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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
2
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
3
1. Name and surname: Anna Sobczyk-Guzenda
2. Education, diplomas and scientific degrees:
2002 Master of Science, Engineer
Lodz University of Technology
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”
Lodz University of Technology
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
4
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
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 2013].
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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
5
IF JCR(2015): 1.759; 5-year IF JCR**
(present): 1.771 [based on webpage
https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:
30 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2015].
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
https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:
40 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2016].
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.
IF JCR*(2016): 2.986; 5-year IF JCR
**(present): 2.814 [based on webpage
https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:
40 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2016].
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.
IF JCR*(2016): 2.986; 5-year IF JCR
**(present): 2.814 [based on webpage
https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:
40 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2016].
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.
IF JCR*(2016): 1.879; 5-year IF JCR
**(present): 1.771 [based on webpage
https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:
30 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2016].
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.
IF JCR*(2016): 2.589; 5-year IF JCR
**(present): 2.538 [based on webpage
https://jcr.incites.thomsonreuters.com]; Polish Ministry of Science and Higher Education points:
35 [based on the appendix to the Minister of Science and Higher Education communiqué of December 2016].
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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-
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; 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-
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].
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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].
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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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.
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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
Dr inż. Anna Sobczyk-Guzenda Załącznik nr 3
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