US20130022658A1 - Depositing material with antimicrobial properties on permeable substrate using atomic layer deposition - Google Patents

Depositing material with antimicrobial properties on permeable substrate using atomic layer deposition Download PDF

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Publication number
US20130022658A1
US20130022658A1 US13/535,155 US201213535155A US2013022658A1 US 20130022658 A1 US20130022658 A1 US 20130022658A1 US 201213535155 A US201213535155 A US 201213535155A US 2013022658 A1 US2013022658 A1 US 2013022658A1
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Prior art keywords
silver
permeable substrate
precursor
injector
substrate
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Abandoned
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US13/535,155
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English (en)
Inventor
Sang In LEE
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Veeco ALD Inc
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Synos Technology Inc
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Priority to US13/535,155 priority Critical patent/US20130022658A1/en
Assigned to SYNOS TECHNOLOGY, INC. reassignment SYNOS TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: LEE, SANG IN
Priority to KR1020120078626A priority patent/KR101529985B1/ko
Publication of US20130022658A1 publication Critical patent/US20130022658A1/en
Assigned to VEECO ALD INC. reassignment VEECO ALD INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: SYNOS TECHNOLOGY, INC.
Abandoned legal-status Critical Current

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous 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
    • C23C16/44—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
    • C23C16/448—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 generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • 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]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • 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]
    • C23C16/45555—Atomic layer deposition [ALD] applied in non-semiconductor technology
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic System; Aluminates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/83—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with metals; with metal-generating compounds, e.g. metal carbonyls; Reduction of metal compounds on textiles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2041—Two or more non-extruded coatings or impregnations
    • Y10T442/2098—At least two coatings or impregnations of different chemical composition
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2926—Coated or impregnated inorganic fiber fabric
    • Y10T442/2984—Coated or impregnated carbon or carbonaceous fiber fabric

Definitions

  • Silver and silver compounds are well known to have superb antimicrobial properties.
  • permeable substrates can be coated or deposited with silver for silver compounds or various medical or health-related applications.
  • silver is a precious metal and is costly. Therefore, fabric or textile coated with silver or silver compounds tends to be expensive.
  • the quality of silver or silver compound coated on such fabric or textile tend to be inconsistent and non-conformal, reducing the overall efficacy of the silver or silver compound coated on such permeable substrates.
  • FIG. 2 is a cross sectional view of the deposition device of FIG. 1 taken along line A-B, according to one embodiment.
  • FIGS. 3A through 3C are cross sectional views of a permeable substrate at different stages of a process associated with coating silver or silver compound, according to one embodiment.
  • Embodiments relate to depositing a layer of antimicrobial material such as silver or a silver compound on a permeable substrate using atomic layer deposition (ALD).
  • a deposition device includes one or more injectors that inject source precursor, reactant precursor, purge gas or a combination thereof onto the permeable substrate as the permeable substrate passes between the injectors. Part of the gas injected by an injector penetrates the permeable substrate and is discharged by the other injector. The remaining gas injected by the injector moves in parallel to the surface of the permeable substrate and is discharged via an exhaust portion formed on the same injector. While penetrating the substrate or moving in parallel to the surface, the source precursor or the reactant precursor becomes absorbed on the substrate or react with precursor already present on the substrate to deposit the antimicrobial material on the substrate.
  • FIG. 1 is a perspective view of a deposition device 100 , according to one embodiment.
  • the deposition device 100 may include, among other components, an upper reactor 130 A and a lower reactor 130 B.
  • a permeable substrate 120 moves from the left to right (as indicated by arrow 114 ) and passes between the upper and lower reactors 130 A, 130 B, depositing the permeable substrate 120 with a layer 140 of material.
  • the entire deposition device 100 may be enclosed in a vacuum or in a pressurized vessel.
  • the deposition device 100 is illustrated as depositing material on the substrate 120 as the substrate moves horizontally, the deposition device 100 may be oriented so that the layer 140 is deposited as the substrate 120 moves vertically or in a different direction.
  • the upper reactor 130 A is connected to pipes 142 A, 146 A, 148 A supplying precursor, purge gas and a combination thereof into the upper reactor 130 A. Exhaust pipes 152 A and 154 A are also connected to the upper reactor 130 A to discharge excess precursor and purge gas from the interior of the upper reactor 130 A.
  • the upper reactor 130 A has its lower surface facing the substrate 120 .
  • the lower reactor 130 B is also connected to pipes 142 B, 146 B, 148 B to receive precursor, purge gas and a combination thereof. Exhaust pipes (e.g., pipe 154 B) are also connected to the lower reactor 130 B to discharge excess precursor and purge gas from the interior of the lower reactor 130 B.
  • the lower reactor 130 B has its upper surface facing the substrate 120 .
  • FIG. 2 is a cross sectional view of the deposition device 100 taken along line A-B of FIG. 1 , according to one embodiment.
  • the upper reactor 130 A may include, among other components, a source injector 202 and a reactant injector 204 .
  • the source injector 202 is connected to the pipe 142 A to receive the source precursor (in combination with carrier gas such as Argon) and the reactant injector 204 is connected to the pipe 148 A to receive gas for generating desired reactant precursor (in combination with carrier gas such as Argon).
  • the carrier gas may be injected via a separate pipe (e.g., pipe 146 A) or via the pipes that supply the source or gas for generating the reactant precursor.
  • the multiple reactors can be arranged in a different sequence. For example, a reactant injector 204 may be placed to the left of a source injector 202 assuming that the substrate 280 moves from the left to the right.
  • Part of the excess radicals (generated by the reactant injector 204 ) pass through a constriction zone 264 and are discharged via an exhaust portion 266 .
  • the exhaust portion 266 is connected to the pipe 154 B.
  • the remaining excess radicals penetrate the substrate 120 , and are discharged via an exhaust portion formed in the injector 208 .
  • the source precursor and the reactant precursor flow perpendicular to the surface of the substrate 120 as well as in parallel to the surface of the substrate 120 . Therefore, a layer of conformal material is deposited on the flat surface as well as the pores or holes in the substrate 120 . Hence, the material is deposited more evenly and completely on the substrate 120 .
  • the distance H between the substrate 120 and the upper/lower reactor 130 A, 130 B is maintained at a low value.
  • the distance H is less than 1 mm, and more preferably less than hundreds of ⁇ ms.
  • silver compounds such as Ag X Al 1-X , Ag X Al 1-X O, Ag X Si 1-X , Ag X Si 1-X O, Ag X Ni 1-X , Ag X Ni 1-X O, Ag X Ti 1-X , or Ag X Ti 1-X O may be deposited on the permeable substrate 120 .
  • TMA trimethylaluminum
  • TEMATi tetraethylmethylaminotitanium
  • H* radicals hydrogen-containing precursors such as NH 3 , CH 4 , B 2 H 6 or reducing agents such as CO may be used as reactant precursor.
  • FIG. 3C is a cross sectional diagram of the substrate 120 deposited with a diffusion barrier 330 on the bumps 324 , according to one embodiment.
  • the bumps 324 may be deposited with the diffusion barrier 330 to prevent active substances in the environment from reacting with silver or a silver compound and degrading the antimicrobial properties of the silver or the silver compound.
  • material such as SiO 2 , Al 2 O 3 and TiO 2 may be used as material for the diffusion barrier.
  • the thickness of the diffusion barrier 330 may be in the range of 5 to 10 nm.
  • FIG. 4 is a flowchart illustrating the processes of manufacturing a permeable substrate deposited with silver or silver compound, according to one embodiment.
  • the intermediate layer 310 is deposited 406 on the permeable substrate 120 by using ALD or other deposition methods.
  • a layer 320 of silver is deposited 410 on the intermediate layer 310 using ALD.
  • the deposition device 100 of FIGS. 1 and 2 may be used.
  • the self-agglomeration of silver or the silver compound is induced 414 by subjecting the permeable substrate 120 to processes such as heat-treatment or radical annealing. As a result, bumps 324 are formed on the intermediate layer 310 .
  • the diffusion barrier layer 330 is then deposited with a diffusion barrier 330 to protect the agglomerated silver or the silver compound against external influences.
US13/535,155 2011-07-23 2012-06-27 Depositing material with antimicrobial properties on permeable substrate using atomic layer deposition Abandoned US20130022658A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/535,155 US20130022658A1 (en) 2011-07-23 2012-06-27 Depositing material with antimicrobial properties on permeable substrate using atomic layer deposition
KR1020120078626A KR101529985B1 (ko) 2011-07-23 2012-07-19 원자층 증착을 이용한 투과성 기판상의 항균 특성 물질의 증착

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US201161511025P 2011-07-23 2011-07-23
US13/535,155 US20130022658A1 (en) 2011-07-23 2012-06-27 Depositing material with antimicrobial properties on permeable substrate using atomic layer deposition

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US13/535,155 Abandoned US20130022658A1 (en) 2011-07-23 2012-06-27 Depositing material with antimicrobial properties on permeable substrate using atomic layer deposition
US13/536,646 Expired - Fee Related US8617652B2 (en) 2011-07-23 2012-06-28 Depositing material on fibrous textiles using atomic layer deposition for increasing rigidity and strength
US14/077,747 Abandoned US20140073212A1 (en) 2011-07-23 2013-11-12 Textile Including Fibers Deposited with Material Using Atomic Layer Deposition for Increased Rigidity and Strength

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US13/536,646 Expired - Fee Related US8617652B2 (en) 2011-07-23 2012-06-28 Depositing material on fibrous textiles using atomic layer deposition for increasing rigidity and strength
US14/077,747 Abandoned US20140073212A1 (en) 2011-07-23 2013-11-12 Textile Including Fibers Deposited with Material Using Atomic Layer Deposition for Increased Rigidity and Strength

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US (3) US20130022658A1 (zh)
JP (1) JP2014521832A (zh)
KR (2) KR20140048990A (zh)
CN (1) CN103890228A (zh)
TW (1) TW201311964A (zh)
WO (1) WO2013015943A1 (zh)

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CN111254413A (zh) * 2020-04-01 2020-06-09 江苏迈纳德微纳技术有限公司 一种原子层沉积技术制备银薄膜的方法
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