Nanophotonics 2021; aop

Review

Lucinda Mulko, Marcos Soldera* and Andrés Fabián Lasagni

Structuring and functionalization of non-metallic

materials using direct laser interference
patterning: a review
https://doi.org/10.1515/nanoph-2021-0591 Keywords: ceramics; composite materials; direct laser
Received October 14, 2021; accepted November 24, 2021; interference patterning; polymers; semiconductors; sur-
published online December 6, 2021 face micro/nano-texturing.

Abstract: Direct laser interference patterning (DLIP) is a

laser-based surface structuring method that stands out for
its high throughput, flexibility and resolution for labora-
1 Introduction
tory and industrial manufacturing. This top–down tech-
1.1 Background
nique relies on the formation of an interference pattern by
overlapping multiple laser beams onto the sample surface
In the last decades, laser sources have become a valuable
and thus producing a periodic texture by melting and/or
tool not only for research environments but also for highly-
ablating the material. Driven by the large industrial sec-
industrialized processes. This rapid deployment of laser
tors, DLIP has been extensively used in the last decades to
technologies has been the consequence of the decrease in
functionalize metallic surfaces, such as steel, aluminium,
the costs of pulsed laser sources with output powers
copper or nickel. Even so, DLIP processing of non-metallic
exceeding 100 W, paving the way for a plethora of
materials has been gaining popularity in promising fields
advanced laser-based manufacturing processes such as
such as photonics, optoelectronics, nanotechnology and
cutting, welding, cladding, drilling, hardening, etc. [1–4].
biomedicine. This review aims to comprehensively collect
Moreover, laser-based surface micro/nanotexturing able to
the main findings of DLIP structuring of polymers, ce-
add or improve specific functionalities has caught the
ramics, composites, semiconductors and other non-metals
attention of the scientific community and the industry in
and outline their most relevant results. This contribution
also presents the mechanisms by which laser radiation order to develop value-added technical surfaces. For
interacts with non-metallic materials in the DLIP process instance, producing deterministic microtextures using
and summarizes the developed surface functions and their laser radiation has led to a wide variety of outstanding
applications in different fields. functions like superhydrophobicity [5], self-cleaning [6]
and friction control [7] as well as to the development of
microfluidic platforms [8] or microelectronic [9] devices. In
the area of biomedical devices and tissue engineering [10],
Lucinda Mulko and Marcos Soldera contributed equally to the work.
surfaces with antibacterial properties [11], biosensors/ac-
*Corresponding author: Dr. Marcos Soldera, Technische Universität tuators [12] with therapeutic effects for dental prostheses
Dresden, Institut für Fertigungstechnik, George-Baehr-Str. 3c, 01069, [13] and neural scaffolds [14] have been developed too.
Dresden, Germany; and PROBIEN-CONICET, Dto. de Electrotecnia, Laser microprocessing technologies have also made their
Universidad Nacional del Comahue, Buenos Aires 1400, Neuquén
mark in the area of optoelectronics [15], energy storage,
8300, Argentina, E-mail: marcos.soldera@tu-dresden.de
Dr. Lucinda Mulko, Technische Universität Dresden, Institut für
light scattering gratings [16] and others.
Fertigungstechnik, George-Baehr-Str. 3c, 01069, Dresden, Germany, Among the laser surface structuring technologies
E-mail: lucinda_emma.mulko@tu-dresden.de. https://orcid.org/ [1, 17], direct laser interference patterning (DLIP) offers a
0000-0001-9238-0634 remarkable combination of throughput, flexibility and
Prof. Dr. Andrés Fabián Lasagni, Technische Universität Dresden, resolution, making this technology suitable for surface
Institut für Fertigungstechnik, George-Baehr-Str. 3c, 01069, Dresden,
structuring even for industrial manufacturing [18]. This
Germany; and Fraunhofer-Institut für Werkstoff- und Strahltechnik
(IWS), Winterbergstraße 28, 01277, Dresden, Germany, technique has its origin in the pioneering works of Nebel
E-mail: andres_fabian.lasagni@tu-dresden.de and co-workers in the 1990s [19–21]. In their investigations,
Open Access. © 2021 Lucinda Mulko et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0
International License.
2 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

N ⃒⃒ ̅→⃒⃒2 N N ̅→ ̅→ → → →
→
they overlapped multiple coherent beams to induce peri- I( r ) ∝ ∑ ⃒⃒⃒E 0i ⃒⃒⃒ + 2 ∑ ∑ E 0i ⋅ E 0j cos((k i − kj ) ⋅ r + ψi − ψj ). (4)
i=1 j<1 i=1
odic arrays of crystallization seeds in amorphous silicon for
obtaining a microcrystalline thin film for solar cells appli- In this way, a periodical intensity distribution is formed
cations. Later in time, the DLIP method has been exten- with a spatial period (repetitive distance between the ele-
sively used to pattern periodic textures on many materials,
ments) given by the overlapping angle described by the
especially on metals like steel, aluminium, titanium alloys
wave vectors and wavelength. The shape of the pattern is
and nickel, among others, which are the most required by
the large industrial sectors, such as automobile, aviation defined by the number of overlapping beams, the phase
and energy. However, DLIP structuring of non-metallic shift between them and the polarization state. Figure 1
materials, such as polymers, ceramics or composites, has shows examples of different configurations of interfering
been gaining attraction in emerging fields like optoelec- beams and the resulting interference patterns. In these
tronics, nanotechnology, biomedical devices and bio- cases, the beams are arranged symmetrically with the same
materials [22]. It is therefore the motivation of this review to overlapping half-angle (θ) and azimuthal angles (φ), and all
thoroughly gather the majority of the published works on the beams have the same phase and polarization direction.
this topic and sum up their most relevant findings. More- The simplest interference pattern is achieved with two
over, the physico-chemical mechanisms by which laser
beams (Figure 1(a)) and has one-dimensional periodicity
radiation interacts with the non-metallic materials in the
with a period defined by Λ = λ/(2sin(θ)). In the examples
DLIP process are described along with a summary of the
developed surface functions, which are linked to specific with three (Figure 1(b)) and six (Figure 1(d)) beams, the in-
applications. tensity maxima give rise to periodic structures placed on a
triangular lattice but with different spatial periods, namely
Λ = 2λ/(3 sin(θ)) and Λ = 2λ/( √3  sin( θ)), respectively. By
overlapping four beams, a square array of periodic features
1.2 Fundamentals of direct laser can be obtained with a period Λ = λ/(3 sin(θ)). Even more
interference patterning complex periodic interference patterns can be produced by
the superposition of three or more beams with different
The DLIP method relies on the superposition of at least two phases and polarization directions [25].
coherent beams on the sample, thereby producing an The wavelength of the laser source must be selected
interference pattern. The overlapping ith beam can be according to the material spectral absorbance, so that the
considered as a polarized plane wave with an electrical material can strongly absorb the laser radiation. It has to
→
field E i oscillating in space and time given by: be mentioned though, that in some cases non-linear ab-
→ → ̅→ → → sorption mechanisms can be triggered by which the laser
E i ( r , t) = E 0i cos(k i ⋅ r − ωt + ψi ), (1)
light can be absorbed in a material transparent to the laser
̅→ wavelength [26]. At the maxima positions of the produced
⃒⃒where ⃒ E 0i is the electrical field amplitude of the ith wave,
⃒⃒→ ⃒⃒ → interference pattern the substrate can undergo local
⃒ ki ⃒⃒ = 2π/λ is its wave vector, λ is the wavelength, r is the
spatial coordinates vector, ω is the angular frequency, t is modifications, like recrystallization, oxidation, melting,
time, and ψi is the phase of the ith beam. Considering the ablation, swelling or even complex processes of reorga-
principle of superposition of waves, the resulting electrical nization [27], depending on the laser parameters and the
field upon overlapping N beams is: optical and thermal properties of the material. To this end,
the laser energy density, or fluence, must be higher than a
→ → N →
→
E ( r , t) = ∑ E i ( r , t). (2) certain threshold to activate the targeted physical modi-
i=1
fication, like melting, ablation, etc. Overlapping laser
The intensity of the resulting interference profile can pulses at a given position increases the cumulated fluence
thus be expressed as [23]: on the material, which in turn induces a stronger modi-
fication of the material, e.g. wider or deeper ablated re-
N →
→ → 2
I ( r ) ∝ ⟨ ∑ E i ( r , t) ⟩, (3) gions. Furthermore, the shape of the microtextures can be
i=1
also modified by rotating the sample after a DLIP step a
where the angle brackets represent the time average over a given angle and re-irradiating the surface. In this way,
time scale much larger than the period of the waves. If the different periodicities and even multi-scale hierarchical
wavelengths of the waves are the same, combining Eq. (2) textures can be fabricated. In summary, the synergy be-
with Eq. (3) gives the expression of the intensity profile of tween the overlapping beams configuration, the struc-
the interference pattern as [24]: turing strategy and the materials properties can yield a
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 3

Figure 1: Schematic showing the set-up (upper row) and the resultant patterning (lower row) with (a) two, (b) three, (c) four and (d) six
overlapping beams together with the calculated intensity of each interference pattern. Figures adapted from ref. [24] (© 2019, Springer
International Publishing).

large palette of achievable textures, shapes and thus, as cellulose or three-dimensional macromolecules of
functionalities [28]. arborescent construction or dendrimers) to composite
Several set-ups based on different optical components materials (cross-linked polymers or hydrogels and block
have been designed to generate the interference pattern on co-polymers, among others) [35–37].
the samples. The advantages and limitations of each Additionally, from a thermodynamic point of view, the
implementation approach have been described and dis- glass transition temperature (Tg) represents an essential
cussed in detail elsewhere [25, 29–34]. indicator for the classification of a plastic compound as a
thermoplastic or thermoset polymer. Thermoplastic poly-
mers can be softened by heating (above Tg) and hardened
2 DLIP processing of polymers by cooling; thus they have the potential to be recycled and
used multiple times. Typical examples of these linear
The word polymer refers to a material formed by large polymers are polyethylene, polycarbonate and polyvinyl
molecules whose structure is composed of multiple chloride. In contrast, thermoset polymers can only be
repeating units. Polymers range from well-known syn- molded once by heating; if they are heated again, they will
thetic plastics, such as polystyrene, to natural bio- not soften because the polymer chains have become
polymers, such as polyesters or polypeptides, and even intertwined. These polymers are cross-linked or highly
macromolecules such as DNA can be considered polymers. branched molecules. Examples of this type are polyester
Their broad spectrum of properties is associated with their resin, epoxy resin and silicones.
molecular mass and molecular weight distribution as well The growing demand for polymers has made it neces-
as by their chain architecture, particularly by the amount of sary to produce and process them with ever more accurate
branching, resulting in unique physical properties such as and faster methods. The unique properties of lasers have
high strength-to-weight ratio, high elasticity, viscoelas- made them a preferable alternative to conventional
ticity and tendency to form amorphous and semi- machining for ultra-fine surface modifications [38]. This is
crystalline structures rather than crystals. In recent years, especially attractive for fragile polymers that crack and
polymer materials science has advanced rapidly, giving rubber-like polymers that creep under the pressure of a
rise to a wide variety of materials ranging from linear conventional power tool [39]. Laser processing of poly-
polymers with simple repeating units (e.g. polypropylene, mers, such as cutting, trimming, marking, shaping and
polycarbonate, polyimide, among others) to more complex softening of polymers, has been done mainly with CO2,
polymers with branched-chains (such as natural polymers Nd:YAG and KrF excimer lasers [2, 17, 40, 41]. When it
4 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

comes to micro and nanoprocessing of surfaces, DLIP ari- on a phase mask to form lattices in polymers. Along these
ses as one of the best options in terms of operational lines, in 1999 Lippert et al. [45] published a paper
versatility and structure uniformity. Due to the diversity of describing the formation of a nm-sized grating in polymers
functionalization, coating, doping or composite formation by laser ablation with an irradiation wavelength of 355 nm.
possibilities offered by these materials, laser-polymer in- A few years later, in 2003, Klein-Wiele and Simon [46] pub-
teractions are complex and multivariate. lished an article in which they reported the fabrication of
This section provides an overview of current advances periodic nanostructures by interference of multiple beams
in the structuring of polymer surfaces by DLIP, from their and sub-picosecond laser pulses at 248 nm on polycarbonate
laser interaction mechanism, through structuring on sim- surfaces. Later, in 2005 Mücklich et al. [47] reported for the
ple polymer surfaces to more complex advanced materials, first time the use of DLIP with Nd:YAG (266 nm) to control cell
describing in each instance their most relevant applica- growth onto PET polymeric substrates using a two-beam
tions. One of the main advantages of thermoplastic poly- interference setup, using the so-called beam splitter config-
mers is related to their minimal chemical change during uration (though at that time the technique was called laser
and after thermal processing, as well as their ductility and interference lithography). This work sowed the seed for all
recycling potential, which is why they are preferred for use subsequent development of DLIP in polymers.
in laser processing as discussed in Sections 2.1 and During that period, the technique became widespread,
partially in Sections 2.2.1 and 2.2.2. However, DLIP struc- particularly using non-polymeric substrates such as
turing has been reported on thermosetting polymers such semiconductors, glasses, transparent oxides and metals
as cross-linked polymers, polyurethanes and silicones as [48–51]. However, the mechanisms that enable absorption
mentioned in Section 2.2.3. and, consequently, material ablation, in polymers are
notoriously different. For example, absorption in metals is
basically performed by the free electrons, and occurs in the
2.1 Conventional polymers first tens of nanometer from the surface [52]. On the other
hand, in polymers absorption takes place due to the pres-
The first polymeric materials structured by DLIP were ence of chromophore groups consisting of π–π* conju-
thermoplastic synthetic polymers with linear (or quasi- gated double bonds or aromatic rings with delocalized π
linear) structure as films such as polycarbonate (PC), pol- electrons [53, 54]. In 2007, Lasagni et al. [53] performed a
yimide (PI), polyether ether ketone (PEEK), polyethylene comprehensive study to elucidate the patterning condi-
terephthalate (PET), and several polyurethanes (PUs). tions by laser interference using a ns-laser in several
These polymers are widely commercially available and are biocompatible thermoplastic polymers of interest in the
commonly used in many industrial applications, like field of medicine. The study linked the chemical structure
packaging, pharmaceutical and food containers, trans- of each polymer, the mechanisms governing laser ab-
parent optical components or high-temperature mechani- sorption and the working parameters of laser structuring
cal components. such as wavelength (266 nm, 355 nm) and laser fluence.
This is the initial in a series of papers that explore the
2.1.1 Single-scale architectures versatility of the technique for structuring polymers films
and their laser ablative mechanisms, which were sup-
In 1987, Ilcisin and Fedosejevs [42] first described a tech- ported by pioneering works [55–57]. Firstly, it is presented
nique for the direct production of holographic diffraction how the threshold laser fluence is directly related to the
gratings on PET and PI films by irradiation with interfering absorption coefficient of the polymer. For instance, poly-
KrF ns-laser beams, although with a slightly different methylmethacrylate (PMMA) fails to absorb laser radiation
configuration than the one used in current systems. In the at both UV wavelengths used, which could be justified
90s, Phillips et al. [43] published a manuscript in which because of the chromophore group in PMMA is a C=O alkyl
periodic line structures with a period of 167 nm and line and the transition of the unpaired electron pair to the
widths varying from 35 to 100 nm were produced on PI by excited state of a π-bond (n–π*) is forbidden, therefore
direct ablation with a KrF laser using an interferometric absorption is low. On the contrary, polymers containing
configuration. In 1996, Karnakis and co-workers [44] car- aryl carbonyl groups such as PI or PC in which the π-bond is
ried out a series of studies on grating formation for opto- conjugated to the aromatic ring, can be structured by DLIP
electronic applications using 248 nm and 193 nm excimer with UV radiation. The same can be explained by the
lasers, including an evaluation of laser-induced periodic concept of the cut-off wavelength of the studied polymers
surface structures and UV holographic techniques based [24]. For example, PI shows an absorption cut-off at
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 5

wavelengths above 350 nm, while the cut-off wavelength of photons, dissociation can be triggered. But while the energy
PMMA is around 250 nm. Hence, since laser ablation only accumulation takes place, the surroundings of the material
takes place when laser radiation is absorbed, a maximum absorb energy by vibrational energy transfer and are there-
absorbance at a defined wavelength is required. fore susceptible to absorption and ablation [65]. On the other
Besides, the researchers reported a correlation be- hand, a photochemical mechanism, by which the molecule
tween laser fluence and the depth of structure [22, 58, 59]. dissociates after excitation to an unstable electronic state and
This behaviour could be defined in two stages. After a ablation takes place after the material decomposes. This
certain threshold fluence value is reached (see Figure 2(a)), mechanism is distinguished by the formation of photo-
i.e. a minimum value below which there is generally no fragmentation products such as atoms, small molecules and
structure and which is closely related to the minimum fragments of the polymer chain which are released from the
energy required to achieve bond breaking [60], the depth of surface at high speed, followed by a non-decompositional
the structure increases linearly with the laser fluence. energetic relaxation back to the basal state of the material
Moreover, if the photon energy is aimed at directly (intersystem crossing, quenching, etc.) [66]. These two
breaking the bond, chemical reactions are initiated, fol- mechanisms are extremes cases of a given process, as
lowed by decompression of the polymer and formation of generally a combined effect drives the ablation of the mate-
gaseous products, which in turn can lead to the release of rial. The researchers relied on this principle to justify how the
larger pieces weakly bound to the polymer and conse- obtained structure depth depended on the laser fluence used
quently to the almost complete removal of the upper layers [53]. Thus, in PI the structure depth was larger when a
of the substrates in the interference maxima positions [61]. wavelength of 355 nm was used, while for PC the deepest
In the second stage, the depth of the structure continues to structures were reached at 266 nm. In the last case, the ab-
increase with laser fluence, although at a lower rate. The sorption is due only to thermal processes since the π–π*
existence of this last stage can be explained by the decrease transition of the aromatic ring is photochemically inactive,
of the effective absorption coefficient resulting from the whereas at 355 nm the C=O chromophore is excited and the
shielding of microfragments of material released in the energy is relocalized to break the bond. Consequently, at
surrounding area of the surface or to the plasma created 355 nm a photochemical contribution is added to the photo-
during the ablation process. This behaviour has been re- thermal ablation process, which probably results in an
ported by other scientists not only for DLIP [24] but also for increased ablation rate. Other publication [67] suggests that
other related ablation processes in thermoplastics at shorter wavelengths the number of polymer fragments
[52, 62–64]. For example, Jia et al. [63] reported an efficient produced during ablation increases, the effective absorption
strategy to perform locally controllable surface foaming on coefficient is reduced and as a result, lower ablation rates are
polypropylene interpenetrated with multilayer graphene obtained. Figure 2(a) shows the two markedly different cases
through a pulsed near-infrared laser. Likewise, Rossa et al. of UV structuring on two polymers. For PI (Figure 2(a-i)) there
[52] investigated surface modifications induced by irradi- is no evident threshold fluence for either of the two working
ation with nanosecond laser pulses of ultraviolet and wavelengths. The linear slope, which linearly correlates flu-
visible wavelengths on cross-linked hydrophilic polymeric ence as a function of pattern depth, and a subsequent non-
materials. They found that microcrater-formation (strong linear slope are observable. At 355 nm PI absorbs more than at
material removal) was the dominant morphological 266 nm and hence the structure depth is larger at 355 nm for
change observed by ablation at 532 nm, while additional all applied fluences. Figure 2(a-ii), on the other hand, shows
and less aggressive surface modifications (laser fluence: that PC requires a minimum fluence value below which
0.9 J cm−2 and number of pulses (N ): 5), mainly microfoams patterning is not possible. This threshold value is particularly
and roughness, developed in the ultraviolet at 266 nm. high for patterning at 266 nm approaching 1.5 J cm−2. A linear
Based on previous work linked to the dynamics of UV correlation between fluence and structure depth is then
laser ablation in polymers [55, 57], Lasagni et al. [53] also observed.
discussed the mechanism that leads to UV-laser ablation in Figure 2(b) displays scanning electron microscope
polymeric materials using ns-pulses. There are two broadly (SEM) images, extracted from another work by the same
discussed mechanisms. On one hand, a photothermal authors [53], of typical topographies obtained by two-beam
mechanism, in which the ablation mechanism is associated interference (line-like) for three laser fluences (ordered in
with cumulative heating processes, as the energy of a single increasing order from left to right) for PI at 355 nm. The
photon is insufficient to break a chemical bond, so the longer spatial period was 6.2 μm while the average width between
wavelength laser radiation is absorbed in the vibrational ablated lines resulted in a range from 3.3 to 6.2 μm. They
modes of the molecule. Once a bond absorbs enough described the profile of the micropatterns as sinusoidal-
6 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Figure 2: (a) Structure depth as function of the laser fluence for (a-i) PI and (a-ii) PC irradiated with laser radiation of 266 nm and 355 nm of
wavelength, respectively. Line-type interference pattern. In all cases the period was 6.2 µm. (b) SEM images illustrating the evolution of the PI
micropattern structured by DLIP at 355 nm from sinusoidal to U-shaped profile (scheme in between images where the dotted line is the laser
fluence threshold value) for line-like at fluence (b-i) 312 mJ cm−2, (b-ii) 676 mJ cm−2 and (b-iii) 1023 mJ cm−2; and pillar-like at fluence (b-iv)
99 mJ cm−2, (b-v) pillar-like at fluence 277 mJ cm−2 and (b-vi) 854 mJ cm−2. (c) AFM images and corresponding profiles (bottom row) of PTT films
structured by DLIP at 266 nm using two (c-i, ii) and three (c-iii, iv) interferences laser beams. Figures (a) to (b) adapted from ref. [53] (© 2007
WILEY‐VCH Verlag GmbH & Co. KGaA). Figure c adapted from ref. [68] (© 2014 American Chemical Society).
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 7

trapezoidal at low laser fluences (300 mJ cm−2) where only a three-dimensional topography due to the Marangoni ef-
small area of the polymer reaches values above the fect, which describes the convective mass transfer due to
threshold fluence (see respective schema below each surface energy gradients. In the case of DLIP in polymers,
Figure 2(b-i–iii)). As the laser fluence increases, more of the this phenomenon is more evident when using lasers of the
surface area exceeds the threshold fluence required to order of nanoseconds and in the region close to the fluence
ablate the polymer, resulting in larger ablation regions, threshold, in other words, in the boundary between the
therefore at medium fluence values (600 mJ cm−2) the maximum and minimum of interference, generating a si-
structure profile becomes sinusoidal (Figure 2(b-ii)), while nusoidal topography of varying thickness in this area.
for high laser fluences (1000 mJ cm−2) a U-shaped profile was Among the most widespread DLIP-related applications
observed (Figure 2(b-iii)). The authors reported comparable is the modification of the surface wettability of a material
findings when the polymer samples were irradiated with a [69, 70]. For example, Estevam-Alves et al. [71] used DLIP to
three-beam interference pattern (Figure 2(b-iv–vi)). In this produce periodic surface structures on PU substrates with
case, the diameter of the ablated circular regions became periods ranging from 0.5 to 5.0 μm using an ns-laser with
progressively larger (3.6–7.2 μm) with increasing fluence 10 ns pulse duration. They investigated the influence of laser
(99–854 mJ cm−2). Furthermore, due to the geometry of energy density on the quality and topographical character-
the interference pattern at fluences of approximately istics of the produced micropatterns and how these influ-
850 mJ cm−2, the circular patterns conformed into a periodic enced surface wettability. Two types of linear periodic
star-shaped pattern. patterns were produced on PU. Firstly, surfaces with spatial
In another study, Martín-Fabiani et al. [68] reported the periods in the submicrometer-range (500–1000 nm) and
application of two- and three-beam DLIP configurations to structure depths of ca. 300 nm, and secondly PU-surfaces
trimethylene polythiophthalate (PTT) thin films. The ex- with spatial periods larger than 2.0 μm and depths between
periments were performed with a single pulse of UV–laser 0.88 and 1.25 μm. To characterize the wettability behaviour
radiation (266 nm) and fluences between 100 and of patterned and untreated PU samples, the researchers
300 mJ cm−2. By changing the incidence angles, the fabri- performed water contact angle (WCA) measurements using
cation of micrometer and submicrometer large-area poly- the sessile droplet method. The results reported that the
mer 1D grooves and cavities arranged in a hexagonal lattice WCA of the slightly hydrophilic PU (81 ± 2°) increases
was achieved. Figure 2(c) shows exemplarily some of the significantly when it is patterned with a periodic structure of
fabricated textures. Additionally, the mechanism of inter- 3 μm and a depth/periodicity aspect ratio of 0.41, adopting a
ference formation in polymer thin films was studied by hydrophobic behaviour (102 ± 2°). This effect, already re-
inspecting different regions of the sample corresponding to ported by others [72], can be explained by considering that
different fluences due to the Gaussian-shape of the laser the surface follows a behaviour according to the Cassie–
beam: from the edge of the irradiated region (minimum Baxter model of heterogeneous wettability, in which air
fluence) towards the center of the laser spot (maximum pockets are trapped between the microcavities of the solid
fluence). Thus, the researchers established three different surface and the liquid droplet. Hence, an originally hydro-
regimes in the process. The morphology obtained outside philic material can be rendered liquid-repellent due to the
the irradiated region corresponds to that expected for a PTT microstructure of its surface. However, at a structured
flat film. Inside the irradiated region, at the edge, slight period of 500 nm and depths of about 200 nm, WCAs lower
signs of a periodical topography were observed, indicating than those of the unstructured surface were obtained, which
that the process was initiated by linear absorption. Still at indicates that the surface is still hydrophilic and follows
the edge, but closer to the center of the laser spot, char- Wenzel’s theory. In this case, the original hydrophilic PU
acteristic interference patterning was observed. Finally, in becomes more hydrophilic as the interfacial contact area
the center of the laser spot, ablation holes appeared along increases (due to the topography) and homogeneous
with these patterns, indicating a non-linear response of the wettability occurs (the structure is not able to retain air at the
material, where above a certain laser fluence a complete solid–liquid interface).
removal of the material occurred. Substrate topography has far-reaching implications
Furthermore, another characteristic effect of laser for early bacterial adhesion and bacterial biofilm for-
ablation can be seen in the topographical DLIP profiles of mation [73, 74] which is why the use of DLIP-modified
Figure 2(c). When exposing a thermoplastic polymer to surfaces has also been explored for the development of
thermal annealing or UV radiation the polymer material antimicrobial or bacterial aversive surfaces. The bacte-
flows from the unexposed regions (low surface energy) to rial adhesion-topography interaction is intricate and
the exposed regions (high surface energy) generating a non-trivial. On the one hand, it has been found that
8 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

uncontrolled irregularities, such as voids or unshaped tested cases, larger or equal periodicities to cell dimensions
pores, facilitate bacterial adhesion and biofilm deposi- (>1 μm) seems to increase bacterial adhesion, while smaller
tion, as it provides more favourable sites for colonization, periodicities (ca. 500 nm) decreased cell adhesion, despite
whereas ultra-smooth polished surfaces do not favour contact time and hydrophobicity. In line with this, Cuello
bacterial adhesion and biofilm deposition [75, 76]. On the et al. [72] studied the effect of the size of linear-type
other hand, several scientists suggest that surfaces with DLIP-micro topographies on a PI film. The DLIP patterning
rough topographies on the order of the nanoscale, was performed with periods of 1 μm, 2 μm and 10 μm. The
particularly of the pillar or needle type, inhibit biofilm antibacterial properties were evaluated by the effect on the
formation [77, 78]. growth of colonies of Pseudomonas aeruginosa bacteria.
Werner and co-workers [74] reported a correlation of The results suggested that a periodic topography only im-
bacterial adhesion and biofilm formation (E. colli) with the parts antifouling and biofilm reduction properties as long
dimensions of the structure on three photoresist resins as the microstructure has periods ranging between 1 and
(SU-8; APTES-(3-aminopropyl) triethoxysilane, (APTES) 2 μm. For larger structures, no bacterial biofilm disruption
and TAF-amorphofluoropolymer, (TAF)). For the three was observed. Figure 3(a) shows atomic force microscopy

Figure 3: (a) AFM images of P. aeruginosa (24 h cultivated) in (a-i) PI unstructured, (a-ii) PI-line-like 1 µm and (a-iii) PI-line-like 10 µm films;
(b) SEM images of B35 cells on DLIP-generated nanopatterns on PEEK with 1000 nm periodicity with (b-i) 50 nm deep grooves and (b-ii) 350 nm
deep grooves. (b-iii) Fluorescence microscopy showing the alignment of B35 cells on PEEK-nanopatterns. Fluorescent staining: DAPI and
phalloidin. (c) Optical images of HPF seeded on (c-i) flat PC films, (c-ii) PC films with a linear type structure with a period of 9 µm and (c-iii) PC
films with a lattice-type structure with a period of 7 µm. In all cases the films were coated with collagen. Figures reproduced from: Figure 3a, ref.
[72] (© 2020 Elsevier B.V.) Figure 3b, ref. [79] (© 2012 Laser Institute of America) and Figure 3c, ref. [81] (© 2005 American Chemical Society).
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 9

(AFM) images of the PI-films contaminated with bacteria, it the cells were again randomly oriented. Regarding cell
is notable how the bacillus bacteria appear to line up in the shape, as opposed to cells seeded on the unmodified PC
valleys of the structures when the size of the structure is film which possesses a characteristic multipolar shape,
slightly larger than the size of the bacteria. HPFs seeded in linear and pillar-shaped patterns are
Another application in the field of biomedicine of poly- mostly bipolar and spindle-shaped. Therefore, while the
mers structured by DLIP is the design of materials for cellular behaviour of flat and line-shaped PCs is very well defined,
uptake and growth for tissue engineering. Neuronal cells, cells grown on pillar-shaped PCs seem to behave in an
especially in the central nervous system (CNS), need guid- intermediate condition between the unmodified surface
ance to reconnect after injury [14]. The strategy proposed by and the linear pattern, thus possessing a bipolar and
Bremus-Koebberling et al. [79] consisted of DLIP fabrication spindle shape, but are randomly oriented on the surface.
of neuronal scaffolds as a tool to guide cells in nerve recon- The DLIP method is a scalable technology for treating
nection. The work studied the geometrical features that in- large areas, which makes it interesting for the fabrication of
fluence cell behaviour, in particular the effect of depth and organic photovoltaic (OPV) devices. It has been used to
size of the structures in the nanometer range (spatial period: achieve structures such as gratings or pillars to improve the
100–1000 nm; depth: 100–600 nm), using two polymers power conversion efficiency by lengthening the optical path
films (PI and PEEK) as scaffold surfaces, which were subse- of incident light within the absorber material, creating light-
quently embossing in PDMS in order to perform biological trapping geometries [82]. For example, Müller-Meskamp et al.
tests. Examination of cell orientation on the nanopatterns [83] used DLIP to generate surface structures on flexible PET
was carried out with B35 neuronal cells cultured in serum-free substrates with linear (4.7 μm period) and hexagonal (0.7 μm
media for up to 96 h to expand the cell body extensions. The period) patterns that were subsequently coated with a
growth of these cells’ dendrites and axons on the linear poly(3,4-ethylene dioxythiophene) poly(styrene sulphonate)
nanogeometries was examined by SEM and fluorescence (PEDOT:PSS) and a ZnPc:C60-based small-molecule organic
microscopy. Selected results are shown in Figure 3(b), in solar cell. All devices showed reasonable electrical perfor-
which a directional growth of the neuronal cells can be mance, with an open-circuit voltage and fill factor compara-
observed along with the pattern (Figure 3(b-ii)) while in other ble to those of glass or flat PET reference. It was further
cases no such alignment occurs (Figure 3(b-i)). The re- demonstrated that both the short-circuit current and power
searchers suggested that axonal alignment along the grooves conversion efficiency were strongly improved by the surface
occurs mainly when the so-called depth-to-width aspect ratio structure and the higher light absorption in the active layer.
is 0.3 or greater. Analogous results were shown in another Benchmarking the power conversion efficiencies against the
work but with a different cell line [80]. In this case, line-like reference cell in flat PET, a relative increase of about 5% was
structured surfaces (periods: 500 nm–10 μm) were fabricated observed for the linear pattern, and a remarkable improve-
on PI to produce topographical signals for cancer tumor cells. ment of 21% for the hexagonal pattern.
The cell-topography interaction was evaluated in vitro using In a similar work, Leo et al. [82] designed a solar cell
mouse mammary adenocarcinoma cells. The results showed based on a small molecule blend of C60 and DCV5T-Me as an
a cell growth guided by the direction of the patterning (more absorber layer deposited on structured PET. The micro-
than 60% of the cell population is located in the grooves of patterns obtained are shown in Figure 4(a) and (b). The best
the structure) for all tested structure sizes, with cells growing performing device (line-like pattern with 1.8 μm period)
on patterns with a spatial period of 500 nm being the most achieved a power conversion efficiency of 7.7%, representing
aligned (up to 80%). an improvement of over 16% relative to the reference. From
Similar results were obtained by Mücklich et al. [81] the current–voltage curve in Figure 4(c), it can be seen that
when studying the growth of human lung fibroblast (HPF) the short-circuit current density of the cells on structured PET
cells on DLIP-modified PC films. Figure 3(c) shows a series increased strongly. Hence, the periodic topography seems to
of bright field optical microscopies through which it is play a key role in the mechanism behind the increased effi-
possible to compare cells grown on a flat (unmodified) and ciency by allowing for a greater light trapping effect in the
DLIP-structured PC surface in two different geometries. As solar cells, lengthening the absorption path and conse-
shown in Figure 3(c-i), in the case of flat PC the cells do not quently concentrating more light on the absorber.
show a specific growth direction, but are randomly ori-
ented and often overlap with each other. In contrast, in the 2.1.2 Multi-scale and complex architectures
case of a surface with linear topography (Figure 3(c-ii)), the
cells show a directional growth parallel to the line patterns. DLIP was explored to produce multi-scaled, or hierarchi-
Finally, in the case of a pillar topography (Figure 3(c-iii)), cal, structures with two or three levels, mimicking the
10 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Figure 4: (a) and (b) SEM images of microstructured PET-DLIP (a-i) to (a-ii) with 1.8 µm period, (b-i) with 2.6 µm period wo/OPV multilayer, and
(b-ii) with 2.6 µm period with OPV multilayer. In figures (a-i) y (b-i) the schematic patterning PET and PET-OPV is shown; (c) Current-potential
curve for planar PET-OPV and DLIP PET-OPV at different periods, top left OPV multilayer scheme. Reproduced from ref. [82] (Licensed under a
Creative Commons Attribution).

complex patterns present on numerous surfaces in nature achieved. Then, to obtain the short-range hierarchical
[84, 85]. For example, Rößler et al. [86] presented the structure, the process was repeated but with smaller
fabrication of three-level periodic structures on PET sur- structure periods (1–2 μm). The total diameter of each spot
faces using DLIP with ns-laser to produce advanced dif- was 50 μm (referred in some publications as holographic
fractive optical elements. To achieve this, several pixel), whereby the distance between two spots was set to
sequential processing steps were used. Briefly, in a first 35 μm. This last step gives the structure the third topo-
step a linear periodic (10 μm spatial period, 266 nm, 10 Hz) graphic sublevel. The sequence of steps by which the hi-
distribution was generated and by a second step identical erarchical structure is obtained is schematized in
to the first one but rotating the sample 90° with respect to Figure 5(a)–(d), while the micrographs of the resulting to-
the initial position the high range pillar-like structure was pographies are shown in Figure 5(e)–(h).

Figure 5: (a)–(d) Process steps for fabricating first the PET structures (the circles in white dotted lines in d indicate the size of each laser spot
and the overlap between them. (e)–(h) SEM images of the structured PET each image corresponds to the process step indicated in each
diagram immediately above in the top row. Figures reproduced from ref. [86] (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA).
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 11

Similarly, Alamri et al. [87] presented several DLIP overlap: 90 pulses, for the second structuring step).
hierarchical structuring strategies on PC films employing a Finally, Figure 6(a-iv) shows a hierarchical pillar-on-pillar
two-beam interference arrangement using a nanosecond structure. For all structuring examples, the laser parame-
ultraviolet laser (263 nm) and multi-pulse fabrication, ters for the first structuring process were kept constant
aiming to fabricate hierarchical structures with selective (fluence: 1.48 J cm−2, structure period: 2.0 μm).
wetting properties. As an example, the series of four SEM Later, Alamri et al. [88] presented an innovative tech-
images in Figure 6(a) is shown. Figure 6(a-i) presents a nique to produce microstructures with complex non-
hierarchical pillar-like structuring process (fluence: symmetrical linear patterns based on the two-beam DLIP
0.51 J cm−2, N: 10 pulses for the second structuring) using approach in order to fabricate surfaces with anisotropic
the two-step fabrication strategy and the 90° between-step functionalities. In this work, PI films mounted on an
rotation of the sample presented above [87]. Figure 6(a-ii) inclinable stage were irradiated with a 4 ns UV laser source
shows a two-level structure with line-like DLIP structures (266 nm), producing linear structures with a period varying
on the lower level covered by orthogonal linear structures from 4.6 μm to 16.5 μm. The resulting saw-tooth topogra-
on the upper level (fluence: 0.51 J cm−2, overlap: 90 pulses, phies were obtained by tilting the sample with respect to
for the second structuring step) and Figure 6(a-iii) shows the optical axis of the set-up. The topography tilt angles
hierarchical structures with lines on the lower level, varied from 0° to 75°, thus achieving a well-defined and
covered by pillars on the upper level (fluence: 1.63 J cm−2, controllable inclination of the structure’s sidewalls. The

Figure 6: Three series of simple and hierarchical DLIP structures SEM images, portraying: Upper row (a): (a-i) PC-pillar-like (fluence:
0.51 J cm−2, N: 10 pulses), (a-ii) PC-lines-on-perpendicular-line-like (0.51 J cm−2, 90 pulses), (a-iii) PC-lines-on-pillar-like (1.63 J cm−2, 90 pulses)
and (a-iv) PC-pillars-on pillars-like (1.63 J cm−2, 120) in all cases the structured period was 2 µm; middle row (b): (b-i) PI-inclined-lines-0° (b-ii)
PI-inclined-lines-45° and (b-iii) PI-inclined-lines-75° (fluence: 0.51 J cm−2, N: 10 pulses) and confocal topography (upper left); lower row (c): (c-i)
PI-line-like (fluence: 1.34 J cm−2, N: 10 pulses), (c-ii, iii) PI-crossline-like (fluence: 1.34 J cm−2, N1st pulse: 10, N2nd pulse: 5). The arrow in (c-i)
indicates the polarization vector. These figures were adapted from ref. [87] (© 2018 Elsevier B.V.), [88, 95] (Licensed under a Creative
Commons Attribution).
12 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

study reports an exhaustive exploratory research on the transparent at the IR wavelength used [95]. The obtained
evolution of the topography as a function of the inclination patterns also showed some particular features. On one
angles and the effect of the depth of the pattern as a hand, the structure depth was significant deeper (ca.
function of the number of pulses. Examples of the struc- 3.9 μm) compared to patterns with the same period ob-
tures produced at different angles (30°, 45° and 75°) at a tained with ns pulses and UV irradiation (up to 1.8 μm) [72]
laser fluence of 1.32 J cm−2 and 20 pulses are shown in the for which the material is a good absorber. On the other
SEM micrographs of Figure 6(b) together with the corre- hand, at the positions of the interference maxima where a
sponding optical confocal images. The SEM images indi- somewhat more disorganized bubble-like structure of the
cate an inclination in the shape of the linear structures for order of the nanoscale is observed. Besides, at the positions
angles of inclination greater than 30° and the presence of of the minima, some redeposition of the ablated material
undercutting of the tilted walls. Furthermore, it was found was reported.
that as the angle of inclination of the sample relative to the Occasionally the LIPSS process does not occur simul-
optical axis increases, the spatial period increases while taneously but can be incorporated in a second step after the
the structure depth decreases. DLIP process to produce controlled hierarchical structures.
In further cases, the hierarchical structures are not For instance, Mezera et al. [94] reported the generation of
generated by sequential DLIP processing but by other hierarchical micro/nano structures on PC surfaces by
simultaneous phenomena inherent to laser radiation, such employing a two-step UV laser processing strategy. In a
as nanometric waviness known as laser-induced periodic first step they used a DLIP nanosecond (3 ns) UV laser
surface structures (LIPSS) [89, 90]. Describing the mecha- (266 nm) to achieve periodic structures on the order of the
nisms of ablation by LIPSS will be the scope of another microscale and subsequently using a ps laser (7–10 ps,
review; here we will just briefly mention certain specific 350 nm) they patterned LIPSS with feature sizes of a few
situations where LIPPS is somehow linked to the DLIP hundreds of nm. Afterward, by using FTIR-ATR, the
process in polymers. There are different opinions as to the chemical changes before and after laser irradiation were
cause of these wave-like structures but in general it re- measured as well as the consequent degradation of the
sponds to self-ordering processes of the material when it is polymer. Figure 7 shows the spectra obtained for three
exposed to ultra-short laser pulses. Some sources suggest different structuring conditions, the first row correspond-
that LIPSS originate from the interference of incident/ ing to LIPSS (PC-LIPPS), the second and third row to DLIP
refracted laser light with scattered or diffracted light near with a spatial period of 1.5 μm (PC-DLIP-1.5 μm) and
the surface [91, 92]. Others, that LIPSS occur due to 10.0 μm (PC-DLIP-10 μm), respectively. For a better un-
shrinkage of the polymer layer during resolidification [93]. derstanding, SEM images of the measured structures are
These structures are associated with irradiation with shown also in Figure 7. In all cases the spectra of the
pulsed UV lasers with pulse lengths on the order of a few structured surfaces (red lines for line pattern or blue lines
nanoseconds, fluences well below the ablation threshold for pillar pattern) are compared with those of the un-
and with a large number of laser pulses. The spatial period structured surface (black lines).
of the observed LIPSS is close to the laser wavelength. In In agreement with previous literature [72, 87], it was
the case of femtosecond laser, ripples are also observed on shown that in all cases, laser processing caused a partial
polymer surfaces at laser fluence above the ablation degradation of the structure, particularly, in the C–H vibra-
threshold, even with a low number of laser pulses [92, 94]. tional region (3000 cm−1), the carbonyl and C=C vibrational
In this regard, Alamri et al. [95] presented the development peaks (1790 and 1500 cm−1) and the C–O–C vibration (ca.
of microstructured PI surfaces with multi-scale periodic 1120 cm−1 and 1280 cm−1). A relative increase in the band
patterns with two-dimensional symmetry by combining intensity was also observed, e.g. LIPSS processing gives rise
DLIP with LIPSS in a one-step process. A femtosecond laser to a broad absorption band related to the OH stretching re-
source emitting at 1030 nm with a pulse duration of 500 fs gion (ca. 3400 cm−1) and two increases, associated with the
and a repetition rate of 1 kHz was used for the experiments. appearance of oligomers or short-chain polymers around
As shown in Figure 6(c), grooves and pillars of several 1630 cm−1 and 1690 cm−1 (see Figure 7(b)). Similarly, the
microns deep with very well-defined line-like structures processing of DLIP structures gives rise to absorption bands
could be obtained after 10 consecutive pulses on PI films. at 3550 cm−1 and 3500 cm−1 (see Figure 7(d)–(g)), which are
In general, the presence of LIPSS in polymers is associated attributed to free phenolic groups. On the one hand,
with multiphoton absorption mechanisms [89, 91]. It was comparing the relative intensity of the spectral bands of the
mentioned in that work that two-photon absorption pro- LIPPS-structured and DLIP-structured PC, it is noticeable that
cess may be involved in the mechanism, as the material is the relative changes due to laser irradiation are more
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 13

Figure 7: ATR-FTIR spectra of unprocessed PC (black curves) overlay with processed by (a)–(c) LIPSS (PC-LIPSS, red curves in and (d)–(f)
PC-DLIP-1.5 µm ridge-like (blue curves) or pillar-like (red curves) and (g)–(i) PC-DLIP-1.5 µm ridge-like (blue curves) or pillar-like (red curves): In
the left the corresponding SEM images. Figures reproduced from. Ref. [94] (Licensed under a Creative Commons Attribution).

prominent for LIPSS than for any of the DLIP periods (e.g. surfaces were characterized under in vitro and in vivo condi-
when contrasting Figure 7(a)–(c) with Figure 7(d)–(f)). On the tions. The results suggested that topographies have a signif-
other hand, comparing DLIP structures with different pe- icant impact on bacterial adhesion and they revealed
riods, the spectra show a smaller band spread/shift due to the different behaviours according to the geometry of the
creation of DLIP structures with a narrow period (1.5 μm) 3D-structures. Thus, after 2 h of bacteria culture (see
compared to those with larger ones (10.0 μm). Moreover, it Figure 8(a)), line (LN) and pillar (PL) patterns enhanced S.
can be observed that pillar-like DLIP texturing affects more aureus adhesion in PS films, while complex microtopography
the degradation of PC than the fabrication of ridge-type DLIP in the form of lamellae reduced S. aureus attachment under
structures. It was suggested that the different levels of poly- static and continuous flow culture conditions. Curiously, the
mer degradation can be attributed to the number of laser textured lamellar (LA) surfaces retained the ability to inhibit
pulses irradiating a spot and the corresponding cumulative S. aureus adhesion when the surface was coated with human
fluence, being higher for PC-LIPPS than for any of the serum proteins and maintained their non-adhesive properties
PC-DLIP surfaces, and slightly higher for PC-DLIP-pillars than when the material was implanted subcutaneously in an in
for PC-DLIP-ridges. Other similar study by the same group vivo model. As an example, SEM images of PS surfaces
[87, 96] on hierarchical patterns on PC-DLIP presented similar contaminated with S. aureus are shown in Figure 8(b)–(d).
conclusions. While large bacterial clusters spread over the entire surface of
In addition to the applications mentioned above, multi- the structured PC pillars (Figure 8(c)), small bacterial clusters
level structures have been used for the development of sur- dispersed on complex laminar-like patterns (Figure 8(d)) as
faces with antimicrobial/antifouling activity. For instance, well as on the flat PC (Figure 8(b)). These studies in connec-
Werner and co-workers [97] analyzed the adhesion behaviour tion with the studies mentioned in Section 2.2.1, suggest a
of Staphylococcus epidermidis and S. aureus model bacteria dependence of the adhesion and orientation of the bacterial
on simple but also complex structures (e.g. lines, sheets, cells on the periodicity and geometry of the DLIP-surfaces.
pillars) achieved by DLIP with periodic spacings from 0.5 μm Thus, it was possible to identify two well-defined cases: (i) for
to 5.0 μm fabricated on PI and polystyrene (PS) foils. These structures with dimensions larger than the cell size, the cell-
14 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Figure 8: Qualitative assessment of S.

aureus adhesion (static conditions, 2 h) to
(a) reference PS-flat compared to (b) pillar-
stamped PS (3 μm) and (c) lamellae PS; (d),
relative adhesion (colony forming units
(CFU) on structured and unstructured sur-
faces of S. aureus in PS with micrometric
structures of lines (LN), pillars (PL) and
lamellae (LA) at different periodic spacings.
Figures reproduced from ref. [97] (© 2016
SPIE).

substrate contact area increases, which contributes to high 2.2 Composite and advanced polymers
bacterial adhesion (similar to that of the smooth surface), (ii)
for topographies with structure periods similar or smaller A composite is defined as a material that involves the
than the bacterial cell size, and particularly when the surface interaction of at least two constituent materials, yielding
geometry is pillar-like, the contact area between the cell and new or enhanced properties. An example of advanced
the substrate was restricted, which tends to lead to lower cell composite polymer are materials composed of a trans-
adhesion. However, much remains to be elucidated and other parent structural polymer and a chromophore polymer or
factors must be considered, including contact time, the type agent with poor mechanical properties (i.e. a thermolabile
and shape of the microorganism and the surface chemistry, polymer or a stable polymer as a colloidal dispersion) that
among others. For example, in the case of spherical cells is deposited, adsorbed, grafted, etc. onto the former (Pol-
(Staphylococcus bacteria), cell retention was lower, while rod- Crom@PolSupp). Conductive polymers as well as cross-
shaped cells (Pseudomona and Escherichia bacteria) tended linked polymers and block co-polymers will be considered
to settle in the cavities of the structure, making biofilm for- as advanced materials in this review due to their extraor-
mation more difficult. Regarding surface chemistry, in Sec- dinary properties and their potential for novel applica-
tion 2.2 will be discussed the combined effect of surface tions, as will be discussed below.
structure an antibacterial coating in composite materials.
Subsequently, other works reported more sophisticated
combinations of structures on these materials. For example, 2.2.1 Chromophore-embedded polymers
Rößler et al. [98] proposed a bilayer system consisting of a
PMMA and PC film that was irradiated with a nanosecond A major concern about laser structuring in polymers is
pulsed laser at a wavelength of 263 nm. The top layer of linked to their inherently low absorptivity in the VIS-IR
PMMA is transparent to the used laser wavelength and thus wavelength range, which makes it intricate to structure by
the irradiated light was absorbed in the bottom layer of PC ns-lasers at wavelengths longer than 260–266 nm. This, in
layer, which produced a periodic structure entrapped be- turn, struggles with the low pulse stability of UV lasers
tween the two layers. To study the in-volume structure, the compared to longer wavelength lasers, especially at the
authors used a cross-section polisher operated with argon scale-up stage of the process [99]. To overcome this draw-
ions combined with SEM/EDX analysis. Periodic round cav- back, several authors have documented the doping of
ities, produced by the decomposition of PC, with a feature size transparent polymers with chromophore agents or photo-
of 500 nm were observed at the interface between the poly- sensitizers such as azo dyes [100], conductive polymers
mers. This in-volume patterning approach has been proposed [101] or fluorescent nanoclusters [102]. The dopants reduce
for the fabrication of long-lasting holographic security de- the ablation threshold and increase the quality of ablated
vices, e.g. in credit or personal cards. features.
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 15

Figure 9: Left column: PC-undoped-DLIP line-like at a wavelength of 263 nm (a) SEM image of one Gaussian spot (pulse duration 3 ns, fluence
3.5 J cm−2, spatial period 0.56 µm), the shaded region forming a circle corresponds to the center of the laser spot where there is a depressed
zone (zone of higher fluence) while the surrounding zone corresponds to the area of lower fluence. Confocal microscope profiles at a fixed
period but varying the laser fluence (a-i, ii) and fixed fluence but varying the spatial period (a-iii, iv). Right column: PC-doped-DLIP line-like with
swelling at 1053 nm (b) SEM image of one Gaussian spot. Confocal microscope profiles of at a fixed period but varying the laser fluence (b-i, ii)
and fixed fluence but varying the spatial period. (a-iii, iv). The black box in each graphic indicates the fluence and the spatial period of
structuring. (c) SEM-FIB image of a swelled PC-doped-DLIP line-like (1053 nm, fluence 1.3 J cm−2, period 7.3 µm). Reproduced from ref. [22]
(© 2017, Optical Society of America).
16 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

To analyze this behaviour, Alamri and Lasagni [22] mechanism at fluences slightly above the threshold flu-
described a series of four measurements to develop an ence, although not as evident as in the experiments with a
empirical model comparing transparent PC (PC-undoped) laser wavelength of 1053 nm. At higher fluences the sub-
and pigmented (PC-doped) PC substrates treated by ns- strate was locally ablated at the positions of the interfer-
DLIP at two markedly different wavelengths, namely UV ence maxima, obtaining results similar to those of the
(263 nm) and IR (1053 nm). Depending on the used laser transparent material treated with UV radiation. At this
processing conditions, the type of material as well as the wavelength, both the matrix and the dye can absorb the
spatial period of the interference pattern, four different laser radiation and, therefore, dual ablation-expansion
behaviours were identified. The interference phenomenon behaviour combined with the interference process is to be
combined with ablation can be well exemplified by expected. Furthermore, in order to study the swelling
PC-undoped foils irradiated with UV laser (Figure 9(a)). The phenomenon in depth, an SEM images of focused ion beam
results revealed that well-defined line-like patterns, which (SEM-FIB) milled cross-cuts of doped polycarbonate
perfectly fitted the periodic intensity distribution, were modified by DLIP (laser fluence 1.3 J cm−2, spatial period
obtained only for a small range of laser fluences 7.13 μm) were presented. The image (Figure 9(c)) showed
(<0.1 J cm−2). For higher laser fluences, the interference that micropores form specifically at laser interference
phenomenon is added to the laser ablation so that the maxima. They suggested that the dynamics of pore crea-
structure fades, giving rise to a partially structured volume. tion and expansion is independent of the interference
The same effect was observed keeping the laser fluence period, for a fixed laser fluence and wavelength. Therefore,
constant at a mean value (0.25 J cm−2) and exploring sys- when the size of the expanding pores is smaller than the
tematically different structuring periods, for periods below spatial period of interference, the pores quench, creating
1 μm (see Figure 9(a-iv)). The Gaussian shape of the abla- non-periodic structures.
tion is to be expected due to the Gaussian intensity profile Another example is the work reported by Broglia et al.
of the laser radiation (see Figure 9(a-i–iv)) [103]. Experi- [105] on which polystyrene doped with azo-colorant by
ments of PC-undoped irradiated with IR reported no DLIP at 355 nm was structured. The colorant incorporation
interaction with the laser over a wide range of fluence. pursuits not only to structure PS but also to achieve a more
PC-doped structured at 1053 nm (Figure 9(b)) corre- uniform and controlled structure compared with pure
sponds to the less frequently swelling phenomenon, also polystyrene. An azo-dye was selected because of its
reported by some authors as foaming [52], combined with photosensitive properties and its ability to absorb light
interference. When the polymer interacts with laser light with high absorption coefficients in the spectral range be-
some polymer chains can be excited and dissociate into tween 300 and 400 nm, given by the presence of the azo
gaseous by-products inside the material producing pores group (–N=N–) in its structure. The range of working flu-
that do not reach the surface of the material and thus ences required to produce sub/micro-arrays was between
increasing the local volume [104]. This represents a clear 0.2 and 1.0 J cm−2. The results of these studies indicated
example of a thermal ablation mechanism as mentioned in that to obtain linear-like textures in the sub-micron range
Section 2.1.1. The dynamics of pore formation can be (ca. 500 nm) a threshold fluence of 0.3 J cm−2 was needed.
considered independent of the interference period, for a However, under these irradiation conditions the system
fixed laser fluence and wavelength. Therefore, when the must also handle the swelling phenomenon which pro-
dimension of the expanding pores is smaller than the duces localized swelling of the material and inhibits the
interference spatial period, the pores interconnect with development of regular periodic sub-micron arrays. Also,
each other forming non-periodic structures. This behaviour they studied the formation of different microstructures by
can be observed in the micrograph of Figure 9(b) and in the DLIP on PS films with azo compound 2-anisidine (PdS) as a
profile plots presented in Figure 9(b-ii and iii). As in the function of fluence. For this, a classical two-beam config-
case of ablation, there is a window of fluence and structure uration was used to obtain linear interference patterns. A
periods where this particular phenomenon is observable. Nd-YAG ns-laser was used with a wavelength of 355 nm
For low laser fluence and especially for large spatial pe- (triple harmonics). Laser ablation can then take place by
riods, the polymer only swelled at the interference max- either or both of these two phenomena: (i) the azo group
ima, while for shorter structure periods or higher fluence absorbs the light and decomposes releasing gaseous ni-
the swelling effect predominated and no clear interference trogen, which subsequently helps to remove the solid
fringes were observed (see Figure 9(b-iv)) [22]. material from the ablated region; (ii) the heat absorbed by
Next, PC-doped substrates were irradiated with UV the dye is transferred to the polymer causing sublimation
laser radiation. Hither, the authors reported a swelling and/or rupture of the polystyrene chain. The first
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 17

phenomenon is associated with the aforementioned (Ag@PMAA) as well as to induce nanocluster formation
photochemical absorption mechanism, while the second and subsequent laser patterning on unreduced silver
one depends on the thermal conductivity of the polymer polymeric films (Ag+@PMAA). The latter system presented
and its ability to absorb heat from the dye. The systematic the most relevant results as a single laser pulse allowed to
study at different fluences also showed the presence of create not only the line-like pattern on the surfaces but
pores in the zones of maximum interference that dis- simultaneously generated the photoreduction of silver. As
appeared when structuring the surface at higher fluences. is observed in Figure 10(a-ii–iv), Ag+@PMAA once struc-
In a similar study, active chromophore agent as tured by DLIP (and simultaneously photoreduced) showed
nanoparticles or clusters embedded in a polymeric matrix a highly ordered pattern of fluorescent lines after treatment
and arranged in the form of DLIP structured films had been with 1, 3 and 5 laser pulses that ablated the material,
reported. Mulko et al. [106] described the use of DLIP at obtaining successively broader patterns. For sake of com-
355 nm with a ns-laser to pattern PMAA doped with pho- parison, Figure 10(a-i) shows that in the case of the pristine
toreductive fluorescent silver nanoclusters surfaces material Ag+@PMAA film (non-irradiated) did not produce

Figure 10: Ag@PMAA: Confocal microscope images Ag@PMAA before (a-i) and after processing by DLIP with increasing number of pulses N:
(a-ii) N = 1 (a-iii) N = 3 and (a-iv) N = 5; CNF@PEEK: SEM analysis of surface structures fabricated with IR at laser fluence of 2.86 J cm−2 (first row)
and 2 J cm−2 UV (second row) radiation with increasing N, spatial period Λ and with inserts of higher magnification images: (b-i) Λ = 2 μm,
N = 200, (b-ii) Λ = 4.3 μm, N = 200, (b-iii) Λ = 8.5 μm, N = 200, (b-iv) Λ = 2 μm, N = 200, (b-v) Λ = 4.3 μm, N = 200, (b-vi) Λ = 8.5 μm, N = 200.
Figures reproduced from ref. [106] (© 2019 Elsevier B.V.) and ref. [107] (© 2019 Elsevier B.V.).
18 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

fluorescence in the detected spectral range, demonstrating representatives are polyaniline [14, 108] (PANI), polypyrrole
that the nanoclusters were produced as a result of the (PPy) [109, 110] and polythiophene and their derivatives, and
interaction of the Ag+@PMAA film with the laser pulse. co-polymers such as poly(3,4-ethylenedioxythiophene) poly-
Hauschwitz et al. [107] addressed the production of styrene sulfonate (PEDOT:PSS), that have been well-known
functional hierarchical microstructures by DLIP in carbon for decades. Particularly, PANI has attracted considerable
fiber (diameter of 5 μm) reinforced polymer composites attention due to its favourable environmental stability, redox
(CNF@PEEK) in order to produce superhydrophobic sur- reversibility and electrical conductivity [110, 111]. Not only is
faces. Taking advantage of the strong absorption of the the production of conductive bulk polymers technologically
carbon fibers in the near-infrared and of the supporting important, but also the fabrication of CPs surface patterns to
polymer in the UV, two-beam DLIP using an ultraviolet produce devices such as biosensors, chemical sensors, mi-
(263 nm) or infrared (1053 nm) ns-laser source was croelectrodes, biomedical devices, artificial muscle and neu-
employed to produce well-defined and melt-free hierar- ral interfaces, battery electrodes, photoelectric cells, among
chical microstructures in carbon fiber reinforced plastics. others [14]. Although these polymers show a poor mechanical
Since the center of the DLIP pixel has a higher fluence due stability, they are generally stable as colloidal dispersions
to the laser intensity Gaussian distribution, dual-scale hi- [112]. To achieve a conductive system with good mechanical
erarchical structures in the fibers with large pillars (60 μm), stability it is necessary that these CPs form composite mate-
generated by the DLIP pixel size, combined with micro- rials in combination with another material such as another
pillars, generated by the interference lines and were pro- polymer [113], glass [114] or metal [14]. Regarding the pro-
duced in a one-step process. The interesting finding of this duction of CPs films, this is generally done by classical
work underlies the different structures that can be clearly chemical or electrochemical oxidative polymerization depo-
observed by changing the working wavelength and sition, and less usually, photochemically, while patterning of
obtaining a plethora of structuring possibilities. Mean- conductive films was initially carried out using lithographic
while, the structuring of CNF@PEEK by IR-DLIP in the ns techniques or combined lithography and nanoimprinting
regime was mainly considered as a photothermal process techniques in multiple steps [115].
resulting in an abrupt heating of the carbon fibers that was In 2007, Acevedo et al. [116] used DLIP to generate
rapidly transferred to the surrounding area, leading to PANI nanoarrays using a UV laser source. In this research
melting and ultimately vaporization of the polymer matrix work it was shown how to obtain well-defined and
around the heated fibers. Differently to IR-DLIP processing, controlled geometrical line-like patterns on PANI films
no cracks or detrimental thermal effects were observed chemically bonded on PC and PI using DLIP. The
during UV-DLIP processing in the available laser power conductive structures were fabricated with a single laser
range. Due to the high absorption of the polymer at the pulse at 355 nm. The authors showed that increasing the
wavelength used, fewer pulses per unit area were required laser fluence, the width of the PANI lines increased
for structuring. By increasing the number of pulses per following three behaviours. In the first case (see
spot, the polymeric matrix vaporizes due to the heat input Figure 11(a-i)), at low laser fluences (<174 mJ cm−2), the
from the fibers in a similar way as described for the IR PANI film was ablated very locally at the positions of the
treatment. However, the formation of hierarchical struc- interference maxima. As the laser fluence increased
tures was observed only for specific cases (period 1.5 μm (Figure 11(a-ii), a larger amount of the laser energy excee-
and pulse overlap larger than 99%). The SEM images in ded the PANI threshold ablation fluence and larger abla-
Figure 10(b) show the structures obtained for both IR-DLIP tion areas were achieved, regardless of the substrate.
(i–iii) and UV-DLIP (iv–vi). In the former, the presence of Finally, for the PANI@PI sample (Figure 11(a-iii)), irradi-
cracked and damaged areas is evident, as well as the non- ated with a fluence of 194 mJ cm−2, not only the PANI upper
trivial formation of structural shapes such as ladder-like film was ablated but also the supporting polymer, PI. As a
structures. For CNF@PEEK obtained for UV-DLIP, struc- result, both the thickness and the width of the PANI lines
tures with a uniform and controllable geometrical pattern decreased, achieving configurations where the PANI dis-
are observed. appeared completely from the ablated zone giving rise to a
surface with alternating conductive-insulator channels,
2.2.2 Conductive polymers produced at the minima and maxima of interference,
respectively.
Electrically conductive polymers (CPs) contain conjugated Acevedo and co-workers [59] investigated also this
π-electron systems that give them unique characteristics behaviour on different PANI substrates structured by
such as hybrid electronic-ionic conductivity. Its clearest DLIP. In another work they succeeded in generating a
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 19

Figure 11: (upper row) SEM images of PANI@PC nanostructures supported at (a-i) laser fluence 325 mJ cm−2; (a-ii) laser fluence 174 mJ cm−2 and
(a-iii) PANI@PI laser fluence 194 mJ cm−2 where the substrate is also ablated. The scheme bottom right the diagram indicates the type of
material ablated; (middle and lower rows) SEM micrographs of the biofilm formed (grown for 24 h) on (b-i) PET, (b-ii) PANI@PET film and (b-iii)
PET-PANI structured by DLIP and AFM micrographs of the bacteria grown for 24 h on (b-iv) PET, (b-v) PANI@PET and (b-vi) PANI@PET-DLIP.
Figures adapted from ref. [116] (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA) and ref. [78] (© 2016 Elsevier B.V.).

PANI@glass substrate with markedly anisotropic conduc- further evidence of no significant electrochemical modifi-
tivity in the direction parallel to the patterned grooves. cation after DLIP treatment, paving the way for using these
Following this work line, Acevedo and Lasagni [117] later microelectrodes as electrochemical devices or as biomed-
developed a method to quantitatively measure the elec- ical platforms.
trical conductivity of PANI films by indirectly sensing the The DLIP structured conductive polymers were further
specific electrical resistance of each pattern. The results reported for the development of antimicrobial surfaces.
indicated specific resistance values changing by an order Gallarato et al. [78] successfully fabricated PANI coated
of magnitude when comparing unstructured PANI films PET films structured by DLIP (PANI@PET) capable of
(PANI@glass) with those structured by DLIP (PANI@glass- decreasing biofilm formation of the bacterium P. aerugi-
DLIP). Furthermore, the electrical resistance was signifi- nosa. They noted that PANI@PET surfaces resulted in a
cantly different when measuring the film in the direction of significant inhibition of bacterial adhesion (more than
the pattern and perpendicular to the pattern. However, the 70%) and biofilm formation (more than 50%). Most
overall average specific conductivity across the untreated remarkably, they also demonstrated that microstructuring
and patterned films was in the range of previously reported PANI via DLIP synergistically increases the antimicrobial
values in doped PANI (0.5–2.8 S cm−1). This represents capacity of the PANI surface, decreasing bacterial
20 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

adhesion by 97.5% and biofilm formation by 65%. Proving period). This phenomenon can be ascribed also to a Cas-
that there is a coactive effect due to the chemical and sie-Baxter behaviour, in accordance with the above-
physico-chemical effects achieved on the original PET film mentioned experiments on patterned PU and observed on
due to multiple factors (chemistry, loading, mechanical other conductive polymers [119].
properties and topography). As can be seen in Figure 11(b-i
and ii) the appearance of P. aeruginosa bacteria growth on 2.2.3 Cross-linked and block co-polymers
PET and PANI@PET showed a spherical shape forming a
dense and homogeneously distributed biofilm along the The use of DLIP has been reported not only on linear
entire surface in 24 h of culture. In contrast, on the DLIP polymers but also for soft materials such as cross-linked
treated sample (PANI@PET-DLIP) (Figure 11(b-iii)) the polymers [120] or semi-interpenetrated networks [101]. For
bacteria, acting in response to the topography, chose a example, Molina et al. [121] used DLIP (355 nm, 10 ns pulse
preferred direction of growth, changed their morphology width) to create patterns on a cross-linked poly(N-
and modified the production of exopolysaccharides. isopropylacrylamide) hydrogels (PNIPAM) doped with a
Several scientists ascribed this as a strategy of the cell to solution of tris (2,2′-bipyridine) ruthenium (II) dye (RBPY).
survive when is exposed to stressful environmental con- In this case, the ablation effect involves a transfer of heat
ditions [11]. This work triggered further research on the from the highly UV-absorbing dye to the transparent
generation of antimicrobial surfaces on PANI coated polymer. The PNIPAM are well-known biocompatible,
polymers structured by DLIP, as surface chemistry and thermoset and thermosensitive smart materials [120] able
micro/nanotopography of solid interfaces play an essential to undergo reversibly volume transitions between hydro-
role in mediating the activity and adhesion of microor- philic (swollen) and hydrophobic (unswollen) states at the
ganisms, which is not yet fully elucidated in coated- lower critical solution temperature (LCST) of
polymers. 32–32.5 °C [112]. The colorless (undoped) PNIPAM hydro-
The DLIP structuring of polymer films coated with gels did not form patterns when irradiated with 355 nm
polypyrrole (PPy) was also reported [118]. For instance, PPy laser light, due to the negligible absorption of the polymer
films deposited on inert polymeric substrates were irradi- at that wavelength. The interesting feature of such mate-
ated by DLIP at 355 nm, so that only the conductive poly- rials is that when the surface is swollen in water, the DLIP
mer film was patterned while the transparent support texture disappeared. This is probably due to the expansion
polymer remained unchanged. The period of the patterned of the gels by swelling. However, it can be observed that
grooves varied from 900 nm to 3.5 μm and the width of the when the hydrogel was dried by heating to a temperature
PPy lines was adjusted by controlling the laser fluence. In above the LCST of the hydrogel, the patterned surface
addition, Fourier transform infrared (FTIR) spectroscopy reappeared; thereby they reported the creation of a smart
and UV–VIS spectroscopy provided information to ensure surface with triggered patterning due to swelling–deswel-
that the chemical structure of PPy remained unaffected ling cycles. A similar behaviour was observed on PNIPAM
after the structuring process in the non-ablated regions. surfaces interpenetrated with PANI and structured by DLIP
The electrical characterization showed a relatively low (PANI@PNIPAM) by Mulko et al. [122]. The presence of the
decrease of conductivity from 13 S cm−1 of the untreated light-absorbing PANI allowed the dry films to be patterned
film to 5.7 S cm−1 after the DLIP treatment. Hence, the by DLIP at 355 nm, which in turn resulted in a surface
patterned films can be used for sensor devices responsive nanofoam superimposed on a lines/groove pattern. In
to specific ions (e.g. gases such as ammonia) based on the addition, the conductive PANI absorbed electromagnetic
electronic properties of the material. The researchers sug- radiation (RF), which was converted to heat and induced
gested that the small dimension of the conductive polymer the phase transition of PNIPAM. In this case, pattern acti-
lines achieved by DLIP would increase the response rate of vation was achieved by exposing the patterned surfaces
the devices as microelectrodes due to two reasons. Firstly, swollen in water to the remote RF radiation inducing the
the mass transport of charge will be enhanced because hydrophilic-to-hydrophobic phase transition by increasing
there is a longitudinal cylindrical diffusion and secondly the temperature above the LCSTs of the material [122].
the volume/surface area ratio is higher for structured films Sola et al. [123] also reported several works where line-
than for flat films [118]. In the same work Acevedo et al. like textures were patterned by DLIP in poly hydroxy ethyl
[118] performed static water contact angle measurements to methacrylate (PHEMA) films. In this case, PHEMA films
evaluate the wettability of structured PPy. The contact were structured to modify their refractive index for
angle increased from 55° on flat PPy to about 75° on ophthalmic purposes. The interference periods were fixed
structured line-like PPy and 72° for pillar-like PPy (3.5 mm at 2.6 μm and 4.7 μm. The pattern characteristics were
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 21

studied over a range of laser fluences between 0.5 J cm−2 (usually assigned to thermal decomposition of short-chain
and 17 J cm−2, and the number of pulses varied from 1 to 5. A organic molecules) arises, which may screen out key
confocal image of the structured zone at low fluence characterization bands. Unfortunately, this type of
(7 J cm−2) is shown in Figure 12(a). At this working fluence behaviour is quite common in polymers such as PC, PEEK
the researchers reported that the laser-matter interaction and PI treated by nanosecond lasers [94]. Nevertheless,
process resulted in swelling of the polymer surface. This Sola et al. [123] reported DLIP-structured µ-Raman spectra
swelling phenomenon, as already mentioned, usually oc- at 532 nm for PHEMA and silicone hydrogels. The Raman
curs in a short range of fluences. In contrast, at higher laser spectra of the DLIP structured areas processed at high
fluences, the structuring of the material occurred pre- fluences (Figure 12(c) and (d) – blue line) showed varia-
dominantly through ablation mechanisms. For example, tions compared to those corresponding to the unprocessed
as observed in the SEM micrograph in Figure 12(b), at a samples (Figure 12(c) and (d) – black line). In particular, in
fluence of 11 J cm−2 for a spatial period of 2.6 μm, heat the PHEMA sample processed at high laser fluence
affected zones appeared as ablation or bubble-like areas (11 J cm−2) there was a strong decrease in the peak intensity
because of the photothermal-mechanical nature of the of several bands (473 cm−1, 604 cm−1, 830 cm−1, 897 cm−1,
laser–matter interaction process. The chemical composi- 1089 cm−1 and 1718 cm−1), while other bands disappear
tion and structural analyses of laser-treated polymers was (734 cm−1, 1204 cm−1, 1230 cm−1). A similar behaviour was
investigated using Raman spectroscopy [123]. This is a detected for the DLIP-modified silicone hydrogel and
powerful technique to explore polymeric films treated by shown in Figure 12. In contrast, at low intensity, laser
laser as long as no increase in the fluorescence background structuring was not accompanied by significant changes in

Figure 12: (a) Confocal image of a PHEMA sample structured (2.6 µm, 1 pulse, 7 J cm−2), (b) SEM micrograph PHEMA samples structured
(2.6 µm, 1 pulse, 11 J cm−2), µ-Raman spectra of Micro-Raman spectra of (c) PHEMA sample in non-processed areas (black line) and in the DLIP
structured regions with a spatial period of 2.6 μm at 7 J cm−2 (green line) and 11 J cm−2 (blue line) laser fluence (d) silicon hydrogel in non-
processed areas (black line) and in the DLIP structured regions with a spatial period of 4.7 μm at 0.5 J cm−2 (green line) and 1.6 J cm−2 (blue line)
laser fluence. Reproduced from ref. [123] with permission from Japan Laser Processing Society.
22 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

the µ-Raman spectra, hence the polymer structure 3.1 Bioceramics

remained almost unchanged after laser irradiation.
Acevedo et al. [58] reported the structure of a block co- Ceramics have been used as biomaterials for decades not
polymer where the swelling phenomenon (already only due to their non-cytotoxicity and resistance to corro-
described in Section 2.2.1) is also observed. They presented sion, but also because an important constituent of bones
the fabrication of advanced architectures using DLIP at are ceramic materials [124]. Particularly, alumina and zir-
266 nm in poly (glycidyl methacrylate-co-styrene) with four conia have been widely used for dental implants and for
different percentages of styrene P(GMA-%S). It was shown prosthesis due to the excellent biocompatibility compared
the transition from a uniform line-like structure with to other ceramics. Roughening the surface of these mate-
interference ablation to a less uniform and more disordered rials can enhance their adherence to surrounding mate-
structure where the swelling phenomenon underlies. The rials, such as cements, dental tissues like dentin and
variables studied being not only the laser fluence used, as enamel or underlying metallic substrates, and improve
is commonly observed, but the percentage of styrene pre- osseointegration [125]. Several studies have proved the
sent in the co-polymer. As expected, the surface of the PS feasibility of structuring zirconia by ns-DLIP employing
homopolymer was ablated at the position of maximum two overlapping beams to pattern periodic grooves with
interference but in the P(GMA-%S) the surfaces were spatial periods between 1 μm and 15 μm and aspect ratios
ablated and swollen in the regions of maximum interfer- up to 0.6 [126]. Roitero et al. [127] performed a thorough
ence. The styrene content in the polymer absorbed the laser microstructural and chemical analysis on ns-DLIP treated
energy giving rise to photothermally ablated regions or yttria-stabilized zirconia yielding new insights into the
promoting chemical decomposition of the acrylate units or material modifications after laser structuring. From SEM
polymer segments. analysis combined with FIB machining, they observed a
network of interconnecting cracks on the treated zirconia
that was independent of the chosen laser wavelength,
532 nm (Figure 13(a)) and 355 nm (Figure 13(b)), and texture
3 DLIP processing of ceramics and periodicity. They found also that the heat-affected zone
semiconductors (HAZ) extended only 1 μm below the surface and it could be
split into two layers as shown in the STEM cross cuts of
Ceramics are characterized by a high hardness, corrosion Figure 13(c)–(f). The top layer, with a thickness of ∼300 nm,
resistance, chemical stability, wear resistance and capa- was mainly formed by recast material characterized by
bility to sustain high strength at higher temperature than columnar grains oriented perpendicular to the surface. The
polymers and metals. Moreover, ceramics can be in- bottom layer was composed of isotropic grains, which were
sulators, semiconductors or conductors and can be used highly deformed due to high dislocation density and
also as biocompatible materials. However, their charac- twinning. Cracks homogenously distributed were observed
teristic brittleness makes ceramics hard to machine, both at the peak (Figure 13(c) and (d)) and valley
increasing the cost of the final part, especially during the (Figure 13(e) and (f)) of the microtexture, crossing through
finishing step [124]. Conventional mechanical machining all the HAZ along the grain boundaries.
methods turned out to be inefficient to treat ceramics due to Laser structuring also induced structural trans-
tool wear, vibrations, and long process times. Alterna- formations, resulting in the appearance of a monoclinic
tively, non-contact techniques that avoid the use of hard phase co-existing with the tetragonal phase which was also
tools, such as ultrasonic machining, electric discharge observed in the untreated sample. Chemical analysis by
machining, direct laser writing, plasma machining, abra- X-ray photoelectron spectroscopy (XPS) revealed that the
sive water jet machining or electron beam machining, have composition remained approximately constant after the
entered the market in recent decades. Nevertheless, when laser step. The pattern formation on zirconia was mainly
it comes to large-area surface patterning with high- explained by thermal mechanisms due to the long pulse
resolution down to the sub-μm scale and with high flexi- duration in the ns range. The absorbed laser energy led to
bility, DLIP appears as a promising industrial solution. In melting and evaporation, but also accompanied by liquid
the following sections, an overview of recent progress flow attributed to the large surface tension gradients
towards surface micropatterning of ceramics by DLIP is [127, 128]. Previous studies from the same research group
given. have shown an increase of fracture toughness, measured as
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 23

Figure 13: Comparison of DLIP processing on zirconia with two different wavelengths: (a) 532 nm and (b) 355 nm. STEM images of FIB-cut
lamella across a ridge peak (c) and (d) and valley (e) and (f). Bright field images are shown in (c) and (d), whereas dark field images in (d) and (f).
Figures adapted from ref. [128] (© 2017 Elsevier B.V.).

flexural strength, of up to 50% in yttria-stabilized zirconia. two laser beams. The experiments were conducted with
The presence of high compressive stress on the surface two different wavelengths in the UV spectrum, namely
combined with a periodic distribution of pore sizes and 266 nm and 355 nm. The authors found significant differ-
grain refinements down to the nanometer scale resulted in ences in the surface morphology upon processing HAp
an increase of the force needed to bring the surface into a with either 355 nm or 266 nm radiation, as shown in the
tensile stress and to trigger crack formation, which ulti- SEM images of Figure 14(a)–(f), respectively. In the latter
mately leads to an increase in the flexural strength [129, 130]. case, the ablation process was mainly dictated by photo-
Similar experiments were conducted on alumina that led thermal mechanisms followed by melting. Due to the low
also to an increase in flexural strength. These findings have thermal conductivity of HAp, large temperature gradients
the potential to increase the resistance and lifetime of dental (2000–3000 K) were established between maxima and
restorative materials based on zirconia and alumina. minima of the interference pattern on the sample resulting in
Due to its outstanding cytocompatibility, synthetic large thermal stresses. Additionally, such stresses were
hydroxyapatite (HAp), Ca5(PO4)3(OH), is one of the most boosted by the presence of pores in HAp that disrupt the heat
used bioceramics for artificial bone replacement that can flow, and that ultimately can destroy the repetitive textures
successfully mimic bone tissues [131, 132]. Furthermore, when large accumulated fluences are applied on HAp or
engineering the surface texture of HAp can enhance the when short spatial periods (<10 μm) are targeted. In turn, the
osseointegration of the implant and induce cell organiza- ablation process of HAp with 266 nm radiation has not only a
tion [133]. Berger et al. [134] have conducted a detailed contribution from photothermal effects but also from photo-
analysis of the influence of ns-DLIP process parameters on chemical reactions. That is, after laser irradiation, the excited
the resulting surface morphology of laser treated HAp. material decomposes into several constituents without a
Line-like and cross-like (pillars) textures with spatial significant temperature rise. Interestingly, even at high
periods of 10 μm and 20 μm were produced by overlapping accumulated fluences, XPS analysis confirmed that no
24 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Figure 14: SEM-micrographs of periodic line-like patterns fabricated on hydroxyapatite with 355 nm laser radiation, 20 µm period and
1.2 J cm−2 of laser fluence with (a) one, (b) 10 and (c) 50 pulses and with 266 radiation, 10 µm period, fluence of 0.6 J cm−2 with (d) one, (e) 10 and
(f) 50 pulses. Figures adapted from ref. [134] (© 2011 Elsevier B.V).

significant modifications in the chemical composition of the films by nanoparticle-assisted pulsed laser deposition
HAp surfaces were produced after the DLIP process. (NAPLD) [137].
As doped ZnO films are frequently used in optoelec-
tronic applications, textures with targeted periodicities in
the range 0.5–1.5 μm have been mainly produced by DLIP
3.2 Semiconductors and oxides for
to enable a strong interaction between visible light and the
electronics periodic surface grating. A detailed morphological analysis
was realized by Eckhardt et al. [138] on DLIP-treated
Transparent conductive oxides (TCOs) are widely used in
aluminum doped ZnO (AZO) films using ns pulses.
sensors and optoelectronic devices based on thin film
Figure 15 shows exemplarily a (a) line-like and (b) hexag-
semiconductors [135]. The outstanding combination of
onal pillar-like texture reported in that work. They found
optical transmittance in the visible spectrum, relatively
that thermal-induced surface tension gradients were the
low electrical resistance, chemical inertness and me-
main mechanism by which molten material was dragged
chanical strength, has made TCOs a key component in
from the intensity maxima positions to the minima, as was
thin film solar cells, OLEDs, touch screens and LCD dis-
also observed in ns-DLIP processing of ZnO:B [139]. During
plays. A surface pattern on the TCO surface can be engi-
neered to manage light conveniently to, for example, trap the cooling phase, the material crystallized forming large
more light in a solar cell or to couple the light generated in grains but also a noticeable distribution of cracks, in
an OLED into the outer medium as well as to tailor the accordance with the findings by Parellada-Monreal et al.
electrical resistivity. [140] and Knüttel et al. [141]. On the contrary, texture for-
DLIP processing on doped and undoped zinc oxide mation on AZO films by ps-DLIP presented a significant
(ZnO) films has been extensively investigated in the last contribution of ablation and a smaller amount of molten
decade, especially using ns-laser sources emitting in the material compared to ns-pulsed processing. This can be
UV spectrum. Nakamura and co-workers have patterned attributed to the shorter thermal diffusion length below
line-like textures and square arrays of holes on ZnO thin 20 nm [142] compared to a thermal diffusion length of
films by interfering four UV (355 nm) beams using a 4f ∼1 μm for ns-pulses, which leads to very localized heating
interference configuration [136]. Then, they grew periodic and temperature rise above the vaporization temperature
ZnO nanocrystals and nanowires on the DLIP structured of AZO. Optical characterization of the DLIP structured ZnO
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 25

Figure 15: SEM micrographs of AZO films structured by DLIP with a (a) line-like pattern and (b) hexagonal pillar-like array. Total transmittance
and haze factor of the hexagonal ((c) and (d), respectively) and line patterns ((e) and (f), respectively). Figures adapted from ref. [143] (© 2013
Elsevier B.V).

films demonstrated the ability of such textures to scatter μc-Si:H tandem solar cells, showing an increase in photo-
and diffract light very efficiently, as shown in the global current by 20% [142] and also as substrate in OLEDs with an
transmittance and haze factor measurements of enhanced external quantum efficiency of more than 25%
Figure 15(c) and (e) and Figure 15(d) and (f), respectively [145].
[143]. This enhanced optical management can be exploited Two-beam DLIP was also successfully used to patten
to boost the efficiency of thin film solar cells [144]. In fact, line-like textures on indium tin oxide (ITO) films with ps-
DLIP-patterned AZO have been used as substrate in a-Si:H/ pulses at a wavelength of 355 nm [146]. In this case, it was
26 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Figure 16: ITO films structured by ps-DLIP with different polarization directions (as indicated by the arrows) and fluences, which in turn,
influenced the alignment and dimensions of LIPSS. Figure reproduced from ref. [146] (© 2019 Optical Society of America).

explored the feasibility of producing hierarchical nano- material in our daily life. Laser processing of silicon wafers
textures by combining the DLIP features with LIPSS, as and thin films has become common practice in the last
shown in the SEM images of Figure 16 for different polari- decade for mainly applications such as selective crystalli-
zation directions and laser fluence. The resulting multi- zation [148], vias drilling for sensors [149], laser scribing for
scaled patterns exhibited a strong anisotropic electrical solar modules interconnections [150], and for realizing
resistance characterized by a ratio between the longitudi- local contact openings at the rear side of solar cells [151].
nal and transverse resistance of more than 50,000. Be- Also, fs-laser surface texturization by LIPSS has been used
sides, InOx thin films were patterned by overlapping two for enhancing the absorption of solar cells by reducing the
beams from a ns-pulsed KrF excimer laser source emitting reflectance of sunlight [152].
UV (248 nm) light [147]. Here, the authors reported two DLIP patterning with ns pulses has been extensively
characteristic ablation regimes which can be correlated to employed to modify the topography of Si wafers [153]. Due
the initial electrical properties of the material. Namely, a to the high evaporation point of Si, it is commonly agreed
transition from a semiconducting behaviour to a con- that Marangoni convection is the dominant mechanism for
ducting characteristic as a function of the UV exposure was the formation of the repetitive microstructures in the ns-
observed. As a consequence, in the early stages of irradi- pulse duration regime [154, 155]. Peláez et al. [154] over-
ation the material ablation can be attributed to photo- lapped two beams from an ArF excimer laser with a
chemical mechanisms, but as the cumulated fluence wavelength of 193 nm at a pulse duration of 20 ns on Si to
increased, thermal ablation was triggered increasing the produce line-like textures with a period of 1.7 μm. They
ablation rate and influencing the quality of the final performed a sound process parameters screening, where
topography. The fabricated relief diffraction gratings with fluence in the range 0.63–1.0 J cm−2 and number of applied
a spatial period of 610 nm were then applied for the pulses in the range 1–5000 were swept. They correlated the
fabrication of Bragg grating mirrors in InOx thin film resulting grooves morphology, i.e. height and FWHM, with
overlaid waveguides, which can be useful for filtering de- the process parameter and explained their formation by an
vices in optical communication applications. analytical model based on thermocapillary forces and
As the mainstream semiconductor for microelectronics surface tension gradients (Marangoni convection), ruling
and photovoltaics, silicon has become a ubiquitous out significant effects from material vaporization. Also
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 27

periodic micropillars arrays were fabricated by over- for inducing the formation of inverted micropyramids by
lapping either three or four beams from a ns-laser source. anisotropic wet chemical etching. For instance, Figure 17
The structure formation was achieved by the same melting, shows a square array of hole patterned with four-beam
material flow and resolidification mechanisms described DLIP (a) and the resulting inverted micropyramid array
above [155]. DLIP patterned microcones on Si allowed for a after the chemical etching (b). Due to the applied fs-pulses,
strong reduction of reflectivity below 10% in the visible the heat affect zone encompasses only ∼10 nm below the Si
spectrum [153], which is significantly lower than the surface avoiding a negative impact on the electronic
reflectivity of 30–40% measured in polished Si over the properties. Although more investigations are needed, this
same spectral range [156]. Although these results are approach can control the reflectivity of Si solar cells
promising for producing silicon solar cells with antire- without comprising their electrical performance.
flective properties, the possible significant crystallographic Other semiconductors were structured by DLIP too [19].
or chemical modifications in the heat affected zone may For instance, Ihlemann’s group reported the fabrication of
deteriorate the electronic properties on the silicon surface complex periodic micro and sub-microstructures on GaN
as well as along several μm below the surface. Therefore, substrates by phase-controlled multiple beam interfero-
more investigations need to be done to assess the feasi- metric projection [34]. In their setup, three linear phase
bility of using this laser-based approach for improving the gratings, rotated by 30° to each other, were used as DOE
overall performance of Si solar cells. and the first diffraction orders from each of the gratings
Also, DLIP based on fs-laser sources was used to were allowed to interfere. The laser source was an excimer
pattern the surface of Si wafers. Given the ultra-short pulse laser emitting 500 fs-pulses at a wavelength of 248 nm.
(USP) duration of 560 fs, at a wavelength of 1030 nm, Oli- LEDs based on epitaxy-grown GaN heterostructures
veira et al. [157] proposed to use a Michelson interferometer were irradiated by overlapping three UV ns-pulsed beams,
to overlap two beams on a Si wafer. Thereby, gratings with resulting in hexagonal arrays of sub-micron sized holes
a spatial period of 720 nm were produced by material [160, 161] as shown in Figure 18(a). Although Kim et al.
ablation at the intensity maxima positions. Another [160] detected an increase in the series resistance of the
configuration able to yield an interference pattern by laser-patterned LED, they attributed it to the locally
overlapping USP is based on a Schwarzschild objective, as reduced thickness of the top layer and not to a deteriorated
reported by Ihlemann and co-workers [158]. With this setup ohmic contact. The grating-like topography of the
they could pattern linear gratings on silicon using a UV DLIP-structured GaN LEDs yielded a significant increase in
excimer laser with pulse durations from 500 fs to 50 ps. the light outcoupling efficiency by more than 55%
Voisiat et al. [159] have used a diffractive optical element compared to the reference device (Figure 18(b)) [161].
(DOE) and two lenses arranged in a 4f configuration to Quantum dots (QD) arrays were grown by a combina-
overlap four and six fs-beams on Si. The resulting square tion of self-assembled epitaxial growth of GaAs/AlGaAs
and hexagonal arrays of microholes were then beneficial and InAs/GaAs heterostructures combined with an in-situ

Figure 17: SEM images of a silicon wafer structured by (a) four-beam DLIP and (b) by post-laser chemical etching with controlled anisotropy.
Reproduced from ref. [159] (© 2014 SPIE).
28 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Figure 18: (a) Topography images of DLIP-treated LED based on GaN. (b) Optoelectronic characterization of structured LEDs, showing an
increase in the performance. (c) AFM images of quantum dot arrays with different coverage of InAs monolayers (ML). Figures reproduced from
ref. [160–162] (© 2014 AIP Publishing LLC, © 2017 Elsevier B.V, Licensed under a Creative Commons Attribution).

DLIP process step [162, 163]. In this case, a beam from a ns- properties resulting in an increased fill factor and open
laser source emitting pulses at a wavelength of 355 nm was circuit voltage.
divided into four beams by beam splitters and directed into In another work, spray-deposited TiO2 was processed
the molecular beam epitaxy (MBE) vacuum chamber with ns-DLIP (1053 nm) to achieve a cross-like texture with
through transparent viewports. As the UV light is strongly a period of 8.5 μm [166]. The film underwent crystallo-
absorbed by the InAs monolayer (ML), strong lateral ther- graphic transformations from anatase to rutile phase at
mal gradients arose between the interference maxima and high number of pulses. Besides, the authors studied the
minima position, driving the atoms towards the cold areas photochemical, wettability and optical properties of the
and forming periodic arrays of nanoislands. Varying the structured TiO2 and found a significantly increased pho-
MBE deposition conditions, the number of InAs mono- tocatalytic behaviour.
layers covering the substrate and the laser polarization,
Wang et al. [164] obtained arrays of QD and nanoislands
with different geometrical shapes and aspect ratios, with a 3.3 Dielectrics
fixed spatial period of 300 nm, as shown in the AFM images
of Figure 18(c). Highly transparent dielectrics like glasses, diamond or
Recently the active material of an antimony(III) sulfide sapphire can be directly patterned using lasers by either
(Sb2S3) based solar cell was patterned with a line-like linear absorption of UV radiation or by non-linear ab-
texture with a spatial period of 1.2 μm using a ns-laser sorption mechanisms triggered by high-energy USP in the
emitting pulses at 532 nm [165]. Interestingly, the re- visible or IR spectrum. The latter phenomenon, which was
searchers observed a double enhancement effect on the described by many studies published elsewhere [26], con-
performance of the solar cells. One the one hand, the pe- sists basically in multi-photon ionization upon irradiating
riodic microtexture increased in the haze factor dramati- the material with USP, so that free electrons are generated
cally, which increased the absorption and short circuit in the conduction band. This step can then be followed by
current. On the other hand, the Sb2S3 film recrystallized an avalanche impact ionization process, whereby the free
forming smaller grains than the as-deposited film, which electrons with high kinetic energy can transfer part of their
led to an enhancement in the recombination and transport energy to valence band electrons, which in turn can cross
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 29

the band gap to the conduction band. Eventually, a suffi- reported the feasibility of structuring float glass by two- and
ciently high number of excited electrons exceeding a given four-beam ps-DLIP using visible radiation (532 nm), varying
threshold can lead to material breakdown and macro- the spatial period and fluence dose [176]. The line- and hole-
scopic ablation [167, 168]. like textures carved on the glass were attributed to non-linear
Particularly, mostly non-linear absorption was absorption as well. Also, low spatial frequency LIPSS
exploited in DLIP manufacturing for structuring trans- perpendicular to the radiation electric field were observed at
parent dielectrics. At the beginning of this century, a few the positions of the interference maxima in both types of
pioneering works were reported by Kawamura and co- textures, as can be seen in the SEM images of Figure 19.
workers [169, 170] dealing with interference patterning on DLIP ablation induced by lineal absorption in several
dielectrics with fs-pulses in the NIR spectrum. They have dielectrics was also observed. For instance, to increase the
succeeded in engraving line-like patterns with a single absorbance and machinability of borosilicate glasses, Ag-
laser shot on diamond [171], silica glass [172], lithium and Er/Yb-dopants were introduced and structured with
fluoride [173] and sapphire [169], among other transparent UV radiation [51, 177, 178]. In this way, high quality relief
materials. Following a similar approach, Han et al. [174] gratings with spatial periods down to the sub-micron scale
have patterned silica glass with hexagonal arrays of holes were achieved. In the same direction, Beinhorn et al. [179]
by overlapping three fs-beams. They explored different reported the fabrication of sub-micron surface gratings on
symmetric and asymmetric hexagonal arrangements by Ta2O5 waveguide layers by overlapping two beams from a
adjusting the overlapping angles between the beams. In fs-pulsed excimer (248 nm) laser source using a
their study, the ablation mechanism was attributed to Schwarzschild objective. Moreover, due to the utilization of
shock waves generated after the multiphoton ionization USP in the fs-range, deep structures with remarkable
and avalanche ionization, which induced plasma expan- quality were patterned.
sion, phase explosion, melting and ultimately lead to local In another study reported by Vlcek et al., thin films of
ablation. As and Ge based glasses from binary (As-S, As-Se, Ge-S)
LIPSS were also observed after DLIP processing of di- and ternary systems (Ge-X-S, where X stands for As, Sb, Ga,
electrics using USP. In fact, Alamri et al. [95] have analyzed the In) were grown on glass slides and then were irradiated
interaction of DLIP patterning with the occurrence of LIPSS on with two overlapping beams emitted from a pulsed KrF
sapphire by using linearly polarized fs-radiation and different excimer laser at a wavelength of 248 nm and pulse duration
fluence doses. In agreement with other sources [175], they of 20 ns [180]. The produced line-like topography featured
found that the absorption of IR laser light (1030 nm) in sap- a spatial period of 540 nm with depth in the range of
phire was mainly governed by multiphoton ionization. 100–300 nm, depending on the sample composition and
Although low spatial frequency LIPSS perpendicular to the number of applied pulses. The mechanism of the relief
DLIP grooves were observed on sapphire, the process window grating formation could be explained by a major contri-
resulted very narrow and strongly dependent on the presence bution from local melting and glass softening followed by
of surface defects. A recent publication from the same group mass transport to the positions of interference minima.

Figure 19: Microstructured sodalime glass by ps-laser radiation in the visible (532 nm) with (a) four and (b) two overlapping beams. In both
cases LIPSS can be seen on the glass surface. The inset in (b) shows LIPSS aligned perpendicular to the laser polarization direction (double
arrow). Reproduced from ref. [176] (Licensed under a Creative Commons Attribution).
30 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

Even though pulses with a duration of 20 ns were shot on varying fluence thresholds (47–74 mJ cm−2) depending on
the surface, local ablation could not be discarded due to the number of laser pulses (up to 30). Their tribological
the high absorption of UV radiation (248 nm) in these behaviour was evaluated by reciprocal sliding tests by the
materials. Finally, the authors evaluated the performance ball-on-disk method under non-lubricated conditions.
of the structured films as resonant waveguide gratings in Because of the reduction of the contact area due to topo-
the IR spectrum (1550 nm). graphical effects in combination with the partial graphi-
In a recent work, thin films of lithium niobate (LiNbO3) tization of the film, the coefficient of friction (COF) was
were patterned by two-beams DLIP using a solid state fre- reduced by approximately 30% in the patterned ta-C films
quency quintupled laser emitting at 213 nm with a pulse compared to the unstructured reference.
duration of 7 ns. The fabricated relief gratings with sub- For characterizing the structured films, the authors
micron spatial periods were successfully used as grating performed SEM imaging and Raman spectroscopy. In the
couplers for coupling NIR light to lithium niobate-on- latter, different zones concentric to a central spot
insulator ridge waveguides [181]. (following the Gaussian shape of the holographic pixel)
were analyzed (see Figure 20(a) and (b)). Four distinct
classes of ta-C were observed, which were monitored ac-
4 Special cases cording to the well-known ratio of intensities of the peaks
of the D-(disordered carbon band, 1350 cm−1) and graphitic
This section discusses DLIP processing of carbonaceous band, G-(1580–1630 cm−1). In the central region of the laser
materials and their derivatives. In a series of linked papers spot (Figure 20(c)), the irradiated energy was high enough
Roch et al. [182–184] studied the influence of surface topog- to soften the ta-C film and also to melt and soften the steel
raphy on the tribological properties of DLIP-structured substrate (characterized by two broad and low D- and
tetrahedral amorphous carbon (ta-C). In the first paper G-peaks in the Raman spectrum). Around the molten steel,
[183], a 355 nm pulsed UV laser with two- and three-beam in the form of a ring, a second region can be identified in
interference configurations was used to fabricate periodic which the carbon layer was partially ablated (Figure 20(d)).
arrays in the form of dots and lines. One of the major A third region can be distinguished in which the ta-C was
results of this study was the appearance of graphitization locally graphitized (splitting of D- and G-peaks and in-
of the film during the laser processing, which occurs at crease of D-peak). Finally, a fourth region (Figure 20(f))

Figure 20: (a) and (b) LSM image and SEM image of the ablated ta-C film (fluence of 410 mJ cm−2, N = 30). The displayed positions correspond
to: (1) the molten substrate, (2) partially ablated ta-C, (3) graphitized ta-C and (4) unmodified ta-C; (c)–(f) Raman spectra at the four different
positions depicting the carbon morphology. Figures reproduced from ref. [183] (© 2013 Elsevier B.V.).
 L. Mulko et al.: Direct laser interference patterning on non-metallic materials 31

where the ta-C remains unmodified (dominated by a broad pulses (10–20). In addition, the repetitive overlap of
peak resulting from the superposition of peaks G and D). laser pulses on the sample surface induced pattern
These findings are consistent with those from other pub- distortion, leading to the formation of cone-shaped ar-
lication of the same research group [185], where they re- rays. The SEM images of Figure 21(a) show the achieved
ported that, depending on the laser energy density used structures for different spatial periods and number of
for DLIP, the tetrahedral carbon film can graphitize or pulses. The number of laser pulses required to achieve
crystallize locally at the positions of the interference this distortion was proportional to the spatial period of
maxima. Complementary, in a third paper the authors the pattern. In this case, Raman spectroscopy analysis
[184] reported that depending on the structuring period, confirmed that the morphology of the carbon nanotubes
the COF increases or decreases compared to the reference was preserved after the laser processing structure.
samples. For small interference periods (approximately Marczak et al. [187] documented how a similar system of
2 μm), induced surface topographies may act as traps for diamond-like carbon (DLC) film patterned by UV
wear particles, whereby the reduction of friction could be (266 nm) DLIP can potentially be used as scaffolds for
attributed to an increase of the contact surface and a targeted cell growth. Experiments were performed on
concomitant increase of adhesive interactions. Alterna- hard, biocompatible 500 nm thick DLC substrates sup-
tively, over periods of 3–10 μm dominant graphitization ported on an inert polymer and preliminarily tested on
effects at the positions of the interference maxima were smooth muscle cell deposits. The fluorescence micro-
observed, which induced changes in the hardness of the scopy image in Figure 21(b-i) exhibits cell growth and
material and thus increasing the COF. migration in every direction on the unstructured surface,
In another work [186], periodic arrays on silicon films while the image in Figure 21(b-ii) hints at cell migration
coated with vertical aligned multi-walled carbon nanotubes along directions parallel to the patterned grooves, giving
were fabricated using a ns-pulsed UV (355 nm) laser. The rise to mature and enlarged cells.
researchers stated that it was possible to obtain high aspect Finally, it is worth mentioning a very recent work by
ratio structures by controlling the number of successive laser Jurkevičiūtė et al. [188] where fs-DLIP was used for the

Figure 21: (a) SEM of one-dimensional vertical CNTs arrays produced (326 mJ cm−2) by interference pattern irradiation with (a-i) 2.86 µm
spatial period and 1 pulse, (a-ii) 2.86 µm, N = 15, (a-iii) 5.73 µm, N = 1 and, (a-iv) 5.73 µm, N = 20 where it is showing the cross section of the
linear arrays. (b) Confocal microscopy images with fluorescent labeling of smooth muscle cells cultured on DLC layers: (b-i) non-patterned slice
and (b-ii) patterned slides with lamellipodia (elongation) response and SEM image of linear migration channels (upper left). Figures (a) and
(b) adapted from ref. [186, 187] (© 2009 IOP Publishing).
32 L. Mulko et al.: Direct laser interference patterning on non-metallic materials

fabrication of sub-micrometer grooves in DLC nano- Author contribution: All the authors have accepted
composites thin films doped with silver nanoparticles. By responsibility for the entire content of this submitted
adjusting the fluence, the researchers controlled the line manuscript and approved submission.
width of the grooves in the range from 150 to 420 nm, for a Research funding: This project has received funding from
fixed spatial period of 564 nm. Furthermore, it was demon- the European Union’s Horizon 2020 research and innovation
strated that the resulting size distributions of silver nano- programme under Grant Agreement No. 825132. It is an
particles in the composite (DLC:Ag) can be controlled by initiative of the Photonics Public Private Partnership www.
selecting the appropriate laser parameters during the DLIP photonics21.org. This work reflects only the author’s view and
process. For example, the DLC film with an Ag content of the EU is not responsible for any use that may be made of the
14.1% and a bimodal mean effective nanoparticle size distri- presented information. L.M. acknowledges the support by the
bution of 17 and 46 nm (DLC:Ag-14) (11 mJ cm−2 laser fluence, Federal Ministry for Economic Affairs and Energy (Grant No.
64,000 pulses) was transformed into unimodal with a mean ZF 4821601LP9). M.S. is thankful to the Alexander von
diameter 14 nm by increasing the fluence (17 mJ cm−2, 64,000 Humboldt Foundation for supporting this work. A.F.L.
pulses). Furthermore, the combined effect of the DLC:Ag acknowledges the financial support of the German Research
material on the structure parameters was studied and it was Foundation (Deutsche Forschungsgemeinschaft DFG) under
concluded that the patterning of nanocomposite thin films the framework of the Reinhart–Koselleck project (323477257).
requires a cumulative fluence 4 to 24 times higher to achieve Conflict of interest statement: The authors declare no
structuring, with respect to their separate components (DLC conflicts of interest regarding this article.
and Ag). This is due to differences in the absorption and
enhancement of the local electric field governed by the effects
of localized surface plasmon resonances in the case of References
DLC:Ag.
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