WO2010041278A1 - Procédé pour obtenir un revêtement à base d'un composé métallique sur un substrat, appareil et substrat - Google Patents

Procédé pour obtenir un revêtement à base d'un composé métallique sur un substrat, appareil et substrat Download PDF

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WO2010041278A1
WO2010041278A1 PCT/IN2009/000555 IN2009000555W WO2010041278A1 WO 2010041278 A1 WO2010041278 A1 WO 2010041278A1 IN 2009000555 W IN2009000555 W IN 2009000555W WO 2010041278 A1 WO2010041278 A1 WO 2010041278A1
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Prior art keywords
substrate
coating
metal
microwave
solution
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PCT/IN2009/000555
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English (en)
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Srinivasrao Ajjampur Shivashankar
Sanjaya Brahma
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Indian Institute Of Science
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/14—Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
    • C23C18/143—Radiation by light, e.g. photolysis or pyrolysis

Definitions

  • the present invention relates to the method for obtaining adherent coating of metal compounds, onto a substrate.
  • the present invention further relates to an apparatus for obtaining adherent coatings of metal compounds, onto a substrate. More particularly, the invention relates to the use of microwave irradiation of suitable chemical reactants in a solution to obtain coatings on surfaces of substrate of various shapes and sizes.
  • the invention further also relates to the coated substrate comprising an adherent coating of a metal compound.
  • thin and thick coatings are a major part of technology.
  • films thin and thick coatings
  • VLSI integrated circuits
  • PVD physical vapour deposition
  • sputtering ion-beam deposition
  • plasma-spray coating plasma-spray coating
  • PLD pulsed laser deposition
  • MBE molecular beam epitaxy
  • CVD chemical vapour deposition
  • ALD atomic layer deposition
  • spin coating spray pyrolysis
  • dip-coating dip-coating
  • sol-gel electrochemical deposition
  • PVD processes In many practical applications, it is necessary to apply a coating over large areas. These include modern semiconductor processing (microprocessor and cell phone devices), solar cells, and decorative coatings. While e-beam evaporation and sputtering are capable of providing coverage of large-area substrates, some other PVD processes such as PLD are not capable of the same.
  • the PVD processes in general, cannot provide "conformal coverage" of objects (substrates) of complex shapes. In other words, PVD processes are "line-of-sight" processes. As such, PVD processes can only provide acceptable coverage of one "flat" side of a substrate, and not of all of its contours and sides. For example, PVD cannot provide a coating of a spherical object. PVD is also a relatively slow process. That is, the coating rate can be rather low.
  • Chemical processes such as CVD and dip coating, can provide coating of large-area substrates, as well as covering substrates of complex shape (conformal coverage). They can usually provide coatings at relatively high rates as well, which can translate into a lower cost of manufacturing.
  • chemical processes generally require substrates to be maintained at elevated temperatures so that chemical reactions proceed at adequate rates. Thus, they cannot be used where the substrate is made of a low-melting material, such as a plastic (polymer).
  • What is therefore desirable is to have a process that is capable of coating large-area substrates of complex shapes at a high rate.
  • the process must enable the coating of low-melting substrates, of the type that would be involved in the technology of "flexible electronics".
  • such a process must be capable of providing coatings of "functional materials", such as complex oxides.
  • Such a versatile process for coating is presently not available.
  • the present invention overcomes the limitation associated in the prior art. Separate from the various processes so far developed in the prior art for thin film (coatings) deposition, there exist in the prior art various chemical methods, which work in the liquid (solution) medium, for the preparation of nanoparticles of different materials. Such methods usually depend on chemical reactions conducted under specific conditions in solution.
  • An objective of the present invention is to develop a method for obtaining an adherent coating of metal compound onto a substrate.
  • Another objective of the present invention is to develop an apparatus for adherent coating of a metal compound onto a substrate and to obtain the substrate coated thereof.
  • the present invention relates to a method for obtaining an adherent coating of metal compound onto a substrate, said method comprising steps of: a) dissolving a metalorganic compound in a solvent followed by stirring to obtain a precursor solution, and b) suspending the substrate to be coated in the solution and subjecting the solution to microwave irradiation to obtain a coating of metal compound onto the substrate; and an apparatus for an adherent coating of a metal compound onto a substrate, said apparatus comprising: a) a reaction chamber comprising microwave system to guide microwave irradiation on to a reaction vessel placed within the chamber, and b) a reaction vessel comprising the substrate in a solution of the metalorganic material for obtaining the coating of a metal compound onto the substrate.
  • Figure 1 A schematic drawing of the apparatus for the microwave irradiation-assisted coating process, including the reaction vessel in which coating takes place.
  • Figure 2 A flowchart showing schematically the steps involved in the said coating process.
  • FIG. 3 Scanning electron micrographs (SEM) of the coating of zinc oxide (ZnO) obtained on a Si (100) substrate using the process of the present invention, (a) Large- area SEM view and (b) Magnified SEM view
  • Figure 4 SEM of the cross-section of a coating of ZnO on Si(IOO), illustrating the uniform thickness and continuity of the coating.
  • Figure 5 X-ray diffraction pattern of a coating of ZnO on Si(IOO), confirming that it is made of crystalline ZnO, even though the coating process is conducted at a relatively low temperature.
  • Figure 6 A coating comprising ZnO nanorods grown on Ge(IOO) substrate (inset) and a low magnification image showing the large-area coating.
  • Figure 7 A coating comprising ZnO nanorods formed on ITO-coated glass substrate (inset) and a low-magnification image to show the large-area coating
  • Figure 8 A coating comprising ZnO nanorods formed on acrylic (PMMA) substrate (inset) and a low-magnification image to show the large-area coating
  • Figure 9 A coating comprising ZnO nanorods grown on Si (100) using cetyltrimethyl ammonium bromide (CTAB) as cationic surfactant. Inset provides a magnified view.
  • Figure 10 A coating comprising ZnO thin film deposited on Si (100) (inset), low magnification image shows large area coating. No surfactant used.
  • Figure 11 A coating comprising ZnO nanorods grown on Si (100) using Zn(acac) 2 .bipy as the starting precursor material. Inset provides a magnified view.
  • Figure 12 A coating comprising Fe 2 O 3 nanoparticles grown on Si (100) using Fe(acac) 3 as the starting precursor material. Inset provides a magnified view. The figure also shows the X-ray diffraction pattern, confirming that the coating comprises crystalline Fe 2 O 3 .
  • Figure 13 A coating comprising Ga 2 O 3 nanoparticles grown on Si (100) using Ga(acac) 3 as the starting precursor material.
  • Inset provides a magnified view. The figure also shows the X-ray diffraction pattern, confirming that the coating comprises crystalline Ga 2 O 3 .
  • the present invention relates to a method for obtaining an adherent coating of a metal compound onto a substrate, said method comprising steps of: a. dissolving a suitable metalorganic compound in a solvent followed by stirring to obtain a precursor solution; and b. suspending the substrate to be coated in the solution, and subjecting the solution to microwave irradiation, to obtain an adherent coating of the desired metal compound onto the substrate.
  • the metal compound (to be coated) is selected from a group comprising metal oxides, non-oxides, metal sulphides, metal oxysulphides, oxy-chalcogenides, nitrides, oxynitrides, metals or metal alloys, or any combination thereof
  • the metalorganic compound, acting as the "precursor" is selected from a group comprising metal acetates, metal beta-diketonates, metal alkoxides, metal amines, and thio-derivatives of metal complexes, and other suitable compounds of one or more metals, which are soluble in a liquid dielectric solvent.
  • the dielectric solvent may be chosen from a group comprising, but not limited to, water, alkanes, alcohols, aromatics, or a combination thereof.
  • the precursor solution contains a surfactant.
  • the surfactant is helpful in preventing agglomeration of solvent particles during irradiation.
  • the surfactant is dissolved in distilled water to obtain a dilute solution having concentration ranging from about O. lmM to about 5mM.
  • the substrate is selected from a group comprising silicon, glass, alumina, fused quartz or polymeric plastic.
  • the substrate optionally comprise a thin coating of an electrically conducting material, the thickness of said coating not exceeding 100 micrometers.
  • the substrates are of arbitrary shape and size, with or without lithographed features.
  • the substrates are either nonconducting or semiconducting substrates.
  • the substrates such as silicon, glass, alumina, fused quartz, or polymeric plastic, each substrate optionally having been coated first with a thin adherent layer of an electrically conducting substance such as a metal or a metal alloy, or an electrically conducting metal compound.
  • the source of the microwave irradiation is provided by reaction chamber comprising of microwave system.
  • the microwave system comprises of domestic or industrial-type microwave ovens, or apparatus.
  • the microwave system provides irradiation having frequency of about 900 MHz to about 10 GHz.
  • the method comprises heat treatment of the coated substrate at a temperature of about 500 0 C for a period of about less than 5 minutes to remove residual surfactant from the coated substrate.
  • the thickness of the coating ranges from about 100 nanometers to about 25 micrometers.
  • the present invention relates to an apparatus for an adherent coating of a metal compound onto a substrate, said apparatus comprising: a. a reaction chamber comprising microwave system which guides microwave irradiation on to a reaction vessel placed within the chamber; and b. a reaction vessel comprising the substrate in a solution of the metalorganic material for obtaining an adherent coating of the desired metal compound onto the substrate.
  • a reflux system is placed outside the reaction chamber.
  • the reflux system is a water-cooled condenser.
  • the microwave system provides irradiation having frequency of about 900 MHz to about 10 GHz.
  • the method comprises heat treatment of the coated substrate at a temperature of about 500 0 C for a period of about less than 5 minutes to remove residual surfactant from the coated substrate.
  • the reaction vessel is transparent to microwaves provided by the microwave system.
  • the present invention relates to a substrate comprising an adherent coating of a metal compound.
  • the substrate is a semi-conductor or a dielectric material selected from a group comprising silicon, glass, alumina, fused quartz or polymeric plastic.
  • the substrate optionally comprise a thin coating of an electrically conducting material, the thickness of said coating not exceeding 100 micrometers.
  • the present invention provides a method for coating a variety of different materials onto a variety of substrates at a low temperature, using chemical reactions assisted by microwave irradiation.
  • the method utilizes a suitable solution in a liquid form containing chosen chemical reactions, so that chemical reactions occur upon said irradiation.
  • the method provides for coating of a thin or thick film of the desired material by immersing the substrate in the said solution during the said microwave irradiation.
  • the method provides for coating a substrate of large and arbitrary physical size, so that the entire surface is covered uniformly with a coating of the desired material.
  • the method provides for coating at a rapid rate, and for alteration in the chemical composition of the desired coating material by altering the composition of the liquid solution suitably.
  • the method provides to control the microstructure of the material in the coating by choosing processing conditions, such as the molecular structure of the chemicals, the concentration of the chemicals in the solution, the solvent used to form the solution and its amount, and the duration of said irradiation.
  • the method employs chemicals known as "surfactants" in the solution to control the microstructure of the material in the coating.
  • the method chooses appropriate surfactant to control the shape and size of the microscopic particles which comprise any such coating.
  • the method provides coating in such a manner that fine lithographed features present in a suitably prepared substrate are covered uniformly by the coating material in a "conformal" manner, .i.e., conforming to the contours of the lithographed feature.
  • the present invention provides the apparatus and method for fabricating thin or thick coatings of a desired material, such as metal oxides, metals, composites of a metal and its oxide, metal sulphides, metal oxysulphides, etc. on a substrate, by subjecting an appropriately prepared liquid solution to microwave irradiation.
  • the apparatus comprises a domestic-type microwave oven or, more generally, a reaction chamber in which the reaction vessel containing the reactants in a solution may be placed, together with the substrate in which the coating is to be applied.
  • the method consists of taking a liquid solution in which the reactants are dissolved in a suitable solvent, together with a surfactant (if any) in a suitable vessel, and subjecting it to microwave radiation of chosen power and duration.
  • the coating formed on the substrate due to the irradiation may have to be heated briefly to an elevated temperature (outside the microwave apparatus) to remove residue (if any) of the surfactant.
  • the present invention describes a microwave irradiation-assisted chemical process, which is conducted in a liquid solution of chemical reactants in a dielectric solvent, whereby a coating of desired thickness of the desired material is obtained rapidly on an electrically non-conducting or semiconducting substrates of arbitrary shape and size. Coatings may also be obtained on a substrate, which has a thin coating of an electrically conducting substance, such as a metal, metal alloy, a metal oxide, a metal nitride, a metal sulphide, etc.
  • the present invention provides a method for coating substrates of large sizes (and small sizes) of arbitrary shape with a desired material, at a rapid rate, through the microwave irradiation of a solution containing appropriate chemical reactants in a suitable liquid solvent. More specifically, the present invention provides a method and related apparatus for the coating of a substrate that is kept in the solution.
  • the apparatus is illustrated schematically in Figure 1. It consists of a chamber into which microwave radiation can be "guided", using such devices as waveguides. Microwave radiation spans the frequency range from about 900 MHz to greater than 10 GHz, and is divided into various bands, such as the Q-band, etc.
  • Fig. 1 represents a chamber into which microwave radiation of such an allowed frequency is guided.
  • the reaction vessel is made of a material that is transparent to microwaves, such as glass or plastic.
  • the vessel may not be made of a metal or an alloy or any electrical conductor, as they are not transparent to microwaves.
  • the domestic-type microwave oven can be used as the reaction chamber, as illustrated in the present invention.
  • the process can be scaled up both to coat substrates of a large size and to coat many substrates in s a single coating process.
  • industrial-type microwave ovens reactors
  • These are available and have been in use for other applications, such as processing polymers and ceramics.
  • Specialised microwave systems can be built and used, and the technology for this is available.
  • the present invention involving the method for coating does not depend on the specific reactor configuration.
  • the domestic-type and industrial-type microwave ovens generally available are of the so-called “multi-mode” type, referring to the fact that many electromagnetic "modes” of microwaves are present in such apparatus. It is also possible to use specialised "mono-mode” microwave systems for the application of coatings described in this invention. Such apparatus uses a single electromagnetic mode of microwaves.
  • the present invention involving the method for coating does not depend on the specific reactor configuration, or on whether the microwaves are multi-mode or mono-mode.
  • the reaction vessel contains a solution, of which the solvent is a microwaves- absorbing dielectric liquid such as (but not limited to) ethanol, methanol, decanol, water, n-hexane, etc.
  • the apparatus includes the substrate on which the desired coating is to be made. This is usually made of a semiconducting or insulating material, such as silicon, glass, alumina, fused quartz, or a polymeric plastic (such as acrylic or nylon). A number of different substrates of different shapes and sizes can be coated.
  • the reason the process is capable of coating substrates of any shape is that the substrates are immersed (suspended) in a liquid, which therefore surrounds the substrate. As a result, chemical reaction occurs on the entire surface of the substrate, leading to a coating.
  • the substrates are PLACED ON A FLAT SURFACE in the apparatus. So, the underside of the substrate does not get coated. These are usually "line-of-sight" processes.
  • the process of the present invention is similar to electrochemical plating in the limited sense that the substrate is suspended in a liquid, and all contours are coated (for example, electrochemical gold coating of jewelry by electroplating).
  • the solution penetrates crevices and other openings in the substrate, thus coating inside these crevices as well.
  • the size of the substrate to be coated is limited only by the size of the reactor. Large industrial reactors are available, and these can be used to coat large substrates.
  • figure 2 represents the method or the process of the present invention, which leads to a coating of the desired material on the substrate chosen and placed in the solution, as shown schematically in Fig. l.
  • the compounds may be metalorganic complexes, metal acetates, metal alkoxides, thio-derivatives of metal complexes, or any other metal compounds which dissolve in a solvent of the kind described above.
  • the quantity of solution taken depends on the size o of the vessel and the thickness of the desired coating.
  • the solution may not contain a surfactant.
  • the solution may also comprise a surfactant, such as poly(vinylpyrrolidone), in an appropriate concentration.
  • a surfactant such as poly(vinylpyrrolidone)
  • the solution is then subjected to microwave irradiation of a power and duration that results in the desired coating on the substrate. After irradiation is complete, the substrate is removed from the reaction chamber, to examine the coating and to use it for the intended purpose. If a surfactant has been used in the coating process, it may become necessary to heat the substrate briefly to about 500 0 C to remove any leftover surfactant material from the coating.
  • figures 3 and 4 show scanning electron micrographs (SEM) of ZnO coatings obtained on Si(IOO) by the process described in this invention, indicating the continuity and uniformity of the coating. Further, Fig.4 provides a measurement of the thickness of the ZnO coating. Figure 5 shows the X-ray diffraction pattern of the coating, which is in complete agreement with the pattern known for ZnO. Specifically, Fig.5 shows that the ZnO coating is crystalline in character, even though it has been prepared by a low-temperature process.
  • the coating is crystalline as prepared. Such crystallinity is important in many practical applications of ZnO and other materials.
  • treatment at an elevated temperature is not necessary in all cases, and is not required at all where no surfactant is used. This is especially important for coatings on polymer (plastic) substrates, which cannot withstand elevated temps. Treatments at elevated temperatures help crystallization and are carried out for two specific reasons: 1) to improve crystallization and 2) to remove the residual surfactant so that the coated material is as pure as possible. If no surfactant is used, no heat treatment is usually required, and is therefore more advantageous.
  • metal precursor metalorganic complex
  • a suitable dielectric solvent HPLC- grade desirable, but lower grade is sufficient
  • Step 2 (optional step)
  • a dilute solution of a surfactant in double-distilled water is prepared separately, and added to the precursor solution, followed by about fifteen minutes of stirring.
  • the surfactant is helpful in preventing agglomeration of particles that might result from the microwave irradiation.
  • Step 3 A suitable substrate is suspended in the solution containing metalorganic complex (optionally along with surfactant) taken in a round-bottomed flask, or other suitable vessel.
  • Step 4 The round-bottomed flask is then placed in a domestic-type microwave oven (operating at 2.45 GHz, with variable power) or an industrial-type microwave reactor (with variable power), equipped with a water-cooled condenser (reflux system) placed outside the microwave oven (as shown in Figure 1). Microwave radiation is switched on, and the solution subjected to microwave radiation at a suitable power, and for a suitable duration of time.
  • Step 5 After irradiation, the substrate is removed carefully from the solution and washed with distilled water and acetone. A visible, adherent coating will be found on the substrate.
  • the substrate with the coating is heated for a few minutes in air at 500 0 C to remove any residual surfactant that might be present.
  • the coated substrate may or may not need post-synthesis annealing, depending on the solvent and surfactant used.
  • the compound of zinc used is a metalorganic complex of zinc, e.g., zinc acetylacetonate.
  • a solution is prepared with one gram of zinc acetylacetonate dissolved in 40 ml of ethanol and stirred well.
  • the vessel is placed in a microwave oven (reaction chamber) and microwave power at 2.45 GHz turned on at about 800 W. The power is maintained for about 5 minutes and then turned off. The substrate is then taken out of the vessel and heated to about 500 0 C in air for about 10 minutes. A coating of ZnO measuring about 2 micrometers in thickness will then be found on the substrate.
  • Example 2 ZnO COATING ON AN ACRYLIC SUBSTRATE Conditions as described in Example 1 above are used, except that the substrate is made of acrylic [poly(methyl methacrylate), usually abbreviated as PMMA] measuring about 20 mm x 20 mm in size, and a thickness of about 1 mm.
  • PMMA poly(methyl methacrylate)
  • the deposition process as in Example 1 is repeated to get a coating on the substrate.
  • the substrate is heated rapidly and briefly (less than one minute) in air to about 500 0 C (using, for example, halogen lamps), so that the polymer plastic substrate (acrylic) does not melt or deform.
  • the result is a uniform coating crystalline ZnO on the acrylic substrate measuring about two micrometers in thickness.
  • Example 2 A COATING OF ZnO NANORODS GROWN ON Ge(IOO) SUBSTRATE Conditions as described above in Example 1 are used, except that the substrate is single-crystalline germanium, Ge (100).
  • the deposition process as in Example 1 is repeated to get a coating on the substrate.
  • the substrate is heated rapidly and briefly (less than 5 minutes) in air to about 500 0 C in air.
  • the result is a uniform coating crystalline ZnO on the Ge substrate measuring about one micrometer in diameter ( Figure 6).
  • Example 7 Conditions as described above in Example 1 are used, except that the substrate is indium tin oxide-coated glass (ITO-coated glass).
  • ITO-coated glass indium tin oxide-coated glass
  • the deposition process as in Example 1 is repeated to get a coating on the substrate.
  • the substrate is heated rapidly and briefly (less than 5 minutes) in air to about 500 0 C.
  • the result is a uniform coating crystalline ZnO on the ITO-coated glass substrate measuring about two micrometers in thickness ( Figure 7).
  • ITO is an electrically conducting, transparent coating, useful in devices such as photovoltaics. It must also be noted that, in general, electrical conductors reflect microwaves (and other electromagnetic) radiation. Hence, it is not at all obvious that the process invented and described here would be successful in coating conducting substrates. Coatings of ZnO may be similarly obtained on substrates such as soda glass and Si(IOO), which are coated with a thin layer of a metal such as aluminium or chromium.
  • Example 1 Conditions as described above in Example 1 are used, except that the substrate is a thin (flexible) plate of acrylic, as in EXAMPLE 2, and the surfactant is cetyltrimethyl ammonium bromide (CTAB) which is a cationic surfactant.
  • CTAB cetyltrimethyl ammonium bromide
  • CTAB cetyltrimethyl ammonium bromide
  • CTAB cetyltrimethyl ammonium bromide
  • Example 1 The synthesis conditions described in Example 1 are used but no surfactant is used here.
  • the deposition process is very simple where the precursor is dissolved in the solvent decanol followed by irradiation of microwaves. About one gram of Zn(acac) 2 and -80 ml of decanol are taken in a round bottom flask, stirred for about 30 minutes and subjected to microwave irradiation at 800 W for about 5 minutes. The substrate was washed with distilled water and acetone and dried in air. No post-synthesis annealing is required (Figure 10).
  • Example 1 Conditions as described above in Example 1 are used, except that the starting precursor material is the adducted precursor of Zn(acac) 2 .
  • the starting precursor material is adducted with a 2, 2' bipyridyl ligand and the molecular formula is (C 10 H 14 O 4 . Zn. CioH 8 N 2 ), denoted by Zn(acac) 2 (bipy).
  • the deposition process as in Example 1 is repeated to get a coating on the substrate.
  • the substrate is heated rapidly and briefly (less than 5 minutes) in air to about 500 0 C in air.
  • the result is a uniform coating crystalline ZnO on the Si(IOO) substrate measuring about one micrometer in diameter ( Figure 11).
  • the process and the precursor of Example 8 illustrates the capability of the present invention to yield coatings of a material with controlled microstructure (tapered ZnO nanorods, in this case).
  • the thin film deposition process of the present invention has the capability to deposit thin films or coating of various metal oxides.
  • a coating of iron oxide (Fe 2 O 3 ) on a substrate of Si(IOO) the compound of iron used is a metalorganic complex of iron, e.g., iron acetylacetonate, (Fe (CsH 7 O 2 ) 3 ), designated by Fe(acac) 3 .
  • Fe (CsH 7 O 2 ) 3 ) 3 designated by Fe(acac) 3 .
  • a solution is prepared with one gram of iron acetylacetonate dissolved in 40 ml of methanol and stirred well.
  • a solution of about 0.3 gram of the surfactant poly(vinylpyrrolidone) (raw - 360000) in about 40 ml of water, and stirred well.
  • This solution is taken in a glass vessel in which is placed a Si(IOO) substrate measuring about 20 mm x 20 mm.
  • the vessel is placed in a microwave oven (reaction chamber) and microwave power at 2.45 GHz turned on at about 800 W. The power is maintained for about 5 minutes and then turned off.
  • the substrate is then taken out of the vessel and heated to about 500 0 C in air for about 10 minutes.
  • a coating of Fe 2 O 3 measuring about -150 nm in thickness will then be found on the substrate ( Figure 12).
  • the condition reported in Example 9 may be used, except that the starting precursor material is Ga(acac)3.
  • the method is repeated and nanoparticle thin film of Ga 2 O 3 is deposited on Si(IOO).
  • the substrate is heated rapidly and briefly (less than 5 minutes) in air to about 500 0 C in air.
  • the result is a uniform coating crystalline Ga 2 O 3 on the Si(IOO) substrate measuring about one micrometer in thickness ( Figure 13).
  • Example 9 The conditions cited in Example 9 may be employed, except that the precursor solution is made of both Zn(acac) 2 and Fe(acac) 3 , taken in 1:2 molar proportion, and dissolved in methanol and stirred well. To this is added a solution of about 0.3 gram of the surfactant poly(vinylpyrrolidone) (mw - 360000) in about 40 ml of water, and stirred well. This solution is taken in a glass vessel in which is placed a Si(IOO) substrate measuring about 20 mm x 20 mm. The vessel is placed in a microwave oven (reaction chamber) and microwave power at 2.45 GHz turned on at about 800 W. The power is maintained for about 5 minutes and then turned off. The substrate is then taken out of the vessel and heated to about 500 0 C in air for about 10 minutes. A coating of crystalline zinc ferrite, ZnFe 2 O 4 will be found on the substrate.
  • the precursor solution is made of both Zn(acac) 2 and Fe(a
  • a thin film of a perovskite such as BaTiO 3
  • a thin film of a perovskite such as BaTiO 3

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  • Thermal Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Ceramic Engineering (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemically Coating (AREA)

Abstract

Cette invention concerne un procédé pour obtenir un revêtement adhésif à base de composés métalliques, sur un substrat. Cette invention concerne également un appareil permettant d'obtenir des revêtements adhésifs à base de composés métalliques, sur un substrat. Plus particulièrement, cette invention concerne l'utilisation d'un rayonnement hyperfréquence de réactifs chimiques appropriés en solution pour obtenir des revêtements sur des surfaces de substrats de diverses formes et tailles. En outre, cette invention concerne également le substrat revêtu comprenant un revêtement adhésif à base d'un composé métallique.
PCT/IN2009/000555 2008-10-06 2009-10-06 Procédé pour obtenir un revêtement à base d'un composé métallique sur un substrat, appareil et substrat WO2010041278A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN2449CH2008 2008-10-06
IN02449/CHE/2008 2008-10-06

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WO2010041278A1 true WO2010041278A1 (fr) 2010-04-15

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4052283A4 (fr) * 2019-10-31 2023-11-22 Indian Institute Of Science Appareil assisté par micro-ondes, système et procédé de dépôt de films sur substrats

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5399388A (en) * 1994-02-28 1995-03-21 The United States Of America As Represented By The Secretary Of The Navy Method of forming thin films on substrates at low temperatures
US20040265507A1 (en) * 2003-06-17 2004-12-30 Rong Xiong Process for the preparation of metal oxide coated organic material by microwave deposition
WO2006014265A1 (fr) * 2004-07-06 2006-02-09 Hewlett-Packard Development Company, L.P. Formation d'une structure
JP2007172870A (ja) * 2005-12-19 2007-07-05 Bridgestone Corp プラズマディスプレイパネルの製造方法
WO2007102676A1 (fr) * 2006-03-07 2007-09-13 Korea Research Institute Of Chemical Technology Nouveau procédé de préparation de composés polymères de coordination poreux à base d'ion zinc et de carboxylates

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5399388A (en) * 1994-02-28 1995-03-21 The United States Of America As Represented By The Secretary Of The Navy Method of forming thin films on substrates at low temperatures
US20040265507A1 (en) * 2003-06-17 2004-12-30 Rong Xiong Process for the preparation of metal oxide coated organic material by microwave deposition
WO2006014265A1 (fr) * 2004-07-06 2006-02-09 Hewlett-Packard Development Company, L.P. Formation d'une structure
JP2007172870A (ja) * 2005-12-19 2007-07-05 Bridgestone Corp プラズマディスプレイパネルの製造方法
WO2007102676A1 (fr) * 2006-03-07 2007-09-13 Korea Research Institute Of Chemical Technology Nouveau procédé de préparation de composés polymères de coordination poreux à base d'ion zinc et de carboxylates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4052283A4 (fr) * 2019-10-31 2023-11-22 Indian Institute Of Science Appareil assisté par micro-ondes, système et procédé de dépôt de films sur substrats

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