Anti-bacterial surfaces, compositions, methods of forming and uses thereof

Abstract

The disclosure relates to anti-bacterial thin films for surfaces. Specifically, the disclosure relates to photocatalytic, superhydrophobic thin films for prevention of certain infectious ambulatory diseases, as well as systems and methods for their formation.

Description

ANTI-BACTERIAL SURFACES, COMPOSITIONS, METHODS OF FORMING AND USES THEREOFBACKGROUND

[0001] The disclosure is directed to anti-bacterial thin films for surfaces. Specifically, the disclosure is directed to photocatalytic, superhydrophobic thin films for prevention of certain infectious ambulatory diseases, as well as systems and methods for their formation.

[0002] Healthcare facilities represent important environments for infection transmission. Healthcare-associated infections (HAI) are a major source of morbidity and mortality and are the second most prevalent cause of death globally. HAI can prolong the duration of the hospital stay, causing high supplementary costs in addition to those already sustained due to the patient’s underlying disease. Moreover, bacteria are becoming increasingly resistant to antibiotics, making HAI prevention even more important nowadays. Human high-touch surfaces in healthcare facilities (See e.g., FIG. 1) such as clinical and housekeeping equipment, and fittings such as water taps, door plates, and bed rails, all have a high potential to spread deadly pathogenic infections.

[0003] Accumulation of bacteria on frequently touched surfaces is key in the transmission of infection. Therefore, careful cleaning and disinfection of MTS surfaces are essential elements of effective infection prevention programs. However, traditional manual cleaning and disinfection practices in hospitals are often suboptimal. This is due in part to a of personnel : the cleaning service has low social standing and in the frequently outsourced cleaning companies, untrained employees, low salaries, and frequent job changes dominate.

[0004] New approaches to reduce germ load on surfaces, such as “self-disinfecting” (SD) surfaces by using surface materials which are either coated with metals or with photocatalytic thin films are currently used as a further option for the improvement of hygiene in the patient environment. The use of such SD surfaces could minimize the impact of poor cleaning and disinfecting practices during both routine and terminal room cleaning and disinfection.

[0005] Antimicrobial coating could be key in fight against hospital-acquired infections. Some metals (Cu, Ti, Zn. Ag) and their oxides are highly effective antimicrobials which control infection by “contact killing” bacteria and viruses. C u / Zn / Ag metal -based antimicrobial coatings are currently in use to healthcare infection prevention in hospitals and other healthcare facilities despite somelimitations. Namely, these coatings may be affected by varying cleaning methods and may cause the emission of bioactive agents into the environment and thereby facilitate potential exposure of humans (especially for patients with weakened immune systems). We use the term “contact killing” to describe the killing of cells due to direct contact between the cell and solid antimicrobial metal particle.

[0006] Photocatalytically active titanium dioxide (TiCh) is widely used as a self-cleaning and self-disinfecting material in many applications to keep environments biologically clean. TiCh can absorb UV light (k < 400 nm) and can photo-stimulate redox reactions on its surface producing Reactive Oxygen Species (ROS) such as hydroxyl radical ( OH-), superoxide radical ( O2”) and singlet oxygen (XO2). The production of them may contribute to the biocidal activity.

[0007] Existing photocatalyst-based coatings suffer two important disadvantages, they require artificial UV light sources to generate ROS and secondly these coatings remain inactive in dark atmosphere as the ROS generated in light declines with time. These significant issues hinder practical applications, necessitating strategies to improve catalytic performance in the visible region.

[0008] Fluorine based superhydrophobic coatings have unique non-wetting properties and are self-cleaning, corrosion-resistant, and resistant to bio-adhesion and bio-films formation (biofilms are a complex of microorganism aggregates associated with bacterial cells adhering to each other on MTS). A large fraction of currently available hydrophobic coatings consist of perfluorinated compounds or organo-silane based chemistries, both of which can be toxic and bioaccumulate in nature.

[0009] The disclosed systems and methods aims to address the deficiencies in the currently available technology.SUMMARY

[0010] Disclosed, in various exemplary implementations, are photocatalytic, superhydrophobic thin films for prevention of certain infectious ambulatory diseases , as well as systems and methods for their formation.

[0011] In an exemplary implementation provided herein is a multi-layered substrate comprising: a photocatalytic interface layer; and a superhydrophobic layer.

[0012] In another exemplary implementation, provided herein is a method of forming multilayered, anti-bacterial substrate comprising a photocatalytic interface layer and a superhydrophobic layer, comprising: Using high-rate reactive sputtering in atomic oxygen atmosphere, depositing thephotocatalytic interface layer; and Using physical vapor deposition, depositing the superhydrophobic layer.

[0013] In yet another exemplary implementation, provided herein is a system for coating a substrate with a photocatalytic interface layer, and a superhydrophobic layer, comprising: a vacuum chamber; a first Coaxial Magnetron Sputtering module, operable to sputter a first bi-layer composite of p-type semiconductors onto a substrate, disposed within the vacuum chamber; a second Coaxial Magnetron Sputtering module, operable to sputter a first bi-layer composite of n-type semiconductors onto a substrate, disposed within the vacuum chamber; an ion source; an Arc Evaporator, disposed within the vacuum chamber, the Arc evaporator being in fluid communication with a source of a composition comprising fluorine; a conveyor, operable to position the substrate sought to be coated in fluid communication with the first and second Coaxial Magnetron Sputtering modules, and the Arc Evaporator module; and the substrate, coupled to the conveyor.

[0014] These and other features of the photocatalytic, superhydrophobic thin films, or substrates (interchangeable) for prevention of certain infectious ambulatory diseases , as well as systems and methods for their formation will become apparent from the following detailed description when read in conjunction with the figures and examples, which are exemplary, not limiting.BRIEF DESCRIPTION OF THE DRAWINGS

[0015] For a better understanding of the photocatalytic, superhydrophobic thin films for prevention of certain infectious ambulatory diseases, as well as systems and methods for their formation, reference is made to the accompanying examples, charts and figures, in which:

[0016] FIG. 1A, is a schematic of a high-contact surfaces in hospital patient room, with FIG. IB, illustrating high-contact surfaces in hospital operating room.;

[0017] FIG. 2, is a schematic showing an exemplary implementation of soluble ion release that is bacteria-lethal for contact killing of certain bacteria responsible for ambulatory infectious diseases;

[0018] FIG. 3, is a schematic illustrating the synergistic effect causing effective charge separation in a first p-type semiconductor bi-layer having non-overlapping bandgap;

[0019] FIG. 4, is a schematic illustration of an Interfacial charge transfer (IFCT) mechanism of p-n junction by CU2O and TiO2in visible wavelength range;

[0020] FIG. 5, is a schematic illustration of an Interfacial charge transfer (IFCT) mechanism of nano- junction by anatase and rutile configurations in visible light wavelength;

[0021] FIG. 6 is a schematic illustration showing the contributory effects of the fluorcontaining superhydrophobic layer with contact killing and photocatalytic mechanisms;

[0022] FIG. 7A, is a schematic illustration of an exemplary implementation of the high-rate magnetron sputtering system with atomic oxygen from an ion source for deposition of the p-type C O thin film, with FIG. 7B, showing schematic illustration of an exemplary implementation of the high-rate magnetron sputtering system with atomic oxygen from an ion source for deposition of the n-type TiO2 thin film;

[0023] FIG. 8A, is a schematic illustration of an exemplary implementation of the coating system disclosed, with FIG. 8B, illustrating a process bi-layer and of p-n junction formation in the coating system disclosed, while FIG. 8C, showing a schematic illustration of a process bi-layer and of p-n junction formation in the coating system disclosed;

[0024] FIG. 9, is a schematic illustration of polymerization of fluorine-based superhydrophobic layer in the coating system disclosed;

[0025] FIG. 10, is an XRD analysis of the fractional concentration of TiO2 and TiO (n-type) bi-layer composition in A, with the fractional concentration of CuO2 / CuO bi-layer composition in B, in an exemplary implementation of the methods and substrates disclosed;

[0026] FIG. 11 , in A is a graph illustrating the fractional concentration in percent of copper (top line), oxygen (mid line), and titanium (lower line) along a glass substrate, with B illustrating the location of each bi-layer on the substrate in a X-Z cross section, while C being a schematic illustrating the spectrum location in the X-Z cross section, D showing the superhydrophobic topology forming the “lotus-leaf effect” and E being an SEM image of the X-Z cross section;

[0027] FIG.s 12A-13B, are schematics illustrating Amplification of TiO2 thin film photocatalytic activity on surface with copper ions / atoms when using CuO2 / CuO p-type bi-layer semiconductors, and TiO2 / TiO n-type bi-layer semiconductors (having portion at anatase and rutile crystal configurations).DETAILED DESCRIPTION

[0028] Provided herein are photocatalytic, superhydrophobic thin films for prevention of certain infectious ambulatory diseases, as well as systems and methods for their formation.

[0029] In an exemplary implementation, Contact-killing surfaces, as well as photocatalytic superhydrophobic surfaces all possess unique antimicrobial properties and their cooperative and synergistic combination are disclosed to create thin films or other substrates, with binary and / or ternary pathogens-destroying potential.

[0030] Accordingly, provided herein are thin films (interchangeable with “substrates”) formed by multilayer deposition process of, for example copper (Cu) and titanium oxide / dioxide layers in mode ion assisting (See e.g., FIG. 2) and followed plasma-assisted deposition and polymerization of fluorine-based superhydrophobic layer.

[0031] Accordingly, provided herein is a multi-layered substrate comprising: a photocatalytic interface layer; and a superhydrophobic layer. Furthermore, the catalytic interface layer is comprised of: a p-n junction formed by a first bi-layer composite of p-type semiconductors and a bi-layer composite of anatase-phase n-type semiconductor and a conductor; and a p-n junction formed by a second bi-layer composite of p-type semiconductors and a bi-layer composite of rutilephase n-type semiconductor and a conductor.

[0032] In the context of the disclosure, the term “semiconductor” any material that acts as an insulator at low temperatures but has appreciable electrical conductivity, resembling a metal, at high temperatures. Metal oxides, for example, are known in the art to be functional semiconductors. Nonlimiting examples of such metal oxides include TiO2, VO2, ZrO2, Fe3O4, Fe2O3, Mn02, NiO, ZnO, Bi2O3 and CuO. Other semiconductors include a typical IV semiconductor, an III-V semiconductor and a II- VI compound semiconductor.

[0033] The term "photocatalytic" refers to the ability of a material to facilitate chemical reactions under light exposure, particularly in the ultraviolet (UV) or visible spectrum."Superhydrophobic" describes a surface with water contact angles greater than 150°, resulting in extreme water repellency. The combination of these properties allows for efficient bacterial inactivation and self-cleaning functionalities. In addition, a "p-n junction" is an interface between p-type and n-type semiconductors, where charge carriers (electrons and holes) are separated to promote photocatalysis. "Bi-layer composite" refers to a structure comprising two distinct layers of materials with complementary properties, such as bandgap alignment or specific crystalline phases.

[0034] In other words, the p-n junction is a fundamental structure in semiconductor technology, formed by joining p-type and n-type semiconductor materials. The p-type region has an abundance of "holes" (positive charge carriers), (see e.g., FIG.s 3, 4) while the n-type region has an excess of electrons (negative charge carriers). When these two regions are brought together (see e.g., FIG. 4), electrons from the n-region diffuse into the p-region and recombine with holes, creating a depletion region at the junction. This region lacks free charge carriers and acts as an insulating barrier. The movement of charges creates an electric field across the depletion region, which opposes further diffusion. Their ability to allow current flow in one direction (forward bias) and block it in the opposite direction (reverse bias) can be beneficial for the photocatalytic affect of the layer.

[0035] In an exemplary implementation, three discrete microorganism-destroying mechanism work in the disclosed coating: contact-killing using certain metal ions sloughed off the p-type semiconductors’ bi-layers, photocatalysis in visual light and contact with superhydrophobic layer. The superhydrophobic coating provide a nculral / incrl interface that can prevent bacterial surface colonization (in other words, forming surface fouling). Each of these mechanisms reinforces the other two.

[0036] In an exemplary implementation the first bi-layer composite of p-type semiconductors, and / or the second bi-layer composite of p-type semiconductors (SCs), each comprises a pair of semiconductors having non-overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range. In certain examples reference is made to first and second p-type SCs, refer to their combination with the two crystalline polymorphs of the n-type SCs bi-layer. In other words, a first p-type SC bi-layer can be, for example, CuO2 / CuO forming p-n junction with a bi-layer of TiO TiO, where the TiO2has an anatase crystalline polymorph, while the second bi-layer composite of p-type SCs can also be CuO2 / CuO forming p-n junction with a bi-layer of TiO2 / TiO, where the TiO2 has an rutile crystalline polymorph.

[0037] The anatase phase in the context of the disclosure, refers to one of the crystalline forms of titanium dioxide (TiO2), with key characteristics that include: better photocatalytic activity than other TiO2 phases due to its larger band gap (~3.2 eV), which enhances its oxidizing ability and facilitates electron (and charge) transfer, as well as having a high specific surface area, more active sites, and higher charge separation efficiency due to reduced electron-hole recombination rates.Conversely, the rutile phase polymorph known for its thermodynamic stability, with properties that include higher stability than anatase but has a smaller band gap (~3.0 eV), which makes it less efficient for photocatalysis under UV light, but higher recombination rates for photogenerated electrons and holes, reducing its photocatalytic efficiency compared to anatase. In an exemplary implementation, and Apart from the p-n junction formed by, for example, the CU2O and anatase TiCh, there exists a considerable proportion of rutile phase in the coatings. This anatase and rutile mixture forms a heterojunction which also contributes to the improved catalytic activity.

[0038] In other words, formation of a heterojunction by combining anatase and rutile polymorphs of, for example, Ti()2, enhances photocatalytic efficiency due to several synergistic mechanisms. Anatase and rutile have different band structures, with anatase having a larger bandgap (~3.2 eV) and a lower conduction band (CB) edge compared to rutile (~3.0 eV). When these phases are combined (see e.g., FIG 5), the heterojunction at their interface facilitates charge separation by enabling electron transfer from anatase to rutile and hole transfer in the opposite direction. This reduces the recombination rate of photogenerated electron-hole pairs, which is a key factor limiting photocatalytic performance. Additionally, the interfacial regions act as electron trapping sites, further enhancing charge carrier lifetimes and improving redox reactions. The mixed-phase structure also broadens the range of light absorption, as rutile’s slightly smaller bandgap allows it to absorb light closer to the visible spectrum, complementing anatase’s UV activity. This combination accelerates oxidation-reduction processes, making the anatase / rutile heterojunction more effective than single-phase Ti()2for various photocatalytic applications such as bacterial degradation.

[0039] Other n-type semiconductors that exhibit anatase-phase and rutile-phase crystal structures beyond titanium dioxide (TiO2) can be used in the coatings disclosed. These materials are typically metal oxides or compounds with similar structural and electronic properties, and can be, for example; SnO2, ZnO, FC2O3. WO3, or mixed metal oxide selected from titanates, or doped TiO2. In an exemplary implementation, the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor and the bi-layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and bi-layer composite of rutile-phase crystalline configuration and a conductor is TiC TiC), SnCWSn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiCh and their corresponding conductor.

[0040] As indicated, to achieve the charge separation in the p-type bi-layer, the band gap of the p-type SCs is non-overlapping. In the context of the disclosure, the term “bandgap” refers to the energy range in a solid where no electronic states exist. It represents the minimum energy required to excite an electron from the valence band (VB, where electrons are bound) to the conduction band (CB, where electrons are free to move and conduct electricity). The size of the band gap determines whether a material behaves as an insulator, semiconductor, or conductor. For semiconductors, the band gap governs their optical and electronic properties, such as light absorption and electrical conductivity.

[0041] In an exemplary implementation, there is an advantage of using a bi-layer of p-type semiconductors with non-overlapping band gaps due to their ability to absorb light across a broader spectral range. One layer can absorb higher-energy photons (shorter wavelengths), while the other absorbs lower-energy photons (longer wavelengths), maximizing light harvesting. Additionally, the difference in band gaps facilitates (see e.g., FIG. 3), efficient charge separation at the interface, reducing recombination of photogenerated carriers and enhancing overall photocatalytic efficiency.

[0042] Other p-type SCs pairs with non-overlapping bandgap that can be used in the catalytic layer can be, with a bandgap of one of them in the visible light range (~1.5-2.8 eV) and another with a non-overlapping bandgap, either higher than 2.8 eV or lower than 1.5 eV. CmO (2.1 eV) can be paired with Cui (3.1 eV), where CmO absorbs visible light and Cui absorbs UV-visible light. Ag2O (1.46 eV) can be paired with ZnSe (2.7 eV), as Ag2O absorbs lower-energy visible to near-infrared light, while ZnSe absorbs higher-energy visible light. ZnTe (2.24 eV) can be paired with Cui (3.1 eV), where ZnTe absorbs visible light and Cui absorbs UV-visible light. Digenite (CusSs, ~2.5 eV) can be paired with Ag2O (1.46 eV), as CusSs absorbs higher-energy visible light, while Ag2O absorbs lower-energy visible to near-infrared light.

[0043] For example, the SCs in each of the first and the second bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact.Contact killing of bacteria by metals released from p-type semiconductors refers in the context of the disclosure, to the process where bacterial cells are killed upon direct contact with a surface that releases metal ions. This mechanism involves both physical and chemical interactions between the bacteria and the metal surface. The etiology of this process begins with the release of metal ions, such as copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing, from the semiconductor surface. These ions interact with the negatively chargedbacterial cell wall through electrostatic attraction, leading to disruption of the cell membrane's integrity (see e.g., FIG. 2). This damage increases membrane permeability, allowing metal ions to penetrate into the bacterial cytoplasm. Once inside the cell, metal ions induce oxidative stress by generating reactive oxygen species (ROS), which overwhelm the bacterial antioxidant defenses. This oxidative damage affects critical biomolecules, including proteins, lipids, and DNA. The ions also interfere with essential cellular processes, such as respiration and energy production, by binding to thiol groups in enzymes or disrupting electron transport chains. In some cases, DNA degradation occurs as a secondary effect of oxidative stress or direct interaction with metal ions. The combined effects of membrane disruption, oxidative stress, and interference with cellular functions ultimately lead to bacterial cell death.

[0044] For p-type semiconductors like CuO2, CuO, Cui, ZnSe, ZnTe, Cu9S5 or Ag2O used in coatings, the release of copper or silver ions plays a central role in this antibacterial activity. These semiconductors can release ions at a controlled rate while maintaining their structural integrity, ensuring sustained antibacterial effects without requiring external activation. The efficiency of contact killing depends on factors such as the rate of ion release, the surface roughness of the coating (which enhances contact), and the specific susceptibility of bacterial strains to metal-induced stress.

[0045] Turning now to the superhydrophobic layer, whereby to create superhydrophobic surfaces that do not interfere with the photocatalytic activity of the previously described semiconductors (e.g., Cu2O, CuO, ZnTe, Ag2O, etc.), fluorine-based compositions can be carefully selected or avoided entirely to ensure compatibility. Examples of fluorine-based and fluorine-free materials that can be used to form superhydrophobic coatings compatible with photocatalytic semiconductors can be, for example, fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS), or, in another exemplary implementation, a non-fluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-CsN4, or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

[0046] In an exemplary implementation, the coating compositions disclosed herein, are formed using the methods provided. Accordingly and in another exemplary implementation, provided herein is a method of forming multi-layered, anti-bacterial substrate comprising a photocatalytic interface layer and a superhydrophobic layer, comprising: Using high-rate reactivesputtering in atomic oxygen atmosphere, depositing the photocatalytic interface layer; and using physical vapor deposition, or plasma deposition accompanied by a corona discharge, depositing the superhydrophobic layer.

[0047] In an exemplary implementation, the process begins with a high-vacuum chamber system comprising a main deposition chamber connected to a load-lock mechanism for sample introduction without compromising the base vacuum. The chamber is configured to maintain a base pressure of about IxlO-7Torr or better using a combination of turbomolecular and backing pumps. Substrate preparation can be carried out, for example ultrasonic cleaning in acetone followed by isopropanol, with subsequent oxygen plasma treatment (50-100W for 3-5 minutes) to activate the surface and maximize bonding sites for the reactive layer and the superhydrophobic, fluorinated coating. The cleaned substrates is mounted in certain examples, on a temperature-controlled stage capable of operation between -10°C and 150°C, as the substrate temperature can affect the reactive layers properties, as well as polymerization kinetics and resulting film morphology.

[0048] In conventional reactive sputtering the oxidizer is introduced as a gas. This gas itself has fairly small chemical reactivity. The use of ion source of in the magnetron reactive sputtering can increase the deposition rate by more than 10 times without altering film properties. This technique has a great potential for industrial applications. The implication of this technique would mean a cost-effective way of great throughput improvement of the current sputtering coaters.

[0049] For example, the step of depositing the photocatalytic interface layer comprises: using high-rate reactive sputtering in atomic oxygen depositing a first bi-layer composite of p-type semiconductors; and using high-rate reactive sputtering in atomic oxygen depositing a first bi-layer composite of n-type semiconductor and a conductor. The method can be implemented by a system comprising a magnetron, or a klystron, and an ion source. In an exemplary implementation, a system for high-rate reactive sputtering in atomic oxygen to deposit a bi-layer composite of p-type semiconductors can be configured with specific components to ensure precise control over deposition and material properties. The primary components can comprise a magnetron or klystron, an ion source, and additional supporting equipment. The magnetron is a plasma-generating device used to sputter target materials by creating a high-density plasma through the application of a strong magnetic field perpendicular to an electric field (see e.g., FIG. 7A, 7B). This configuration traps electrons near the target surface, enhancing ionization of the working gas (typically argon) and enabling efficient sputtering of the target material. The klystron, if used, serves as an RF amplifier togenerate and sustain high-frequency electromagnetic waves that ionize the gas and maintain plasma stability during deposition.

[0050] An ion source is employed in certain examples, to introduce reactive atomic oxygen into the chamber, which reacts with the sputtered material to form oxide-based p-type semiconductors. The ion source can also be used to pre-clean the substrate or assist in modifying surface properties during deposition. A reactive gas flow controller used in certain examples with the system, regulates the oxygen flow rate, ensuring consistent stoichiometry in the deposited layers. The system also requires a vacuum chamber to maintain low-pressure conditions essential for sputtering, along with a high-vacuum pump to remove residual gases and maintain the desired pressure range between stages of forming the multi-layered coating.

[0051] Additional components used with the systems disclosed, can be a substrate holder, which may be heated or rotated to improve film uniformity and adhesion, and a power supply capable of delivering DC or RF power to the magnetron or klystron. A shutter can be placed between the target and substrate to control deposition timing and prevent contamination during plasma stabilization. Optical emission spectroscopy (OES) or mass spectrometry can be integrated for real-time monitoring of plasma composition and reactive species during deposition.

[0052] In this system, atomic oxygen plays a role in forming oxide-based p-type semiconductors by reacting with sputtered metal atoms at the substrate surface. The system configuration allows precise control of parameters such as discharge power, oxygen partial pressure, and substrate temperature and motion for achieving the desired phase composition and bandgap properties in the bi- layer composite. For example, as illustrated in FIG. 8B, CmO and CuO could be sequentially deposited by adjusting the oxygen flow rate and discharge power to control their relative stoichiometry. This setup ensures high-quality thin films with tailored optical and electronic properties suitable for applications like photocatalysis.

[0053] Accordingly and in another exemplary implementation, illustrated in FIG. 8A, provided herein is a system for coating a substrate with a photocatalytic interface layer, and a superhydrophobic layer, comprising: a vacuum chamber 5; a first Coaxial Magnetron Sputtering module 3, operable to sputter a first bi-layer composite of p-type semiconductors onto a substrate, disposed within the vacuum chamber 5; a second Coaxial Magnetron Sputtering module 1, operable to sputter a first bi-layer composite of n-type semiconductors onto a substrate, disposed within the vacuum chamber 5; An ion source 2; an Arc Evaporator (1, 3), disposed within the vacuumchamber 5, the Arc evaporator being in fluid communication with a source of a composition comprising fluorine; a conveyor 4, operable to position the substrate sought to be coated in fluid communication with the first and second Coaxial Magnetron Sputtering modules, and the Arc Evaporator module; and the substrate (not shown 6), coupled to the conveyor 4.

[0054] Depositing the superhydrophobic surface coating is further illustrated in FIG. 9, showing a schematic illustration of polymerization of fluorine-based superhydrophobic layer in the vacuum chamber. As illustrated, once deposition of the p-n heterojunction semiconductors is completed, the chamber is filled with CF4 molecules, and exposed to corona discharge. For precise control of the CF4 input, mass flow controllers calibrated specifically for fluorinated gases are essential, with operational flow rates typically ranging from 5-50 seem depending on the chamber volume and desired deposition rate.

[0055] In certain exemplary implementation, for the corona discharge component, a high-voltage AC power supply can be used; operating at 10-30 kV with frequencies between 20-50 kHz that connects to a custom-designed electrode configuration positioned for example between about 2 cm and 5 cm above the substrate surface. The corona discharge creates a non-equilibrium plasma zone with high electron energy and relatively low gas temperature, which is advantageous for initiating the fragmentation of CF4 molecules without excessive thermal damage to the substrate already coated with the reactive layer.

[0056] The primary plasma source can utilize a radio frequency (RF) generator operating at, for example, 13.56 MHz coupled with an impedance matching network to minimize reflected power. Power densities typically range from 0.1 -1.0 W / cm2depending on desired film properties. A parallel plate capacitively coupled plasma (CCP) configuration, when used, can provide uniform plasma distribution, alternatively inductively coupled plasma (ICP) sources can be used for higher plasma densities at lower pressures. The chamber can further include optical emission spectroscopy ports for real-time monitoring of CF3+, CF2+, and CF+radical concentrations (see e.g., FIG. 9), which serve as indicators of the polymerization process efficiency.

[0057] In an exemplary implementation, the vacuum chamber is brough to the operating pressure, followed by adjusting substrate temperature to between about 20°C and about 40°C, for fluoropolymer chain growth while maintaining sufficient surface mobility of reactive species. CF4 gas is introduced to reach a working pressure of between about 10 mTorr and about 50 mTorr, withthe pressure influencing the mean free path of reactive species and consequently the deposition rate and film uniformity.

[0058] Corona discharge is initiated first at low voltage (~12 kV) and gradually increased to operating voltage (~20 kV) while monitoring current to avoid arcing. This pre-ionization phase creates initial CF4 fragmentation and surface activation (see e.g., FIG. 9). The RF plasma is then ignited with an initial power of ~50W and ramped to the process setpoint of 150-300W within 30 seconds. During this stabilization period, a bias voltage of -100 to -200V can be applied to the substrate to enhance ion bombardment and improve film adhesion.

[0059] As illustrated, the polymerization process involves plasma chemistry where CF4 molecules undergo electron impact dissociation forming CF3, CF2, and CF radicals along with fluorine atoms. These reactive species recombine at the substrate surface forming cross-linked fluorocarbon networks. CF2-rich environment, controlled by rate of increase in operating voltage, temperature, gas flow and other parameters serve as the primary building blocks for the formation of PTFE-like structures. The process further comprises oxygen addition (e.g., 0.5-2% relative to CF4 flow) which configured enhance cross-linking through the formation of C-O-C bridges.

[0060] Deposition rates can range from 5-20 nm / minute depending on power density, pressure, and gas flow rates. In an exemplary implementation dual-scale roughness is employed to achieve superhydrophobicity. Nanoscale roughness from the inherent polymer structure supplemented with microscale features. This dual-scale morphology is achieved through, for example, pulsed plasma modulation, alternating between high power (e.g., 300W, 10 seconds) and low power (e.g., 100W, 30 seconds) regimes, creating different growth rates that result in the desired hierarchical surface structure.

[0061] Further, the system can comprise a central processing module (CPM) in communication with the first and second Coaxial Magnetron Sputtering modules, the Arc Evaporator module, the ion source, and the conveyor, the CPM further comprising at least one processor in communication with a non-transitory memory device, storing thereon a computer-readable media with set of executable instructions, configured when executed to cause the at least one processor to (see e.g., FIG. 8C,): Using the first Coaxial Magnetron Sputtering module, sputter a first bi-layer composite of p-type semiconductors; and Using the second Coaxial Magnetron Sputtering module, or the Arc Evaporator module, sputter or deposit respectively a first bi-layercomposite of n-type semiconductors; Using the Arc Evaporator module, deposit a composition comprising fluorine in a pattern configured to form a superhydrophobic layer.

[0062] Moreover, the set of executable instructions is further configured, when executed by the at least one processor in the step of Using the second Coaxial Magnetron Sputtering module, or the Arc Evaporator module, sputter or deposit respectively a first bi-layer composite of n-type semiconductors to cause the at least one processor to: form a predetermined portion of anatase-phase crystalline configuration; and form a predetermined portion of rutile-phase crystalline configuration.EXAMPLES:Example I: Characterization

[0063] A coating was formed on glass using p-type bi-layer of CuO / CuO2 forming p-n junction with n-type bi-layer of TiO / TiO2 SCs, where FIG. 10, showing an XRD analysis of the fractional concentration of TiO2 and TiO (n-type) bi-layer composition in A, with the fractional concentration of CuO2 / CuO bi-layer composition in B, in an exemplary implementation of the methods and substrates disclosed.

[0064] Likewise, FIG. 11, illustrating in frame A the fractional concentration in percent of copper (top line), oxygen (mid line), and titanium (lower line) along the glass substrate, with frame B illustrating the location of each bi-layer on the substrate in a X-Z cross section, while frame C being a schematic illustrating the spectrum location in the X-Z (forward and up) cross section. Frame D is SEM picture showing the superhydrophobic topology forming the “lotus-leaf effect” and E being an SEM image of the X-Z cross section. Furthermore, FIG.s 12-13B, are schematics illustrating Amplification of TiO2 thin film photocatalytic activity on surface with copper ions / atoms when using CuO2 / CuO p-type bi-layer semiconductors, and TiO2 / TiO n-type bi-layer semiconductors (having portion at anatase and rutile crystal polymorph configurations as discussed herein.

[0065] The term "comprising" and its derivatives, as used herein, are intended to be open ended terms that specify the presence of the stated features, elements, components, groups, integers, and / or steps, but do not exclude the presence of other unstated features, elements, components, groups, integers and / or steps. The foregoing also applies to words having similar meanings such as the terms, "including", "having" and their derivatives.

[0066] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. “Combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. The terms “a”, “an” and “the” herein do not denote a limitation of quantity, and are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the nanowire(s) includes one or more nano wire). Reference throughout the specification to “one exemplary implementation”, “another exemplary implementation”, “an exemplary implementation”, and so forth, when present, means that a particular element (e.g., feature, structure, and / or characteristic) described in connection with the exemplary implementation is included in at least one exemplary implementation described herein, and may or may not be present in other exemplary implementations. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various exemplary implementations.

[0067] In the context of the disclosure, the term "operable" means the system and / or the device and / or the program, or a certain element or step is fully functional, sized, adapted and calibrated, comprises elements for, and meets applicable operability requirements to perform a recited function when activated, coupled, implemented, actuated, effected, realized, or when an executable program is executed by at least one processor associated with the system and / or the device. In relation to systems and circuits, the term "operable" means the system and / or the circuit is fully functional and calibrated, comprises logic for, having the hardware and firmware necessary, as well as the circuitry for, and meets applicable operability requirements to perform a recited function when executed by at least one processor.

[0068] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Furthermore, the terms “first,” “second,” and the like, herein do not denote any order, quantity, or importance, but rather are used to denote one element from another.

[0069] Likewise, the term "about" means that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but may be approximate and / or larger or smaller, as desired, reflecting tolerances, conversion factors, rounding off, measurement error and the like, and other factors known to those of skill in the art. In general, an amount, size,formulation, parameter or other quantity or characteristic is "about" or "approximate" whether or not expressly stated to be such.

[0070] The term “module,” as used herein, means, but is not limited to, a software or hardware component, such as a field programmable gate array (FPGA) or an application specific integrated circuit (ASIC), which performs certain tasks. A module may advantageously be configured to reside on an addressable storage medium and configured to execute on one or more processors. Thus, a module may include, by way of example, components, such as software components, object-oriented software components, class components and task components, processes, functions, attributes, procedures, subroutines, segments of program code, drivers, firmware, microcode, circuitry, data, databases, data structures, tables, arrays, and variables. The functionality provided for in the components and modules may be combined into fewer components and modules or further separated into additional components and modules.

[0071] The term “computer-readable storage medium” should be taken to include a single medium or multiple media (e.g., a centralized or distributed database, and / or associated caches and servers) that store the one or more sets of instructions. The term “computer-readable storage medium” shall also be taken to include any medium that is capable of storing, encoding or carrying a set of instructions for execution by the machine and that cause the machine to perform any one or more of the methodologies of the present disclosure. The term “computer-readable storage medium” shall accordingly be taken to include, but not be limited to, solid-state memories, optical media, and magnetic media.

[0072] "In the context of the disclosure, the term “p-n junction” refers to an interface formed within a semiconductor device between a p-type semiconductor region, which contains an excess of positively charged carriers (holes), and an n-type semiconductor region, which contains an excess of negatively charged carriers (electrons), wherein the junction exhibits rectifying electrical characteristics permitting current flow preferentially in one direction.

[0073] "In the context of the disclosure, the term **non-overlapping band gap** refers to a condition in which the forbidden energy ranges (band gaps) of two adjacent or proximate semiconductor materials do not share any common energy levels, such that the valence band maximum and conduction band minimum of one material fall entirely outside the corresponding band gap energy range of the other material, thereby preventing direct band-to-band alignment between the two materials."

[0074] In the context of the disclosure, actinic radiation at a visible spectrum wavelength range refers to electromagnetic radiation (EMR) having photon energies sufficient to induce photochemical reactions, wherein the EMR falls within the visible portion of the electromagnetic spectrum, e.g. between about 380 nm and about 700 nm, encompassing wavelengths perceptible to the human eye, and including in particular the higher-energy, shorter-wavelength portions thereof such as the violet and blue spectral regions, which are capable of causing chemical changes in the light-sensitive photocatalytic materials disclosed, upon absorption.

[0075] In the context of the disclosure, the term "contact killing" refers to the rapid inactivation and destruction of bacteria upon direct physical contact with an antimicrobial metal surface, wherein the mechanism proceeds through sequential damage to the bacterial cell envelope upon contact with the metal surface, influx of toxic metal ions into the cell, disruption of intracellular components including the respiratory chain and DNA, and ultimately cell death, without requiring the bacteria to be immersed in or exposed to a solution of dissolved metal ions.

[0076] The term “fluid communication” may suggest a route and / or system of routes for the flow of a fluid. The term “fluid communication” may also suggest the traveling and / or transporting of a fluid including gas. The term “fluid communication” may include [but is not limited to] the general ability or capacity for fluid to flow between the parts, sections, or components under consideration.

[0077] Accordingly, and in an exemplary implementation, provided herein is a multi-layered substrate comprising: a photocatalytic interface layer, and a superhydrophobic layer, (i) wherein the catalytic interface layer is comprised of: a p-n junction formed by a first bi-layer composite of p-type semiconductors and a bi-layer composite of anatase-phase n-type semiconductor and a conductor, and a p-n junction formed by a first bi-layer composite of p-type semiconductors and a bi-layer composite of rutile-phase n-type semiconductor and a conductor, (ii) the first bi-layer composite of p-type semiconductors, and / or the second bi-layer composite of p-type semiconductors, each comprises a pair of semiconductors having non-overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range, wherein (iii) the first and second bi-layer composite of p-type semiconductors are the same, or (iv) are the different, wherein (v) the semiconductors in each of the first and the second bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact, (vi) the metal operable to affect contact killing of bacteria is copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing, wherein (vii) the first and / or second bi-layer composite of p-type semiconductors comprises CuCh, CuO, Cui, Ag2O, ZnSe, ZnTe, CU9S5, or a pair of semiconductors comprising copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) having nonoverlapping bandgap, wherein (viii) the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor, (ix) the bi-layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and bi-layer composite of rutile-phase crystalline configuration and a conductor is TiCh / TiO, SnO Sn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiCh and their corresponding conductor, wherein (x) the superhydrophobic layer is comprised of a fluorine-based composition, (xi) the fluorine-based composition is comprised of fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS), (xii) the superhydrophobic layer is comprised of a non-fluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-CsN^ or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

[0078] In another exemplary implementation, provided herein is a method of forming multilayered, anti-bacterial substrate comprising a photocatalytic interface layer and a superhydrophobic layer, comprising: Using high-rate reactive sputtering in atomic oxygen atmosphere, depositing the photocatalytic interface layer, and using physical vapor deposition, depositing the superhydrophobic layer, wherein (xiii) the step of depositing the photocatalytic interface layer comprises: using high-rate reactive sputtering in atomic oxygen depositing a first bi-layer composite of p-type semiconductors, and Using high-rate reactive sputtering in atomic oxygen depositing a first bi-layer composite of n-type semiconductor and a conductor, (xiv) the n-type semiconductor in the step of depositing a first bi-layer composite of n-type semiconductor and a conductor, is configured to form a predetermined portion of anatase-phase crystalline configuration, and a predetermined portion of rutile-phase crystalline configuration, (xv) the method implemented in a system comprising an ion source and a magnetron, wherein (xvi) the first bi-layer composite of p-type semiconductors, comprises a pair of semiconductors having non-overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range, wherein (xvii) the semiconductors in the first bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact, (xviii) the metal operable to affect contact killing of bacteria upon contact is copper (Cu), Titanium (Ti),Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing, wherein (xix) the first bi-layer composite of p-type semiconductors comprises CuCh, CuO, Cui, Ag2O, ZnSe, ZnTe, CU9S5, or a pair of semiconductors comprising copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) having non- overlapping bandgap, wherein (xx) the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor, (xxi) the portion of bi-layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and the portion of bi-layer composite of rutile-phase crystalline configuration and a conductor is TiO TiO, SnO Sn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiO2 and their corresponding conductor, wherein (xxii) the superhydrophobic layer is comprised of a fluorine-based composition, wherein (xxiii) the fluorine-based composition is comprised of fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS), or (xxiv) a nonfluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-CsN^ or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

[0079] In yet another exemplary implementation, provided herein is a system for coating a substrate with a photocatalytic interface layer, and a superhydrophobic layer, comprising: a vacuum chamber, a first Coaxial Magnetron Sputtering module, operable to sputter a first bi-layer composite of p-type semiconductors onto a substrate, disposed within the vacuum chamber, a second Coaxial Magnetron Sputtering module, operable to sputter a first bi-layer composite of n-type semiconductors onto a substrate, disposed within the vacuum chamber, an ion source, an Arc Evaporator, disposed within the vacuum chamber, the Arc evaporator being in fluid communication with a source of a composition comprising fluorine, a conveyor, operable to position the substrate sought to be coated in fluid communication with the first and second Coaxial Magnetron Sputtering modules, and the Arc Evaporator module, and The substrate, coupled to the conveyor, (xxv) the system further comprising a central processing module (CPM) in communication with the first and second Coaxial Magnetron Sputtering modules, the Arc Evaporator module, the ion source, and the conveyor, the CPM further comprising at least one processor in communication with a non-transitory memory device, storing thereon a computer-readable media with set of executable instructions, configured when executed to cause the at least one processor to: using the first Coaxial Magnetron Sputtering module, sputter a first bi-layer composite of p-type semiconductors, and using the second Coaxial MagnetronSputtering module, or the Arc Evaporator module, sputter or deposit respectively a first bi-layer composite of n-type semiconductors, using the Arc Evaporator module, deposit a composition comprising fluorine in a pattern configured to form a superhydrophobic layer, wherein (xxvi) the set of executable instructions is further configured, when executed by the at least one processor in the step of using the second Coaxial Magnetron Sputtering module, or the Arc Evaporator module, sputter or deposit respectively a first bi-layer composite of n-type semiconductors, to cause the at least one processor to: form a predetermined portion of anatase-phase crystalline configuration, and form a predetermined portion of rutile-phase crystalline configuration, wherein (xxvii) the first bi-layer composite of p-type semiconductors, comprises a pair of semiconductors having non- overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range, (xxviii) the semiconductors in the first bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact, wherein (xxix) the metal operable to affect contact killing of bacteria upon contact is copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing, wherein (xxx) the first bi-layer composite of p-type semiconductors comprises CuCh, CuO, Cui, Ag2O, ZnSe, ZnTe, CU9S5, or a pair of semiconductors comprising copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) having non-overlapping bandgap, wherein (xxxi) the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor, (xxxii) the portion of bi-layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and the portion of bi-layer composite of rutile-phase crystalline configuration and a conductor is TiC TiC), SnO Sn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiCh and their corresponding conductor, wherein (xxxiii) the fluorine-based composition is comprised of fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS), wherein (xxxiv) the superhydrophobic layer is comprised of a non-fluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-C3N4, or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

[0080] The above examples and description of the photocatalytic, superhydrophobic thin films for prevention of certain infectious ambulatory diseases, as well as systems and methods for their formation, have been provided only for the purpose of illustration, and are not intended to limitthe disclosed technology in any way. As will be appreciated by the skilled person, the disclosed technology can be carried out in a great variety of ways, employing more than one technique from those described above, all without exceeding the scope of the invention.

Claims

What is claimed:

1. A multi-layered substrate comprising :a) a photocatalytic interface layer; andb) a superhydrophobic layer.2 The multi-layered substrate of Claim 1, wherein the catalytic interface layer is comprised of:a) a p-n junction formed by a first bi- layer composite of p-type semiconductors and a bilayer composite of anatase-phase n-type semiconductor and a conductor; andb) a p-n junction formed by a first bi- layer composite of p-type semiconductors and a bilayer composite of rutile-phase n-type semiconductor and a conductor.3 The multi-layered substrate of Claim 2, wherein the first bi-layer composite of p-type semiconductors, and / or the second bi-layer composite of p-type semiconductors, each comprises a pair of semiconductors having non- overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range.4 The multi-layered substrate of Claim 3, wherein the first and second bi-layer composite of p-type semiconductors are the same.5 The multi-layered substrate of Claim 3, wherein the first and second bi-layer composite of p-type semiconductors are the different.6 The multi-layered substrate of any one of Claims 2-5, wherein the semiconductors in each of the first and the second bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact.7 The multi-layered substrate of Claim 6, wherein the metal operable to affect contact killing of bacteria is copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing.8 The multi-layered substrate of any one of the preceding Claims, wherein the first and / or second bi-layer composite of p-type semiconductors comprises CuCh, CuO, Cui, Ag2O, ZnSe, ZnTe, CU9S5, or a pair of semiconductors comprising copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) having non-overlapping bandgap.9 The multi-layered substrate of any one of Claims 1-7, wherein the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor.

10. The multi-layered substrate of Claim 9, wherein the bi- layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and bi-layer composite of rutile-phase crystalline configuration and a conductor is TiC TiC), SnC Sn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiO2 and their corresponding conductor.

11. The multi-layered substrate of any one of the preceding Claims, wherein the superhydrophobic layer is comprised of a fluorine-based composition.

12. The multi-layered substrate of Claim 11 , wherein the fluorine-based composition is comprised of fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS).

13. The multi-layered substrate of Claim 11 , wherein the superhydrophobic layer is comprised of a non-fluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-CsN^ or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

14. A method of forming multi-layered, anti-bacterial substrate comprising a photocatalytic interface layer and a superhydrophobic layer, comprising:a) Using high-rate reactive sputtering in atomic oxygen atmosphere, depositing the photocatalytic interface layer; andb) Using physical vapor deposition, depositing the superhydrophobic layer.

15. The method of Claim 14, wherein the step of depositing the photocatalytic interface layer comprises:a) Using high-rate reactive sputtering in atomic oxygen depositing a first bi-layer composite of p-type semiconductors; andb) Using high-rate reactive sputtering in atomic oxygen depositing a first bi-layer composite of n-type semiconductor and a conductor.

16. The method of claim 15, wherein the n-type semiconductor in the step of depositing a first bi-layer composite of n-type semiconductor and a conductor, is configured to form a predetermined portion of anatase-phase crystalline configuration; and a predetermined portion of rutile-phase crystalline configuration.

17. The method of Claim 14, implemented in a system comprising an ion source and a magnetron.

18. The method of Claim 15, wherein the first bi-layer composite of p-type semiconductors, comprises a pair of semiconductors having non-overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range.

19. The multi-layered substrate of any one of Claims 14-18, wherein the semiconductors in the first bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact.

20. The method of Claim 19, wherein the metal operable to affect contact killing of bacteria upon contact is copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing.

21. The method of Claim 18, wherein the first bi-layer composite of p-type semiconductors comprises CuCh, CuO, Cui, Ag2O, ZnSe, ZnTe, CU9S5, or a pair of semiconductors comprising copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) having non-overlapping bandgap.

22. The method of Claims 16, wherein the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor.

23. The method of Claim 22, wherein the portion of bi-layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and the portion of bi-layer composite of rutile-phase crystalline configuration and a conductor is TiC TiC), SnC Sn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiO2 and their corresponding conductor.

24. The method of Claim 14, wherein the superhydrophobic layer is comprised of a fluorine-based composition.

25. The method of Claim 24, wherein the fluorine-based composition is comprised of fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS).

26. The method of Claim 24, wherein the superhydrophobic layer is comprised of a non-fluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-CsN^ or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

27. A system for coating a substrate with a photocatalytic interface layer, and a superhydrophobic layer, comprising:a) A vacuum chamber;b) A first Coaxial Magnetron Sputtering module, operable to sputter a first bi-layer composite of p-type semiconductors onto a substrate, disposed within the vacuum chamber;c) A second Coaxial Magnetron Sputtering module, operable to sputter a first bi-layer composite of n-type semiconductors onto a substrate, disposed within the vacuum chamber;d) An ion source;e) An Arc Evaporator, disposed within the vacuum chamber, the Arc evaporator being in fluid communication with a source of a composition comprising fluorine;f) A conveyor, operable to position the substrate sought to be coated in fluid communication with the first and second Coaxial Magnetron Sputtering modules, and the Arc Evaporator module; andg) The substrate, coupled to the conveyor.

28. The system of Claim 27, further comprising a central processing module (CPM) in communication with the first and second Coaxial Magnetron Sputtering modules, the Arc Evaporator module, the ion source, and the conveyor, the CPM further comprising at least one processor in communication with a non-transitory memory device, storing thereon a computer-readable media with set of executable instructions, configured when executed to cause the at least one processor to:a) Using the first Coaxial Magnetron Sputtering module, sputter a first bi-layer composite of p-type semiconductors; andb) Using the second Coaxial Magnetron Sputtering module, or the Arc Evaporator module, sputter or deposit respectively a first bi-layer composite of n-type semiconductors;c) Using the Arc Evaporator module, deposit a composition comprising fluorine in a pattern configured to form a superhydrophobic layer.

29. The system of Claim 28, wherein the set of executable instructions is further configured, when executed by the at least one processor in the step of Using the second Coaxial Magnetron Sputtering module, or the Arc Evaporator module, sputter or deposit respectively a first bi-layer composite of n-type semiconductors to cause the at least one processor to:a) form a predetermined portion of anatase-phase crystalline configuration; and b) form a predetermined portion of rutile-phase crystalline configuration.

30. The system of Claim 28, wherein the first bi-layer composite of p-type semiconductors, comprises a pair of semiconductors having non-overlapping band gap, with one half-pair semiconductor having a bandgap configured to absorb actinic radiation at a visible spectrum wavelength range.

31. The system Claims 28, wherein the semiconductors in the first bi-layer composite of p-type semiconductors comprises a metal operable to affect contact killing of bacteria upon contact.

32. The system of Claim 31 , wherein the metal operable to affect contact killing of bacteria upon contact is copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) or a composite comprising one or more of the foregoing.

33. The system of Claim 32, wherein the first bi-layer composite of p-type semiconductors comprises CuCh, CuO, Cui, Ag2O, ZnSe, ZnTe, CU9S5, or a pair of semiconductors comprising copper (Cu), Titanium (Ti), Zinc (Zn), Silver (Ag) having non-overlapping bandgap.

34. The system of Claims 29, wherein the bi-layer composite of anatase-phase n-type semiconductor, is identical to the bi-layer composite of rutile-phase n-type semiconductor.

35. The system of Claim 34, wherein the portion of bi-layer composite of n-type semiconductor having an anatase phase crystalline configuration and a conductor and the portion of bi-layer composite of rutile-phase crystalline configuration and a conductor is TiC TiC), SnC Sn, ZnO / Zn, Fe2O3 / Fe, WO3 / W, or a mixed metal oxide selected from titanates, or doped TiO2 and their corresponding conductor.

36. The system of Claim 24, wherein the fluorine-based composition is comprised of fluoroalkyl silanes, fluorinated poly(dimethylsiloxane) (PDMS).

37. The system of Claim 24, wherein the super hydrophobic layer is comprised of a non-fluorine-based composition selected from PDMS, graphitic Carbon-Nitride (g-CsN^, polypropylene (PP) combined with g-CsN^ or a combination of non-fluorine-based compositions adapted to form a superhydrophobic surface configured not to interfere with photocatalytic activity of the photocatalytic layer.

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