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We review the results of Monte Carlo studies of chosen nonlinear optical effects in host-guest systems, using methods based on the bond-fluctuation model (BFM) for a polymer matrix. In particular, we simulate the inscription of various types of diffraction gratings in degenerate two wave mixing (DTWM) experiments (surface relief gratings (SRG), gratings in polymers doped with azo-dye molecules and gratings in biopolymers), poling effects (electric field poling of dipolar molecules and all-optical poling) and photomechanical effect. All these processes are characterized in terms of parameters measured in experiments, such as diffraction efficiency, nonlinear susceptibilities, density profiles or loading parameters. Local free volume in the BFM matrix, characterized by probabilistic distributions and correlation functions, displays a complex mosaic-like structure of scale-free clusters, which are thought to be responsible for heterogeneous dynamics of nonlinear optical processes. The photoinduced dynamics of single azopolymer chains, studied in two and three dimensions, displays complex sub-diffusive, diffusive and super-diffusive dynamical regimes. A directly related mathematical model of SRG inscription, based on the continuous time random walk (CTRW) formalism, is formulated and studied. Theoretical part of the review is devoted to the justification of the a priori assumptions made in the BFM modeling of photoinduced motion of the azo-polymer chains.

Among light-responsive materials for photonics, azo polymers occupy an important position due to their optical response and the related concepts of consecutive applications. However, scientific insight is still needed to understand the effects of irradiation on the modification of the azo polymer structure and the effect of this modification on incoming probing light. In this work, we report on a surface relief grating with a maximum depth of a record-high value of 1.7 µm, inscribed holographically in a custom synthesized glassy azo polymer belonging to the poly(ether imide) family. We show that the specifically deformed polymer, forming an amplitude-modulated relief grating, has a unique dual effect on an incoming light beam of different diameters. When illuminated by a narrow probe beam, the structure acts as a variable-depth grating, enabling a continuous tuning of the diffraction efficiencies in the entire theoretically predicted range and, thus, generating or eliminating diffracted waves of specified order. Alternatively, when illuminated by a wide probe beam, the whole structure acts as an optical component reshaping the Gaussian light intensity profile into the profiles resembling the squares of Bessel functions of the zeroth- or higher orders. Moreover, a physical justification of the effects observed is provided.

We studied the impact of light polarization on photoinduced dynamics of model azo-polymer chains in two dimensions, using bond-fluctuation Monte Carlo simulations. For two limiting models—sensitive to and independent of light polarization—their dynamics driven by photoisomerization of azo-dyes as well as by thermal effects was studied, including characterization of mass transport and chain reorientations. The corresponding schemes of light–matter interaction promote qualitatively different dynamics of photoinduced motion of azo-polymer chains. In particular, they can inhibit or trigger off a directed mass transport along a gradient of light illumination. The generic dynamics of single chains is superdiffusive and is promoted by breaking a symmetry present in the polarization independent model.

In the herein paper, the possibility of obtaining spontaneous surface relief gratings (SSRGs) on azo-polymeric film surfaces, using a single laser beam of 1.13 mJ energy in pulse mode, was investigated. Chain rigidity is essential to have SSRG of reasonable quality so three azo modified polymers, with different main-chain rigidity, were considered: poly(chloromethyl styrene) (PCMS), a linear polysiloxanes and a cyclic polysiloxane. The AFM studies on azo-polysiloxanes revealed unregulated networks with amplitudes of only 1 nm, while on PCMS orderly SSRGs were observed. These results showed that the more rigid azo-polymer, PCMS, had better capacity to generate SSRGs of high quality. The SSRG periodicity was correlated with the number of laser pulses, i.e. higher pulse number led to lower periodicity. The SSRGs formation was associated with polymeric chains self-organization favoured by photo-fluidisation.

We present the optical and photochromic properties as well as surface quality of thin films of the methacrylic copolymers containing 2-methylquinoline and quinoline azo-dyes in side chain. The extinction coefficient and refractive index were determined using spectroscopic ellipsometry combined with transmittance measurements. Photo-responsive behavior was investigated by determination of trans–cis photoisomerization rates under irradiation with unpolarized 365 nm light. We found that optical properties as well as photoisomerization rates of investigated polymers are dependent on the presence of a methyl substituent in the 2nd position of the quinoline moiety. The quality of the thin films was examined using Atomic Force Microscopy measurements.

Human substance needsśś have been enriched by the development of smart-responsive materials possessing unique responsiveness and mechanical variability. However, acquiring these features in photoresponsive energy-driven elastomers is challengeable but highly desirable. Here, we report fabrication of physically-crosslinked elastomers based on an aliphatic polycarbonate terminated with one azobenzene derivative as the end group. Upon irradiation of UV light, the aliphatic polycarbonate shows unusual mechanical transformation from trans-azobenzene-rich elasticity to cis-azobenzene-rich plasticity, which is contrary to the photo-triggered mechanics of other azopolymers. This indicates that stronger interaction may be established between the terminated cis-azobenzenes and the benzene rings in the side chain of polymer, leading to a higher crosslinking density appeared in the cis-azobenzene-rich sample. This azobenzene-terminated polymer is an energy-driven elastomer, which has photo-switchable supramolecular interactions, showing photo-tunable mechanical properties (the half-life period of the cis-azobenzene is 16.9 h). More interestingly, the photoinduced mechanical change occurs at room temperature, enabling the aliphatic polycarbonate to behave as non-thermally switchable ultra-strong adhesive for different substrates, which is specifically suitable for smart dressings to promote wound healing. This switchable mechanical feature of elastomers may be a reference for smart elastomers towards advanced applications. The development of photoresponsive energy-driven elastomers with unique responsiveness and mechanical variability is challenging. Here, the authors describe elastomers based on reversible cis-trans isomerization transition of azobenzene terminated aliphatic polycarbonate, allowing mechanical transformation for smart photo/thermal switchable adhesion and wound healing as medical dressings.

Surface relief gratings (SRGs) are fundamental diffractive elements for optical wavefront control, but in azobenzene-containing polymers their inscription at large modulation depths is limited by growth saturation and profile distortions, which hinder efficient operation at infrared wavelengths. Here, we develop a quantitative optical modeling framework that combines Fresnel propagation, vectorial focusing, and finite-element electromagnetic simulations to describe how the writing field interacts with the evolving azopolymer surface during holographic inscription. The analysis shows that increasing surface modulation progressively reduces the effective optical driving force for further growth through the combined action of periodicity-dependent pattern reconstruction and relief-induced perturbation of the writing field. Experiments performed on SRGs with different periodicities reveal the same periodicity-dependent saturation trend predicted by the simulations. Within the investigated parameter range, a periodicity of 7.5 μm provides the best compromise between achievable depth, profile fidelity, and diffraction angle. Under these conditions, we inscribe near-sinusoidal SRGs with modulation depths approaching 3 μm in a single all-optical step, and, using a stitching strategy, extend the patterned area to 1 mm² while preserving modulation-depth uniformity. This enables an azopolymer-based grating operating at the telecommunication wavelength of 1.55 μm. These results establish a quantitative framework for understanding deep-SRG inscription limits in holographically written azopolymer gratings and provide practical design rules for reconfigurable infrared diffractive photonics.

Light-responsive polymers and especially amorphous azopolymers with intrinsic anisotropic and polarization-dependent deformation photo-response hold great promises for remotely controlled, tunable devices. However, dynamic control requires reversibility characteristics far beyond what is currently obtainable via plastic deformation of such polymers. Here, we embed azopolymer microparticles in a rubbery elastic matrix at high density. In the resulting composite, cumulative deformations are replaced by reversible shape switching – with two reversible degrees of freedom defined uniquely by the writing beam polarization. We quantify the locally induced strains, including small creeping losses, directly by means of a deformation tracking algorithm acting on microscope images of planar substrates. Further, we introduce free-standing 3D actuators able to smoothly undergo multiple configurational changes, including twisting, roll-in, grabbing-like actuation, and even continuous, pivot-less shape rotation, all dictated by a single wavelength laser beam with controlled polarization. Light-responsive polymers with polarization-dependent deformation are promising material to develop tunable devices usually limited by irreversible dynamic control. Here, the authors use controlled polarization of visible light to produce arbitrary deformations into amorphous composites containing azopolymer microdomains to unlock the next level of complex actuation in soft lightdriven robots.

Graphene is a two-dimensional (2D) material with a single atomic crystal structure of carbon that has the potential to create next-generation devices for photonic, optoelectronic, thermoelectric, sensing, wearable electronics, etc., owing to its excellent electron mobility, large surface-to-volume ratio, adjustable optics, and high mechanical strength. In contrast, owing to their light-induced conformations, fast response, photochemical stability, and surface-relief structures, azobenzene (AZO) polymers have been used as temperature sensors and photo-switchable molecules and are recognized as excellent candidates for a new generation of light-controllable molecular electronics. They can withstand trans-cis isomerization by conducting light irradiation or heating but have poor photon lifetime and energy density and are prone to agglomeration even at mild doping levels, reducing their optical sensitivity. Graphene derivatives, including graphene oxide (GO) and reduced graphene oxide (RGO), are an excellent platform that, combined with AZO-based polymers, could generate a new type of hybrid structure with interesting properties of ordered molecules. AZO derivatives may modify the energy density, optical responsiveness, and photon storage capacity, potentially preventing aggregation and strengthening the AZO complexes. They are potential candidates for sensors, photocatalysts, photodetectors, photocurrent switching, and other optical applications. This review aimed to provide an overview of the recent progress in graphene-related 2D materials (Gr2MS) and AZO polymer AZO-GO/RGO hybrid structures and their synthesis and applications. The review concludes with remarks based on the findings of this study.