State of the Art on Thin Films of Metals, Metalloids and Lanthanides and Their Binary Compounds Prepared by PLD and RPLD Techniques

Abstract

This article reviews the state of the art of laser ablation and deposition techniques applied so far to more than 50 elements, including metals, metalloids and lanthanides, yielding a wide variety of compounds in the form of thin films. Laser deposition processes have been performed in high-vacuum (HV) reactors at pressure values ranging between 10⁻¹ and 10⁻⁵ Pa, namely pulsed laser deposition (PLD), or, under different reactive gas ambient (O₂, N₂, CH₄, NH₃ and many others), so-called reactive pulsed laser deposition (RPLD), with the aim to form thin films with desirable chemical compositions. While a few metals have not been deposited as pure metallic films because they have no immediate technological interest, others, like alkali and alkaline earth metals, cannot be deposited in pure metallic form due to their very strong reactivity with oxygen, water vapor and hydrogen molecules which are always present, even in ultra-high-vacuum (UHV) systems, at pressure values of 10⁻⁵–10⁻¹⁰ Pa. Furthermore, elements of the Mendeleev periodic table with an atomic number higher than 88, such as actinides and synthetic elements, are dangerous to handle and deposit in the form of thin films due to their high radioactivity; therefore, they are excluded from this review. The inclusion of the non-metal thin films of carbon (C) and related chemical compounds prepared by PLD and RPLD in the present review is justified by the extensive research and the numerous scientific articles reported in the field. All the results obtained by PLD and RPLD techniques so far are discussed and presented in tabular format to guide the reader.

1. Introduction

Laser-ablation-based physical vapor deposition has evolved from an early demonstration of laser-assisted vacuum film growth to a mature thin-film synthesis route used across materials science, photonics, and micro/nanoelectronics [1,2,3,4]. The earliest widely cited report of laser-based vacuum thin-film deposition is the work of Smith and Turner (1965), who deposited thin films using a ruby laser [1]. Since then, pulsed laser deposition (PLD) and its reactive variant (RPLD) have evolved and become established methods for producing thin films from an exceptionally broad palette of solids, including metals, metalloids, lanthanides, and their compounds [2,3,4,5].

A key reason for the lasting impact of PLD is that it couples a highly localized, high-power-density energy source—the laser pulse—to a condensed-matter target, to generate an energetic, transient ablation plume that can deliver atoms, ions, clusters, and droplets to a facing substrate [2,3,4]. This highly non-equilibrium nature enables film growth under conditions unreachable by thermally equilibrated vapor sources. This virtue is particularly relevant for the growth of novel compounds and metastable phases, and materials requiring tight control of composition and microstructure [2,3,4,5]. At the same time, the plume energetics that make PLD so versatile yield persistent challenges, most notably the deposition of particulates/droplets and, depending on conditions, a limited throughput, issues that still constrain the industrial translation of such systems [6,7,8,9].

For metals, metalloids, and lanthanides, PLD/RPLD offers opportunities but sets constraints that are strongly dictated by physical chemistry. On the one hand, the method can deposit technologically relevant metallic films (e.g., transition and noble metals) and synthesize oxides/nitrides/carbides by introducing reactive gases (RPLD), thereby enabling tunable stoichiometry and new functional properties [10,11,12,13,14,15]. On the other hand, certain classes, especially highly reactive alkali and alkaline earth elements, are intrinsically difficult to deposit as pure metallic films because of the residual reactive species (e.g., H₂O, O₂, H₂) present even in ultra-high-vacuum environments [16]. In effect, the high kinetic energy (up to 200 eV) of ablated species further enhances such unintended reactions during their flight and upon incidence on the growth surface [16].

The present review focuses on thin films of metals, metalloids, lanthanides and their binary compounds produced by PLD and RPLD and organizes the available literature in a way intended to guide both newcomers and specialists [2,3,4,5]. However, beyond rendering prior reports, a central goal of this work is to associate the answers to “what has been deposited?” to the underlying “why can or can it not be deposited?” by emphasizing the ablation regimes, plume dynamics, gas-phase reactions and growth mechanisms that govern film formation [17,18,19,20,21,22,23]. This mechanistic framing is necessary to interpret trends across the periodic table (e.g., volatility, reflectivity, reactivity, oxidation thermodynamics) and identify actionable knowledge gaps and technical bottlenecks for future PLD/RPLD research on metallic, metalloids and lanthanide-containing films.

In the following section we summarize the PLD/RPLD process chain, in a physics- and chemistry-oriented manner, from laser radiation absorption in the target to material ejection, plume expansion, reactive chemistry and film growth. Highlighting the role of laser wavelength, intensity and pulse duration (ns/ps/fs), background pressure, and substrate conditions we aim to justify the nature of ablation products and ultimately the structure and composition of deposited films. This discussion provides the conceptual basis for the subsequent materials-focused sections and for critically analyzing the reasons why the literature focuses on specific element group compound families and laser sources.

2. PLD and RPLD: Physical Processes and Ablation Regimes

2.1. From Laser Pulse to Ablation Plume: Regimes and Thresholds

Figure 1 presents a schematic of a PLD/RPLD reactor system, incorporating all major required components. The laser beam is focused on target T and irradiates it with a usually short laser pulse to produce ablation of the target material. The process begins with the absorption of short laser pulse radiation in a shallow volume near the surface of the target. Depending on the optical and thermal properties of the target material, the laser wavelength and the pulse duration, extremely rapid heating and/or non-thermal excitation and dissociation of the target are produced. Above an effective laser radiation intensity, defined as the ‘ablation threshold’ and expressed in J/cm², material is ejected in the form of atoms, ions, nanoparticles/clusters, and, in many practical cases, micron-scale particulates and droplets produced by subsurface boiling, melt expulsion, shock-driven fracture, or other ejection pathways [24,25,26,27]. Because these ejection mechanisms depend critically on laser pulse duration and the energy coupling into the target, PLD is often discussed in terms of distinct ablation regimes, namely the contrasting nanosecond (ns) pulse and the ultrashort (ps/fs) pulse ablation regimes, where energy deposition can be much faster than any significant heat diffusion [28,29].

For metallic targets, optical reflectivity and absorption depth are major determinants of how efficiently radiation energy at a given wavelength couples into the target surface. This effect directly impacts on ablation efficiency, plasma temperature and the balance between smooth vaporization and melt-related particulate. This is one reason why many PLD studies preferentially use UV excimer wavelengths (e.g., 248 nm) and frequency-multiplied Nd:YAG harmonics, rather than long-wavelength infrared sources, especially for ablating highly reflective metals. Importantly, these wavelength and pulse-duration choices not only affect the quantity of ablated material, but they also shift the distribution of kinetic energies and charge states within the plume, thus altering surface mobility, defect creation, oxidation and reduction kinetics during growth [28,29,30].

2.2. Plume Expansion and Background-Gas Effects

After ejection, the ablated material expands away from the target as a transient plasma plume, typically with strong directionality and normally to the target surface, rapidly evolving in density, temperature and composition. In high vacuum, at typical PLD base pressures of 10⁻³–10⁻⁵ Pa, the plume undergoes a relatively collision-poor expansion, allowing energetic species to reach the substrate and promoting dense films even at modest substrate temperatures [2,3,29]. This, however, increases the probability that energetic impacts generate defects or resputter weakly bound adatoms. When a background gas is introduced, whether inert (e.g., Ar) or reactive (e.g., O₂, N₂, NH₃, CH₄), collisions broaden and slow down the plume, reduce the energy of ejected species, change arrival angles and significantly modify nucleation and growth modes [30,31,32,33].

This pressure-dependent plume thermalization has two direct consequences relevant to the present review [5,30,33]. First, it changes the competition between smooth film growth and particulate incorporation, because droplet trajectories, fragmentation, and sticking can be altered by collisional scattering [6,7,8,9]. Second, it controls reactive chemistry pathways in RPLD, where film composition is not simply transferred from a target but emerges from coupled processes (ablation stoichiometry, gas-phase reactions, surface reactions and possible preferential re-evaporation of volatile species).

2.3. Reactive PLD (RPLD): Chemistry and Stoichiometry Control

RPLD extends PLD by intentionally introducing a reactive ambient so that compound formation proceeds during plume flight and/or on the growth surface [2,5]. In practice, RPLD is frequently used to produce oxides, nitrides, carbides and related binary phases, by ablating metal (or compound) targets in reactive gases under controlled partial pressures, as presented in the tables and material sections of this manuscript [10,11,12,13,14,15]. In the RPLD experiments, the collision frequency and therefore the reaction probability strongly depend on the ambient gas pressure, which ranges between tenths and hundreds of Pa. At pressure values lower than tenths of Pa, the reaction probability in gas phase is too low; conversely, at pressures higher than hundreds of Pa, the collision frequency in the gas phase is so high that no material is deposited on the substrate.

The collision frequency (ν) between the ablated species and the reactive gas molecules is given by:

$$\mathrm{\nu }=\mathrm{n}\times \mathrm{\sigma }\times {\mathrm{v}}_{\mathrm{rel}}$$

where n is the ambient gas density, σ is the collision cross-section and v_rel is the relative velocity between the ablated material and the ambient gas molecules.

The above scaling law for collision frequency highlights why lanthanides require higher ambient pressures. Due to their large atomic mass, lanthanide species possess high momentum; therefore, a higher background gas density (n) is mandatory to achieve sufficient scattering events. This also prevents high-energy bombardment of the growing film which would otherwise compromise the stoichiometry and structural integrity.

The resulting film stoichiometry is therefore governed by a set of coupled chemical, thermodynamic and kinetic processes: the chemical reactivity of ablated species that are often highly energetic and partially ionized, the collision frequency in the gas phase and the ability of the growth surface to incorporate (or reject) reactive species under the selected substrate temperature and energy flux [28,29,30]. This coupling of mechanisms is especially important for the material families emphasized here, such as metals and lanthanides, because their oxidation and nitridation thermodynamics prevail. For metals the thermodynamic and kinetic models are dominated by kinetic energy of the ablated material, while for lanthanides and metalloids, the Gibbs free energy of formation (ΔG) plays the main role in determining whether the film maintains the desired phase or not. For example, many lanthanides exhibit high oxygen affinity (ΔG << 0) and thus, in the case of lanthanide oxides, this necessitates the fine-tuning of oxygen partial pressure to avoid over-oxidation or target poisoning during the RPLD experiments. In fact, even small changes in residual oxygen or water vapor can shift the film growth away from the desired metallic state. Consequently, the “success” of a reported RPLD recipe should be interpreted not only by nominal gas pressure, but also by (i) plume energetics determined by wavelength, pulse duration and fluence, (ii) chamber background gas composition and pumping dynamics, and (iii) surface kinetics such as oxygen vacancy formation, re-evaporation and diffusion-limited growth [30,33]. Concerning the morphology of the deposited films, it is well known that low laser fluences yield the lowest droplet density on the film surface, resulting in superior morphological quality. However, film crystallinity and compactness significantly improve at higher fluences. This is because an increase in laser fluence enhances the kinetic energy of the ablated species, thereby promoting the surface mobility of adatoms on the substrate and allowing them to reach thermodynamically stable lattice sites, i.e., better crystallinity [8]. The stoichiometry of the deposited films depends on the type and pressure of the ambient gas. In the specific case of nitride thin-film deposition, the nitrogen content depends primarily on the gas species (N₂ or NH₃) and the pressure within the deposition chamber. The higher the partial pressure of the ambient gas, the higher the nitrogen content in the deposited film.

2.4. Film Growth: Energetic Deposition, Microstructure, and Particulates

PLD and RPLD are high-energy deposition processes in which the energy of light is transferred to the material and ablates it in thermodynamic equilibrium. The ablated species impact on the substrate with kinetic energies substantially higher than those met in thermodynamically equilibrated processes. We underline that in this work alternative and competitive vapor deposition techniques, such as reactive magnetron sputtering, and thermal and electron-beam evaporation, are not discussed; however, relevant studies utilizing these methods are cited in the text where appropriate. In fact, a major difference is due to the high laser pulse intensity. Provided suitable conditions such as, for example, laser parameters, lattice matching, and chemical ambient are met, it can lead to a plurality of growth routes from single crystal epitaxy to amorphous metal or oxide compositions. However, such a high laser fluence values can cause resputtering, severely increasing defect density and producing film erosion. Such unwanted effects could be counterbalanced by controlling the ambient pressure and laser parameters, depending on the nature of the materials. For metals, this can influence grain size, texture, residual stress and electrical resistivity; for compounds, it can influence phase selection and oxygen (or nitrogen) vacancy concentrations and thus the functional properties of the grown film [31,32]. A persistent limitation is the presence of droplets/particulates, which can dominate surface roughness and limit device-quality films unless mitigated via plume filtering, geometry choice, target conditioning or suitable laser parameters [6,7,8,9]. The present manuscript examines materials along the periodic table with the aim to explicitly connect growth mechanisms to target classes [17,18,19,20,21,22,23]. In a paradigm, low-melting-point metals under ns irradiation are more prone to the formation of particulates by melt expulsion [6,7,24]. In contrast, ultrashort-pulse regimes suppress such melt-driven mechanisms but potentially introduce different nanoparticle formation routes [26,28,29]. Such trade-offs justify the increasing use of diagnostics and mitigation strategies aiming to control the entire process chain and optimize material growth.

2.5. Technology and Diagnostics

Table 1. Typical experimental conditions applied in PLD and RPLD.

Target–Substrate Distance	2–6 cm
Target Rotation	1–3 Hz
Substrate Temperature	300 K
Laser Spot Size	Around 1.0 mm2
Base Pressure in PLD Experiments	10−5–10−3 Pa
Reactive Gas Ambient Pressure in RPLD Experiments	In the range tenths-hundreds Pa
Total Number of Laser Pulses
Target Surface Cleaning	Thousands
Film Deposition	Tens of thousands
Laser Fluence	1–10 J/cm2 in ns regime a few J/cm2 in ps regime tenths of J/cm2 in fs regime
Laser Repetition Rate	5–10 Hz
Film Thickness	0.01–1 μm
Film Diameter	5–10 mm

presents a set of typical experimental conditions and laser parameters used in the growth of thin films by PLD and RPLD techniques. A recurring theme in modern PLD/RPLD is the move toward more quantitative, feedback-informed control using in situ or time-resolved diagnostics that associate plume properties to grown film qualities [28,29,30,31,32]. Even though the present manuscript already lists common ex situ characterization tools and typical experimental ranges (e.g., target–substrate distance, base pressure, fluence ranges for ns/ps/fs, and commonly used lasers) as shown in Table 1, a key trend is the ability to, in a reproducible way, correlate the plume composition/energetics with the stoichiometry and microstructure of the grown material [28,29,30,31,32,33]. This is particularly relevant for reactive systems (oxides/nitrides/carbides) and for chemically sensitive metallic targets (e.g., reactive light metals and lanthanides), where minor uncontrolled variations in, for example, background gas chemistry can govern the oxidation reactions and determine the final phase of the produced material.

3. Metals, Metalloids and Lanthanides Ablated and Deposited by PLD and RPLD Techniques

Laser ablation and deposition techniques have been applied to more than 50 elements (metals, metalloids and lanthanides) to successfully prepare thin films and a wide variety of binary compounds. Laser deposition can be carried out in high vacuum (PLD) or under a reactive gas ambient (RPLD) such as ${\mathrm{O}}_2$, ${\mathrm{N}}_2$, ${\mathrm{C}\mathrm{H}}_4$, and ${\mathrm{N}\mathrm{H}}_3$, with the aim of forming thin films with the desirable chemical composition and functional properties. In several cases, deposition of the pure metallic element is not reported because either (i) it has limited technological interest in thin-film form or (ii) it is intrinsically difficult to stabilize as a metal due to strong reactivity with oxygen, water and hydrogen-containing residual gases that are present even in UHV systems. This limitation is particularly severe for alkali metals and some alkaline earth metals, whose intrinsic reactivity can be further enhanced by the high kinetic energy of ablated species typically found in PLD/RPLD plumes [16].

This study categorizes the elements into property-driven groups organized in reference to their reactivity/volatility, tendency to oxidization or other reactions, compound families and practical feasibility of PLD vs. RPLD. In text, the notation ${\mathrm{A}\mathrm{B}}_x$ indicates that the chemical element A can exhibit multiple oxidation or other reaction states when bonded with the chemical element B. Literature reports concerning deposition conditions, material properties and applications are summarized in tabular form. In this work we discuss why certain targets/compounds dominate the PLD/RPLD literature and where key limitations arise. In cases where PLD/RPLD reports are absent, available alternative deposition methods are cited; in addition, we distinguish a lack of feasibility from a lack of application-driven interest, aiming to underline the current exploitation potential of each material.

3.1. Highly Reactive S-Block Metals and Early-Period Reactive Elements (Alkali + Alkaline Earth)

This group is characterized by a strong affinity for oxygen- and/or hydrogen-containing species and, for alkali metals, also by high volatility; consequently, many studies target stable compounds (oxides, halides, phosphates) or rely on alternative deposition methods rather than direct PLD of the pure metal. When PLD/RPLD is used successfully, the reactive gas ambient, or the unavoidable residual gases, often become the dominant factor controlling the metallic or compound nature of the deposited layer.

Lithium (Li): Lithium is a highly reactive alkali metal group 1A with oxidation state +1. Although it is the least reactive alkali metal, a pure Li thin film has not been obtained successfully using PLD. In practice, this shifts attention toward Li thin-film compounds, such as lithium oxide Li₂O [34,35] and lithium chloride LiCl [36], typically prepared by deposition techniques other than PLD. From a PLD/RPLD point of view, Li is a representative case where the limitation is not targeting ablation itself, but preservation of a metallic phase against rapid reaction with residual gases during plume transport and on-surface growth.

Sodium (Na): Sodium, like the other alkali metals Li, K, Rb, Cs and Fr, has high chemical reactivity with residual gas in vacuum deposition systems. This is particularly critical in laser ablation/deposition, and therefore Na has never been prepared by PLD as a thin film. Sodium thin films have instead been achieved by other competitive deposition methods [37]. Na illustrates a general reactive-metal barrier for PLD energetic species and unavoidable background chemistry can dominate film composition even when the intended target is the elemental metal.

Potassium (K): Potassium cannot be grown as a pure thin film using PLD or other physical vapor deposition techniques because of its extremely high chemical reactivity and volatility. Even under UHV conditions of 10⁻⁵–10⁻¹⁰ Pa, energetic ablated material atoms, excited atoms, and ions form oxides and hydrides both during flight from target to substrate and on the substrate surface. In the PLD/RPLD framework, K emphasizes that vacuum level alone is not a sufficient descriptor for chemically active systems, because trace species can control the final material phase.

Rubidium (Rb): Rubidium belongs to the alkali metals and is highly reactive; therefore, it cannot be deposited as a pure metallic thin film by laser ablation of a bulk Rb target. Rubidium thin films have been obtained by other physical deposition processes [38,39]. Reported interest in Rb thin films is linked to its optical, photoelectric and electronic properties relevant to photocathodes, optical devices and magnetometers. Rb further supports the trend that for alkali metals, compound stabilization and/or non-PLD routes dominate the thin-film literature.

Cesium (Cs): Cesium is the most reactive alkali metal and reacts violently with water and oxygen. Its oxidation state is +1. Despite this reactivity, studies exist on electrical properties of pure Cs ultra-thin layers [40] and cesium oxide Cs₂O thin films grown by alternative deposition techniques [41]. Several studies also address cesium halides, e.g., CsCl in cancer-related diagnosis/treatment contexts and CsI as a sensing material in scintillation detectors for ionizing radiation monitoring [42,43,44,45]. Of PLD/RPLD relevance, Cs highlights how for the most reactive alkalis technological interest is often realized through stable compound films rather than the elemental metal.

Francium (Fr): Francium is a rare, highly reactive and radioactive alkali element with oxidation state +1 and no practical applications in bulk or thin-film form; accordingly, the thin-film literature essentially does not include Fr and its binary compounds. This element marks the combined limit of reactivity and radioactivity where PLD/RPLD thin-film studies are not realistically accessible.

Beryllium (Be): Beryllium is an alkaline earth metal group IIA whose surface forms a 1–10 nm thick oxide layer even at room temperature. For this reason, deposition of pure Be thin films is typically performed by evaporation and sputtering rather than PLD, where ablated atoms/ions are energetic and can be highly reactive [46,47]. The continuing interest in Be is related to its superconducting properties. From a PLD/RPLD standpoint, Be shows how a readily formed native oxide can steer the community away from PLD for the elemental film even when bulk properties are attractive.

Magnesium (Mg): Magnesium is a lightweight alkaline earth metal, among the most reactive in its group, with common oxidation state +2. Mg and Mg-based compounds have important applications due to its lightweight character, mechanical properties and biocompatibility [48,49]. Mg thin films have been used as photocathodes in RF guns because of their reported quantum efficiency of ${1.8\times 10}^{-3}$ and relatively low work function of 3.6 eV [50,51]. MgO thin layers have been grown by laser ablation of a Mg target in an O₂ atmosphere [52]. In this review, Mg represents an instructive intermediate case where PLD of the pure metal is feasible for targeted applications, while RPLD enables controlled conversion into a stable oxide when that is the functional requirement.

Calcium (Ca): Calcium is a highly reactive alkaline earth metal and while it has not been widely deposited as a pure thin film, there is extensive research on thin films of its chemical compounds. In particular, calcium phosphate CaP [53] and hydroxyapatite HA thin films [54,55] are major targets in biomaterials. Ca illustrates the broader trend for oxygen-affine metals, where PLD/RPLD research advances through compound film growth chosen for stable chemistry and application pull rather than through elemental-metal films.

Strontium (Sr): Strontium is highly chemically reactive like other alkaline earth metals, and its deposition as a pure thin film is described as practically impossible and of limited commercial interest. In contrast, Sr-based compounds, such as strontium oxide SrO, are in demand for industrial applications in microelectronic devices, as buffer layers and phosphor materials [56,57]. In laser ablation terms, Sr follows the same pattern observed for Ca, since stable binary compounds dominate because they better match both chemical feasibility and device-driven needs.

Barium (Ba): Barium is a highly reactive alkaline earth metal, making it very difficult to obtain pure layers. Ba has not been prepared as a thin layer using any deposition technique. Its common oxidation state is +2, and it reacts strongly with oxygen to form BaO [58,59]. Another important Ba compound is barium dichloride BaCl₂, with applications in wastewater treatment [60,61]. Within the theme of this review [5,30,33], Ba represents the practical-end member where elemental thin films are essentially inaccessible, and thus thin-film science and applications must proceed through stable compound chemistry.

3.2. Metalloids and Carbon: Semiconductors and Bonding-Driven Materials (B, C, Si, Ge, As, Se, Sb, Te)

This group is strongly represented in the PLD/RPLD literature because (i) these are core elements in semiconductor, optical and sensing technologies and (ii) reactive backgrounds (${\mathrm{O}}_2$, ${\mathrm{N}}_2$, $\mathrm{C}{\mathrm{H}}_4$, $\mathrm{N}{\mathrm{H}}_3$) allow direct steering toward technologically important binary compounds (oxides, nitrides, carbides) without changing the target stoichiometry by chemical synthesis. Compared with highly reactive alkali metals, these elements more often allow stable deposition either as the elemental film or as a controlled compound, making them useful reference systems for connecting ablation/plume conditions to phase formation.

Boron (B): Boron is the lightest among the metalloids (Si, Ge, As, Sb, Te, Po, At). Boron thin layers have been grown by PLD under various experimental conditions [62,63] and are used as neutron detector material due to their high reaction cross-section for thermal neutron beams. Boron nitride BN has been synthesized by laser ablation of a B target in nitrogen atmosphere [64,65], showing a direct route to nitride formation through reactive deposition.

Carbon (C): There is a vast body of literature on laser ablation/deposition of carbon and carbon-based compounds such as carbon nitrides ($\mathrm{C}{\mathrm{N}}_{\mathrm{x}}$), which justifies inclusion of this non-metal element in the present review [66,67,68,69,70]. Thin layers of C, $\mathrm{C}{\mathrm{N}}_{\mathrm{x}}$ and diamond-like carbon (DLC) are notable for high hardness, chemical inertness, a low friction coefficient and optical/semiconducting properties [71,72,73,74,75]. Graphene layers have also been deposited by laser ablation of a carbon target, highlighting that PLD can access distinct carbon bonding/phases depending on the conditions [76].

Silicon (Si): PLD and RPLD thin films of silicon and its binary compounds are key materials in high-technology semiconductor devices [77,78,79]. Silicon-based compounds such as $\mathrm{S}\mathrm{i}{\mathrm{O}}_2$, SiC and SiN, synthesized by laser ablation of Si in ${\mathrm{O}}_2$, $\mathrm{C}{\mathrm{H}}_4$, ${\mathrm{N}}_2$ and $\mathrm{N}{\mathrm{H}}_3$ atmospheres, have applications in numerous fields [80,81,82,83,84,85,86]. This element/compound set is a clear example where reactive environments provide a practical chemistry knob to tune film composition and functionality (insulating $\mathrm{S}\mathrm{i}{\mathrm{O}}_2$, robust SiC, dielectric SiN) from a single elemental target [80,81,82,83,84,85,86].

Germanium (Ge): Germanium is a metalloid semiconductor with properties similar to silicon. Ge thin films and Ge-based compounds such as $\mathrm{G}\mathrm{e}{\mathrm{O}}_2$ and $\mathrm{G}\mathrm{e}{\mathrm{N}}_{\mathrm{x}}$ have been deposited using PLD and RPLD techniques [87,88,89,90]. Because of its transparency to infrared radiation and high refractive index, Ge thin films are suited for electronics, infrared optics and fiber optics [87,88,89,90].

Arsenic (As): Arsenic is a strongly toxic metalloid. It has not been prepared as a pure thin coating due to high vapor pressure, tendency to oxidize and toxicity inhibiting commercial applications. Despite this, as remains technologically important in semiconductor technology through III–V compounds (e.g., GaAs) [91].

Selenium (Se): Selenium is sometimes considered a metalloid due to its intermediate chemical/physical properties, and it is treated here as a metalloid element. Se thin films have been deposited by laser ablation of a pure bulk Se target in a high-vacuum system [92,93,94]. Its main reported properties include tunable band gap and high refractive index, supporting optical-device and sensor applications.

Antimony (Sb): Antimony is a toxic metalloid with common oxidation state +5. Ultra-thin Sb films have been deposited via PLD, and there is substantial literature on Sb-based binary compounds, including antimony selenide ($\mathrm{S}{\mathrm{b}}_2\mathrm{S}{\mathrm{e}}_3$), antimony sulfide ($\mathrm{S}{\mathrm{b}}_2{\mathrm{S}}_3$) and antimony oxides ($\mathrm{S}\mathrm{b}{\mathrm{O}}_{\mathrm{x}}$), prepared by PLD and other deposition techniques [95,96,97,98,99,100]. These compounds are studied for applications relating to solar cells, hydrogen storage and memory devices.

Tellurium (Te): Tellurium is a metalloid with chemical properties similar to selenium and sulfur. Pure Te thin layers have been grown by laser ablation of a Te target in a high-vacuum system [101]. Important Te-related thin-film materials include CdTe (deposited by PLD) and tellurium oxides ($\mathrm{T}\mathrm{e}{\mathrm{O}}_{\mathrm{x}}$) generally prepared by other deposition methods, with applications spanning optoelectronics, solar cells, nanosensors, LEDs, photocatalysis, and imaging [102,103,104,105].

3.3. First-Row Transition Metals: Metallic Films vs. Functional Oxides/Nitrides (Sc–Zn)

This group is central to PLD/RPLD because many elements form multiple stable oxidation states and technologically important oxides, nitrides and carbides, where reactive-gas control (especially O₂ and N₂) often determines whether the deposited film is metallic or compound. In practice, the literature frequently emphasizes compound films when the elemental metal has limited thin-film demand (or is difficult to stabilize), while metals are targeted when conductivity, magnetism, superconductivity, photocathode performance or corrosion resistance is the primary driver.

Scandium (Sc): Scandium is the first transition element in the group B. There is no literature on deposition of Sc thin films, either by PLD or other deposition techniques, most likely because of the absence of immediate technological applications. The main binary compound is scandium sesquioxide (Sc₂O₃), prepared as thin films by laser ablation of an Sc₂O₃ bulk target under low oxygen pressure [106].

Titanium (Ti): Several research groups have published on Ti thin films and titanium-based compounds deposited by PLD and RPLD [107,108,109,110,111,112,113]. Key examples are titanium nitride (TiN), titanium carbide (TiC) and titanium dioxide (TiO₂), that have been grown by laser ablation of a Ti target in reactive gas atmospheres. These materials support applications spanning protective coatings, optical coatings, biocompatibility, microelectronics, gas sensing and solar cells.

Vanadium (V): Vanadium thin films have not attracted strong interest, whereas vanadium-based compounds are widely studied. In particular, vanadium oxides (VO_x) and vanadium nitride (VN) have been grown by PLD and RPLD [114,115,116,117,118]. Many other deposition techniques are also used for vanadium compounds [119,120,121], with functional performances typically linked to compound phase and stoichiometry rather than the elemental nature.

Chromium (Cr): Chromium is a hard transition metal. Deposition of pure Cr thin films has been achieved by various methods though not frequently by PLD [122,123,124]. Chromium oxides (CrO_x) have the extensive thin-film literature on different deposition techniques [125,126,127]. Reported applications for CrO span protective coatings, solar energy, electronics/spintronics, gas sensors and biomaterials.

Manganese (Mn): While pure manganese is not commonly prepared as a thin film, manganese oxides (MnO_x) are deposited by RPLD and by several other techniques [128,129,130]. These oxides are discussed for medical and sensor-related applications. This is a typical example where reactive deposition targets functional oxide chemistry rather than the elemental metal film.

Iron (Fe): Iron has not been deposited using PLD in the surveyed literature, while many papers report pure Fe thin films grown by alternative deposition techniques [131,132,133]. The most important Fe-containing thin-film materials are iron oxides (FeO_x) [134,135,136]. FeO_x have also been synthesized by RPLD [137,138]. Magnetic and electrical devices are indicated as key application areas for FeO_x thin films.

Cobalt (Co): Cobalt thin layers have been achieved by PLD (reported first in 2008) [139], and Co films have also been deposited by methods such as MOCVD and ALD [140,141]. Reported applications include giant magnetoresistance devices, MOSFETs, magneto-optic recording media, and spintronic devices. Cobalt oxide (CoO_x) thin films have been prepared by laser ablation of a Co target at low O₂ pressure [142].

Nickel (Ni): Nickel thin layers have been deposited using PLD [143,144] and other alternative techniques [145,146]. NiO thin films have been widely deposited by laser ablation of a nickel target in oxygen atmosphere [147,148,149], as well as by other deposition methods [150,151]. The balance between metallic Ni (conductive/ferromagnetic) and NiO (functional oxide with distinct electrical/chemical behavior) is representative of how oxygen availability can flip the dominant phase and application space in PLD/RPLD studies.

Copper (Cu): Cu thin films were grown by different techniques and have important applications as photocathodes in RF cavities due to good photo-emissive and physical properties [152,153,154,155,156,157,158]. A large body of thin-film research also targets copper oxides (CuO_x) because of their high optical absorption coefficient [159,160,161,162,163,164,165]. Cu is therefore a clear “metal vs. oxide” split-case where the thin-film objective (conductive metal vs. absorbing oxide) largely decides between PLD (metal) or RPLD/oxygen-assisted oxide growth.

Zinc (Zn): Zinc commonly exhibits oxidation state +2 in binary compounds. Technologically important Zn compounds include ZnO, ZnS, ZnSe and ZnTe, but among these only ZnO thin films are reported as deposited by RPLD in the compiled literature [166,167,168]. The remaining Zn-based binary compounds are typically grown by other physical deposition processes [169,170,171,172,173,174] and are used in optoelectronics (semiconductors, solar cells), catalysis and bio/medical contexts.

3.4. Post-Transition Metals: Low Melting Points, Oxides and Transparent Conductors (Ga–Bi)

This group is marked by comparatively low melting point elements, frequent oxide formation and strong application pull in optoelectronics and sensing, so the thin-film literature often emphasizes compound films (notably oxides, sulfides, halides) and established device-relevant stacks rather than pure-metal PLD as an end goal. In PLD/RPLD processes, the reactive ambient and stoichiometry control are typically the key levers for obtaining functional phases (e.g., GaN/Ga₂O₃, CdO, In₂O₃, SnO₂, PbO_x, Bi₂O₃).

Gallium (Ga): Gallium is solid at room temperature but becomes liquid slightly above it (melting point ~30 °C), and deposition of pure Ga thin films has not been obtained. In contrast, Ga-based binary compounds such as gallium nitride (GaN) [175,176,177] and gallium sesquioxide (Ga₂O₃) [178,179,180] have been obtained (mainly by deposition methods other than PLD for many reports), reflecting that Ga thin-film relevance is primarily tied to compound semiconductors for optoelectronics and power devices rather than metallic Ga layers.

Indium (In): Indium is a rare post-transition metal with low oxidizing power. The literature on pure In films deposited by PLD is limited and attributed here to its low commercial interest [181]. Its main oxidation state is + 3. Much stronger emphasis is placed on indium sesquioxide (In₂O₃) deposited by RPLD [182,183] and on indium tin oxide (ITO) thin films produced by various deposition techniques [184,185], consistent with the role of these oxides as transparent conducting materials in optoelectronics and solar cells.

Tin (Sn): Tin is a post-transition metal with oxidation states +2 and +4, and the literature focus is on its oxide compounds rather than on pure Sn thin films. The most studied Sn-based thin-film materials include SnO₂ (by PLD and RPLD) [186,187,188], ITO [189,190], and alloys such as Al-Sn [191,192] and Cu-Sn [193,194]. This element is therefore representative of systems where functional performance is mainly engineered through oxide chemistry and alloying, rather than by depositing the elemental metal alone.

Thallium (Tl): Thallium is a post-transition metal with oxidation states +1 and +3 and has limited scientific/commercial interest in thin-film form. Reported thin-film studies emphasize Tl binary compounds such as thallium sulfides (TlS_x) [195,196] and thallium oxides (TlO_x) [197,198], rather than pure Tl films.

Lead (Pb): Lead is a post-transition metal (oxidation states +2 and +4) with extensive literature on pure Pb thin films grown by PLD and cathodic arc techniques [199,200], as well as on key Pb binary compounds. Important Pb compounds discussed include lead oxides (PbO_x) [201,202], lead sulfide (PbS) [203,204], and lead bihalides (PbX₂, X = halogen) [205,206].

Bismuth (Bi): Bismuth is described as a strongly diamagnetic metalloid with very low thermal conductivity and high electrical resistivity, properties exploited in electronic devices and pharmaceutical-related applications. Many papers report growth of pure Bi thin layers by laser ablation of Bi targets [207,208,209], and Bi₂O₃ is identified as the main Bi compound grown by both PLD and RPLD [210,211]. Bi thus provides a clear metal vs. oxide pair inside the same element, where oxygen availability and targeted functionality determine whether PLD (metal) or RPLD/oxidizing conditions (oxide) dominate.

3.5. Refractory and Noble Transition Metals: Photocathodes, Corrosion Resistance, Catalysis and High-Temperature Coatings (Y–Hg)

This subgroup is dominated by elements used in demanding environments (high temperature, high corrosion, high wear) and in advanced electronic/energy technologies, so the literature often separates into (i) pure-metal films grown in high vacuum (when conductivity, catalytic activity, or photoemission is desired) and (ii) oxide/nitride/carbide films grown in reactive atmospheres to access stable functional phases. Compared with the first-row transition elements, many late 4d/5d metals are chemically inert, so reports on their binary compounds via RPLD can be scarce, while refractory metals show extensive compound families (oxides, nitrides, carbides, sulfides) because those phases carry most of the functionality.

Yttrium (Y): Yttrium is considered a rare-earth element despite being a transition metal, with common oxidation state +3, and its most important inorganic compound is yttrium sesquioxide (Y₂O₃). Y thin films have been studied for photoemission, with low work function (~3.1 eV) and relatively high quantum efficiency (~3.3 × 10⁻⁴), and Y films have been obtained by laser ablation of bulk Y in high-vacuum systems. Y₂O₃ thin films have been built by laser ablation of Y in oxygen atmosphere, and the principal applications of yttrium oxide are in solid-state lighting, displays, lasers and scintillators [212,213,214,215,216,217].

Zirconium (Zr): Zirconium is a transition metal with oxidation state +4. Zr thin films have been synthesized by laser ablation of Zr bulk targets using high-vacuum systems [218,219]. This review highlights biomedical relevance (e.g., dental implants) and it also stresses the technological importance of Zr-based compounds such as ZrO₂, ZrN and ZrC. These compound families are frequently emphasized because they provide chemically inert, biocompatible and refractory coatings where the elemental film is not always the optimal endpoint [220,221,222,223,224].

Niobium (Nb): Niobium is a valuable transition metal with notable superconductive properties and is described as having the highest superconducting transition temperature among pure metals. Nb thin films have been deposited by laser ablation of Nb in high-vacuum systems [225,226,227], with a key application being photocathodes in superconducting radio-frequency (SRF) cavities. The most important Nb-based binary compounds discussed are NbO_x, NbN and NbC, reflecting how oxide/nitride/carbide chemistry expands the accessible property set beyond the elemental film [228,229,230,231,232].

Molybdenum (Mo): Molybdenum is a heavy transition metal with many oxidation states, most commonly +4 and +6 in MoO₂/MoO₃, and it also forms sulfides (MoS_x) and nitrides (e.g., MoN). PLD has been applied to deposit pure Mo thin layers [233,234], while RPLD is reported for MoO_x, MoS_x, and MoN_x films grown in O₂, H₂S and N₂ atmospheres, respectively. This spread of phases underlines why Mo is frequently treated as a refractory platform element where reactive ambient selection directly maps to functional film families [235,236,237,238,239,240].

Technetium (Tc): Technetium is a radioactive transition metal used in nuclear medicine and cancer diagnostics applications. Tc has not been prepared as a pure thin coating because of radioactivity and only a few studies are reported on Tc₂O₇ thin films [241,242].

Ruthenium (Ru): Ruthenium is chemically stable and capable of multiple oxidation states, with RuO₄ and RuO₂ among the most studied Ru-based compounds. Pure Ru thin-films have been deposited by laser ablation of a Ru target in a high-vacuum system [243,244]. Ru oxide thin films are also widely studied in the frame of various techniques including laser ablation of RuO_x targets in O₂ atmosphere [245]. This combination (metal film + conductive/stable oxide) explains Ru’s recurring role in electrical-contact and device-related thin film research in the compiled literature [246,247,248].

Rhodium (Rh): Rh is a noble, low-reactivity transition metal (group 9) described as extremely rare and expensive. Pure Rh thin films have been prepared by laser ablation of a Rh target in high-vacuum systems [249,250], and its high hardness, corrosion resistance and catalytic activity motivate applications such as protective coatings and jewelry decoration. There are no literature reports on Rh-based compound thin films prepared via PLD/RPLD.

Palladium (Pd): Palladium is presented as similar to platinum, with a key and distinguishing property being its capability to absorb large amounts of hydrogen. Several research groups have deposited and studied Pd thin films using PLD [251,252,253], but there is no evidence of PLD/RPLD experiments achieving binary Pd compounds.

Silver (Ag): Silver is a low-reactivity metal with very high electrical and thermal conductivity and high reflectivity in the visible region. PLD experiments have achieved pure Ag films [254,255,256,257,258], and Ag-based compounds such as silver oxides (AgO_x) have also been grown by RPLD. This metal/oxide split supports applications ranging from reflective and conductive coatings to the oxide-enabled functionalities described in the tables.

Cadmium (Cd): Cadmium is similar to zinc and commonly shows oxidation state +2; it is used in nuclear contexts due to its high neutron absorption cross-section. Pure Cd thin films have not been deposited by PLD, while CdO thin films have been grown using RPLD and spray pyrolysis [259,260], with interest driven by its tunable band gap, photoconductivity and chemical stability for devices such as photodetectors and display/solar-related components.

Hafnium (Hf): Hafnium is described as corrosion-resistant with a high melting point and a good thermal neutron absorption cross-section. The most important Hf-based binary compounds highlighted are HfO₂, HfC and HfN, with HfC specifically noted for an extremely high melting point and value in aerospace applications such as hypersonic vehicles [261,262,263,264].

Tantalum (Ta): Tantalum is a refractory transition metal with high melting point and notable hardness. Ta thin films prepared by PLD have been studied by different groups [265,266]. Its main binary compounds listed include Ta₂O₅, TaN_x, TaC and TaS₂, prepared by different deposition techniques [267,268,269,270,271,272,273,274]. This element is therefore treated largely through its compound set when targeting dielectric, barrier, or high-temperature coating functionality.

Tungsten (W): Tungsten is described as one of the hardest elements and the metal with the highest melting point, as well as high electrical and thermal conductivity that motivates its use in electrodes, heating elements and field electron emitters. There is a rich body of PLD literature on W thin films [275,276], and major compound families include WO_x, WN_x and WC_x [277,278,279,280,281,282,283,284]. The manuscript also emphasizes tungsten-based binary alloys for radiation absorption, strength/hardness, wear/corrosion resistance, and strong thermal/electrical conductivity, supporting aerospace parts, cutting tools and radiation shielding.

Rhenium (Re): Rhenium is a heavy transition metal, and its main binary compounds reported include ReN_x, ReS₂ and ReB₂, prepared via PLD/RPLD and other techniques [285,286,287,288,289]. Like tungsten, it is used in super alloys and superconductors, with well-known super alloys including W–Re and Mo–Re systems used for jet engines because of wear and corrosion resistance [290,291,292,293].

Osmium (Os): Osmium is described as hard, very dense, and with a high melting point, with wear and corrosion resistance as key mechanical properties. Os thin films have been grown by laser ablation in high vacuum and also by hollow cathode plasma CVD, with principal applications in electrical contacts and heat-resistant alloys [294,295]. OsO₂ and OsB₂ thin films prepared by alternative deposition methods rather than PLD/RPLD are reported [296,297].

Iridium (Ir): Iridium is highlighted for the highest chemical corrosion resistance and very high melting point, supporting uses such as high-temperature apparatuses, OLED devices and crucibles. There is extensive literature on Ir thin films grown by laser ablation [298,299,300], and IrO₂ is identified as the main binary compound [301,302]. IrO₂ is emphasized for its high chemical/thermal stability, high electrical conductivity and good electrochemical properties, enabling applications such as fuel cells, water electrolysis and sensors.

Platinum (Pt): Platinum (group 10) is discussed as corrosion-resistant and chemically inert, often classed as a noble metal. Many deposition techniques have been used for pure Pt thin films, while the literature on Pt binary compounds is described as very scarce due to Pt’s high chemical inertness [303,304,305].

Gold (Au): Gold is described as the most noble transition metal exhibiting very low reactivity, close to platinum. Pure Au thin films have been grown by several groups using different deposition techniques [306,307,308,309,310], while AuO_x can be grown only in highly reactive environments (e.g., RPLD) or in selective oxidation experiments due to its excellent chemical stability [311,312].

Mercury (Hg): Mercury is the only metallic element that is liquid under standard conditions and is used in instruments such as thermometers, barometers and fluorescent lamps; it readily forms amalgams with many metals. A pure Hg thin film has not been successfully grown by PLD, but Hg thin films [313,314] and several Hg binary compounds have been grown using alternative deposition techniques [315,316,317,318,319,320]. This is a practical example where physical state and handling constraints strongly limit PLD applicability, even though thin films might be scientifically interesting.

3.6. Lanthanides: Oxide-Dominated Thin Films and Reactivity/Cost Constraints (La–Lu)

Lanthanides are strategically important for optics, lighting, catalysis, high-$k$ dielectrics and related technologies, but pure metallic lanthanide films are difficult because of high cost and strong reactivity with oxygen-containing molecules (O₂, ${\mathrm{H}}_2$O) that remain present even in UHV systems. As a result, the lanthanide portion of the PLD/RPLD literature is largely compound-led, with oxides being the most frequently targeted phases and oxygen pressure acting as a practical control knob to approach nominal stoichiometry.

Lanthanum (La): La is the first lanthanide and is among the most reactive of the series, typically with oxidation state +3. The manuscript notes that pure La thin films have never been deposited, while La₂O₃ and LaS thin films have been grown by PLD/RPLD [321,322,323]. La₂O₃ (RPLD in ${\mathrm{O}}_2$) is associated with a high dielectric constant, high melting point and wide band gap for applications such as ${\mathrm{N}\mathrm{O}}_x$ gas sensors, optical glasses and ceramics, whereas LaS (PLD in UHV) is linked to low work function/low resistivity for field emission and display devices.

Cerium (Ce): Ce exhibits oxidation states +3 and +4 and is highly reactive, readily forming ${\mathrm{C}\mathrm{e}\mathrm{O}}_2$. ${\mathrm{C}\mathrm{e}\mathrm{O}}_2$ thin films can be prepared by laser ablation in UHV, and also under low-pressure oxygen to compensate oxygen depletion, which is a common issue when ablating oxides in vacuum. The interest in ${\mathrm{C}\mathrm{e}\mathrm{O}}_2$ is tied to high thermal stability, chemical inertness, oxygen storage capacity and high refractive index, supporting applications in glass manufacturing, automotive industry and catalysis [324,325,326].

Praseodymium (Pr): Pr commonly exhibits oxidation state +3 (also +4). Its very high cost limits availability and publication volume for several elements. The main investigated Pr compounds are praseodymium oxides (${\mathrm{P}\mathrm{r}\mathrm{O}}_x$), which are noted for chemical stability and favorable electrical/thermal conductivity and magnetic susceptibility. Applications highlighted include optical fiber systems, high-power magnets and glass coloration technologies [327,328].

Neodymium (Nd): Nd is primarily +3, but can also show +2 and +4 in some compounds. Nd₂O₃ is described as a metal-oxide semiconductor (MOS) and is presented as the most investigated Nd-based thin-film compound, deposited by laser ablation of Nd targets in Ar/${\mathrm{O}}_2$ atmospheres. Reported application areas include solid-state lasers, fiber lasers, color sunglasses and catalysts [329].

Promethium (Pm): Pm is radioactive and practically absent in nature, and the manuscript states that chemical/physical investigations (including thin films) are rare due to the high cost, radioactivity and scarcity. This is one of the clearest examples in Section 3 where safety/supply constraints, rather than PLD/RPLD capability, dominate the literature landscape [330].

Samarium (Sm): Sm is reported with oxidation state +3, and this review highlights photocathode-relevant parameters (low work function and high quantum efficiency) while also noting nuclear-industry relevance via a high thermal-neutron reaction cross-section. The most studied Sm compound in PLD is ${\mathrm{S}\mathrm{m}}_2{\mathrm{O}}_3$, emphasized for high resistivity, a high dielectric constant and large band gap. Applications listed include electronics, nuclear industry and glass manufacturing [331,332,333].

Europium (Eu): Eu is among the more reactive lanthanides and shows oxidation states +2 and +3. The manuscript focuses on Eu oxide thin films (${\mathrm{E}\mathrm{u}\mathrm{O}}_{\mathrm{x}}$, including ${\mathrm{E}\mathrm{u}}_2{\mathrm{O}}_3$) prepared by PLD, highlighting high melting point, thermal resistance and strong fluorescence. Applications include lighting/displays, nuclear industry and ceramics [334,335].

Gadolinium (Gd): Gd is a lanthanide with oxidation state +3 and has multiple radioactive isotopes. The manuscript points to biomedical relevance of Gd isotopes (contrast-agent use is cited) as a main motivation for interest in Gd-containing materials. In thin-film contexts, Gd is also discussed for its use as a dopant in functional materials rather than as a pure-metal film target [336].

Terbium (Tb): Tb is not found in nature as a free element and is often used as a dopant in thin-film materials for photonics and biosensing. Tb is reported with oxidation state +3 (also +4), and terbium oxides (${\mathrm{T}\mathrm{b}\mathrm{O}}_{\mathrm{x}}$) are linked to fluorescent lamps, television and cathode-ray tubes [337,338,339].

Dysprosium (Dy): The literature on pure Dy metallic films is lacking as for most lanthanides, while Dy is frequently used as a dopant in various thin-film systems. Reported Dy compound families include ${\mathrm{D}\mathrm{y}}_2{\mathrm{O}}_3$ and Dy halides (${\mathrm{D}\mathrm{y}\mathrm{X}}_3$), with oxides valued for their thermal/chemical stability, high dielectric constant and wide band gap, and halides for their magnetic devices, solid-state lasers and medical-sector uses [340,341,342,343,344].

Holmium (Ho): Ho is described as one of the most reactive lanthanides and as having the highest magnetic permeability among elements, forming Ho₂O₃ and Ho halides readily. This paper emphasizes Ho₂O₃ thin-film studies for lasers, ceramics and nuclear reactors, while noting that lanthanide halogen compounds are comparatively neglected in the thin-film literature, likely due to limited commercial interest [345,346].

Erbium (Er): Er is described with oxidation state +3 and the manuscript affirms it does not exist as a pure metal but rather as compounds (e.g., oxides/halides). ${\mathrm{E}\mathrm{r}}_2{\mathrm{O}}_3$ thin films (PLD and magnetron sputtering) are highlighted for their chemical/thermal stability, high dielectric constant and wide band gap, with applications including gate dielectrics, lasers and fiber-lasers, electronics and display monitors [347,348,349,350].

Thulium (Tm): Tm is listed with oxidation state +3 and is known as very expensive. It is often used as a dopant in solid-state lasers. Pure Tm thin films have not been grown by any deposition technique, although ${\mathrm{T}\mathrm{m}}_2{\mathrm{O}}_3$ is the most studied compound due to optical properties supporting lasers, ceramics and glass applications [351,352].

Ytterbium (Yb): Yb is commonly used as a dopant and it is reactive with oxygen and halogens with oxidation states +2 and +3. A considerable literature is noted for Yb thin films and ${\mathrm{Y}\mathrm{b}\mathrm{O}}_x$ films by techniques alternative to PLD/RPLD, while halide thin films receive comparatively little attention, attributed to limited industrial interest [353,354,355,356].

Lutetium (Lu): Lu is the last/heaviest lanthanide and is described as extremely expensive (commercial price noted as about six times higher than gold), with main oxidation state +3 but also 0/+1/+2. ${\mathrm{L}\mathrm{u}\mathrm{O}}_{\mathrm{x}}$ (e.g., Lu₂O₃) thin films are prepared by laser ablation of Lu₂O₃ targets in different oxygen atmospheres [357]. This review highlights its good thermal stability, wide band gap (~5.5 eV) and high dielectric constant as the key properties enabling use in laser crystals, ceramics and glasses [358,359].

3.7. Radioactive and Ultra-Rare Elements: Scope Limits and Thin-Film Feasibility (Po, At, Fr, Ra)

A small set of elements is effectively absent from PLD/RPLD thin-film studies because radioactivity, scarcity and handling hazards dominate over any potential thin-film application pull. In fact, we notice that highly radioactive metallic elements such as Fr, Tc, At, Po and Ra have not been deposited using PLD (or other techniques), with the exception of Tc, which has been deposited by ionic evaporation. Consistent with this, actinides and synthetic elements having an atomic number higher than 88 amu are excluded from the review because of high radioactivity.

Polonium (Po): Po is classified here as a radioactive metalloid because of its intermediate properties between metals and non-metals. Po has only a few applications, primarily limited by high radioactivity and associated hazards, and its compounds (mostly synthetically produced) have no significant commercial/industrial relevance. Only a few early studies exist on pure Po thin films and its oxide (PoO), with the most recent cited work being from 1954 (Bagnall and D’Eye) [360].

Astatine (At): Although At is a non-metal, it is treated as a metalloid in the manuscript due to its position in the periodic table. It is described as very rare and highly radioactive, making bulk chemical/physical properties difficult to study, and it exists mainly as a decay product of heavier radioactive elements. Only a few studies exist on this element and its chemical products, and essentially none on thin films.

Francium (Fr): Fr has been already treated and discussed in the highly reactive s-block metals (Section 3.1).

Radium (Ra): Ra is presented as the last element considered in the present review as one of the rarest naturally occurring metals (after protactinium), first isolated by Marie and Pierre Curie in 1898. It is described as the first radioactive element used in radiotherapy. There are no scientific publications on thin films of this very rare radioactive element.

4. Brief Description on Tabulated Findings

The results discussed in Section 3 are summarized in tabular form to provide a compact guide to materials achieved by PLD and RPLD across the categories of metals, metalloids, lanthanides, and their binary compounds. The tables include only those elements and binary compounds for which the relevant literature exists. They intend to help the reader to quickly identify feasible target materials and processing parameters.

In particular:

Table 2. Metallic thin films grown by PLD: Properties and applications.

Ablated Metal	Residual Gas	Deposited Thin Film	Properties	Main Applications	Ref.
Mg	HV	Mg	Good mechanical and optical properties, high biocompatibility, high quantum efficiency.	Smart windows, switchable solar absorbers, optical switching, reflective coatings, photocathodes.	[48,50,51]
Ti	HV	Ti	High corrosion resistance, thermally resistant.	Spacecraft, missiles, bicycles.	[107]
Co	HV	Co	Low resistivity, high Curie temperature, variable optical properties.	High density data storage, bio-sensing, drug delivery, catalyst.	[139]
Ni	HV	Ni	Chemical stability, good electrical conductor.	Spintronics, storage devices, protective coatings.	[143,144]
Cu	HV	Cu	Excellent electrical and thermal conductivity, thermal stability.	Photocathode in RF cavities, microelectronics, solar cells, sensors.	[152,153,154,155]
Se	HV	Se	Tunable band gap, high refractive index.	Optical devices and sensing.	[92,93,94]
Y	HV	Y	Low work function, high quantum efficiency.	Photocathodes for RF cavities.	[212,213,214,215]
Zr	UHV	Zr	Corrosion and high-heat resistance, low absorption neutron, biocompatible.	Dental implants, catalysis, nuclear plants, ceramics.	[218,219]
Nb	UHV	Nb	Good photo-emissive performance, low thermal expansion and high thermal stability.	Photocathodes for SRF cavities, aerospace industry.	[225,226,227]
Mo	HV	Mo	Heat and wear resistance, chemically inert.	Protective coatings, optoelectronic devices.	[233,234]
Ru	HV	Ru	Chemically and thermally stable, good catalyst.	Data storage, electrical contacts.	[243]
Rh	He	Rh	High hardness, corrosion resistance, catalytic activity.	Protective coatings, decoration for jewelry, electrical contacts.	[249]
Rh	HV	Rh			[250]
Pd	HV	Pd	Hydrogen absorber, corrosion-resistant.	Material for hybrid vehicles as catalytic converter, hydrogen technologies.	[251,252,253]
Ag	HV	Ag	Huge electrical and thermal conductivity, high reflectivity.	Biosensors, antimicrobial coatings, good biocompatibility.	[254,255,256]
In	HV	In	High optical transparency, good electrical conductivity.	Display for smartphone and tablet.	[181]
Ta	HV	Ta	Extremely high melting point, excellent corrosion resistance, superconductor, biocompatible.	Reaction turbines, tools, biocompatible material.	[265,266]
W	UHV	W	High electrical and thermal conductivity, very high hardness.	Electrodes, heating elements, field emitters.	[275]
W	Ar	W			[276,277]
Os	HV	Os	Excellent tribological properties.	Electric contacts, wear-resistant alloys.	[294]
Ir	HV	Ir	Corrosion resistance, very high melting point.	High-temperature apparatuses, OLED devices, crucibles.	[298,299,300]
Pt	HV	Pt	Corrosion resistance, chemically inert.	Cancer drugs, pacemakers, stents, jewelry, electronics.	[303]
Au	HV	Au	Excellent thermal and electrical conductivity, chemically inert.	Aerospace components, jewelry, connectors and printed circuits, dental material.	[306,307]
Au	UHV	Au			[308]
Au	Ar, He, N2	Au			[309]
Pb	HV	Pb	Corrosion-resistant, relatively high quantum efficiency.	Photocathodes for SRF cavities, X radiation shield	[199]
Bi	HV	Bi	Very low thermal conductivity, high electrical resistivity, diamagnetic metal.	Sensors, electronic devices, cosmetic ingredient.	[207]
Bi	UHV	Bi			[208,209]

summarizes the results concerning pure-metal deposition including the whole variety of metal elements reported.

Table 3. Thin films of binary metallic chemical compounds prepared by PLD and RPLD techniques.

Ablated Material	Reactive Gas Ambient	Deposited Thin Film	Deposition Technique	Properties	Main Applications	Ref.
Mg	O2	MgO	RPLD	Excellent electrical insulation, good thermal conductivity, high chemical inertness.	Electrical insulation, refractory material.	[52]
Sc2O3	O2	Sc2O3	PLD	High melting point, high thermal and optical properties, good resistance to corrosion.	High-reflectance coatings, electronics, fuel cells.	[106]
TiN	N2	TiN	PLD	High hardness, low electrical resistivity, thermal and chemical stability.	Microelectronics, protective coatings	[108]
Ti	N2	TiN	RPLD			[109]
TiC	HV	TiC	PLD	High hardness, excellent wear resistance, good thermal and chemical stability.	Cutting tools, good biocompatibility, corrosion-resistant coatings.	[110]
Ti	CH4	TiC	RPLD			[111]
TiO2	O2	TiO2	PLD	Good mechanical, chemical, and thermal stability, high transparency.	Optical coatings, solar cells, gas sensing, good biocompatibility.	[112]
Ti	O2	TiO2	RPLD			[113]
VO2	HV	V2O5	PLD	Metal–insulator transition, good corrosion resistance.	Infrared detectors, chemical sensors, resistive switching devices.	[114]
V	O2	VO2	RPLD			[115,116]
VN	N2	VN	PLD	High hardness, thermal stability, superconducting behavior.	Protective coatings, micro-supercapacitors, microelectronics.	[117]
V	N2	VN	RPLD			[118]
Cr2O3	O2	CrOx	PLD	Highly resistant to heat, corrosion, and wear.	Resonant tunneling diodes, field effect transistors, electronic devices.	[127]
Mn	O2	MnOx	RPLD	Catalyst, energy storage, biocompatibility.	Photovoltaic cells, catalysis, biomaterial.	[128]
MnO	O2	MnOx	PLD			[129]
Fe	O2	FeOx	RPLD	Variable refractive index and extinction coefficient, high spin polarization.	Spintronic, gas sensors, magnetic and electrical devices.	[137,138]
Co	O2	CoOx	RPLD	Redox properties, p-type semiconductor.	Pigments for ceramics, catalysts, electrochemical devices.	[142]
Ni	O2	NiO	RPLD	High electrical resistivity, p-type conductivity, high chemical and mechanical stability.	Optoelectronic devices, solar cells, gas sensors.	[147,148,149]
Cu	O2	CuOx	RPLD	High optical absorption, antibacterial performance.	Oxygen and humidity sensors, antibacterial applications.	[159,160,161,162,163,164]
ZnO	O2	ZnO	PLD	Good piezoelectrical, photoelectrical and optical performance.	Electric transducers, gas sensors, ultrasonic oscillators and low- loss optical waveguides.	[166]
Zn	O2	ZnO	RPLD			[167,168]
Ga	N2	GaN	RPLD	High electron mobility, good thermal conductivity, excellent chemical and thermal stability.	Semiconductor for optoelectronic applications, laser diodes, solar cells.	[175,176]
Ga	NH3	GaN	RPLD			[175,177]
Ga2O3	O2	Ga2O3	PLD	Excellent electrical breakdown resistance, high optical transparency, good chemical stability.	High-voltage power devices, gas sensors, UV photodetectors.	[178]
Y2O3	O2	Y2O3	PLD	High melting point, chemical stability, high dielectric constant.	Oxygen sensors, high temperature coatings, cutting tools.	[216]
Y	O2	Y2O3	RPLD			[217]
Zr	O2	ZrO2	RPLD	Chemical inertness, low thermal conductivity, biocompatible.	Orthopedic implants, cutting tools, refractory material.	[221]
ZrO2	O2	ZrO2	PLD			[220]
Zr	N2	ZrN	RPLD	Ceramic material, biocompatible.	Cutting tools, medical devices, superconductor.	[222]
ZrN	N2	ZrN	PLD			[223]
ZrC	CH4	ZrC	PLD	High melting point, excellent high-temperature stability, good corrosion and wear resistance.	Hard resistant coatings, nuclear fuel particles coatings, field emitter coatings.	[224]
Nb	O2	NbOx	RPLD	High dielectric constant and refractive index, transparent in the visible range.	Oxygen sensors, optical glasses, material for nuclear plants.	[228,229]
Nb	N2	NbNx	RPLD	High hardness, high melting point and oxidation resistance.	Photon detectors, coatings for superconductive cables, protective coatings.	[230,231]
NbC	HV	NbC	PLD	High hardness, good wear resistance, thermal conductivity.	Protective coatings in nuclear plants, cutting tools, composite materials.	[232]
Mo	O2	MoOx	RPLD	Wide band gap, high work function.	Gas sensors, protective coatings.	[235]
MoO3	O2	MoOx	PLD			[236]
Mo	H2S	MoSx	RPLD	Lubricating material.	Dry lubricant, catalyst.	[237,238]
Mo	N2	MoNx	RPLD	Chemical and thermal stability, hardness and wear resistance.	Optical and anti-reflective coatings, energy storage.	[239,240]
RuO2	O2	RuOx	PLD	Good thermal and chemical stability, high specific capacitance.	Thin-film resistors, positive electrode in supercapacitors.	[245]
Ag	O2	AgOx	RPLD	Optical band gap, high electrical conductivity.	Optical response, biomedicine, energy storage.	[257,258]
Cd	O2	CdO	RPLD	Tunable band gap, high photoconductivity, chemical stability.	Solar cells, flat panel display, photodetectors.	[259]
In	O2	In2O3	RPLD	Transparent conducting oxide, high electrical conductance.	Gas sensors, solar cells, panel displays, organic light-emitting diodes.	[182,183]
In-Sn	O2	ITO	RPLD	Large band gap, transparent to visible light, low electrical resistivity.	Optoelectronic devices, automobile and aircraft windows, antireflection coatings.	[184,185]
Sn	O2	SnO2	RPLD	Thermal and chemical stability.	Displays, solar cells, ceramic glazes.	[186,187]
SnO2	O2	SnO2	PLD			[188]
Al-Sn	Ar	Al-Sn	PLD	Corrosion and fatigue resistance.	Bearings.	[191]
Cu + Sn	Ar	Cu-Sn	PLD	Wear and corrosion resistance, good thermal and electrical properties.	Structural engineering applications, home appliances.	[193]
Hf	O2	HfO2	RPLD	Exceptional thermal stability, high melting point.	Optical coatings, high-temperature aerospace material.	[261]
HfO2	O2	HfO2	PLD			[261]
HfC	HV	HfC	PLD	Excellent hardness, high melting point, good wear resistance and chemical stability.	Devices needing high temperature resistance, rocket engine components.	[262]
Hf	N2	HfN	RPLD	Excellent corrosion resistance, good thermal and electrical stability.	Wear-resistant coating for cutting tools, high temperature components.	[263]
Ta	O2	TaOx	RPLD	Very high dielectric properties, high refractive index, wide optical band gap.	Anti-reflective coatings, optical waveguides, electronic components.	[267]
Ta2O5	O2	TaOx	PLD			[268]
Ta	N2	TaNx	RPLD	Tunable electrical properties, excellent corrosion resistance, good thermal stability, chemical inertness.	Hard coatings, integrated circuits, microelectronic devices.	[269,270]
TaC	HV	TaC	PLD	Very high melting point, corrosion-resistant, good electrical and thermal conductivity.	High temperature cutting tools, coatings, turbines and jet engine nozzles.	[271]
W	O2	WOx	RPLD	Wide band gap semiconductor, near-infrared absorption.	Gas sensors, smart windows, thermal insulation coatings.	[278]
WO3	HV	WO3	PLD			[279]
W	N2	WNx	RPLD	Very high hardness, good electrical conductivity, ceramic material.	Microelectronics, semiconductor devices, component for fusion reactors, turbine blades.	[240,280]
W	CH4	WCx	RPLD	High electrical and thermal conductivity, low coefficient of thermal expansion, high melting point.	Industrial cutting tools, wear parts, high-temperature applications, durable jewelry.	[281,282]
Re	N2	ReNx	RPLD	High elastic modulus, huge hardness.	Electronic components, protective coatings.	[285]
ReS2	HV	ReS2	PLD	Good electric conductivity, catalytic activity.	Microelectronics, optoelectronics, energy storage, catalytic hydrogen production.	[287]
ReB2	HV	ReB2	PLD	High melting point, excellent hardness.	Cutting tools, wear-resistant coatings.	[288,289]
Ir	O2	IrO2	RPLD	Corrosion resistance, high electrical conductivity, thermally stable.	Fuel cells, sensors, electrodes.	[301]
Au	O2	AuOx	RPLD	Chemically inert but thermally instable.	Catalyst, electronics, nanotechnology.	[311]
Bi	O2	Bi2O3	RPLD	Wide band gap, high refractive index, high dielectric permittivity.	Optical coatings, high-quality optical fiber, fuel cells, sensor technology.	[210]
Bi2O3	HV	Bi2O3	PLD			[211]

presents respective binary chemical compounds with their main properties and technological applications.

Table 4. Thin films of metalloids prepared by PLD technique.

Ablated Metalloid	Residual Gas	Deposited Thin Film	Properties	Main Applications	Ref.
B	HV	B	High absorption cross-section of thermal neutrons.	Thermal neutron detectors.	[62,63]
Si	HV	Si	Semiconducting properties.	High-technology semiconductor devices, thin-film solar cells.	[77,78,79]
Ge	UHV	Ge	Transparent to infrared radiation, chemically stable.	Transistors and integrated circuits, infrared lenses, solar cells.	[87,88]
Se	HV	Se	Tunable band gap, high refractive index.	Optical devices, photocells, solar cells.	[92,93,94]
Sb	Ar	Sb	High optical absorption coefficient, high carrier mobility.	Opaque material, dopant in electronic semiconductors.	[95]
Te	HV	Te	High infrared transmission, tunable electrical performance and band gap energy.	Optoelectronics, transistors, gas sensors.	[101]

is a summary reporting on metalloid thin-film growth, their main properties and potential technological applications.

Table 5. Thin films of binary metalloid chemical compounds prepared by PLD and RPLD techniques.

Ablated Material	Reactive Gas Ambient	Deposited Thin Film	Deposition Technique	Properties	Main Applications	Ref.
B	N2	BN	RPLD	High hardness, thermal and chemical refractory compound.	Electronics, super-hard coatings, refractory material.	[64,65]
Si	O2	SiO2	RPLD	High hardness, chemically stable, insulating.	Anti-reflective coatings, corrosion protection, surface passivation layers.	[80]
SiO2	HV	SiO2	PLD	High hardness, chemically stable.	Anti-reflective coatings, corrosion protection, surface passivation layers.	[81]
Si	CH4	SiC	RPLD	High thermal conductivity, mechanical strength, chemical inertness.	Sensors, actuators, protective coatings and cutting tools.	[82]
SiC	HV	SiC	PLD			[83]
Si3N4	N2	SiNx	PLD	High electrical insulation, notable thermal stability, excellent mechanical properties.	Anti-reflective coatings, waveguides, biomedical applications.	[85]
Si	NH3	SiN	RPLD			[84,86]
Ge	O2	GeO2	RPLD	High reflective index, low optical dispersion, transparent in the infrared region.	Optical fibers, catalysis, energy storage.	[89]
Ge	N2 + Ar	GeNx	RPLD	High dielectric constant, thermal stability.	Suitable for high-temperature electronics, optoelectronics.	[90]
Sb2Se3	HV	Sb2Se3	PLD	Band gap and electrical conductivity tunable with thickness.	Solar photovoltaic absorber material, optoelectronic devices.	[97]
Sb2S3	UHV HV	Sb2S3	PLD	High absorption coefficient in the visible region, good photosensitivity.	Solar absorbers photocathodes, microwave switching.	[99]
Cd-Te	Ar + O2	Cd-Te	PLD	Low cost, high absorbing coefficient.	Solar cells, gamma ray detectors.	[102,103]

reports on the respective metalloid binary chemical compounds grown, with their main properties and applications.

The surveyed literature indicates that PLD of elemental targets is often performed not only in high vacuum, but also in controlled ambient gases (frequently noble gases), aiming either to tailor film structure, or to increase deposition rate by confining the ablated material [361,362]. In addition, many PLD studies of oxides and nitrides are effectively carried out under low partial pressures of oxygen or nitrogen to approach nominal stoichiometry by tuning O and N incorporation in the growing film [117,276]. This practical overlap between PLD-in-gas and RPLD underscores the reactive background as a frequently decisive parameter for stabilizing the desired compound phase and composition.

Table 6. Thin films of binary lanthanide compounds prepared by PLD and RPLD techniques.

Ablated Material	Gas Ambient	Deposited Thin Film	Deposition Technique	Properties	Main Applications	Ref.
La	O2	La2O3	RPLD	High dielectric constant, high melting point, wide band gap.	NOx gas sensors, optical glasses, ceramics.	[321]
LaS	UHV	LaS	PLD	Low work function, low electric resistivity, high melting point.	Field emission, display devices.	[322,323]
CeO2	O2	CeO2	PLD	High thermal stability, good oxygen storage capacity, chemical inertness.	Glass manufacturing, automotive industry, catalyst.	[324,325,326]
Pr6O11	O2	PrOx	PLD	High chemical stability, good electrical and thermal conductivity, high magnetic susceptibility.	Optical fibers, high-power magnets, colorant for glass.	[327,328]
Nd	O2 + Ar	Nd2O3	RPLD	Very high melting point, high dielectric constant.	Solid-state lasers, color sunglasses, catalyst.	[329]
Sm2O3	O2	Sm2O3	PLD	High resistivity, high dielectric constants, large band gap.	Electronics, nuclear industry, glass manufacturing.	[332,333]
Eu2O3	O2	EuOx	PLD	High melting point, thermal resistance, strong fluorescence.	Lighting and displays, nuclear industry, ceramics.	[335]
Er2O3	UHV	Er2O3	PLD	Huge band gap, high dielectric constant.	Gate dielectrics in semiconductor devices, display monitors.	[347]
Lu2O3	O2	Lu2O3	PLD	Good thermal stability, wide band gap, high k dielectric constant.	Laser crystals, ceramics, glasses.	[357]

is dedicated to lanthanides and lanthanide-based binary compounds prepared by PLD and RPLD. Further to intrinsic experimental challenges this is a topic of high interest because of its strategic applications. The deposition of pure metallic lanthanide films remains particularly difficult due to the very high cost of pure lanthanides and their strong reactivity with oxygen-containing molecules such as ${\mathrm{O}}_2$ and ${\mathrm{H}}_2$O, which are always present in vacuum deposition systems. Consequently, the lanthanide literature mostly concerns compounds, especially oxides, grown in reactive atmospheres to leverage stable functional compositions.

Table 7. Carbon and chemical compounds containing carbon thin films prepared by PLD and RPLD techniques.

Ablated Material	Gas Ambient	Deposition Technique	Deposited Thin Film	Properties	Main Applications	Ref.
C	HV	PLD	C	Chemical inertness, low friction coefficient.	Aircraft and spacecraft parts, sailboat masts, electrodes for energy, batteries.	[66,67]
C	HV	PLD	Graphene	Extremely high electric conductivity.	Light sensors, molecular filter, energy storage.	[76]
C	HV	PLD	DLC	High hardness, wear resistance, chemical inertness.	Cutting tools, microelectronics and photoelectronic components, protective coatings.	[68]
C	NH3	RPLD	CNx	Thermal and chemical stability, good optical and semiconducting properties.	Sensing, imaging, light-emitting diode (LED) fabrication, energy conversion.	[69]
C	N2	RPLD	CNx			[70,71]

complements the work by summarizing the reports on carbon and related compounds obtained by PLD and RPLD, to outline the exceptionally broad literature on laser ablation/deposition of this element.

In conclusion, Table 2, Table 3, Table 4, Table 5, Table 6 and Table 7 provide a consolidated map of elements that have been deposited as pure films, or are predominantly studied as binary compounds, and are or will be employed in technological applications.

Finally,

Table 8. Ablation threshold, laser fluence and reactive gas pressure for metals, metalloids and lanthanides.

Chemical Elements	Ablation Threshold	Laser Fluence (J/cm2)	Reactive Gas Pressure (Pa)
Metals	High	0.5–10	1–20
Metalloids	Low	0.2–0.8	0.5–10
Lanthanides	Medium-Low	0.3–1.0	10–100

summarizes the ablation thresholds and laser fluences for all the chemical elements investigated in this study, grouped as metals, metalloids, and lanthanides. The ranges of reactive gas pressures used during RPLD experiments are also reported. In brief, metals have the highest ablation thresholds due to high reflectivity and high thermal conductivity; metalloids, having lower thermal conductivity than metals, show lower ablation thresholds but a greater tendency to expel macroparticles and droplets. Lanthanides, being very heavy, in RPLD experiments, require high background pressures to promote thermalization and reduce stoichiometric imbalance due to scattering. In contrast, for the synthesis of binary compounds of metals and metalloids, in RPLD experiments, the reactive gas pressure typically ranges from 0.5 to 20 Pa.

Moreover, Figure 2 shows a periodic table heatmap that categorizes the investigated chemical elements based on their PLD/RPLD feasibility. Specifically, green indicates elements with high feasibility (e.g., many transition metals), yellow represents those with moderate feasibility (such as several lanthanides), and red highlights elements (including most alkali and alkaline earth metals) that are challenging to ablate due to high reactivity, radioactivity, or extreme thermodynamic instability of the target.

5. Conclusions and Outlook

The present review provides a comprehensive account of thin-film growth by pulsed laser deposition (PLD) and reactive pulsed laser deposition (RPLD), encompassing elemental metals, metalloids, lanthanides, and a representative set of binary compounds, thereby offering a consolidated reference to guide future investigations in the field.

Despite the well-established versatility of PLD and RPLD, the analysis conducted here indicates that the viability of thin-film growth is predominantly determined by the material-specific characteristics rather than the availability of experimental means. In this context, the dominant constraint of the processing feasibility is mainly the chemical reactivity and/or the volatility of the materials. Many transition and post-transition elements are widely exploited in the form of thin-film functional oxides, nitrides, carbides, sulfides, or halides. The highly reactive alkali and alkaline earth metals are practically impossible to stabilize in pure metallic films, since the highly energetic ablated species readily react with the residual gases, even under UHV conditions, in addition to plasma erosion deteriorating the deposited film.

The nature, stoichiometry, microstructure and overall quality of the grown materials are strong functions of the experimental parameters. The most common experimental parameter ranges are summarized in Table 1 and reported growth results are found in Table 2, Table 3, Table 4, Table 5, Table 6 and Table 7. Results are associated with sets of suitable experimental parameters, including laser wavelength, laser pulse duration and fluence, pulse repetition rate, number of pulses, base pressure, reactive gas type/pressure, target–substrate distance, and substrate-related variables. The experimental parameters collectively control the plasma-plume properties, growth kinetics, stoichiometry, and microstructure of the produced material. This is consistent with several metal PLD experiments which have been performed in gas ambient, of usually noble gases, to tailor the structure and/or confine the plume, while oxide and nitride growth frequently rely on low O₂/N₂ pressures to approach the nominal stoichiometry by tuning oxygen and nitrogen incorporation. The review highlights the strong reactivity of lanthanides and the practical constraints of high cost that limit operations to oxides’ growth. In instances where PLD/RPLD reports are lacking for a given element or compound, alternative deposition methods have been referenced to distinguish between the genuine absence of a fundamental processing limitation and a lack of research or technological interest.

From the applications viewpoint, the literature indicates that PLD remains a particularly versatile research tool for exploring new compositions and phases. However, two limitations affect its industrial scale adoption. The particulate (droplet) formation and the relatively low deposition rates, are both recognized as key shortcomings of PLD/RPLD. These affect the reliability of the methods in large-scale operations.

Overall, the consolidated tables and section structure used here are intended not only to catalog, but also to expose recurring processes, property relationships and constraints that can guide future PLD/RPLD research toward better stoichiometry control, improved film uniformity, and reduced particulate contamination.

These conclusions directly motivate the outlook and future research directions towards where the most impactful opportunities are laid. Strengthening the physics and chemistry interpretation, the laser–material coupling and the reactive growth pathways will enable minimization of current constraints, reproducibility of growth and prospectively the wider technological uptake.

In the above context, a first research direction may focus on laser–material coupling and the community’s strong reliance on ultraviolet excimer lasers and Nd:YAG laser harmonics. For materials with wavelength-dependent absorption, systematic studies relating optical constants to ablation regimes, plume composition, and film quality are limited today, and extending investigations beyond the most common UV harmonics may reveal more efficient growth domains. A second major direction concerns the improved composition and phase control in reactive growth. An explicit link of reactive ambient to kinetic pathways at the substrate will enable predictive selection of conditions and will stabilize the material phases sought.

A third direction is mitigating droplets/particulates to promote industrial scalability. Beyond reporting the existence of droplets, future studies should quantify particulate density versus fluence, background pressure, and target conditioning, in order to develop, verify, benchmark and widely adopt mitigation strategies.

A fourth research direction will address the broad disparity in reported results and experimental methodologies, with the objective of improving comparability and establishing standardized experimental and analytical protocols across the field. The tabulated data presented in this work compile results spanning several decades and encompassing a wide range of experimental conditions and instrumentation. Our analysis verifies the scarcity of consistent findings and underlines the need for defining a broadly accepted parametric framework. Establishing such a unified research space will not only address the prevailing challenges but it will significantly accelerate progress, enhance the practical and strategic means and open up the space for the industrial exploitation of PLD and RPLD.