WO2023031951A1 - Nanostratifiés antimicrobiens utilisant des procédés de dépôt en phase vapeur tels que le dépôt de couche atomique - Google Patents

Nanostratifiés antimicrobiens utilisant des procédés de dépôt en phase vapeur tels que le dépôt de couche atomique Download PDF

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WO2023031951A1
WO2023031951A1 PCT/IN2022/050576 IN2022050576W WO2023031951A1 WO 2023031951 A1 WO2023031951 A1 WO 2023031951A1 IN 2022050576 W IN2022050576 W IN 2022050576W WO 2023031951 A1 WO2023031951 A1 WO 2023031951A1
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substrate
chamber
deposition
metal
vapor deposition
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PCT/IN2022/050576
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English (en)
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Prerna Goradia
Neil Amit GORADIA
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Prerna Goradia
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Priority to US17/988,895 priority Critical patent/US20230072705A1/en
Publication of WO2023031951A1 publication Critical patent/WO2023031951A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45527—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
    • C23C16/45529—Atomic layer deposition [ALD] characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations specially adapted for making a layer stack of alternating different compositions or gradient compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/405—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides
    • C23C16/407—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth

Definitions

  • the present invention broadly relates to thin layer deposition methods for composites. More particularly, the present invention relates to vapor deposited methods for coating the articles involving physical vapor deposition, thermal evaporation, aerosol assisted deposition, chemical vapor deposition, specifically atomic layer deposition (ALD) and combinations of methods for forming the nanolaminates.
  • ALD atomic layer deposition
  • Antimicrobial surface coatings work to suppress the growth of bacteria and harmful microorganisms, and stop the spread of microbes. In addition to deterring bacteria, germs and molds, the coating also minimizes stains and degradation of plastic on the surfaces they are applied to. These antimicrobial agents come in a variety of types like chlorhexidine, ammonium compounds, and silver compounds and so on. Though these coatings provide microbial resistance but there had been drawbacks with the migration of these antimicrobials into the article due to uneven deposition or corrosion of the article.
  • PVD physical vapor deposition
  • CVD chemical vapor deposition
  • the coatings in the prior art involve wet and dry techniques which might not be controlled on the film morphology and thickness ( Gonzalez, A.S.; Riego, A.; Vega, V.; Garcia, J.; Galie, S.; Gutierrez del Rio, I.; Martinez de Yuso, M.d.V.; Villar, C.J.; Lombo, F.; De la Prida, V.M. Functional Antimicrobial Surface Coatings Deposited onto Nanostructured 316L Food-Grade Stainless Steel. Nanomaterials 2021, 11, 1055. https://doi.org/10.3390/nanoll041055).
  • the selective atomic layer deposition is based on the fact that the TiO 2 thin film is selectively deposited only on the regions exposing OH-terminated alkanethiolate monolayers of the gold substrates, because the regions covered with CH 3 -terminated monolayers do not have any functional group to react with precursors.
  • Self assembled monolayers in the prior art are flimsy layers and growing an ALD layer on top of this may compromise the robustness of the coating (Seo, Eun K et al. “Atomic Layer Deposition of Titanium Oxide on Self- Assembled-Monolayer-Coated Gold.” Chemistry of Materials 16 (2004): 1878-1883.).
  • CA2987938A relates to a nano-engineered coating for cathode active materials, anode active materials, and solid-state electrolyte materials for reducing corrosion and enhancing cycle life of a battery, and processes for applying the disclosed coating.
  • the protective coating is obtained by atomic layer deposition (ALD) or molecular layer deposition (MLD) only.
  • US10821619B2 relates to a razor blade having one or more coatings formed by the atomic layer deposition (ALD) process, the formed coatings being uniform, conformal, and dense.
  • the coatings may be on an entire surface of a blade flank, and at least a portion or an entire surface of a blade body.
  • US10195602B2 relates to a photocatalytic system having enhanced photo efficiency/ photonic efficacy that includes a thin nucleation material coated on a substrate.
  • the nucleation material enhances lattice matching for a subsequently deposited photocatalytic active material.
  • the principle object of the present invention is to provide thin film coatings using vapor deposited methods and specifically atomic layer deposition and physical vapor deposition, which can be applied on various surfaces, including glass, the soft polymeric materials and or hard surfaces such as surgical instruments/ medical devices, as well as, synthetic and organic materials.
  • the present invention attempts to overcome the problems faced in the prior art, and discloses thin film deposition coatings suitable for use on a variety of substrate articles and equipments. These coatings besides providing even surface depositions, give large area coverage, and unique properties. Specifically, the present invention relates to a method of coating substrates by vapor deposition based antimicrobial coatings. It provides stable coatings on the sensitive surfaces such as glass or medical equipments wherein besides providing antimicrobial properties, these coatings have application in other areas which exploit properties such as optical, mechanical, electrical and others. Further, the thickness and the composition of the coatings can also be controlled,
  • the present invention discloses vapor deposited coatings using atomic layer deposition and physical vapour deposition on surfaces while not altering the characteristics of the articles and method of preparing the same.
  • the invention further discloses a method of forming antimicrobial coatings wherein the first coating is of a first material and the second coating is of a second material.
  • the second coating in the sequential process may be deposited on top surface of the first coating, wherein the first and second coating layers may be similar or different, and the coating is deposited using an ALD process and/ or combinations with other chemical and physical vapor deposition methods.
  • the invention discloses a method of making nanolaminates by vapor deposition process, the method including the steps: i) depositing conformal atomic layers on a substrate placed on a chuck by transferring the substrate in a first chamber for chemical vapor deposition, comprising: a) flowing a carrier gas and a purge gas in the chamber; b) setting temperature of the chuck and a heater in the chamber, followed by stabilizing the chamber; c) flowing the carrier gas and purge gas at a flow rate designated for coating the atomic layer; d) passivating surface of the substrate by pulsing a precursor 1 for a designated amount of pulse time, followed by removing excess precursor 1 by purging with carrier gas; e) pulsing a precursor 2 for a designated amount of pulse time to complete the surface reaction in the first chamber, followed by removing excess precursor 2 by purging with carrier gas; wherein steps (d) and (e) forming one monolayer are repeated multiple times as per the
  • the present invention discloses a method where chemical vapor deposition is used for depositing at least a layer of material selected from a group comprising tungsten, titanium, molybdenum, silicon, tantalum, nickel, zinc, copper, gold, chromium, yttria, and their oxides, nitrides and other inorganic and organometallic derivatives and combinations thereof.
  • the precursor for layering in the chemical vapor deposition is selected from a group comprising organic compounds such as metal alkoxides, metal alkyls, metal diketonites, metal amindinates, metal carbonyls, metal chlorides, organometallics, organic -inorganic materials and combinations thereof.
  • At least one of the precursor is further selected from a group such as Mo, Ta and Ti deposited from respective pentachlorides; Ni, Mo, and W deposited at low temperatures from respective carbonyl precursors; Tetrakis (dimethyl amino) titanium (TDMAT), diethyl zinc and a range of materials that can form metal oxides such as ZnO, SnO2, ZrO2, Y2O3; the noble metals Pt, Ag, Au and the metal nitrides; aliphatic or aromatic organic precursors consisting of molecules with -OH, -COOH, -NH2, -CONH2, -CHO, -COCI, - SH, -CNO, -CN, alkenes, functional groups, but not limited to and combinations thereof.
  • TDMAT Tetrakis (dimethyl amino) titanium
  • TDMAT Tetrakis (dimethyl amino) titanium
  • TDMAT Tetrakis (dimethyl amino) titanium
  • TDMAT Tetrakis (dimethyl amino) titanium
  • the present invention discloses a method where at least one carrier gas and purge gas are selected from a group of inert gases comprising argon, nitrogen, helium and combinations thereof and the flow rate of the gases is in the range of 20 to 200 seem.
  • the heater temperature in the chamber is in the range 16 - 250 °C.
  • the chuck on which the substrate is placed is heated to the desired temperature in the thermal treatment to aid the deposition process and yield a conformal coating of nanolaminates.
  • the chamber body is made of at least one selected from the group comprising aluminum, stainless steel and combinations thereof and the chamber can be further selected from an ultra-high vacuum chamber or an atmospheric chamber and is stabilized by maintaining the temperature and pressure.
  • the inert atmosphere is maintained using at least a gas selected from a group comprising helium, argon, nitrogen and combinations thereof.
  • the pulse for precursor is given for a time ranging from mS to 5 seconds and at least one of the coatings has a thickness ranging from about 0.1 nm to about 200 nm.
  • the present invention discloses a method where physical vapor deposition is for depositing layers of metal containing materials selected from a group comprising titanium, titanium nitrate, tantalum, tantalum nitrate, compounds of metals such as copper, silver, gold and combinations thereof and derivatives of nitrides, oxide, carbide, boride but not limited to.
  • the substrate temperature is substantially lower than the melting temperature of the target material, making it feasible to coat temperature-sensitive materials. Examples of commonly used PVD processes include thermal evaporative deposition, ion plating, pulsed laser deposition, and sputter deposition.
  • the substrate for coating is glass, soft polymeric materials, hard surfaces such as surgical instruments/ medical devices, powder, synthetic and organic materials or combinations thereof. Further, the transfer of substrate from one chamber to another involves minimum queue time and exposure to ambient conditions, with maintenance of an inert and/or a vacuum environment.
  • the coating for substrate by vapor deposition method is selected from a group comprising chemical vapor deposition (CVD) such as atomic layer deposition (ALD), spatial ALD, Molecular layer deposition (MLD), plasma assisted ALD, self-assembled monolayers (SAM), aerosol assisted deposition (AACVD) and physical vapor deposition (PVD) such as thermal spray, sputtering, thermal evaporation, patterning of layers with lithography and combinations thereof.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • MLD Molecular layer deposition
  • SAM self-assembled monolayers
  • PVD physical vapor deposition
  • coating by chemical vapor deposition of substrates is done with at least one selected from aerosol assisted CVD (AACVD) or deposition with self-assembled monolayers (SAM) with organic molecules using dip, spray to electrostatically charge the surface of the nanolaminates.
  • patterning of layers with lithography is done as the final step before the deposition of the last layer
  • the nanolaminates/ substrates coated by the method of the present invention based on the optical, mechanical, electrical, and magnetic properties of the coatings has applications in a variety of areas such as semiconductor, energy storage, MEMS, life sciences and drug delivery, but not limited to.
  • FIG. 1 illustrates the schematic representation of the method of making nanolaminates by vapor deposition process , in accordance with an embodiment of the present invention
  • Fig. 2 illustrates the schematic representation of the ALD Process Parameters for thermal deposition of ZnO at 250 °C and 451 cycles, in accordance with an embodiment of the present invention
  • Fig. 3 illustrates the combination of wafer stacks (samples), in accordance with an embodiment of the present invention
  • Fig. 4 illustrates the thickness measurements of the TiO 2 and ZnO verified using ellipsometry, in accordance with an embodiment of the present invention.
  • Fig. 5 illustrates the thickness measurements of Cr/Au verified using a Dektak profilometer, in accordance with an embodiment of the present invention.
  • the present invention relates to method of manufacturing nanolaminates by employing sequential surface reactions, wherein the antimicrobial coatings are provided by employing vapor deposited techniques such as chemical vapor deposition using atomic layer deposition (ALD) and physical vapor deposition on the substrate surfaces.
  • ALD atomic layer deposition
  • ALD can be counted as the most advanced version of the traditional CVD process and has several advantages compared to the others, including conformal coatings, large area coverage, and unique physical and optical properties. It is also possible to molecularly dope and form nanocomposites/nanolaminates with organic materials.
  • FIG. 1 illustrating the schematic representation of the method of making nanolaminates by vapor deposition process, in accordance with an embodiment of the present invention.
  • the vapor deposition process comprises of coating nanolaminates by a combination of chemical vapor deposition and physical vapor deposition steps.
  • a substrate which may be glass, soft polymeric materials, hard surfaces such as surgical instruments/ medical devices, powder, synthetic and organic materials or combinations thereof, is coated for the first coating of conformal atomic layers in a first chamber by chemical vapor deposition(CVD), by following the following step of flowing the carrier gas and purge gas, setting the chuck, cone and chamber heaters and stabilizing the chamber.
  • CVD chemical vapor deposition
  • the chuck on which the substrate is placed is heated to the desired temperature in the thermal treatment to aid the deposition process and yield a conformal coating of nanolaminates.
  • the stabilization of chamber is enabled by maintaining the temperature and pressure.
  • At least one of the carrier gas and the purge gas maybe selected from a group of inert gases comprising argon, nitrogen, helium and combinations thereof and the flow rate of the gases is in the range of 20 to 200 seem.
  • the temperature of the chuck and the heater is set tol6 to 250°C followed by stabilizing the chamber.
  • the surface of the substrate is passivated by pulsing a precursor 1 for a designated amount of pulse time and thereafter removing any excess precursor 1 by purging with carrier gas.
  • the pulse time could range between 0.1 milliseconds to 5 seconds.
  • a precursor 2 is pulsed for a designated amount of pulse time and thereafter removing any excess precursor 2 by purging with carrier gas.
  • the pulse time could range between 0.1 milliseconds to 5 seconds. Any further coating could be carried out subsequently after waiting for 5 seconds of the last cycle of coating and purging. Further, the steps of pulsing precursor 1 and precursor 2 may be repeated several times as per the required thickness of the conformal atomic layer.
  • the precursors for layering may be selected from a group comprising organic compounds such as metal alkoxides, metal alkyls, metal diketonites, metal amindinates, metal carbonyls, metal chlorides, organometallics, organic -inorganic materials and combinations thereof.
  • At least one of the precursor is further selected from a group comprising at least one of Mo, Ta and Ti deposited from respective pentachlorides; Ni, Mo, and W deposited at low temperatures from respective carbonyl precursors; Tetrakis (dimethyl amino) titanium (TDM AT), diethyl zinc and a range of materials that can form metal oxides such as the noble metals Pt, Ag, Au and the metal nitrides; aliphatic or aromatic organic precursors consisting of molecules with , alkenes, functional groups, and oxidizer such as oxygen, ozone, water, air and combinations and or a reducer such as hydrogen gas or a plasma excited reactant and combinations thereof.
  • TDM AT Tetrakis (dimethyl amino) titanium
  • the steps may be repeated between 100-1000 times as per the thickness of the layer.
  • the chemical vapour deposition process may be used for depositing on the substrate at least a layer of material selected from a group comprising tungsten, titanium, molybdenum, silicon, tantalum, nickel, zinc, copper, gold, chromium, yttria, and their oxides, nitrides and other inorganic and organometallic derivatives and combinations thereof.
  • the substrate is transferred to a second chamber for a second coating of one or more metal-based layers by physical vapor deposition (PVD).
  • PVD physical vapor deposition
  • the physical vapor deposition process could enable depositing layers of metal containing materials selected from a group comprising titanium, titanium nitrate, tantalum, tantalum nitrate, compounds of metals such as copper, silver, gold and combinations thereof and derivatives of nitrides, oxide, carbide, boride.
  • the subsequent steps include transferring a metal containing material to be deposited on the substrate from a condensed phases in the target to a vapour phase by way of sputtering and evaporation.
  • Sputtering includes bombardment of target by energetic species selected from a group of inert gas such as argon, nitrogen to achieve a thin film vapor-phase deposition on the substrate. Also, evaporation of the target is conducted by resistive heating it to its evaporation point using electrical energy to achieve the vapor-phase species which nucleates and deposits on the substrate. Further steps include setting the chamber temperature and pressure, followed by loading the substrate into the chamber, enabling vaporization of the material from the target, and transporting the material to be deposited to the substrate, where further nucleation and deposition of the film takes place.
  • energetic species selected from a group of inert gas such as argon, nitrogen
  • evaporation of the target is conducted by resistive heating it to its evaporation point using electrical energy to achieve the vapor-phase species which nucleates and deposits on the substrate.
  • Further steps include setting the chamber temperature and pressure, followed by loading the substrate into the chamber, enabling vaporization of the material from the target, and transporting the material to be deposited to
  • an inert atmosphere is provided using at least a gas selected from a group comprising helium, argon, nitrogen and combinations thereof, which promotes condensation of the metal containing layer on the substrate.
  • Supersaturation includes covering of almost all active sites on the substrate by a precursor of the material to make a fully reacted layer on the surface.
  • the precursor that is to be administered enters the second chamber in the vapor phase and gets deposited by reacting with the substrate functionalities or the layer from the earlier half-reactions.
  • the substrate is heated under inert atmosphere to a temperature as per the desired property of the nanolaminate that is required. The process is repeated for the coating of the similar or different material in an alternate or sequential manner.
  • the two deposition processes could be carried out in any sequence one after the other.
  • the physical vapour deposition process could precede the chemical vapour deposition process based on the type and property of coatings required.
  • the resulting thickness of at least one of the conformal atomic layers and metal-based layers could be ranging between about 0.1 nm to about 200 nm.
  • At least one coating includes a plurality of monolayers, wherein a first layer of material and a second layer of material for the coating have same or different characteristics and the coating is deposited using a chemical vapor deposition process or physical vapor deposition process.
  • the coatings for substrates by vapor Deposited method is selected from a group comprising chemical vapor deposition (CVD) such as atomic layer deposition (ALD), spatial ALD, Molecular layer deposition (MLD), selfassembled monolayers (SAM), aerosol assisted deposition (AACVD) and physical vapor deposition (PVD) such as thermal spray, sputtering, thermal evaporation, patterning of layers with lithography and combinations thereof.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • MLD Molecular layer deposition
  • SAM selfassembled monolayers
  • PVD physical vapor deposition
  • thermal spray sputtering, thermal evaporation, patterning of layers with lithography and combinations thereof.
  • the coating by chemical vapor deposition of substrates is done with at least one selected from aerosol assisted CVD (AACVD) or deposition with self-assembled monolayers (SAM) with organic molecules using dip, spray to electrostatically charge the surface of the nanolaminates.
  • AACVD aerosol assisted CVD
  • SAM self-assembled monolayers
  • body of the first and the second chamber is made of at least one selected from the group comprising aluminum, stainless steel and combinations thereof.
  • the first and the second chamber are selected from an ultra-high vacuum chamber or an atmospheric chamber.
  • the process includes patterning of layers with lithography being carried out before the deposition of the final layer to impart a texture to help in repelling microbes.
  • Atomic Layer Deposition is a special type of the chemical vapor deposition (CVD) technique.
  • the technique comprises of introducing the gaseous reactants (precursors) into the reaction chamber via chemical surface reactions, wherein the precursors are pulsed alternately, one at a time, and separated by inert gas purging in order to avoid gas phase reactions.
  • the excess gas is pumped away and a second gas is introduced that gets condensed and is further chemisorbed on top of the first layer.
  • the excess second gas is pumped away and the whole process can be repeated to deposit a second monolayer of the same or different material.
  • This sequence can be repeated as many times as necessary to deposit the desired total coating thickness.
  • This successive, selfterminated surface reaction of the reactants result in controlled layering of the desired material.
  • the unique self-limiting growth mechanism results in perfect conformality and thickness uniformity of the film even on complicated 3D structures ( Figure 2).
  • FIG. 2 illustrating the schematic representation of the ALD Process Parameters for thermal deposition of ZnO at 250 °C and 451 cycles, in accordance with an embodiment of the present invention.
  • the coating is done by the ALD process comprising the steps: a) flowing the carrier gas and purge gas, wherein the purge gas is at 5-60 seem and carrier gas at 20 -200 seem; b) Setting the chuck, cone and chamber heaters at 100 to 250 °C ; c) Stabilizing the chamber for 10 min ; d) Flowing the carrier gas at 60 seem and the purge gas at 200 seem and waiting for 60 seconds; e) Pulsing oxygen-containing precursors, preferably water for 0.06 seconds and waiting for 5 seconds, followed by pulsing the precursor Diethyl zinc for 0.1 second into the vaccum chamber and subsequently waiting for 5 seconds for the coating; wherein step e is repeated 1000-1500 times as per the thickness of the layer; f) Flowing the carrier gas at 5 seem and
  • FIG. 3 illustrating the combination of wafer stacks (samples), in accordance with an embodiment of the present invention.
  • the table describes the details of the samples prepared using nanolaminates containing layers of ALD (CVD) and thermal evaporation (PVD);
  • FIG. 4 illustrating the thickness measurements of the TiO2 and ZnO verified using ellipsometry, in accordance with an embodiment of the present invention.
  • Ellipsometry is done to measure the thickness of the film, where, the measurement is performed by polarizing an incident light beam, reflecting it off a smooth sample surface at a large oblique angle and then re-polarizing the light beam prior to its intensity measurement.
  • FIG. 5 illustrating the thickness measurements of Cr/Au verified using a Dektak profilometer, in accordance with an embodiment of the present invention.
  • Dektak profilometer measures height or trench depth on a surface. In this surface contact measurement technique, a very low force stylus is dragged across a surface and leveling of data is done in the software and cursor locations and step heights are provided in the form of print out.
  • the invention provides a method of making nanolaminates by vapor deposition process, the method comprising the steps: i) depositing conformal atomic layers on a substrate placed on a chuck by transferring the substrate in a first chamber for chemical vapor deposition, comprising : a) flowing a carrier gas and a purge gas in the chamber; b) setting temperature of the chuck and a heater in the chamber, followed by stabilizing the chamber; c) flowing the carrier gas and purge gas at a flow rate designated for coating the atomic layer; d) passivating surface of the substrate by pulsing a precursor 1 for a designated amount of pulse time, followed by removing excess precursor 1 by purging with carrier gas; e) pulsing a precursor 2 for a designated amount of pulse time to complete the surface reaction in the first chamber, followed by removing excess precursor 2 by purging with carrier gas; wherein steps (d) and (e) forming one monolayer are repeated multiple times as per
  • the invention discloses a method where chemical vapor deposition is for depositing at least a layer of material selected from a group comprising tungsten, titanium, molybdenum, silicon, tantalum, nickel, zinc, copper, gold, chromium, yttria, and their oxides, nitrides and other inorganic and organometallic derivatives and combinations thereof.
  • the precursor for layering in the chemical vapor deposition is selected from a group comprising organic compounds such as metal alkoxides, metal alkyls, metal diketonites, metal amindinates, metal carbonyls, metal chlorides, organometallics, organic -inorganic materials and combinations thereof.
  • At least one of the precursor for the coating is further selected from a group such as Mo, Ta and Ti deposited from respective pentachlorides; Ni, Mo, and W deposited at low temperatures from respective carbonyl precursors; Tetrakis (dimethyl amino) titanium (TDMAT), diethyl zinc and a range of materials that can form metal oxides such as ZnO-SnO2, ZrO2, Y2O3; the noble metals Pt, Ag, Au and the metal nitrides; aliphatic or aromatic organic precursors consisting of molecules with -OH, -COOH, -NH2, - CONH2, -CHO, -COCI, -SH, -CNO, -CN, alkenes, functional groups, but not limited to and combinations thereof.
  • TDMAT Tetrakis (dimethyl amino) titanium
  • TDMAT Tetrakis (dimethyl amino) titanium
  • TDMAT Tetrakis (dimethyl amino) titanium
  • TDMAT Tetrakis (dimethyl
  • Precursor 2 generally reacts with adsorbed precursor 1 to complete the half reaction for the deposition of one atomic layer and may be an oxidizer such as oxygen, ozone, water, air and combinations and or a reducer such as hydrogen gas or a plasma excited reactant but not limited to.
  • Precursor 1 is the organometallic and the precursor 2 is the reactant that completes the reaction to make it an oxide, nitride etc.
  • the invention discloses a method where at least one carrier gas and purge gas is selected from a group of inert gases comprising argon, nitrogen, helium and combinations thereof and the flow rate of the gas is in the range of 20 to 200 seem. Further, the heater temperature in the chamber is in the range 16 - 250 °C.
  • the chamber body in which the reaction takes place is made of at least one selected from the group comprising aluminum, stainless steel and combinations thereof.
  • the chamber can be selected from an ultra-high vacuum chamber or an atmospheric chamber and is stabilized by maintaining the temperature and pressure.
  • the invention discloses a method where the pulse for the precursors is given for a time ranging from 0.1 mS to 5 seconds.
  • the thickness of the conformal atomic layer coatings is in the range of 0.1 nm to 200 nm.
  • the chuck on which the substrate is placed is heated to the desired temperature.
  • the precursors may also be heated to generate enough vapor pressure for delivery.
  • the plasma assisted ALD can also be used, where plasma-assisted atomic layer deposition (ALD) is an energy-enhanced method for the synthesis of thin films at low temperatures in which plasma is employed during one step of the cyclic deposition process.
  • ALD plasma-assisted atomic layer deposition
  • the invention also discloses a method wherein spatial ALD may also be one of the methods for coating, wherein the substrate is moved in space below a special gas curtain, and the precursor gases are separated by inert gas curtains.
  • the spatial ALD separates the two precursors in space, rather than in time.
  • the substrate is moved back and forth between the two precursor gases to replicate the sequential exposures. This eliminates the evacuation and purge steps that make traditional ALD slow.
  • Spatial ALD can operate in atmospheric conditions which make it very practical. At the same time, it can produce thin-film layers of materials that are dense and pinhole-free. Also, it can deposit thin films at low temperatures (typically ⁇ 350 °C) and at the same time can be couple orders of magnitude faster than conventional ALD, and is scalable as it can deal with large substrates.
  • the invention discloses a method of antimicrobial coatings wherein self assembled monolayers such as thiols, phosphonic acids, silanes may be used for further enhancement of antimicrobial properties and other features for medical devices, steel substrates, glass displays.
  • self assembled monolayers such as thiols, phosphonic acids, silanes
  • Aerosol assisted CVD may also be applied to administer molecules especially low vapor pressure molecules to the surfaces.
  • the anti-bacterial, anti-viral and anti-fungal property with the films deposited is expected to be far better because of the unique combination of materials.
  • MLD molecular layer deposition
  • ALD atomic layer deposition
  • MLD can help in deposition of organic -inorganic materials.
  • the backbone of the organic precursors can be aliphatic, or aromatic.
  • the organic precursors usually consist of molecules with -OH, -COOH, -NH2, -CONH2, -CHO, -COCI, -SH, -CNO, -CN, alkenes, etc. functional groups.
  • organometallic precursors can be for the deposition of hybrid organic-inorganic MLD layers, for example, zinc alkyls such as Zn(CH2CH3)2, diethylzinc can react with diols such as ethylene glycol or trimethylaluminium can react with ethylene glycol.
  • metal alkyls of Mg and Mn such as Mg(Cp)2 and Mn(Cp)2 where Cp is the cyclopentadienyl ligand could be considered, metal alkyls based on magnesium (Mg) and manganese (Mn) that react with diols, can possibly be used.
  • Mg magnesium
  • Mn manganese
  • Other possible metal alkyls are ferrocene, Fe(Cp)2, nickelocene, Ni(Cp)2 and cobaltocene, Co(Cp)2, but not limited to.
  • the invention discloses a method of coating nanolaminates where physical vapor deposition is for depositing layers of metal containing materials selected from a group comprising titanium, titanium nitrate, tantalum, tantalum nitrate, compounds of metals such as copper, silver, gold and combinations thereof and derivatives of nitrides, oxide, carbide, boride but not limited to.
  • PVD Physical vapor deposition
  • a vapor in the form of atoms, molecules, or ions, of the coating material supplied from a target. They are then transported to and deposited on the substrate surface, resulting in coating formation.
  • the substrate temperature is substantially lower than the melting temperature of the target material, making it feasible to coat temperature-sensitive materials.
  • Examples of commonly used PVD processes include thermal evaporative deposition, ion plating, pulsed laser deposition, and sputter deposition.
  • sputtering is more suitable for target materials that are difficult to deposit by evaporation, such as ceramics and refractory metals.
  • coatings prepared by sputtering usually have a better bonding strength to the substrate than those deposited by evaporation.
  • Thermal evaporation basically uses a resistive heat source to evaporate a solid material in a vacuum environment to form a thin film.
  • the material is heated in a high vacuum chamber until vapor pressure is produced.
  • the evaporated material, or vapor stream traverses the vacuum chamber with thermal energy and coats the substrate.
  • Sputtering sources often employ magnetrons that utilize strong electric and magnetic fields to direct charged plasma on the sputter target.
  • the sputter gas is typically an inert gas such as argon.
  • the argon ions created as a result of these collisions lead to the good deposition.
  • evaporation of the target is conducted by resistive heating to achieve the vapor-phase deposition on the substrate. In this method, the target is heated to its evaporation point using electrical energy.
  • the vapor phase species then reaches the substrate where it nucleates to form the layer. Further, supers aturation comprises covering of almost all active sites on the substrate by a precursor of the material to make a fully reacted layer on the surface.
  • the precursor that is to be administered enters the chamber in the vapor phase and gets deposited by reacting with the substrate functionalities or the layer from the earlier half-reactions.
  • the transfer of substrate from one chamber to another involves minimum queue time and exposure to ambient conditions, with maintenance of an inert and/or a vacuum environment.
  • the substrate for coating is glass, soft polymeric materials, and hard surfaces such as surgical instruments / medical devices, powder, synthetic and organic materials or combinations thereof.
  • the invention discloses a method where at least one coating comprises a plurality of monolayers, wherein a first layer of material and a second layer of material for the coating have same or different characteristics and the coating is deposited using a chemical vapor deposition process or physical vapor deposition process.
  • the coatings for substrates by Vapor Deposited method is selected from a group comprising chemical vapor deposition (CVD) such as atomic layer deposition (ALD), spatial ALD, Molecular layer deposition (MLD), selfassembled monolayers (SAM), aerosol assisted deposition (AACVD) and physical vapor deposition (PVD) such as thermal spray, sputtering, thermal evaporation, patterning of layers with lithography and combinations thereof.
  • CVD chemical vapor deposition
  • ALD atomic layer deposition
  • MLD Molecular layer deposition
  • SAM selfassembled monolayers
  • PVD physical vapor deposition
  • Coating by chemical vapor deposition of substrates is done with at least one selected from aerosol assisted CVD (AACVD) or deposition with self-assembled monolayers (SAM) with organic molecules using dip, spray to electrostatically charge the surface of the nanolaminates.
  • AACVD aerosol assisted CVD
  • SAM self-assembled monolayers
  • the invention discloses a method where the nanolaminates based on the optical, mechanical, electrical, and magnetic properties of the coatings has applications in a variety of areas such as semiconductor, energy storage, MEMS, life sciences and drug delivery, but not limited to.
  • Laminates ensure good antimicrobial performance as compared to single films and when the films are very thin, the lower layers influence the overall antimicrobial activity.
  • Example 1 In this example nanolaminates with several quartz wafers, with different combinations of the ALD layering were prepared as depicted in Figure 3. The figure describes the details of the samples prepared using nanolaminates containing layers of ALD (CVD) and thermal evaporation (PVD). The thickness of the TiO2 and ZnO was verified using ellipsometry ( Figure 4) and that of the Cr/Au was verified using a Dektak profilometer ( Figure 5). The verification of the thickness of the TiO2 and ZnO layers was done respectively (Table 1 & 2).
  • the average thickness of the deposited TiO2 layer turned out to be around 40 nm.
  • Example 2 Further as gold is known to have exceptional antimicrobial properties, layers of chromium (Cr) (for adhesion) and Gold (Au) were deposited onto the samples to evaluate this (Table 3).
  • thermal evaporation methodology involved a resistive heat source to evaporate a solid material in a vacuum environment to form a thin film. The material is heated in a high vacuum chamber until vapor pressure is produced. Thermal evaporation deposits both metals and nonmetals, including aluminum, chrome, gold, indium, and many others. Complex applications include the co-deposition of several components and can be achieved by carefully controlling the temperature of individual crucibles. In this deposition the rate of deposition was monitored using quartz crystal rate sensor. The samples were cleaned using piranha solutions and the rest of the parameters are presented below.
  • the thickness of the resultant film measured using a Dektat profilometer was recorded to be an average of 96 nm.
  • the layers of the metal were deposited using the thermal evaporator tool, the important point being the combination of vapor-phase metal with other photocatalytic materials as an important aspect of the invention.
  • Example 3 Microbiological studies: Further the antimicrobial ability of the described stacks was studied by using various standard methods. ASTM-2149 test was done for checking the anti microbial activity of the coatings. 10 ul vol. of approx. 1-5 x 10 4 CFU/ml of cell culture was applied on to the glass quart which was placed individually into separate sterile plates. The glass quart was left into incubator at 37 deg. for 10 min for drying. After drying, this glass quart was put into the 100 ml phosphate buffer and each sample was vertex for 1 hour contact time, then it was removed and it was added into the Neutralizer solution. It was placed into different sterile petri dishes and neutralizing media was poured into each quart.
  • ASTM-2149 test was done for checking the anti microbial activity of the coatings. 10 ul vol. of approx. 1-5 x 10 4 CFU/ml of cell culture was applied on to the glass quart which was placed individually into separate sterile plates. The glass quart was left into incubator at 37 deg. for
  • Example 4 Another test was done to check the antimicrobial activity of glass quart against E.coli organism. 10 ul vol. of approx. 1-5 x 10 6 CFU/ml of cell culture was applied on to glass quart which was placed individually into separate sterile plates and the above glass quart was left into incubator 37 deg. for 10 min for drying. After drying, this glass quart was put into the 100 ml phosphate buffer for 1 hour contact time, then removed it and added it into neutralizer solution along with microbes. It was placed into different sterile petri dishes and neutralizing media was poured into each quart. Each sample was vortexed for 2 min to facilitate the release of the carrier load from the sample surface into neutralizing broth then the analysis was performed. Their controls were plated with SCDA by taking 1 ml volume. Incubated the plates for 37 deg. 48 hrs. After incubation took out the readings with the help of colony counter and the results were interpreted. (Table 7)
  • test samples Glass quart when compared with Lab Glass slide SAMPLE as reference sample showed antimicrobial activity against E. coli bacteria. (Table 8)
  • the coating of the present invention had several unique mechanisms of action compared with single layer coatings and the ZnO and TiOz layers together provided an extremely synergistic effect.
  • the polarity of the surfaces was also studied, with the results presented in the table below (Table 9).
  • the TiO2 and ZnO yielded a more hydrophobic surface but the effects of the overall film-stack also affected the layers on top. Further, the spectrophotometric profile was also measured and the sample 4 showed a good transmittance.
  • Example 5 Autoclave experiment: A single ZnO layer was grown both on borofloat glass and Stainless Steel.
  • the experimental conditions for ZnO deposition via ALD were as follows: Borofloat wafers and coupons of Stainless Steel were cleaned using piranha solutions. The deposition of ZnO was done as before. The process parameter used was 200 °C chamber temperature for a total of 580 cycles. The rate of deposition was 1.1 Angstroms/cycle. The thickness of the resulting coatings was verified using ellipsometry and the results are presented below (Table 10). The resultant thickness was around 66 nm. [0078] TablelO: Validation using ellipsometry 5-point measurement
  • test Carrier Inoculums 10 ⁇ l vol. of approx. 1-5 x 10 6 CFU/ml of cell culture was applied on to the substrates which were placed individually into separate sterile plates. Further the SS substrate was allowed to dry in the incubator at 37 deg. for 10 min. After drying, this SS substrate was put into the 100 ml phosphate buffer; each sample was vortexed for 1 hour contact time, followed by adding it into neutralizer solution.
  • the methodology of anti-microbial coatings using the atomic layer deposition (ALD) in the present invention can be regarded as a special type of chemical vapor deposition (CVD), where the process consists of introducing a precursor gas that attaches to all surfaces of the article as a monolayer.
  • CVD chemical vapor deposition
  • ultra-thin, biocompatible ALD coatings can yield hermetic encapsulation of the device/ surfaces, with a fraction of film thickness compared to other coating methods and with superior film uniformity and conformality, ensuring pinhole-free coverage. It can enable the use of common base materials, e.g., plain glass and stainless steels instead of costly base materials.
  • the thermal ALD of many other metals is challenging because of their very negative electrochemical potentials.
  • the present invention intends to provide a big change in the field of antimicrobial coating by composite vapor deposition techniques.
  • strong reducing agents can facilitate low-temperature thermal ALD processes for several electropositive metals.
  • titanium and tantalum can be deposited from their respective metal chlorides and aluminum metal can be deposited using an aluminum dihydride precursor and AICI3.
  • the deposition of antimicrobial metal layers by ALD is also covered in this work, where the coatings are non-toxic and of non-sensitizing/inert nature.
  • vapor phase deposition and especially ALD is an important method where thin, conformal, hermetic, non-toxic, aseptic coatings can be deposited.This would be useful for applications such as display screens, surgical tools and in the medical implants for instance.
  • microelectronics are being increasingly combined with miniaturized devices embedded into body parts such as the heart etc. and protecting these devices from the body environment is important for the smooth functioning of the device. Going forward this technology will be important also for orthopedic devices and for the medical and health-care industry in general.
  • Hydrophobicity and Oleophobicity Anti-stick in nature (as evidenced by increasing hydrophobicity).
  • the coatings can be synthesized to repel micro-organisms by their intrinsic hydrophobic nature.
  • Non-reactive/ inert surface so can be used in variety of applications.
  • the coatings were stable even after multiple cycles of autoclaving.
  • Oxidation protection the layers impart an oxidation protection to the underlayers.
  • the coatings can be designed to impart excellent wear and abrasion resistance.

Abstract

La présente invention se rapporte à un procédé de fabrication de nanostratifiés à l'aide de procédés de dépôt en phase vapeur tels que le dépôt chimique en phase vapeur et le dépôt physique en phase vapeur, qui peuvent être appliqués sur diverses surfaces, y compris le verre, les matériaux polymères souples ou les instruments chirurgicaux, ainsi que des matériaux synthétiques, composites et organiques. L'invention se rapporte à des procédés de fabrication de nanostratifiés par utilisation de réactions de surface séquentielles, les revêtements antimicrobiens étant fournis par l'utilisation d'un procédé de dépôt de couche atomique (ALD), d'un dépôt par pulvérisation thermique et/ou d'un dépôt assisté par aérosol.
PCT/IN2022/050576 2021-08-30 2022-06-23 Nanostratifiés antimicrobiens utilisant des procédés de dépôt en phase vapeur tels que le dépôt de couche atomique WO2023031951A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014008365A1 (fr) * 2012-07-06 2014-01-09 Applied Materials, Inc. Dépôt de films de n-métal comportant des alliages d'aluminium
WO2014066482A1 (fr) * 2012-10-23 2014-05-01 Applied Materials, Inc. Dépôt de films comportant des alliages d'aluminium ayant une teneur en aluminium élevée

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014008365A1 (fr) * 2012-07-06 2014-01-09 Applied Materials, Inc. Dépôt de films de n-métal comportant des alliages d'aluminium
WO2014066482A1 (fr) * 2012-10-23 2014-05-01 Applied Materials, Inc. Dépôt de films comportant des alliages d'aluminium ayant une teneur en aluminium élevée

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