Solution processed thin films and laminates, devices comprising such thin films and laminates, and method for their use and manufacture

Abstract

Devices having a thin film or laminate structure comprising hafnium and/or zirconium oxy hydroxy compounds, and methods for making such devices, are disclosed. The hafnium and zirconium compounds can be doped, typically with other metals, such as lanthanum. Examples of electronic devices or components that can be made include, without limitation, insulators, transistors and capacitors. A method for patterning a device using the materials as positive or negative resists or as functional device components also is described. For example, a master plate for imprint lithography can be made. An embodiment of a method for making a device having a corrosion barrier also is described. Embodiments of an optical device comprising an optical substrate and coating also are described. Embodiments of a physical ruler also are disclosed, such as for accurately measuring dimensions using an electron microscope.

1 . A device, comprising a thin film or laminate structure comprising at least one hafnium and/or zirconium oxy hydroxy sulfate (MO 2-x-z/2 (OH) z (SO 4 ) x ) compound, hafnium and/or zirconium oxy hydroxy tungstate (MO 2-x-z/2 (OH) z (WO 4 ) x ) compound, hafnium and/or zirconium oxy hydroxy borate (MO 2-3x/2-z/2 (OH) z (BO 3 ) x ) compound, hafnium and/or zirconium oxy hydroxy phosphate (MO 2-3x/2-z/2 (OH) z (PO 4 ) x ) compound, and/or hafnium and/or zirconium oxy hydroxy silicate (MO 2-2x-z/2 (OH) z (SiO 4 ) x ) compound, where M is hafnium or zirconium, x and z may be fixed or variable, and have any value for x in a range of from about 0.1 to about 3.5/(polyatomic ion charge), and any value for z in a range of from 0.0 to about 3.8. 
     
     
         2 . The device according to  claim 1  where the compound further comprises lanthanum, and has a formula M 1-z La z O 2-x-z/2 (SO 4 ) x  (MSOx:La), where M is hafnium or zirconium, x and z may be fixed or variable, and have any value for x in a range of from about 0.1 to about 3.5/(polyatomic ion charge), and any value for z in a range of from 0.0 to about 3.8. 
     
     
         3 . The device according to  claim 1  further comprising an optical substrate where the thin film or laminate structure forms a coating on the optical substrate. 
     
     
         4 . The device according to  claim 3  where the coating is an antireflective coating and/or the coating is transparent to visible or ultraviolet light. 
     
     
         5 . The device according to  claim 3  where the optical substrate and coating define a dielectric mirror, an X-ray mirror, an interference filter, a diffractive grating, and/or a waveguide. 
     
     
         6 . The optical device according to  claim 3  where the coating is selectively doped to provide a doped light-emitting layer having luminescent ions selected from Mn 2+ , Sb 3+ , Sn 2+ , Bi 3+ , Eu 3+ , Tb 3+ , Eu 2+ , Gd 3+ , T  3+ , and combinations thereof. 
     
     
         7 . The device according to  claim 1  where the device is a master plate for imprint lithography and the thin film or laminate structure is deposited onto a flexible or glass substrate, the thin film or laminate structure comprises a first layer of HafSOx deposited onto the substrate and a second layer comprising ZircSOx:Cu, and where the laminate structure comprising the first and second layers is patterned by exposure to an energy source. 
     
     
         8 . The device according to  claim 7  where exposure to light or an electron beam through a mask causes the two layers to interdiffuse in exposed areas, thereby rendering previously undoped HafSOx layer soluble, the soluble HafSOx layer being removed to define at least partial printing features of the master plate. 
     
     
         9 . The device according to  claim 1  wherein the thin film or laminate has a permittivity value within the range of from about 9 to about 12, a breakdown field up to at least 6 MV cm −1 , and a leakage current near 1 nA cm −2  at field strengths of 1 MV cm −1 . 
     
     
         10 . The device according to  claim 1  where the compound is HafSOx, HafSOx/La, ZircSOx, ZircSOx:La, HafSOx:Ce, or ZircSOx:Ca, the device having leakage current less than 50 nA cm −2  and permittivity values of from about 9 to about 12. 
     
     
         11 . The device according to  claim 1  where the device is a field effect transistor comprising HafSOx:La and/or ZircSOx:La as a gate dielectric and zinc indium oxide and/or zinc tin oxide as channels, the transistor having an on-to-off ratio of greater than 10 6 , and gate leakage currents are in the range of pA cm  −2 . 
     
     
         12 . The device according to  claim 1  selected from metal and metal/ceramic-based thermal protection systems, organic-based displays and electronics, solar cells, high emissivity coatings, interface coatings for oxide-based ceramic matrix systems, protective coatings on phosphors, environmental barrier coatings for metal- and ceramic-based systems, fibers for composites and fiber lasers, corrosion protection in molten metal processing, monolithic materials for thermal insulation, and catalyst supports. 
     
     
         13 . The device according to  claim 1  where the thin film or laminate structure comprises a metal-acid film comprising a metal cation and an acid anion, where the acid anion is removed by ion exchange with an aqueous basic solution, the basic solution comprising a Group I metal hydroxide, soluble Group II metal hydroxide, soluble Group III metal hydroxide, soluble lanthanide hydroxide, ammonium hydroxide, and/or aqueous tertiary amine, or any combination thereof.