and a content of these dopants on chemical

structure, phase composition, surface topography, optical properties, water

photowettability, bactericidity and photoactivity in visible light of the TiO2 coatings

deposited on glass and silicon substrates.

Both, literature data and my own experience, gained throughout many years of

research, allowed me to make a decision to undertake a modification of titanium dioxide

coatings in order to intensify photocatalysis as well as photowetting processes, to prolong

duration of their activity and to extend the excitation range of wavelengths towards visible

light. As a precursor for the TiO2 matrix, titanium (IV) chloride has been selected since the

coatings it yields are characterized by substantially better photocatalytic and optical

properties. I realized the abovementioned task by an introduction, to the TiO2 structure,

of a minority additive belonging to the group of transition metals – namely iron [A.

Sobczyk-Guzenda, S. Owczarek, H. Szymanowski, A. Wypych-Puszkarz , L. Volesky, M. Gazicki-Lipman, Plasma

enhanced chemical vapor deposition of iron doped thin dioxide films, their structure and photowetting effect,

Thin Solid Films 589 (2015) 605–612; A. Sobczyk-Guzenda, S. Owczarek, D. Batory, J. Balcerzak, M. Gazicki-

Lipman, H. Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited with the help of RF

PECVD method. Part I. Chemical and phase composition, Ceramics International 43 (2017) 3993-4004; A.

Sobczyk-Guzenda, S. Owczarek, Ł. Kołodziejczyk, W. Jakubowski, M. Gazicki-Lipman, H. Szymanowski, The

effect of thermal annealing on Fe/TiO2 coatings deposited with the help of RF PECVD method. Part II. Optical

and photocatalytic properties, Ceramics International 43 (2017) 4005-4014; A. Sobczyk-Guzenda, W.

Szymanski, A. Jedrzejczak, D. Batory, W. Jakubowski, S. Owczarek, Bactericidal and photowetting effects of

titanium dioxide coatings doped with iron and copper/fluorine deposited on stainless steel substrates, Surface &

Coatings Technology, 347 (2018) 66-75], copper together with fluorine [A. Sobczyk-Guzenda, Sławomir

Owczarek, M. Fijalkowski, D. Batory, M. Gazicki-Lipman, Morphology, structure and photowettability of TiO2

coatings doped with copper and fluorine, Ceramics International 44 (2018) 5076–5085; A. Sobczyk-Guzenda,

W. Szymanski, A. Jedrzejczak, D. Batory, W. Jakubowski, S. Owczarek, Bactericidal and photowetting effects of

titanium dioxide coatings doped with iron and copper/fluorine deposited on stainless steel substrates, Surface &

Coatings Technology, 347 (2018) 66-75] and fluorine alone [A. Sobczyk-Guzenda, S. Owczarek, A.

Wojciechowska, D. Batory, M. Fijałkowski, M. Gazicki-Lipman, Fluorine doped titanium dioxide films

manufactured with the help of plasma enhanced chemical vapour deposition technique, Thin Solid Films 650

(2018) 78–87].

Modification of chemical structure of TiO2 by an introduction of iron

As a precursor compound constituting the source of iron, I have selected liquid iron

pentacarbonyl Fe(CO)5). In order to supply the reaction chamber with its vapours, a

reconstruction of the existing equipment was necessary, which consisted in adding a thermally

controlled liquid container and a system of precise control valves. As a substrate, I used

silicon wafers and/or amorphous quartz plates, depending on needs. During deposition, these


19

substrates were placed directly on the lower water-cooled electrode, whose temperature

amounted to 80oC.

The subsequent step was comprised of determining the optimum iron content in the

coatings. There are numerous publications in the literature that present doping with iron of

TiO2 coatings prepared with different methods. Based on these data, however, it is very

difficult to find out the optimum content of iron in the TiO2 coatings RF PECVD deposited

from the proposed precursors. Different authors report satisfactory photocatalytic effects for

different concentration of this element, depending on deposition technique and precursors

used. The ultimate photocatalytic effect will always vary with such factors as chemical and

phase composition, surface topography as well as type and concentration of the additives.

These characteristics, in turn, should depend on substrate material and precursors used,

deposition and annealing rates or deposition temperature, which are all different for different

deposition methods. Specifics of each technique may cause such defects in the coating

structure and morphology which are hard to obtain with another method. In turn, these

changes in structure can significantly increase or decrease the photoactivity of TiO2 coatings.

This is a reason why, in the first stage of my work with the enrichment of TiO2 coatings with

iron, I did determine the range of this element concentrations for which, in general, the

material positively responded to radiative activation and calculated, from the results of optical

transmission measurements, the values of optical gap i.e. the range of wavelengths for which

photoactivation took place. [A. Sobczyk-Guzenda, S. Owczarek, H. Szymanowski, A. Wypych-Puszkarz, L.

Volesky, M. Gazicki-Lipman, Plasma enhanced chemical vapor deposition of iron doped thin dioxide films, their

structure and photowetting effect, Thin Solid Films 589 (2015) 605–612].

At the first stage of the studies, I synthesized TiO2 coatings doped with iron within a

broad range of 0.1 to 11.5 atomic % of iron. An analysis of phase composition and

chemical structure of the sample containing the lowest iron content (0.1 at.%) with the

Raman spectroscopy showed that it had an amorphous structure, similar to that of plain

TiO2. An increase of iron concentration in the samples resulted in the appearance of

signals corresponding to two crystalline phases of titanium dioxide, anatase and rutile.

At the content of iron equal 5.5. atomic %, the anatase peak disappeared, with the

intensity of the rutile maxima decreasing on behalf of new emerging signals,

corresponding to a crystalline Fe2O3 phase. At the concentration of iron equal 11.5

atomic % the coating was, again, completely amorphous. An analysis of chemical

bonding of the investigated coatings with the Fourier transform infrared (FTIR)

spectroscopy shows that iron is incorporated into the coating structure through newly

formed Fe-O-Ti bonds. That result is important because, in the molecule of iron precursor,

the oxidation stage of iron is zero. The FTIR result indicates, therefore, that this element is

oxidized in the plasma zone and becomes capable of forming chemical bonds with the TiO2

matrix. This hypothesis is confirmed by a lack, in the FTIR spectrum, of a maximum at 2014

cm-1

originating from the vibrations of a Fe-CO bond system present in iron pentacarbonyl

Fe(CO)5.

The most characteristic absorption bands present in the FTIR spectra of iron doped

titanium dichloride coatings are those situate below the wavenumber of 510 cm-1

. They are

associated with Ti-O bond vibrations in rutile and anatase (at 434 cm-1

) crystalline cells. At

high contents of iron, there is another broad peak emerging which changes its position


20

towards larger wavenumbers with increasing Fe concentration. This is an indication of a

presence of FexOy types of structures, and the Fe2O3 structure (which gives a

characteristic absorption band above 667 cm-1

) in particular.

Surface morphology assessment, performed with the help of scanning electron

microscopy (SEM), shows that surfaces of all the coatings are practically flawless, with an

evident influence of iron on that morphology. The higher iron concentration, the more

globular structures appear on those surfaces. An AFM microscopic analysis reveals an

increase of roughness with the increasing content of that element. In addition, larger

spherical agglomerates, which very likely correspond to the Fe2O3 phase, begin to

appear at the iron concentration of 5%.

The values of optical gap (Eg) of the TiO2 coatings, both unmodified and modified

with iron, have been computed from their absorption spectra in the UV-Vis range with

an application of Tauc model. The results demonstrate that a small addition of iron

brings about a lowering of the gap, i.e. a “red shift” of the absorption edge towards

visible light. After passing certain boundary concentration, located somewhere between

1.5 and 2.5 atomic %, an opposite effect is observed and namely a “blue shift” of the

absorption threshold. While in the former case one deals with a simple effect of addition

of respective values for titanium and iron oxides, stemming from a successive

substitution of Ti atoms with Fe atoms in the 3D lattice of TiO2, the latter one is a

quantum effect resulting from the presence of a separate Fe2O3 phase. That phase, of a

low magnitude of its optical gap forms „islands” regularly distributed in the TiO2

matrix of a high Eg value, and such systems are capable of producing quantum effects,

consisting in a shift of absorption edge towards higher energies.

Studying changes of water wettability of the coatings under the effect of UV light

shows that an addition of iron substantially intensifies that process. In this case, a

superhydrophilic effect, unattainable in the case of bare titanium dioxide, was arrived at

after only 5 minutes of illumination. At iron contents above 5 atomic %, a substantial

worsening of that effect took place. The results presented above allowed me to eliminate

from further considerations concentrations of iron higher than 5 atomic %. [A. Sobczyk-Guzenda,

S. Owczarek, H. Szymanowski, A. Wypych-Puszkarz, L. Volesky, M. Gazicki-Lipman, Plasma enhanced chemical

vapor deposition of iron doped thin dioxide films, their structure and photowetting effect, Thin Solid Films 589

(2015) 605–612].

In the subsequent two articles, published in Ceramics International, I gave a detailed

characteristics of the elemental and phase composition, chemical structure, optical properties

and photowetting behavior of TiO2 coatings with iron content up to 5 atomic %, this time

deposited at the temperature of ca. 200oC [A. Sobczyk-Guzenda, S. Owczarek, D. Batory, J. Balcerzak,

M. Gazicki-Lipman, H. Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited with the

help of RF PECVD method. Part I. Chemical and phase composition, Ceramics International 43 (2017) 3993-

4004; A. Sobczyk-Guzenda, S. Owczarek, Ł. Kołodziejczyk, W. Jakubowski, M. Gazicki-Lipman, H.

Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited with the help of RF PECVD

method. Part II. Optical and photocatalytic properties, Ceramics International 43 (2017) 4005-4014]. In

addition, I also studied the effect of thermal annealing of those coatings at 500oC on the above

properties.

An X-ray electron spectroscopy (XPS) analysis of the coatings confirmed that their

iron content was comprised in the range of 0.5 to 4.7 atomic %. As a reference, a film of plain


21

TiO2 of the oxygen to titanium ratio close to stoichiometric, was used. In contrast, a slight

excess of oxygen was observed in the case of iron doped materials. This was a likely result of

a presence on the coating surface of an extra carbon content, compared to that of plain TiO2.

In addition, a titanium content in the films obviously decreased with an increasing

concentration of iron dopant, which may be used as an indirect proof of the substitution of

titanium atoms in the TiO2 matrix with iron. Surface content of carbon was equal

approximately 20 atomic % and it increased in the case of materials of the highest

photoactivity. This observation strongly suggests that the surface presence of carbon results

from the photocatalytic activity of the coating rather than from the incorporation of organic

fragments of the precursor. That hypothesis was confirmed by carbon depth profile

measurements, which showed that the volume carbon, of a content of 2.2 atomic % only,

appeared at the iron concentration in the material exceeding 3 atomic %. That concentration

increases with the iron content in the films, but it never exceeds 4.2 atomic %. And it is this

amount of carbon that, indeed, must have originated from the Fe(CO)5 precursor used.

Independent of iron concentration, before thermal annealing the content of chlorine

remains at constant level amounting to approximately 1 atomic %. XPS analysis also shows

that iron in the coatings predominantly occupies the third oxidation number, with a small

amount of it, present only in the films of the highest iron concentration, remaining at the

second oxidation number. This is a likely result of the fact that at higher concentrations of

Fe(CO)5 a deficiency of oxygen is observed in the reaction mixture. Somewhat higher

concentrations of Fe2+

ions have been detected in thermally annealed coatings. The reason for

that is a formation of separate iron oxide phases which undergo reduction at high

temperatures, which remains in accord with the Fe-O p(O2)-T phase diagram.

Deposition onto a substrate placed on a hot electrode, whose temperature is as high as

200oC, brings about changes in phase composition of the coatings compared to the water

cooled electrode of temperature lower than 100oC. Maxima characteristic for rutile appear

already in a coating of plain TiO2, with an average domain size of 2.8 nm. Since the structure

of material synthesized on water cooled electrode is completely amorphous, the above result

means that, under glow discharge conditions, the high temperature TiO2 polymorph such

as rutile may appear at relatively low temperatures amounting to 200oC. Following a

subsequent annealing at 500oC, rutile maxima increase their intensity and additional anatase

related peaks emerge. X-Ray diffractograms of iron doped coatings reveal a substantial

influence of this element on their crystallization. Up to the Fe content of 2.5 atomic %,

its admixture brings about an increase of the coating crystallinity. Above this threshold

value of iron concentration, the intensity of rutile reflexes decreases, they become

broader and the most intensive peak hkl (110) disappears. The effect observed is very

likely due to the formation of a separate phase, containing iron oxides, which hinders

crystallization of TiO2. In addition, a shift of the (110) maximum towards lower 2Θ values is

observed, which suggests that a fraction of iron atoms is interstitially built-in into the TiO2

structure as well. It may also be connected with the appearance in that structure of Fe2+

ions

of atomic radius lower than that of Fe3+

ions. Thermal annealing of iron enriched coatings

results in an increase of their degree of crystallinity with doubling of rutile coherent domains.

In the article presented, I also described in detail chemical structure of the coatings. To

do that, I employed the FTIR technique using an additional detector that enabled recording of


22

spectra in the far infrared range of 600-50 cm-1

. In this range, there is a number of absorption

bands recorded, corresponding to the vibrations of chemical bonds of inorganic connections,

including TiO2. Absorption in this range not only allows one to identify particular bonds but it

also provides information concerning crystalline structure of the investigated material. This

range is rather poorly described in the literature. On the basis of the fragmentary

literature data together with the results of my own FTIR studies of TiO2 coatings, I was

able to comprehensively interpret that range of absorption, which constitutes a major

contribution to the knowledge of this material and, generally, to the field of Materials

Engineering.

In the FTIR spectra of non-annealed TiO2, presented in this article, I have identified

three main maxima originating from the vibrations of Ti-O bonds and assigned to the

wavenumbers of 212 cm-1

, 382 cm-1

and 510 cm-1

. The latter two are typical for rutile, while

the most characteristic and most intensive band at 212 cm-1

corresponds neither to rutile, nor

to anatase, although its position is closer to the theoretical one for the high temperature phase.

The shift may be due to the fact that, in this coating of generally amorphous structure, there is

a low amount of coherent domains of rutile. Along increasing iron content in the material, the

exact position of this maximum shift in the direction of higher wavenumbers. After thermal

annealing of the plain TiO2 coating, this band is found in its right position at 190 cm-1

,

characteristic for rutile. In addition, at the wavenumber of 440 cm-1

there appears a peak,

absent before the annealing, of anatase that has crystallized from the amorphous phase. This

interpretation has been further confirmed by the XRD results. Similar is the behavior of iron

enriched coatings, with the position of the main rutile band after thermal annealing being

substantially closer to the theoretical value than before annealing. In addition, for iron

concentrations of 1.4 atomic % or higher, the 190 cm-1

band becomes asymmetric. The higher

wavenumber slope of that band is substantially broader because of additional peak appearing

at approximately 278 cm-1

. This peak may have been resulting either from anatase content or

from the vibrations of a Fe-O-Ti bond system. However, since XRD analysis does not reveal

any presence of anatase, one can assume that this band is associated with the Fe-O-Ti

chemical moieties. That assumption is additionally justified by the fact that the intensity of the

278 cm-1

band increases with an increasing iron concentration in the film. [A. Sobczyk-Guzenda,

S. Owczarek, D. Batory, J. Balcerzak, M. Gazicki-Lipman, H. Szymanowski, The effect of thermal annealing on

Fe/TiO2 coatings deposited with the help of RF PECVD method. Part I. Chemical and phase composition,

Ceramics International 43 (2017) 3993-4004].

The studies presented above were continued in another article published in Ceramic

International [A. Sobczyk-Guzenda, S. Owczarek, Ł. Kołodziejczyk, W. Jakubowski, M. Gazicki-Lipman, H.

Szymanowski, The effect of thermal annealing on Fe/TiO2 coatings deposited with the help of RF PECVD

method. Part II. Optical and photocatalytic properties, Ceramics International 43 (2017) 4005-4014]. In that

publication, I presented the coatings surface topography and optical properties, as well as

bactericidal activity and water photowettability activated by both UV radiation and visible

light.

In the AFM image of a plain TiO2 coating, one can see small globular structures

uniformly distributed on its surface. For non-annealed coatings of low iron content, larger

numbers of the globules of different dimensions are observed with an increasing degree of

packing. Thermal annealing homogenizes their texture which, very likely, is bound to the


23

increase of crystallinity. At the iron concentration of 4.5 atomic % the structures are less

evident for both non-annealed and thermally annealed materials, which indicates an

increasing fraction of amorphous phase. The alteration of surface topography well

corresponds to the determined values of roughness.

The course of transmission spectra in the visible range of radiation is typical for TiO2

coatings. Interference fringes appearing in the spectra originate from the differences of the

refractive index between the coating and the substrate. The most pronounced changes are

recorded for the position of absorption edge. An addition of small amounts of iron brings

about a shift of absorption edge towards visible light (red shift), but only up to a certain

point. After reaching a level of 2.5 atomic %, further increase of iron concentration is

followed by a shift of the edge in the reverse direction (blue shift). In order to determine

the wavelength range for which a coating undergoes an activation, the magnitudes of optical

gap (Eg) have been calculated for every material investigated. For non-annealed coatings, the

values obtained stayed within the range of 3.16 and 2.90 eV, while those of thermally

modified films were comprised in the 3.19 and 3.03 eV range. In both cases, these values

were dependent on the concentration of iron in the coating. This means that the coatings of

the iron content of ca. 2.5 atomic %, independent of whether non-annealed or thermally

annealed, are activated with visible light, of the wavelengths of 428 and 409 nm,

respectively. It has to be stressed that the effect is stronger for the non-annealed

materials of lower crystallinity. For the iron concentrations higher than 2.5 atomic %, the Eg

values began to rise again in both instances.

Thickness of the coatings was comprised in the range of 240 and 350 nm, with that

containing the largest amount of iron being the thickest at the same time. This is very likely

connected to the fact that, under experimental conditions used, deposition rates of iron oxides

are higher than those of titanium oxides. Thermal annealing produces only a slight decrease of

thickness.

As far as index of refraction (n) of the investigated materials is concerned, it assumes

the highest values for those having the iron content of 2.5 atomic %. At the wavelength of 550

nm, they are equal 2.35 and 2.45, respectively, for the non-annealed and thermally annealed

coatings. The coefficient k in turn has values of 10-5

- 10-4

for non-annealed coatings, and

slightly only higher of 10-4

-10-3

for annealed coatings. In the case of titanium dioxide films,

these values confirm high optical quality of the materials studied.

The studies of photowettability of the coatings investigated have been carried out in

two different variations: either by subjecting these materials to the UV-B radiation, or by

illuminating them with the natural sunlight for 4 hours. Following their activation with the

UV-B radiation, most of the iron enriched coatings exhibited a strongly hydrophilic

character. In the case of non-annealed materials of Fe content up to approximately 1.4

atomic %, the superhydrophilic effect, that is, the total dissolution of water on the test

surface, was achieved after 6 minutes of their UV-B exposure. Further increase of iron

content in the coatings was accompanied by the worsening of the superhydrophilic

effect. This effect was still achieved for two samples of the lowest concentration of iron,

but it took relatively longer times amounting to 18 and 24 minutes. In addition, a

phenomenon of “oversaturation” was also observed, for which the water contact angle


24

returned to the initial value despite further illumination of a sample. Such levels of

water wettability were never achieved by plain non-modified titanium dioxide coatings.

After their activation, all the coatings were stored in the darkroom in order to study

the water contact angle return to its initial values. Coatings of low iron concentration

maintained their strong hydrophilic properties for the longest time. Within a continuous, 10

hours long, residing at dark the samples did not return to their original contact angles. The

initial value was only arrived at after 3 days of remaining in the darkroom. The return

was faster for plain TiO2 coatings and those containing higher concentrations of iron –

in both cases the initial value was returned to after 24 hours. Similar was the behavior of

thermally annealed coatings, with their return being much faster. The above results

show unambiguously that I have succeeded in modifying titanium dioxide coatings in

such a way that, under UV-B illumination, they exhibit very strong photoactive

properties. What is more, these properties are maintained within a much longer period

of time than it is in the case of plain TiO2.

In order to verify the effectiveness of the coatings of interest under natural conditions,

they were subjected to a four hour long illumination with sunlight. This time, again, the non-

annealed materials with iron content between 0.5 and 1.4 atomic % turned out to be the most

effective ones. They exhibited a substantial activity after 4 hours of illumination already.

Thermal annealing brought about only a minor improvement of surface wettability compared

to plain TiO2. Although the superhydrophilic effect has not been attained within 4 hours

long illumination with the sunlight, one can clearly state that the non-annealed coatings

obtained undergo activation by visible light. In order to achieve real

superhydrophilicity, one simply needs a longer time or higher dose of radiation.

Finally, bactericidity studies performed with Escherichia Coli strain of bacteria, show

that the highest cell destroying power is exhibited by the thermally annealed coating of plain

titanium dioxide. This is a very likely result of a presence in its structure of anatase

polymorph. A slightly worse result (survivability higher by 7%) was obtained for the non-

annealed coatings of plain TiO2 and for the iron enriched materials of Fe content below 1.5

atomic %. To summarize, among self-cleaning titanium dioxide coatings deposited from

TiCl4 and Fe(CO)5 precursors with the RF PECVD technique, the best utility properties

are exhibited by the materials with the iron content lower than 2 atomic % [A. Sobczyk-

Guzenda, S. Owczarek, Ł. Kołodziejczyk, W. Jakubowski, M. Gazicki-Lipman, H. Szymanowski, The effect of

thermal annealing on Fe/TiO2 coatings deposited with the help of RF PECVD method. Part II. Optical and

photocatalytic properties, Ceramics International 43 (2017) 4005-4014].

Modification of TiO2 chemical structure by an introduction of copper and fluorine

Another metallic additive, introduced to the structure of TiO2 in order to improve its

photocatalytic properties, was copper. Because of a lack of liquid metalorganic connections

of this element available on the market, I have selected as a precursor copper

bis(6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanodionate), solid under normal conditions,

but characterized by high vapour pressure. In addition, this compound contains fluorine, a

non-metallic element, which well responds to the newest trends in titanium dioxide literature

promoting, as a means of intensification of that material photoactivity, its double doping with

either metal/metal or metal/non-metal systems [35-36]. In order to facilitate an introduction of


25

a vapour of solid precursor into the plasma reactor, another necessary reconstruction of that

reactor, taking into account precursor sublimation, has been carried out. This reconstruction

comprises an integration, inside the chamber, of a resistively heated element of strictly

controlled temperature of sublimation. The amount of precursor vapour introduced to the

chamber in a unit of time is regulated by the control of sublimation temperature. The rest of

the process operational parameters remained unchanged and the same types of quartz and

silicon substrates were used in this case. During deposition, the temperature of the hot

electrode amounted to approximately 200oC. In the described process, both elements copper

and fluorine were incorporated in the coating structure. Depending on precursor sublimation

temperature, controlled within the range of 60oC to 100

oC, the copper content in the coating

varied between 0.4 atomic % and 3.4 atomic %, while that of fluorine changed from 1.7

atomic % to 9.4 atomic %. Rising sublimation temperature above 100oC resulted in thermal

degradation of the precursor in the initial phase of deposition.

Like in the case of iron enriched TiO2 films, there was a substantial amount of carbon

deposit on the coating surface. That deposit disappeared in the deeper layers of the coatings,

in which the total amount of carbon was much smaller. The XPS analysis of the films’

chemical structure reveals the presence of the fourth state of oxidation of titanium while the

majority of copper remains in the second oxidation state and it is bound to oxygen, although

certain amount of Cu-F bonding is also present. This analysis also shows an occurrence of

Cu-O bonds in which copper is reduced, under glow discharge conditions, to the first state of

oxidation. A deconvolution of fluorine F 1s band, on the other hand, presents the majority of

fluorine being bound to titanium. In addition, one can find maxima corresponding to such

fluorine connections as Ti-O-F, C-F and Cu-F. An FTIR analysis of chemical composition of

the coatings shows that the vibrations of Ti-O bonds remain in the position characteristic for

rutile. These bands are particularly strong in the case of coatings containing 0.9 and 1.4

atomic % of copper. Results of XRD analysis of these coatings show also their highest degree

of crystallinity – that degree decreases in samples of copper content above 1.4%. In the case

of higher concentration of both additives in the coatings, the position of the discussed FTIR

band shifts towards higher wavenumbers, which indicates an increasing amount of amorphous

phase. Another evident absorption band, present only in the spectra of the modified coatings,

is situated at the wavenumber of approximately 620 cm-1

and it corresponds to the vibrations

of Ti-F bonds formed with the fluorine dopant. This band becomes stronger with an

increasing concentration of both elements added. Similar is the behavior of two other peaks,

present at 900 cm-1

and at 735 cm-1

. These peaks correspond to the vibrations of Cu-O-Ti and

Cu-O bonds, respectively. The results presented above prove that I have succeeded in

incorporating both doping elements into the TiO2 matrix in such a way, that they are

chemically bound to that matrix.

Scanning Electron Microscopic (SEM) analysis of the coatings shows that none of the

surfaces investigated is completely smooth. Their microscopic images contain, typical for

TiO2 coatings, globular structures. The addition of copper and fluorine only increases film

inhomogeneity. The results of surface topography studies, carried out with the AFM

technique, remain in a good agreement with phase composition data acquired with the XRD

method. The most similar morphology is exhibited by the coatings containing 0.9 and 1.4

atomic % of copper, characterized by the highest degree of packing of the sharp structures.


26

The surfaces of the coatings holding 3.4 atomic % of copper and 9.4 atomic % of fluorine, in

turn, contain large numbers of depressions, which are also observed in the case of materials

enriched with fluorine alone (described in the further part of this text). This result indicates

that, at certain critical concentration, etching of the growing film by plasma originated

fluorine species begins to takes place. That hypothesis is confirmed by the roughness data

acquired with the AFM technique.

UV-Vis light transmission studies reveal high transparency of the majority of the

coatings in the visible range. An exception to this rule comprises the coating

characterized by the highest amounts of both additives. The same studies show that the

lowest magnitudes of optical gap Eg, amounting to 2.95 eV and 2.96 eV, have been

obtained for the coatings characterized with the highest degree of crytallinity. The above

values are only slightly higher than those obtained in the case of iron doped materials.

They can be excited with the wavelength of 420 nm, which means that in this case too, I

have succeeded in synthesizing TiO2 coatings activated in visible light. After passing the

critical concentration of the dopants, amounting to 1.4 atomic % of copper and to 3.5 atomic

% of fluorine, just as it has been observed for iron doped coatings, an increase of the Eg gap

value takes place. Ellipsometric measurements show that all the copper-&-fluorine containing

films are characterized by refractive index values higher than that of plain TiO2. The highest

magnitude of n, amounting to 2.359, I have recorded in the case of the coating

containing 0.9 atomic % of copper and 2.0 atomic % of fluorine [A. Sobczyk-Guzenda, S.

Owczarek, M. Fijalkowski, D. Batory, M. Gazicki-Lipman, Morphology, structure and photowettability of TiO2

coatings doped with copper and fluorine, Ceramics International 44 (2018) 5076–5085]. This value is

comparable to those obtained for iron enriched coatings [A. Sobczyk-Guzenda, S. Owczarek, Ł.

Kołodziejczyk, W. Jakubowski, M. Gazicki-Lipman, H. Szymanowski, The effect of thermal annealing on

Fe/TiO2 coatings deposited with the help of RF PECVD method. Part II. Optical and photocatalytic properties,

Ceramics International 43 (2017) 4005-4014], and higher than that of fluorine modified material

[A. Sobczyk-Guzenda, S. Owczarek, A. Wojciechowska, D. Batory, M. Fijałkowski, M. Gazicki-Lipman, Fluorine

doped titanium dioxide films manufactured with the help of plasma enhanced chemical vapour deposition

technique, Thin Solid Films 650 (2018) 78–87].

The effect of superhydrophilicity has been achieved in the cases of two samples,

both characterized by a presence of evident rutile reflexes in their diffractograms. In

both cases this effect was observed after 10 minutes of illumination. This is a little longer

time than those recorded for the films doped with iron and with fluorine alone.

However, a competitiveness of the discussed coatings stems from a substantial

prolongation, in their case, of the duration of the superhydrophilic effect during the

storage under dark conditions. For the sample containing 1.4 atomic % of copper, for

instance, the contact angle return dynamics is much slower with the initial value being

arrived at only after five days of a darkroom storage. The above result constitutes an

evidence of a durability of the photowetting effect which, in the case of the coatings

doped with copper-&-fluorine, is substantially higher than for the iron enriched

material. It is important to note that this effect is recorded despite a longer excitation

time, which makes it a valuable information broadening the scope of our knowledge in

the field of TiO2 modification by doping.

Photoactivity of the coatings subjected to the effect of daylight was also

confirmed by the results of water wettability measurements. Films containing 1.4 atomic


27

% of copper and 3.5 atomic % of fluorine were light activated, with their water contact

angle being lowered by 40 degrees. Their return to the original magnitude of that angle was

faster than in the case of UV irradiation [A. Sobczyk-Guzenda, S. Owczarek, M. Fijalkowski, D. Batory,

M. Gazicki-Lipman, Morphology, structure and photowettability of TiO2 coatings doped with copper and

fluorine, Ceramics International 44 (2018) 5076–5085].

Modification of TiO2 chemical structure by an introduction of fluorine

The subsequent aim in my work on modified TiO2 coatings was an incorporation into

their structure of sole fluorine [A. Sobczyk-Guzenda, S. Owczarek, A. Wojciechowska, D. Batory, M.

Fijałkowski, M. Gazicki-Lipman, Fluorine doped titanium dioxide films manufactured with the help of plasma

enhanced chemical vapour deposition technique, Thin Solid Films 650 (2018) 78–87]. In that way I was

going to determine a contribution of this element to the double doping of titanium dioxide

with the copper/fluorine system [A. Sobczyk-Guzenda, S. Owczarek, M. Fijalkowski, D. Batory, M.

Gazicki-Lipman, Morphology, structure and photowettability of TiO2 coatings doped with copper and fluorine,

Ceramics International 44 (2018) 5076–5085]. As a source of fluorine, I chose pentafluoropropionic

acid. Silicon wafers and quartz plates were used as substrates and they were placed on the

lower hot electrode at the temperature of approximately 200oC. Initial results allowed me to

establish the range of resulting fluorine content in the films to be spread between 0.6 atomic

% and 6.7 atomic %.

Elemental analysis of the coatings, performed with the XPS technique, revealed an

increased oxygen to titanium ratio in the fluorine enriched material compared to plain TiO2.

This is likely a result of an introduction of extra amount of oxygen, originating from the

carboxyl group of pentafluoropropionic acid. Just as it was observed in the cases of iron as

well as copper-&-fluorine doped coatings, a substantial amount of carbon deposit originating

from the photocatalytic activity of the material was found on its surface, too.

A deconvolution of the core level XPS Ti 2p band has shown that, in the case of the

plain TiO2 coating as well as that of low fluorine content (0.6 atomic %), positions of Ti 2p3/2

and Ti 2p1/2 peaks are typical for Ti4+

. However, crossing the content of 1 atomic % of

fluorine results in a shift of these positions towards higher bond energy. In the case of the

highest fluorine concentration this shift is large and it amounts to 1.1 eV. This effect is

connected with a presence of Ti-F bonding in the films. A deconvolution of the O 1s band, on

the other hand, reveals a presence, along with that of Ti-O and Ti-OH (C-OH) bonding typical

for titanium dioxide, also oxygen-fluorine bonds. The components of the XPS F 1s bands

comprise: the Ti-F peak as the main maximum accompanied by signals corresponding to the

bonds present in titanium oxyfluoride (TiOFx), whose intensity increases with the increasing F

content in the coatings.

The results of FTIR analysis, performed in the range of both medium and far infrared,

apart from the vibrations of Ti-O bonds, revealed a presence of such bonds as Ti-OH, Ti-F as

well as O-F, Ti-O i Ti-O-C, which could not be associated with any of the titanium dioxide

polymorphs. FTIR analysis confirmed both effects: oxygen substitution with fluorine in

Ti-O bonds as well as a formation of additional Ti-O-F bonding.

As revealed by XRD analysis, an addition of fluorine to a TiO2 coating impedes

crystallization of rutile normally present in a unmodified material. The larger

concentration of fluorine, the stronger is that effect.


28

SEM microscopic analysis of the coating surface morphology shows that it is smooth

and homogeneous at low concentrations of fluorine. In the case of materials containing more

than 1 atomic % of this element, that surface becomes non-homogeneous with spherical

structures appearing. The amount of these structures increases with an increasing content of

fluorine in the coating. The results of phase composition and surface morphology obtained

with the help of SEM microscopy, have been confirmed by AFM observations. On the surface

of plain TiO2, there are sharp structures of small dimensions visible. With an increasing

content of fluorine in the coating, these structures begin to disappear and they are replaced by

hollow forms leading to the non-homogeneity observed with the SEM technique.

UV-Vis absorption spectra of all the coatings reveal their high transparency, with

the transmission amounting to 90% within the entire spectral range of 400-1100 nm.

This value is typical for quartz used as substrate in these tests. The same result indicates an

absence of any quartz etching by gaseous fluorine produced in the process. The results of

optical gap computation show that no shift of absorption edge is observed in this case.

The Eg values of the fluorine doped TiO2 coatings are approximately the same as those

obtained for plain titanium dioxide. This finding can be explained by the fact that the

films containing more than 1 atomic % of fluorine possess amorphous structure. We are

very likely dealing here with two contradictory phenomena. The first effect is that of

doping and it lowers the magnitude of Ep. The second one, resulting from a decrease of

the coating crystallinity, brings about an increase of its magnitude. The effects cancel

each other and the resulting value of optical gap remains at more or less the same level.

The magnitudes of refractive index (n) and extinction coefficient (k) for the wavelength of

550 nm have been determined from ellipsometric measurements. The value of n for a plain

TiO2 coating amounts to 2.28 and it increases to 2.31 after adding a small quantity of

fluorine. Further addition of this element brings about a decrease of refractive index.

That decrease is due to the appearance, in the structure of a coating, of large amounts of

Ti-F and TiOFx moieties. For all the coatings investigated, extinction coefficient (k) takes

up low values amounting to approximately 10-5

. In addition, an admixture of fluorine

lowers deposition rates of TiO2 coatings.

In spite of the fact that the coatings produced did not exhibit any crystalline

structure, for all of those that contained more than 1.8 atomic % of fluorine the

superhydrophilic effect was achieved after a very short time of illumination. Almost

certainly, the high water wettability is due to a presence of TiOFx moieties, and most likely

TiOF2 groups, which are known to exhibit high photocatalytic activity and the ability to form

chemical bonds with hydroxyl groups. In the course of their storage at dark, I have not

recorded any differences between plain TiO2 coatings and those doped with fluorine.

For all the samples tested, water contact angle returned to its initial value after 10 hours

of dark storage [A. Sobczyk-Guzenda, S. Owczarek, A. Wojciechowska, D. Batory, M. Fijałkowski, M.

Gazicki-Lipman, Fluorine doped titanium dioxide films manufactured with the help of plasma enhanced

chemical vapour deposition technique, Thin Solid Films 650 (2018) 78–87].


29

Task 5. Determination of the effect of a type and a content of metallic dopants on chemical

structure, phase composition, surface topography, mechanical properties, bactericidity

and water photowettability of the TiO2 coatings deposited on metal substrates.

Most of the literature reports include TiO2 coatings deposited on such substrates as

glass, quartz or silicon single crystal. It is assumed that the properties of materials synthesized

under these conditions will be similar to those of the samples deposited on different

substrates, for instance on polymers or conducting materials. As a result, there is a limited

number of publications dealing with thin titanium dioxide films synthesized on a surface of

metallic substrates, especially on a surface of medical grade 319LVM stainless steel. A use of

such a substrate should substantially broaden the scope of applications of the coatings,

including implants and medical equipment. In one of my earlier works, dealing with that

subject, I compared the properties of the plain TiO2 coatings deposited from metalorganic

precursor to those of the sol-gel films synthesized from the same compound. [A. Sobczyk-

Guzenda, B. Pietrzyk, W. Jakubowski, H. Szymanowski, W. Szymański, J. Kowalski, K. Oleśko, M. Gazicki-

Lipman, Mechanical, photocatalytic and microbiological properties of titanium dioxide thin films synthesized

with the sol-gel and low temperature plasma deposition techniques, Materials Research Bulletin 48 (2013) 4022-

4031]. The article published in Surface and Coatings Technology is a continuation of these

studies [A. Sobczyk-Guzenda, W. Szymanski, A. Jedrzejczak, D. Batory, W. Jakubowski, S. Owczarek,

Bactericidal and photowetting effects of titanium dioxide coatings doped with iron and copper/fluorine deposited

on stainless steel substrates, Surface & Coatings Technology 347 (2018) 66-75]. The results presented in

that article concern films, both unmodified and modified with iron or with a copper/fluorine

system, deposited from an inorganic precursor, titanium (IV) chloride onto 316LVM medical

grade steel. It presents the effect of the kind and the amount of a dopant on the structure,

mechanical properties, surface topography, bactericidal activity and photowetting of these

films. In both cases, three the most representative concentrations of the doping elements have

been selected in such a manner that they never exceed 3.5 atomic %.

Surface topography studies, performed with the AFM technique, in most samples

reveal a presence of globular structures, characteristic for titanium dioxide coatings. The least

homogeneous surface is exhibited by a coating of plain TiO2. A broad distribution of the

globular dimensions, in the range of 10-120 nm, is observed in that case. In addition, some

globules coalesce, forming agglomerates. At low concentrations of metallic dopant, the

surface becomes more homogeneous with the globular size distribution narrowed to the 10-70

nm range. An increase of metal dopant concentration above 1.4 atomic % brings about, again,

a broadening of the size distribution.

Phase composition analysis, performed with the XRD technique, show that the

majority of the coatings have amorphous structure. The exception is made by the films

of the iron content of 0.5 atomic % and 1.4 atomic %, for which maxima characteristic

for TiO2 polymorphic forms have been recorded. The coating of lower Fe concentration

is characterized by higher degree of crystallinity, with a mixture of rutile and anatase

being dedected in its structure. XRD results have been confirmed by Raman analysis. The

results of phase composition indicate the importance of a substrate significantly affecting the

structure of the growing film. In my opinion, two factors play important roles here: one is

comprised of electrical conductivity differences between different substrates while the other

concerns epitaxial effect of a silicon substrate.


30

FTIR analysis of the coating structure shows a presence of Ti-O, Fe-O and Cu-O

as well as Ti-F, respectively for iron and copper/fluorine doped coatings. This confirms

the hypothesis that the dopant atoms are, indeed, bound to TiO2 matrix.

Hardness of a plain TiO2 coating, measured with the nanoindentation method, amounts

to 8.9 GPa and it is similar to that exhibited by the films deposited by Skwronski et al. with

the help of magnetron sputtering [42], and higher than those presented in our article

concerning coatings synthesized from metalorganic precursor. [A. Sobczyk-Guzenda, B. Pietrzyk, W.

Jakubowski, H. Szymanowski, W. Szymański, J. Kowalski, K. Oleśko, M. Gazicki-Lipman, Mechanical,

photocatalytic and microbiological properties of titanium dioxide thin films synthesized with the sol-gel and low

temperature plasma deposition techniques, Materials Research Bulletin 48 (2013) 4022-4031]. A

modification of TiO2 coating with small (up to 1 atomic %) amounts of dopant results in

an increase of hardness to 11.2 GPa and 12.3 GPa, for an addition of Cu/F and Fe

atoms, respectively. Further increase of dopant content produces successive lowering of

hardness, with an addition of iron bringing about less evident decrease than in the case

of copper-&-fluorine doping.

The results described above do not allow one to unambiguously state that hardness of

the TiO2 coating depends exclusively on its phase composition. A hypothesis is constructed

that it also depends on microstructure, i.e. on porosity, roughness and grain size shown in the

AFM images. According to Hall-Petch theory, the lower its grain size, the larger is the

coating’s hardness [43]. The tendency of change of Young modulus is similar to that of

hardness. In the case of a low metal content (up to 1 atomic %) its magnitude is an increasing

function of metal concentration, and it begins to drop at higher dopant contents.

A subsequent test of mechanical properties comprised an assessment of coating

adhesion to the 316LVM substrate. This was done by a measurement of critical force with the

help of nanoindenter. The values of critical force (CL) were contained within the 8 to 13.5

mN range. For plain TiO2, this value amounted to 8.8 mN, with an addition of small amount

of admixtures resulting in its increase to 11.4 mN and to 12.5 mN, respectively for Cu/F and

Fe dopants. Further increase of their concentration resulted in the return to lower values.

An important element of diagnostics of materials intended for applications as medical

implants or surgical tools is comprised of microbiological studies. It is important that the

material tested (titanium dioxide in this case) does not easily undergo colonization by the

bacteria. To assess that, a surface colonization of the coatings with the Escherichia Coli

bacterial strain was investigated. Compared to a control sample, comprised of uncoated

316LV steel substrate, the unmodified TiO2 coating was colonized with 19.7% of bacterial

cells only [A. Sobczyk-Guzenda, W. Szymanski, A. Jedrzejczak, D. Batory, W. Jakubowski, S. Owczarek,

Bactericidal and photowetting effects of titanium dioxide coatings doped with iron and copper/fluorine deposited

on stainless steel substrates, Surface & Coatings Technology 347 (2018) 66-75]. This result is significantly

lower than those obtained in one of our earlier works for the coatings deposited from

metalorganic precursor with the RF PECVD technique (39% of colonization) and for the sol-

gel coatings produced from the same precursor (50% of colonization). [A. Sobczyk-Guzenda, B.

Pietrzyk, W. Jakubowski, H. Szymanowski, W. Szymański, J. Kowalski, K. Oleśko, M. Gazicki-Lipman,

Mechanical, photocatalytic and microbiological properties of titanium dioxide thin films synthesized with the

sol-gel and low temperature plasma deposition techniques, Materials Research Bulletin 48 (2013) 4022-4031].

In the case of copper content higher than 1 atomic %, I have observed a drop of a number of

adhered Escherichia Coli cells down to 10%. This result allows me to state that an


31

admixture of more than 1 atomic % of copper should substantially reinforce the

bacteristatic effect of TiO2 coatings. In the case of iron doping, at low concentrations of

this element, the amount of adhered bacteria was comparable to that observed for a

plain TiO2 coating. An increase of iron concentration led to a higher susceptibility of the

coating to bacterial colonization.

Another microbiological test performed was an assessment of a bactericidal effect of

the coatings produced on Escherichia Coli cells. For a unmodified TiO2 coating, the rate of

survival of the bacteria was 60%, independent of whether organic TEOT or inorganic

TiCl4 was used as a precursor for the deposition. In accord with the assumption made,

the coatings doped with the Cu/F system exhibited an increasing bactericidal activity

with increasing dopant concentration. The lowest rate of bacterial survivability,

amounting to 20%, was observed in the case of the highest concentration of the dopants.

An addition of small amounts of iron, lower than 1 atomic %, increased survivability

rate to 71% with farther lowering of the coating bactericidity accompanying an increase

of this element concentration. What is interesting, I have not observed any correlation

between the results of microbiological tests and the phase composition of the coatings

investigated.

In contrast to microbiological testing, the results of water wettability

measurements can be correlated with the crystallinity data obtained with the XRD

technique. The values of water contact angle for the non-illuminated samples show that

the coatings of amorphous structure are characterized by hydrophobic surfaces.

Crystallization of a coating with the appearance of anatase and rutile phases brings

about a change of surface character to hydrophilic. Following an illumination with the

UV light, all the modified coatings show wettability higher than that of plain TiO2. In

addition, all the iron containing coatings exhibit substantially higher photoactivity, with

the superhydrophilic effect being obtained for the samples having 0.5 atomic % and 1.4

atomic % of iron. The same samples are characterized by the highest degree of

crystallinity. Finally, I have also found out that the coating of the lowest copper-&-

fluorine content shows a relatively high photo-wettability in spite of the fact that,

according to the XRD measurements, it possesses a completely amorphous structure.

The main achievement of mine, having a substantial contribution to the development of

the discipline of Materials Engineering is showing that, with the help of the radio

frequency plasma enhanced chemical vapour deposition (RF PECVD) technique, one is

able to produce photoactive TiO2 coatings, both unmodified and modified with metallic

and/or non-metallic elements.

The results of my studies, included in ten selected most important publications, have a

substantial impact on the progress of our knowledge in the field of titanium dioxide

research, thus broadening the scope of that knowledge with the materials synthesized

with the help of the RF PECVD technique having potential optical, self-cleaning and

bactericidal applications.


32

In order to illustrate the significance of that achievement, I allow myself to refer to a few of

bibliographical data. In the years 2007-2018, in the field of modifying PECVD synthesized

films of titanium dioxide with different dopants (introduced directly into the coating structure)

twelve scientific articles appeared, which were listed in the ScienceDirect database. Of that

number, six publications are of my co-authorship and, in all of them I occupy both the most

important positions: that of the first author and that of the corresponding one. None of the

remaining six articles deals with the same doping elements as those used in our work.

Apart from such a broadly understood main achievement, I have made eleven more detailed

substantial contributions concerning a synthesis of TiO2 coatings with the PECVD technique:

1. I have determined optimum parameters of TiO2 deposition on metal, silicon and

glass substrates from the tetraetoxytitanium (TEOT) organic precursor.

2. I have carried out a detailed comparative study of phase composition, as well as

self-cleaning and mechanical properties of the TiO2 coatings synthesized with the

PECVD and sol-gel methods.

3. I have proven that the photowetting effect may also be exhibited by the TiO2

coatings (deposited from TEOT) of amorphous structure.

4. I have determined the ways of depositing both TiO2 and SiO2 coatings allowing

one to successfully applying them in stack multilayer optical interference filters.

5. I have shown that, by using either liquid or solid precursors and the RF PECVD

technique, one is capable of introducing, in a broad range of concentrations,

such elements as iron, fluorine and copper/fluorine system, into TiO2 structure.

6. I have shown that, by means of a small change of substrate temperature during

the deposition of TiO2 coatings, one can control their phase composition and, in

consequence, affect future applications of these coatings.

7. I have determined the range of metallic dopant concentrations affecting the

degree of TiO2 crystallinity.

8. I have shown that the introduction of fluorine into TiO2 structure hinders its

crystallization, which indirectly affects the lack of excitation shift in the direction

of visible light.

9. I have manufactured iron and copper doped TiO2 coatings, characterized by a

shift of the absorption edge in the direction of longer wavelengths (with respect to

unmodified TiO2 coatings) by the values of ca. 40 nm and ca. 30 nm, respectively.

10. I have proven that the introduction of copper-&-fluorine into the structure of a

TiO2 coating substantially elongates the durability of the photowetting effect,

when compared to the same coatings enriched with iron.


33

11. I have provided a number of documented data substantially broadening the

state-of-knowledge in the area of interpretation of IR absorption of TiO2

coatings, both unmodified and modified with iron and fluorine, in the far

infrared absorption range.

5.2.4. Perspectives of further development

My further research work is going to run multi-directionally. Amongst other things, I am

planning to:

1. Broaden the application scope of obtained TiO2 coatings, both unmodified and modified, as

a potential component of elastic polymer solar cells. The mentioned coatings should act as

protective self-cleaning coatings as well as antireflection coatings. In this case making a

specific electrical research (i.a. voltage current characteristic, resistivity measurement and

void content calculation) and specific strength tests together with material aging

examination is a must. Besides, it is planned to measure a recombination time of the

electron-hole pairs by a photoluminescence method.

2. Perform biological and cytotoxicity research in a broader scope, to check if mine TiO2

coatings are organism safe.

3. With the help of RF PECVD method modify the surface of a powdered TiO2 in order to

incorporate formations, effecting in a rise of their dispersion in both natural and synthetic

polymer lattice. It is planned to prepare a photobiodegradable composite being used in

agriculture as a wrapped foil of a predicted durability. It will be a continuation of

preliminary studies yielding in promising results [pos. II.E5, II.E7, II.E10 in Appendix No.

6].

4. Produce by RF PECVD method and study another semiconductor oxide materials, e.g.

ZnO2, ZrO2 which show similar self-cleaning effect to mine modified TiO2 coatings.

5. Do research into preparing a new metamaterial group, consisting of layered arrangements

like grapheme and ceramic coating.

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6. Discussion of other scientific, didactic and organizational achievements

6.1. Scientific activity before receiving a PhD degree

In 2002 I took the PhD studies on the Faculty of Mechanical Engineering in the field of

Medical Instrumentation and Equipment and I graduated in 2006. In 2003 I started my

research work at the Nonmetal Materials Unit belonging to Institute of Materials Science and

Engineering at Lodz University of Technology. Originally, my area of interest was plasma

modification of prospective extenders for polyethylene and propylene biodegradable

composites, such as potato starch and cow’s milk whey [pos. II.E20 in Appendix No. 6]. I

also participated in the research grant No. 4 T08E 04923 „Low temperature plasma

https://www.sciencedirect.com/science/article/pii/S0169433207012743#!















http://www.sciencedirect.com/science/article/pii/S0926860X09008680




http://www.sciencedirect.com/science/journal/0926860X

http://pubs.acs.org/author/Liu%2C+Rui

http://pubs.acs.org/author/Wang%2C+Ping

http://pubs.acs.org/author/Wang%2C+Xuefei

http://pubs.acs.org/author/Yu%2C+Huogen

http://pubs.acs.org/author/Yu%2C+Jiaguo

http://pubs.rsc.org/en/results?searchtext=Author%3ASajid%20Ali%20Ansari

http://pubs.rsc.org/en/results?searchtext=Author%3AMohammad%20Mansoob%20Khan

http://pubs.rsc.org/en/results?searchtext=Author%3AMohd%20Omaish%20Ansari

http://pubs.rsc.org/en/results?searchtext=Author%3AMoo%20Hwan%20Cho

http://www.sciencedirect.com/science/article/pii/S0926860X0400050X







http://www.ncbi.nlm.nih.gov/pubmed/?term=Natori%20H%5BAuthor%5D&cauthor=true&cauthor_uid=19491534

http://www.ncbi.nlm.nih.gov/pubmed/?term=Kobayashi%20K%5BAuthor%5D&cauthor=true&cauthor_uid=19491534

http://www.ncbi.nlm.nih.gov/pubmed/?term=Takahashi%20M%5BAuthor%5D&cauthor=true&cauthor_uid=19491534

http://www.ncbi.nlm.nih.gov/pubmed/19491534

http://pubs.acs.org/author/Dozzi%2C+Maria+Vittoria

http://pubs.acs.org/author/D%27Andrea%2C+Cosimo

http://pubs.acs.org/author/Ohtani%2C+Bunsho

http://pubs.acs.org/author/Valentini%2C+Gianluca

http://pubs.acs.org/author/Selli%2C+Elena









35

modification of starch in a fluidized bed reactor”. In October 2003 I started focusing on

problems related to production of thin titanium dioxide coatings for photocatalytic

applications, obtained from nonorganic precursor with the help of RF PECVD method [pos.

II.E21, II.E22, II.E24, II.E25, II.A1, II.A13, II.A14 in Appendix No. 6]. In December 2003

and November 2004 I undertook monthly foreign scientific internships at the Institute for

Microsystems Technology IMTEK at Albert-Ludwig’s University Freiburg, Germany. At that

place I was engaging in a production of aluminum oxide coatings by a hybrid method joining

magnetron sputtering with RF PECVD technique [pos. II.E23 in Appendix No. 6]. In

November 2007 I defended my PhD dissertation entitled: „Titanium dioxide (TiO2) thin films

withphotocatalytic properties”. The work was requested by external reviewer, dr hab. Paweł

Uznanski from Molecular and Macromolecular Research Center (CBMiM PAN) in Lodz, to

be awarded.

6.2. Achievements after receiving a PhD degree

In 2007-2008 I was focusing on a research on an improvement of poly-para-xylylene

coatings and its derivatives adhesion to different kinds of substrates, which was undertaken

within the grant no. N205 072 31/3208 “Thin poly-para-xylylene coatings and its derivatives:

macromolecule topology, substrate adhesion, biocompability and biomedical

applications”funded by MNSW [pos. II.E1 in Appendix No. 6].

In 2008-2010 I took part in a research on preparing nonorganic composites on a matrix

of geopolymers strengthened with glass, carbon and basalt fibers. In the same times I did

research on changes in wettability of used in prosthodontics metallic substructure under

variable abrasive blasting parameters [pos. II.E3 in Appendix No. 6].

Since February 2012 I have been engaged in a research on plasmochemical

modification of such extenders as: smoke-black, nanotubes, fullerenes and silica, which are

used in gum production in order to improve dispersion rate of mentioned extenders in a

polymer matrix. The research work was done in collaboration with a team of prof. Bielinski

from the Institute of Polymers and Pigments Technology, belonging to Chemical Department

at Lodz University of Technology. The initial results were so promising that we applied

together to the National Science Center for a grant entitled “The new generation of carbon

fillers for the preparation of advanced polymer composites”, which was executed in the years

2013-2016, and in which I was a project contractor [pos. II.E9 in Appendix No. 6].

In the years 2013-2015 I did research on a usage of low temperature plasma for

surface modification of natural polymers and powdered TiO2, as extenders of polymer matrix

(polyvinyl chloride, polystyrene) in order to obtain photo-biodegradable composite materials.

In 2012 and 2013 I got a funding, from Young Scientists Foundation of Mechanical

Department of Lodz University of Technology, on a research applied to modification of

extenders for TiO2 – polystyrene and TiO2 – polyvinyl chloride composites. It resulted in

three articles (pos. II.E5, II.E7, II.E10 in Appendix No. 6).

In 2012-2016 I took part in a research on preparing an elastic transistor, wherein a thin

film of poly-para-xylylene acts as dielectric, headed up in collaboration with a team of prof.

Jacek Ulanski from Molecular Physics Unit. The research was funded by the National Science


36

Center from grant No. 2012/07/B/ST8/03789, entitled: „Thin films of xylylene polymers for

organic electronics: synthesis, structure and properties”, in which I was a project contractor.

In 2014 I undertook 8 months scientific internship in the Institute of Nanomaterials,

Advanced Technologies and Innovations at Liberec University of Technology in Czech

Republic, where I took part in measurements and data analysis of: thin films internal stress

research by means of Dektak 150 profilometer produced by Bruker company, surface

morphology by means of SEM microscope model Carl Zeiss ULTRAPlus and surface

topography specified with a use of AFM microscope model JPK NanoWizard III. Transition

metal oxides coatings and hydroxyapatite coatings served as test materials. The collaboration

resulted in three articles [pos. I.B5, I.B8, IB9 in Appendix No. 6].

The experience I gained, being a contractor of multilayered optical filters grant, made

me in 2015 a head of NCN grant No.2014/13/B/ST8/04293, entitled „Thin (SiO2)x(Si3N4)1-x

coatings with optical property gradient manufactured with the PECVD method”. One of the

executors of this grant was a scientist from beyond the Lodz University of Technology, who

works in Molecular and Macromolecular Research Centrum of the National Science

Academy. In this project, me together with a six-person team, we’ve managed to develop a

technology of preparing a “rugate” type gradient optical filters on quartz, glass and polymer

(polyester, polycarbonate) substrates. Organosilicon compounds, like hexamethyldisilazane

(HMDS) and tetramethyldisilazane (TMDS) in a mixture with nitrogen and oxygen, were

used as coatings material. The filters are characterized by a gradient of their chemical

composition what influences the gradient of a refractive index. Thanks to obtained results it

was possible to prepare SiOxCy (n≈1.7) and SixNyCz (n≈2.3) coatings, as well as structures of

a varying composition. The mentioned structures, of a molecular formula

(SiOxCy)n/(SixNyCz)1-n, are characterized by a refractive index equal from 1.6 to 2.3. These

type of coatings can be broadly used in optics or optoelectronics. Thanks to positive results of

conducted research it was possible to create two patent applications [pos. II.C4, II.C5 in

Appendix No. 6]. I have also published two articles [pos. II.A12, II.E18 in Appendix No. 6].

Another two articles have been sent to such magazines as Coatings and Material Engineering.

The last manuscript is during preparation process.

I am broadening my experience with thin TiO2 coatings, prepared with RF PECVD

methods, during the implementation of the NCN research grant entitled „The effect of plasma

parameters on the properties of optical coatings deposited by GIMS method” (UMO-

2014/13/B/ST8/04279). The project is essential because it pertains to plasma diagnostics

during TiO2 coatings deposition by PVD (Physical Vapour Deposition) methods. The

diagnostics of thin films preparation process let us understand the chemical phenomena and

reactions taking place in plasma and also result in improving the properties of prepared

coatings. The project pertains to a modern GIMS (Gas Impulse Magnetron Sputtering)

technology and research that was never undertaken before. In this project I am responsible

for measurements of chemical structure, morphology and also optical and photocatalytic

properties, which I am trying to connect with plasma composition generated by various

process parameters. One article related to this topic is currently in review and another two are

being prepared to be sent.

Since 2015 I have been taking active participation, as an executor and leader of a task

related to the characteristics of obtained rhenium based coatings, in a project No.


37

CuBR/II/NCBR/2015,entitled: “Deposition of protective and decorative coatings based on

rhenium and its compounds”, executed on behalf of KGHM Polska Miedz S.A. In the

mentioned grant I was a manager of a task related to assessment of: chemical composition,

chemical structure, phase composition and mechanical properties of rhenium based materials.

The work is being executed in association with a team from the Materials Engineering

Department of Warsaw University of Technology, Wroclaw University of Technology,

Research and Development Center of KGHM CUPRUM sp. z o.o. company and BOHAMET

s.a. company. The promising results of the project are giving hope for implementation of two

developed technologies. Because of the signed nondisclosure agreement I am not allowed to

come up with more detailed information about the research.

In 2015-2018 I was engaged in a grant PBS3/B9/45/2015, “Innovative surgery

technology with implanted device (IP) broadening an effectiveness of degenerative spine

treatment – model research”, as an executor. In this project I was cooperating with LfC sp. z

o.o. company from Czerwiensk (near Zielona Gora), which sells and brings to the market

medical products used in orthopedic surgery and neurosurgery. Besides, IBTM sp. z o.o

company from Czerwiensk and BIONANOPARK Sp z o.o company from Lodz were also a

part of the consortium. In the mentioned grant I was responsible for evaluating the structure,

physic-chemical properties and thermodynamic properties of bone cements which were

implanted into osteoporotically changed vertebras, and also for choosing the cement which

could be used in an implanting device designed within this project. In this grant I was in

charge of a two-person team. Two articles are being prepared from this topic. During the

project a few interesting ideas, applying to the synthesis of a new bone cement, have

appeared. Currently, we are preparing to experimentally prove the possibility of actualizing

these ideas and we are getting ready to write another research project.

For several years my research subject matter has comprised in problems related to

DLC coatings doped with Si, Ag, Cu, P, Ca and Ti. It is aimed at preparation of implant

coatings, i.a. hip joint prosthesis, intramedullary nails or stabilization plates in such a way to

provide its maximal biocompatibility to a human body. For the coating deposition there are

used both RF PECVD and magnetron sputtering method. In case of DLC coatings doped with

Ag and Si deposited by RF PECVD method I took part in process parameters optimization for

Si and Ag/DLC coatings, what was a part of M.ERA.NET research grant entitled “Carbon

coatings doped with Ag/Si for biomedical applications” - CarLa No M-

ERA.NET/2012/02/2014 [pos. II.A7 in Appendix No. 6]. In this project we collaborated with

prof. I.N. Mihailescu form the National Institute for Laser Plasma & Radiation Physics and

TEHNOMED IMPEX CO S.A. company in Bucharest Romania and also with Medgal sp. z

o.o. company from Ksiezyno (Poland). In the LIDER project No. LIDER/040/707/L-

4/12/NCBR/2013, entitled "MOdifiedBIOmaterials - MEDicine future" – MOBIOMED, I

took care of chemical structure analysis performed by means of FTIR (Fourier Transform

Infrared Spectroscopy) and XPS (X-ray Photoelectron Spectroscopy) techniques and also

research on surface wettability changes right after coatings deposition and after corrosion tests

of DLC coatings doped with above-mentioned additives [pos. II.A8, II.A9, II.A10, II.A11 in

Appendix No. 6]. On 18th

of May 2017 we received a prestigious SIEMENS research award

for our research on DLC coatings with silicon additive, a preparation technology of which

was implemented in Medgal sp. z o.o. company. Moreover I am also a coauthor of a Polish


38

patent and German patent application, entitled “A method of preparation of silicon containing

carbon coating on medical implants” [pos. II.C1, II.C2 in Appendix No. 6].

In the scope of biomaterial research I was also checking an amount of metal ions (Ti4+

,

V5+

and Nb5+

) going to SBF solution, in 3 month long-term tests, from titanium alloys

Ti6Al4V and Ti6Al7Nb, after cementation and covering with DLC coatings. I performed the

mentioned test by electrochemical analyzer with use of mercury electrode. This work was a

part of a grant No PBS3/A5/44/2015, entitled “High stressed tribologic junctions for

biomedical applications”.

I also performed surface wettability research, using a method of geometry of a drop

located on an examined surface, in order to determine surface energy of medical implants

used in orthopaedics and prosthetics stomatology, what was published in three articles [pos.

II.E2, II.E12, II.E15 in Appendix No. 6]. Moreover, I have been preparing research on

chemical structure of materials, by means of FTIR spectroscopy, and interpreting obtained

spectra, for a long time. It resulted in three another articles [pos. II.A3, II.A6, II.A17 in

Appendix No. 6].

Due to the fact that at my place of employment, the Institute of Materials Science and

Engineering at Lodz University of Technology, there is done an intensive research on

graphene and its properties in order to find its new types of applications, I participate in

research work on this material. That is why I have been taking part in a research on preparing

water cleaning filters made of composite materials, since 2016. This work is being funded

from B+R projectNo. POIR.04.01.04-00-0089/15, of an acronym HydroGraf, from

Operational Programme Smart Growth 2014-2020, operation 4.1 “Research and

Development”. For project realization there was created a consortium consisting of a leader –

Lodz University of Technology, and Amii sp. z o.o. company form Lodz, a pioneer producer

of water cleaning filters in Poland. The project framework contained four concepts of filter

preparation. I was engaged in a production of a filter on the basis of a polymer fabric with

graphene flakes. The concept was based on covering polymer fabrics by flake graphene, so

that they can be used in filters which simultaneously filter in a mechanical way and by

adsorption of the pollutant to graphene. Furthermore, I took part in a research on chemical

structure of all composites prepared in this project.

Since the beginning of 2008 I participate in a research on production of high-sensitive

sensor for microorganisms detection, i.a. flu virus. The work is funded from grant No

TECHMATSTRATEGI/347324/12/NCBR/2017, of DIAMSEC acronym, entitled “Ultra-

sensitive sensor platform for fast detection of epidemiologic and pandemic hazards”. As an

executor, Lodz University of Technology is in a consortium with Gdansk University of

Technology (a leader), Warsaw University of Technology and ETON Group Sp. z o.o.

company. The team, that I work in, has a task to create a sensor with a graphene substrate,

which has to work as a chemical bond, that enables connection of antibodies detecting

proteins found in all kinds of flu strains. In this project I am responsible for quality

assessment of obtained substrate, for its chemical structure modification and also for

examination of quantity of joined antibodies to the grapheme substrate.

Since 2008 I have 6 oral presentations at international and national conferences [pos.

II.L1-II.L6 in Appendix No. 6], I took part in 21 poster presentations [pos. III.B1-III.B21 in

Appendix No. 6], and I participated in preparation of conference presentations that were


39

shown at 29 conferences [pos. 1-29 in Appendix No. 7]. In addition, I presented the results of

research in the form of oral presentations (six times) at meetings with members of a

consortium of projects [pos. II.J9; II.J12 in Appendix No. 6].

In 2017-2018 I prepared two expert assessments that were ordered by companies [pos.

III.M1 and III.M2 in Appendix No. 6]. In 2014 I was a member of international group of

experts from Poland, Czech Republic and Bulgaria in the project “Training bridge, science

and practice” in the program “Education for Competitiveness”. The meeting took place at

Technical University in Liberec.

Because of the fact that lots of my work concerning TiO2 was published in

international articles, I am asked for reviewing related manuscripts in journals from such

academic publisher as Elsevier, Springer and Wiley. I wrote 25 reviews in total.

I was awarded three times. I got two awards of Main Rector of Technical University of

Lodz for scientific achievements and 1 prestigious Siemens Award for the work “New

biocompatible Si-DLC layer for bone implants – pioneering industrial implementation”. In

2014 I obtained scientific scholarship given within the competition of TUL Rector.

In my career as an academic teacher I have given lectures on Thermochemistry of

Solids, Environmental Protection, Recycling of Materials and Work Safety Regulations,

Plastics, Technical Chemistry, Specialised Test Methods, Applications of Modern

Engineering Materials, Introduction to Materials Science, Materials Science, Biomedical

Engineering. I have taught also laboratory classes: Plastics, Materials Science (laboratory in

Polish and in English), Thermochemistry of Solids, Surface Engineering of Polymers,

Applications of Modern Polymeric Materials, Technical Chemistry, Plastics, Construction and

Maintenance Materials, Plastic Forming and Welding, Modern Functional Materials,

Physical-Chemical Evaluation Methods of Biomaterials, Materials Science and Biomedical

Engineering. Additionally, I led student projects as part of Directional Projects, Dissertation

Laboratory, Applications of Modern Materials and I mentored interim works.

I participated in creation of modules – Technical Chemistry, Physical Chemistry and

Plastics. I prepared laboratory instructions for such laboratory classes as Plastics,

Thermochemistry of Solids, Technical Chemistry, Physical Chemistry and Surface

Engineering of Materials.

Since 2010 I supervised 7 master theses and 3 bachelor theses. Moreover, I supervise

one PhD dissertation whose opening of the doctoral thesis is planned for September 2018. I

am an auxiliary supervisor of two PhD theses that will be finished till the end of 2018. In

order to popularize science I organized and conducted laboratory classes in Chemistry for

primary and secondary school students during I Materials Engineering Picnic at TUL, that

was held on 27th

May 2017.

As a part of organizational activity, from 2007 to 2010 I acted as a registrar of the

commission during the dissertation defenses in the field of study Mechanical Engineering

(specialization: Apparatus and Medical Equipment). In 2012 I was a member of a team that

prepared the report for Accreditation Commission of Universities of Technology (KAUT),

Materials Science was selected field of study for the accreditation. In 2012-2013 I was a

member of the Recruitment Commission. In 2013/2014 academic year I cared for first-year

Materials Science students at Mechanical Department. In 2013 I helped in equipping

Laboratory of Chemistry and Plastics in newly built Factory of 21st century Engineers at


40

TUL. In years 2015 and 2016 I was in the Didactic Commission in the field Materials

Science. In 2016 I participated in preparation of documentation for Polish Accreditation

Committee (PKA) accreditation of Materials Science field of study. I am also a common

member of Polish Society of Biomaterials and Polish Materials Science Society. I was in the

organizing committee in 6th Scientific Conference “Modern Technologies in Surface

Engineering” in Spała in 2016. I organized SENM Workshops as a part of 7th

International

Conference Smart Engineering of New Materials SENM in Łódź in 2017. I am responsible for

some apparatus and instruments in the Institute of Materials Science and Engineering at Lodz

University of Technology - FTIR spectrometer (Nicolet model iS50), FTIR microscope

(Nicolet model iN10), UV-Vis spectrometer (Evolution 220), TGA Thermogravimetric

Analyzer (TA Instruments model TGA55), electrochemical analyzer (voltoammeter) and

instrument for measuring contact angle using Drop Shape Analysis method (Krüss).

In 2008 I was a participant in a course of trainings that concerned the rules of

application and disposal of european funds in 2007-2013 in the Innovative Economy, Human

Capital, Infrastructure and Environment operational programs. In 2010 I did the training

“Flow and heat transfer problems in laboratory practice - introduction to the Ansys-CFX

software” as a part of the project “Increasing the competences of the academic staff and

graduates' skills in the aspect of modern methods of analysis, simulation and optimization in

the design and operation process”. In September 2013 took part in training on operating Joel

JSM 6610LV scanning microscope, JOEL IB-09010CPW ion polisher, model iS50 FTIR

spectrometer and iN10 FTIR microscope and TA TGA 55thermogravimetr (in 2017).What is

more, in 2014 I participated in training course concerning Moodle educational platform that

allows to implement distant learning. In 2016 I got trainings on self-presentation, delivering

speeches and self-image creation.

6.3. SUMMARY OF SCIENTIFIC ACHIEVEMENTS BEFORE AND AFTER

OBTAINING THE PhD DEGREE WITH PRESENTATION OF

ACHIEVEMENTS IN THE FIELD OF INTERNATIONAL,

ORGANIZATIONAL AND DIDACTIC ACTIVITY

No. Achievement

Amount

Before PhD

degree

After PhD

degree Total amount

1. Articles within JCR base 2 21 23

2. Articles out of JCR base 6 19 25

3. “corresponding author”

function 6 18 24

4. Conference Papers (active

participation) 13 (10) 56 (27) 69 (37)

5.

Accomplished original project,

construction and technological

achievements

- 7 7

6.

Gained International and

National patents and patent

applications

- 5 5


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