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(12) Patent Application Publication (10) Pub. No.: US 2012/0202037 A1 Ryabova (43) Pub US 20120202037A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2012/0202037 A1 Ryabova (43) Pub. Date: Aug. 9, 2012 (54) SOLUTION DERIVED NANOCOMPOSITE Publication Classification PRECURSORSOLUTIONS, METHODS FOR (51) Int. Cl. MAKING THIN FILMS AND THIN FILMS C09D I/00 (2006.01) MADE BY SUCH METHODS HOB I/2 (2006.01) BSD L/18 (2006.01) BOSD I/28 (2006.01) (75) Inventor: Elmira Ryabova, Mountainview, BOSD 3/6 (2006.01) CA (US) BOSD 3/12 (2006.01) (52) U.S. Cl. ......... 428/220; 427/558; 427/557; 427/542: (73) Assignee: ADVENIRA, INC., Mountainview, 427/541; 106/14.15; 252/519.3 CA (US) (57) ABSTRACT (21) Appl. No.: 13/365,066 Solution derived nanocomposite (SDN) precursor solutions are disclosed that comprise one or more metal precursors that are dissolved in a liquid comprising polar protic and polar (22) Filed: Feb. 2, 2012 aprotic solvents. The precursor Solutions are characterized by the formation of a gel after a shear force is applied to the Related U.S. Application Data precursor Solution or to a thin layer of precursor Solution. Also disclosed are methods using Such precursor Solutions to make thin films, thin films made using the precursor Solu (60) Provisional application No. 61/438,862, filed on Feb. tions, thin films having a minimum surface area and devices 2, 2011. containing thin films as disclosed herein. Patent Application Publication Aug. 9, 2012 US 2012/0202037 A1 |aumôr: is 8 is US 2012/0202037 A1 Aug. 9, 2012 SOLUTION DERVED NANOCOMPOSITE hybrid sol-gels can be made by UV induced polymerization PRECURSORSOLUTIONS, METHODS FOR or as a product of the specific reaction. Additional curing, if MAKING THIN FILMS AND THIN FILMS necessary, is generally performed at between about 20° C. MADE BY SUCH METHODS and 200° C. 0007 Solution sol-gel processes generally involve dip, spin or spray coating and are therefore limited in the Surface 0001. This application claims priority to U.S. Provisional area of the substrate that can be coated with the thin film. Application Ser. No. 61/438,862 filed Feb. 2, 2011 entitled Examples include optical lenses and biomedical devices Such Solution Derived Nanocomposite Precursor Solutions and as implants and vascular stents. The maximum surface area Methods for Making Thin Films the entire disclosure of that can be covered by Such techniques is typically less than which is expressly incorporated herein by reference. about 50 cm. General purposeroll coaters have not been used Successfully because of the difficulties in forming and main TECHNICAL FIELD taining a dynamic wetting line using non-Newtonian fluids. 0002 Solution derived nanocomposite (SDN) precursor SUMMARY OF THE INVENTION Solutions are disclosed that comprise one or more, preferably two or more, metal precursors that are dissolved in a liquid 0008. In one embodiment an SDN precursor solution con comprising polar protic and polar aprotic solvents. The pre tains (1) one or more, preferably two or more, Sol-gel metal cursor Solutions are characterized by the formation of a gel precursors and/or sol-gel metalloid precursors, (2) a polar after a shear force is applied to the precursor Solution or to a protic solvent and (3) a polar aprotic solvent. The amount of thin layer of precursor Solution. Also disclosed are methods each component is such that the SDN precursor solution using Such precursor Solutions to make thin films, thin films forms a gel after a shear force is applied to the precursor made using the precursor Solutions, thin films having a mini solution or a thin layer of precursor solution. In a preferred mum surface area and devices containing thin films as dis embodiment, the amount of polar aprotic solvent is about closed herein. 1-25 vol% of the precursor solution. 0009. The metal in the sol-gel metal precursors can be one BACKGROUND OF THE INVENTION or more of the transition metals, the lanthanides, the actinides, the alkaline earth metals and Group IIIA through Group VA 0003. Thin film coatings or layers of multilayer film stacks metals or combinations thereof with another metal or metal are found in many devices. For example, binary and ternary loid. metal-nonmetal compounds, including but not limited to 0010. The metalloid in the sol-gel metalloid precursors YO, ZrO, YZO, Hfo, YHO, Al-O, AIO, ZnO, AZO, can be one or more of boron, silicon, germanium, arsenic, ITO, SiC, SiN. SixCyNZ, SixOyNZ, TiO, CdS, ZnS, antimony, tellurium, bismuth and polonium or combinations Zn2SnO, SiO, WO, CeO and so on, have been deposited thereof with another metalloid or metal. as thin film coatings or layers of multilayer film stacks for 0011. The sol-gel metal precursors can be metallic com various purposes. Such thin films include transparent conduc pounds selected from organometallic compounds, metallic tive oxide (TCO) electrodes, passivating films, back surface organic salts and metallic inorganic salts. The sol-gel metal field (BSF) layers, diffusion barriers, up-converters, down loid precursors can be metalloid compounds selected from converters, selective emitter masks, ion storage layers such as organometalloid compounds, metalloid organic salts and found inlithium ion batteries or electrochromic devices, solid metalloid inorganic salts. When more than one metal or met electrolytes, moisture barriers, abrasion resistance layers, alloid is used it is preferred that one be an organic compound thermal barriers, impedance correction layers, Surface modi Such as analkoxide and the other an organic or inorganic salt. fication layers, dielectric thin films, reflective and antireflec 0012. The polar protic solvent used in the precursor solu tive layers and the like. tion is preferably an organic acid or alcohol, more preferably 0004. There are a number of known methods for deposit a lower alkyl alcohol such as methanol and ethanol. Water ing such thin films. These methods can be divided into two may also be present in the solution. categories: vacuum techniques such as PVD, CVD. ALD and 0013 The polar aprotic solvent can be a halogenated MBE and non-vacuum techniques such as electroplating, alkane, alkyl ether, alkyl ester, ketone, aldehyde, alkylamide, CBD and screen printing. All of these approaches are expen alkyl amine, alkyl nitrile or alkyl sulfoxide. Preferred polar sive and time consuming. aprotic solvents include methylamine, ethylamine and dim 0005 Sol-gel processes have been used to make thin films. ethyl formamide. Sol-gel thin films can be made using a sol-gel medium con 0014. In one embodiment, the metal and/or metalloid pre taining a colloidal Suspension of particles or a sol-gel Solu cursor is dissolved in the polar protic solvent. The polar tion. Processes using sol-gel solutions generally involve aprotic solvent is then added while the solution is stirred applying a thin film of a sol-gel precursor Solution that con under conditions that avoid non-laminar flow. Acid or base, tains metal precursors such as metal salts in combination with which is used as a catalyst for polymerization of the metal metal alkoxides. In some applications, the thin film is and/or metalloid precursors, can be added before or after the annealed attemperatures from 200° C. to 900° C. See e.g. US addition of the polar aprotic solvent. Preferably, the acid or 2004/OO58.066 and US 2007/O190361. base is added drop wise in a one step process while stirring. 0006 Hybrid sol-gel thin films have also been made. Such 0015. If too much polar aprotic solvent is added gelation thin films contain inorganic and organic components and can can occur. Accordingly, the amount of polar aprotic solvent be divided into two classes: (1) those that contain organic can be determined empirically for each application. The molecules, prepolymers or polymers embedded in an inor amount of polar aprotic solvent needs to be below the amount ganic matrix and (2) those that contain inorganic and organic that causes gelation during mixing but be sufficient to cause components that are connected by covalent bonds. Such gelation of the precursor Solution after a shear force is applied US 2012/0202037 A1 Aug. 9, 2012 to the precursor Solution, e.g. during application to a surface, 0025. The “sol-gel precursor solutions' (sometimes or when a shear force is applied to a thin film of the precursor referred to as “SDN precursor solutions” or “precursor solu solution that has been deposited on the surface of a substrate, tions') disclosed herein are different in that gelation is deter e.g. by application of a doctor blade to the precursor Solution mined by the properties of the mixed solvent used to make the thin film. sol-gel precursor Solution. Rather than use a single solvent, 0016. In another embodiment, processes are disclosed for the solvent used is a mixture of (1) a polar protic solvent Such making a Solid thin film layer. The process includes applying as methanol or ethanol and (2) a polar aprotic solvent Such as precursor Solution to one or more Surfaces of a substrate dimethyl formamide, methyl amine or ethanol amine. By where the precursor Solution contains (1) one or more sol-gel metal precursors and/or sol-gel metalloid precursors, (2) a controlling the relative amounts of the protic and aprotic polar polar protic solvent and (3) a polar aprotic solvent. Preferably, Solvents and the amount of sol-gel precursors in solution (and the application of the precursor provides sufficient shear force other components that may be present) gel formation in the to cause gelation of the precursor Solution to form a gelled precursor Solution can be controlled so that it occurs shortly thin layer. Alternatively, a shear force can be applied to a thin after application on the Surface of a Substrate as a thin wet film of precursor Solution deposited on a Substrate.
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