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  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G39/00—Compounds of molybdenum
  • C01G39/02—Oxides; Hydroxides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • H—ELECTRICITY
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  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K50/00—Organic light-emitting devices
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  • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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  • C01—INORGANIC CHEMISTRY
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  • C01P2004/00—Particle morphology
  • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
  • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
  • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
  • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius
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  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/10—Solid density
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  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
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  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/80—Compositional purity
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L33/36—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
  • H01L33/40—Materials therefor
  • H01L33/42—Transparent materials

Definitions

• the present invention relates to a method of making high purity MoO 2 and in particular to near theoretical density MoO 2 plates, products containing such plates.
• ITO Indium-tin oxide
• ITO Indium-tin oxide
• aluminum-doped ZnO are typical sputtering target materials
• work function typically about 4.7 eV
• the invention relates to high purity MoO 2 powder by reduction of ammonium molybdate or molybdenum trioxide using hydrogen as the reducing agent in a rotary or boat furnace. Consolidation of the powder by press/sintering, hot pressing, and/or HIP is used to make discs, slabs, or plates, which are used as sputtering targets.
• the MoO 2 disc, slab, or plate form is sputtered on a substrate using a suitable sputtering method or other physical means to provide a thin film having a desired film thickness.
• the thin films have properties such as electrical, optical, surface roughness, and uniformity comparable or superior to those of indium-tin oxide (ITO), zinc-doped ITO, and aluminum-doped ZnO in terms of transparency, conductivity, work function, uniformity, and surface roughness.
• ITO indium-tin oxide
• the thin films can be used in organic light-emitting diodes (OLED), liquid crystal display (LCD), plasma display panel (PDP), field emission display (FED), thin film solar cell, low resistivity ohmic contacts, and other electronic and semiconductor devices.
• OLED organic light-emitting diodes
• LCD liquid crystal display
• PDP plasma display panel
• FED field emission display
• thin film solar cell low resistivity ohmic contacts, and other electronic and semiconductor devices.
• the term "stoichiometric MoO 2 powder” refers to a powder that contains a stated percentage of MoO 2 , i.e., Mo and O in a ratio of ' 1 :2.
• a 99% stoichiometric MoO 2 powder would contain 99% MoO 2 powder and 1 % of another material, a non-limiting example of such being oO 3 .
• the present invention generally provides high purity MoO 2 powder by reduction of ammonium molybdate or molybdenum trioxide using hydrogen as the reducing agent in a rotary or boat furnace. Consolidation of the powder by press/sintering, hot pressing, and/or HIP is used to make discs, slabs, or plates, which are used as sputtering targets.
• the MoO 2 disc, slab, or plate form is sputtered on a substrate using a suitable sputtering method or other physical means to provide a thin film having a desired film thickness.
• the thin films have properties such as electrical, optical, surface roughness, and uniformity comparable or superior to those I of indium-tin oxide (ITO), zinc-doped ITO and aluminum-doped ZnO in terms of transparency, conductivity, work function, uniformity, and surface roughness.
• ITO indium-tin oxide
• ZnO aluminum-doped ZnO in terms of transparency, conductivity, work function, uniformity, and surface roughness.
• the thin films can be used in organic light-emitting diodes and other electronic and semiconductor devices.
• the term "work function” refers to the energy needed to move an electron in an atom from the Fermi level to vacuum level, i.e., outside of the atom. In the present invention, the work function will vary depending on surface conditions, for example v impurities.
• an embodiment of the present invention is directed to a method of making high purity MoO 2 powder. The method includes: (a) placing a molybdenum component into a furnace; and (b) heating the molybdenum component in a furnace containing a reducing atmosphere.
• any suitable molybdenum source can be used as the molybdenum component.
• Suitable molybdenum sources include compounds that can provide high purity MoO 2 when used in the present method.
• Suitable sources for the molybdenum component include, but are not limited to, ammonium dimolybdate salt, molybdenum trioxide, and combinations thereof.
• the molybdenum component is heated to a sufficiently high temperature to convert the molybdenum component to high purity MoO 2 , typically greater than 99% stoichiometric MoO 2 powder.
• the furnace temperature in the present method can be less than 1 ,250°C, in some cases less than 1 ,000°C, in other cases less than 800°C, in some situations less than less than 700°C, and in other situations less than 650°C. Also, the furnace temperature in the present method can be at least 100°C, in some cases at least 250°C, and in other cases at least 500°C. The furnace temperature can be any of the stated temperatures or it can range between any of the furnace temperature values stated above. [0014] In an embodiment of the invention, the molybdenum component is heated at the furnace temperature for a period of time sufficient to convert the molybdenum component to high purity MoO 2 , typically greater than 99% stoichiometric MoO 2 powder.
• the period of time can vary depending on the furnace temperature, where higher temperatures generally result in shorter required heating times.
• the heating time can be at least 5 minutes, in some cases at least 10 minutes, in other cases at least 15 minutes, in some situations at least 30 minutes, in other situations at least 45 minutes, in some circumstances at least one hour, and in other circumstances at least 90 minutes.
• the heating time can be up to 8 hours, in some cases up to 6 hours, in other cases up to 5 hours, in some situations up to 4 hours, and in other situations up to 3 hours.
• the period of time the molybdenum component is heated at the furnace temperature can be any of the stated periods of time or can range between any of the periods of time stated above.
• Any suitable furnace can be used in the present invention.
• Suitable furnaces include those that can expose the molybdenum component to the desired temperatures for the desired periods of times indicated above and under desired environments and/or atmospheres.
• Suitable furnaces that can be used in the present invention include, but are not limited to, stationary tube furnaces, rotary tube furnaces, and calciners.
• Any suitable atmosphere can be used in the furnace of the present invention. Suitable atmospheres promote the formation of high purity MoO 2 , typically greater than 99% stoichiometric MoO 2 powder.
• a reducing atmosphere is employed in the furnace.
• the reducing atmosphere includes hydrogen.
• the molybdenum component is placed in a flat-bottomed boat, which is placed in a furnace and heated in a desired atmosphere as described above.
• 6.8 kg of ammonium dimolybdate is placed in a flat-bottomed boat and the boat is heated in a stationary tube furnace for from two to three hours at a temperature ranging from 500°C to 700°C.
• the method of making high purity MoO 2 powder provides MoO 2 powder comprising greater than 99% by weight of a stoichiometric amount of MoO 2 .
• the MoO 2 powder can be characterized as having an average particle size of at least 0.1 ⁇ m, in some cases at least 0.5 ⁇ m, and in other cases at least 1 ⁇ m. Also, the MoO 2 powder can have an average particle size of up to 50 ⁇ m, in some cases up to 100 ⁇ m.
• the average particle size of the MoO 2 powder can be any of the stated values or can range between any of the values stated above.
• a further embodiment of the present invention is directed, to a method for making a plate that includes: (A) isopressing a greater than 99% stoichiometric MoO 2 powder component to a billet; (B) vacuum and/or pressure sintering the billet under conditions to maintain the greater than 99% MoO 2 stoichiometry; and (C) forming a plate that includes greater than 99% stoichiometric MoO 2 [0020]
• the invention involves a method for making a plate that ; includes subjecting a greater than 99% stoichiometric MoO 2 powder component to hot pressing conditions, and thereby forming a plate that includes greater than 99% stoichiometric MoO 2 Hot pressing conditions generally occur at high pressure, such that a plate forms with a low strain rate at a temperature high enough to induce a sintering process and a creep process.
• the hot pressing step is carried out with transient liquid phase assisted hot pressing, a pressing technique that involves powder consolidation at a temperature where liquid and solid phases coexist due to chemical reactions, partial melting, or eutectic liquid formations.
• the plate made in accordance to the invention is made into a sputtering target.
• the sputtering target is made by subjecting the plate including greater than 99% stoichiometric MoO 2 to machining until a sputtering target having desired properties and/or dimensions is obtained.
• the machining the plate is subjected can include any machining suitable for making sputtering targets having suitable properties/dimensions. Examples of suitable machining steps include but are not limited to laser cutting, milling, turning, and lathe-techniques.
• the sputtering target may be polished to improve its surface roughness. Examples of suitable diameters for circular sputtering targets, for instance, can range from 1 inch (2.54 cm) to 25 inches (63.5 cm), preferably from four inches (10.2 cm) to eight inches (20.4 cm). Examples of suitable thicknesses for such circular sputtering targets can range from 1/8 inch (0.3 cm) to two inches, three inches, four inches, five inches, or more, and preferably less than one inch (less than 2.54 cm).
• Any suitable pressure to form a individual billet can be applied when the MoO 2 powder is isopressed. Suitable pressures are those that allow a metal-powder compact to form between the MoO 2 powder and the billet.
• the pressure can be at least 5,000 psi, in some cases at least 7,500 psi, in other cases at least 10,000 psi, in some situations at least 15,000 psi, and in other cases at least 20,000 psi.
• the pressure can be up to 100,000 psi, in some cases up to 75,000 psi, in other cases up to 50,000 psi, in some situations up to 40,000 psi, and in other situations up to 30,000 psi.
• the pressure in the isopressing step can be any of the stated pressure values or can range between any of the pressure values stated above.
• Suitable sintering conditions are those under which the MoO 2 powder forms a coherent bonded mass without melting.
• the length of time for sintering will depend on the sintering temperature.
• the billet is sintered under vacuum or at a suitable partial pressure of oxygen for at least 15 minutes, in some cases at least 30 minutes, in other cases at least 1 hour, in some situations at least 2 hours, and in other situations at least 3 hours.
• the billet can be vacuum sintered for up to 10 hours, in some cases up to 20 hours, in other cases up to 7 hours, in some situations up to 6 hours, and in other situations up to 5 hours.
• the period of time the billet is sintered under vacuum or at a suitable partial pressure of oxygen can be any of the stated periods of time or can range between any of the periods of time stated above.
• the sintering temperature is at least 1 ,000°C, in some cases at least 1 ,100°C, in other cases at least 1 ,200°C, and in some situations at least 1 ,250°C.
• the sintering temperature can be up to 2,500°C, in some cases up to 2,000°C, in some situations up to 1 ,750°C, and in other situations up to 1 ,500°C, depending on the exact composition of the Mo0 2 powder and the billet.
• the sintering temperature can be any of the stated temperature values or can range between any of the temperature values stated above.
• Suitable pressing conditions are those at which the pressed and sintered MoO 2 powder can be formed into a plate while maintaining greater than 99% MoO 2 stoichiometry.
• the plate is subjected to hot isostatic pressing.
• the plate formed by the method described above, has a density that is at least 85%, in some cases at least 90%, in other cases at least 95%, and can be up to 99%, and in some cases up to 100%, of the theoretical density of MoO 2 .
• the density of the plate can be any of the stated density values or can range between any of the density values stated above.
• a further embodiment of the present invention is directed to a method for sputtering that includes subjecting the plate including greater than 99% stoichiometric MoO 2 as described above to sputtering conditions, and thereby sputtering the plate.
• Any suitable method of sputtering may be used in the invention.
• Suitable methods are those that are able to deposit a thin film on the plate.
• suitable sputtering methods include, but are not limited to, magnetron sputtering, pulse laser sputtering, ion beam sputtering, triode sputtering, and combinations thereof.
• Other methods can be used in the invention, in addition to sputtering, to deposit thin films on the plate. Any suitable method of depositing a thin film in accordance with the invention may be used. Suitable methods of applying a thin film to the plate include, but are not limited to, electron beam evaporation and physical means such as physical vapor deposition.
• the present invention is additionally directed to a method for making a thin film. The method includes the steps of sputtering a plate including greater than 99% stoichiometric MoO 2 , removing MoO 2 molecules from the plate, and depositing the MoO 2 molecules onto a substrate to thereby form a thin film.
• Suitable sputtering methods as described above can be used in this embodiment.
• the thin film applied by the present method can have any desired thickness.
• the film thickness can be at least 0.5 nm, in some situations 1 nm, in some cases at least 5 nm, in other cases at least 10 nm, in some situations at least 25 nm, in other situations at least 50 nm, in some circumstance at least 75 nm, and in other circumstances at least 100 nm.
• the film thickness can be up to 10 ⁇ m, in some cases up to 5 ⁇ m, in other cases up to 2 ⁇ m, in some situations up to 1 ⁇ m, and in other situations up to 0.5 ⁇ m.
• the film thickness can be any of the stated values or can range between any of the values stated above.
• the present invention is also directed to thin films made in accordance with the invention as described above.
• the thin film has a work function that is higher as compared to the work function of indium-tin oxide films having the same dimensions.
• the work function can be from 5.0 eV to 6.0 eV, and in some cases at least 5.2 eV, or any of the stated values individually.
• the thin film has a surface roughness that is less than the surface roughness as compared to a thin film of indium-tin oxide.
• the surface roughness can be less 10 nm, in some cases less than 5 nm, in other cases less than 4 nm, and in some situations less than 3 nm.
• the surface roughness is typically greater than 0.1 nm.
• the surface roughness can be any of the stated values or can range between any of the values stated above.
• the thin film has a mean transmission of greater than 85% at a wavelength of from 350 to 800 nm.
• the thin film has a resistivity that is less than 500 ⁇ -cm, in some cases less than 300 ⁇ 'cm and in other cases less than 250 ⁇ m.
• the thin film resistivity is typically greater than 1 ⁇ -cm.
• the thin film resistivity can be any of the stated values or can range between any of the values stated above. It is highly conducting with metallic behavior as a function of temperature.
• a very thin film is provided.
• the thin film is at least 100 A, in some cases at least 250 A, and in other cases at least 500 A.
• the thin film can be up to 5,000 A, in some cases up to 3,000 A, in other cases up to 2,500 A, and in some situations up to 2,000 A.
• An embodiment of the invention is directed to an organic light- emitting diode that includes: (a) a metal electrode; (b) an electron transport layer; (c) an emitter layer; (d) an electrically conductive polymer (hole transport layer); and (e) a thin film as described above located on a substrate.
• Suitable substrates for the thin film used in the organic light-emitting diode include, but are not limited to, plastic substrates, glass substrates, ceramic substrates, and combinations thereof.
• the plastic substrates include, but are not limited to, polynorbornene, polyimide, polyarylate, polycarbonate, polyethylenenaphthanate (PEN), polyethyleneterephthalate (PET), and the like.
• a non-limiting example of a ceramic substrate includes sapphire.
• the invention encompasses products used in various applications.
• a thin film made in accordance to the invention can be used in thin film transistor (TFT)-liquid crystal display (LCD) applications.
• TFT thin film transistor
• LCD liquid crystal display
• the invention encompasses a thin film used in solar cell applications and battery applications.
• the invention is a containing LCD device containing that has both (i) a common electrode (about 1500 A) and (ii) a Pixel electrode (about 500 A).
• the invention encompasses solar cells in which MoO 2 functions as a front electrode for the following illustrative device structure: MoO 2 front contact/p-layer/junction layer/n-layer/ Al back contact, in which the p-layer releases electrons when it is struck by light, resulting in a lack of electrons, and n-layer is negatively charged.
• the invention encompasses ohmic contacts (transparent, thin oxide/metal contacts) to both reduce the total contact resistance as well as allow emission of light from light emitting diodes (such as GaN LED), or diode lasers.
• optical display devices include a film that contains greater than 99% stoichiometric MoO 2 disposed over at least a portion of a substrate.
• the film can be formed by: (a) sputtering a plate comprising greater than 99% stoichiometric MoO 2 ; (b) removing MoO 2 molecules from the plate; and (c) depositing the MoO 2 molecules onto the substrate, thereby forming a MoO 2 thin film.
• the film can be formed by: [0046] (a) sputtering a plate comprising greater than 99% Mo; (b) removing Mo molecules from the plate; and (c) forming MoO 2 molecules under a partial pressure of oxygen in a chamber to produce the MoO 2 thin film onto the substrate.
• Any suitable sputtering method can be used in the present invention.
• the thin film has a thickness of at least 0.1 nm, in some cases at least 0.5 nm, in other cases at least 1 nm, in some situations at least 2 nm, in other situations at least 5 nm, in some instances at least 8 nm, in other instances at least 10 nm, and in particular situations at least 25 nm.
• the film can have a thickness of up to 10 ⁇ m, in some cases up to 7.5 ⁇ m, in other cases up to 5 ⁇ m, in some situations up to 2.5 ⁇ m, in other situations up to 1 ⁇ m, in some instance up to 0.5 ⁇ m, in other instances up to 0.25 ⁇ m, and in particular instances up to 0.1 ⁇ m.
• the film thickness can be or can vary between any of the values recited above.
• the thin film in the optical display device can have a film thickness of from 50 A to 2,500 A.
• the thin film has a thickness of at least 50 A, in some cases at least 100 A, in other cases at least 250 A, and in some situations at least 500 A.
• the film can have a thickness of up to 2,500 A, in some cases up to 2,000 A, in other cases up to 1 ,500 A, and in some situations up to 1 ,000 A.
• the film thickness can be or can vary between any of the values recited above.
• one or more suitable MoO 2 containing films are included.
• Non-limiting examples of suitable films include, but are not limited to single MoO 2 phase films, impurity-doped MoO 2 films, MoO 2 -doped tin oxide films, MoO 2 -doped indium tin oxide films, MoO 2 -doped ZnO/ln 2 O 3 films, MoO 2 -doped ZnO/SnO 2 /ln 2 O 3 films, MoO 2 -doped ZnO films, MoO2-doped SnO2 films, MoO 2 -doped ZnO/AI 2 O 3 films, MoO 2 -doped Ga/ZnO films, MoO 2 -doped GaO/ZnO films, MoO 2 -doped zinc stannate (Zn 2 SnO 4 ) films, and MoO 2 - MoO 3 composite films.
• the sputtering plate can be any suitable shape and size.
• the sputtering plate can be in the shape of a square, a rectangle, a circle, or an oval.
• the square sputtering plate can be square and have dimensions of from 0.1 cm X 0.1 cm to 5 cm X 5 cm, in some cases from 0.5 cm X 0.5 cm to 4 cm X 4 cm, in other cases from 1 cm X 1 cm to 3 cm X 3 cm, in some situations from 2 cm X 2 cm to 3 cm X 3 cm and in other situations, the square sputtering plate has dimensions of about 2.5 cm X about 2.5 cm.
• the rectangular sputtering plate can be have a shorter side of length at least 0.1 cm, in some cases at least 0.5 cm, in other cases at least 1 cm, in some situations at least 2 cm, in other situations at least 2.5 cm, in some instances at least 3 cm, in other instances at least 4 cm, and in particular situations at least 5 cm.
• the longer side of the rectangle can be up to 6 cm, in some cases up to 5 cm, in other cases up to 4 cm, in some situations up to 3 cm, in other situations up to 2.5 cm, in some instance up to 2 cm, in other instances up to 1 cm and in particular instances up to 0.75 cm.
• the dimensions of the rectangular sputtering plate can vary between any of the dimensions recited above so long as the dimension of the longer side is greater than the dimension of the shorter side.
• the MoO 2 or MoO 2 containing sputtering target can be bonded to a backing plate to form a large area sputtering target.
• a segment-forming sputtering method can be used.
• the large area sputtering plate can be any suitable shape and size. As a non-limiting example, the large area sputtering plate can be in the shape of a square, a rectangle, a circle, or an oval.
• the square sputtering plate can be square and have dimensions of from 0.1 m X 0.1 m to 6 m X 6 m, in some cases from 0.5 m X 0.5 m to 5.5 m X 5.5 m, in other cases from 1 m X 1 m to 4 m X 4 m, in some situations from 2 m X 2 m to 3 m X 3 m and in other situations, the square sputtering plate has dimensions of about 2.5 m X about 2.5 m.
• the large area rectangular sputtering plate can be have a shorter side of length at least 0.1 m, in some cases at least 0.5 m, in other cases at least 1 m, in some situations at least 2 m, in other situations at least 2.5 m, in some instances at least 3 m, in other instances at least 4 m, in particular situations at least 5 m, and in particular instances at least 5.5 m.
• the longer side of the rectangle can be up to 6 m, in some cases up to 5 m, in other cases up to 4 m, in some situations up to 3 m, in other situations up to 2.5 m, in some instance up to 2 m, in other instances up to 1 m, and in particular instances up to 0.75 m.
• film in the optical display devices is formed using one or more methods selected from the group consisting of metallo-organic chemical vapor deposition (MOCVD), metallo-organic deposition (MOD), and Sol-Gel technique.
• MOCVD metallo-organic chemical vapor deposition
• MOD metallo-organic deposition
• Sol-Gel Sol-Gel technique.
• MOCVD or "Metallo-Organic Chemical Vapor Deposition” refers to a chemical vapor deposition method of film growth in which all materials to be deposited are present in a vapor phase above the deposition surface.
• the sources of chemical vapor deposition are metallo-organic compounds which have oxygen as a hetero atom in order to bond a metal atom to one or more organic ligands.
• molybdenum ethyl-hexanoate can be used as a metallo-organic precursor to produce a MoO 2 thin film.
• precursors can be contained in vitreous silica boats or in a vitreous silica reaction tube, and the compounds are heated close to the boiling point, after which an argon carrier gas is introduced with suitable oxygen partial pressure to oxidize the compound under reducing atmosphere to produce MoO 2 molecules and subsequently deposit onto substrates in a reaction chamber.
• Sol-Gel Process refers to processing using metal alkoxides of network forming cations as solution precursors.
• the cations can be M(OR) x where M represents a metal and R represents an alky group.
• the starting alkoxide for the sol-gel MoO 2 can be molybdenum acetyl-acetonate (in methanol). Hydrolysis can then be accomplished by combining the solution with ethanol to yield a polymerized solution.
• the precursor solution is stable for only a few days, after which time clarity is lost and gelation can occur.
• the precursor solution can be applied onto the substrate, followed by spinning at, for example, 1000 rpm to produce a thin wet film.
• Another technique to produce a thin film is by immersion of the substrates in precursor solution using a withdrawal rate of, for example, 580 mm/min.
• the wet films can then be heat-treated in a vacuum and hydrogen atmosphere (a reducing atmosphere) to give rise to MoO 2 thin film on substrates.
• MOD Process or "Metallo-Organic Decomposition Process” refer to processes that are similar to MOCVD and/or Sol-Gel processes.
• metallo-organic compounds as precursors, which have oxygen as the hetero atom to bond a metal atom to one or more organic ligands, are also used.
• the compounds are dissolved in appropriate solvents, a non-limiting example being xylene.
• molybdenum ethyl-hexanoate or molybdenum acetylacetonate can be used as a metallo-organic compound to produce MoO 2 thin film.
• the liquid films are formed by spinning the precursor solution on the substrates.
• a MoO 2 containing film can also be produced by mixing several different metallo-organic solutions.
• molybdenum ethyl-hexanoate can be mixed with tin ethyl- hexanoate in a solvent, such as xylene, at a ratio whereby a desired stoichiometry is achieved.
• the MOCVD or MOD techniques utilize metallo-organic chemicals including molybdenum ethyl-hexanoate.
• the thin film in the present optical device can have a work function of from 4.5 to 6 eV, in some cases from 4 to 5.5 eV, and in some situations from 4.5 to 5.5 eV.
• the thin film can generally have a roughness of less than about 5 nm, in some cases from 0.1 nm to 5 nm, and in other cases from 0.1 to 2.5 nm.
• the thin film can have a mean transmission of greater than 85%, in some cases greater than 90%, and in other cases greater than 95% at a wavelength of from 350 nm to 800 nm.
• the thin film can have a resistivity of less than 300 ⁇ 'cm, in some cases less than 250 ⁇ cm and in other cases less than 200 ⁇ 'cm.
• the optical device is an organic light emitting diode and the MoO 2 containing film is an anode.
• the organic light-emitting diode includes: (a) a metal cathode; (b) an electron transport layer; (c) an emitting layer; (d) a hole transport layer; and (e) the film comprising MoO 2 as an anode layer.
• the thin film can be located on a substrate selected from plastic substrates, glass substrates, ceramic substrates, and combinations thereof.
• the plastic substrate can include one or more plastics selected from polynorbomene, polyimide, polyarylate, polycarbonate, polyethylene- naphthanate, and polyethyleneterephthalate.
• the ceramic substrate can include sapphire.
• the optical device is a light emitting diode and the MoO 2 containing thin film can be an ohmic contact.
• the light-emitting diode can include: (a) a substrate; (b) a buffer layer; (c) an N-type semiconductor material; (d) a junction layer; (e) a P-type semiconductor material; (f) a p-type metal contact; and (g) an n-type metal contact.
• suitable substrates are those that include a material selected from sapphire, SiC, Si, GaN, GaP, GeSi, AIN, and combinations thereof.
• suitable buffer layer materials are those that include one or more compounds of Group 1MB elements and Group VB elements from the periodic table of the elements.
• the term "periodic table of the elements" refers to the periodic table format used by the IUPAC .
• the buffer layer includes AIN, GaN, or a combination thereof.
• the N-type semiconductor material can include, but is not limited to, materials containing one or more compounds doped with one or more elements selected from Si, Se, Te, and S. Non-limiting examples of such compounds include compounds of Group 1MB elements and Group VB elements from the periodic table of the elements and compounds selected from compounds of Group IIB elements and Group VIB elements from the periodic table of the elements.
• Non-limiting examples of suitable compounds of Group IIIB elements and Group VB elements include Si- doped compounds selected from GaN, GaAs, GaAIAs, AIGaN, GaP, GaAsP, GalnN, AIGalnN, AIGaAs, AIGalnP, PbSnTe, PbSnSe, and combinations thereof.
• Non-limiting examples of suitable compounds of Group IIB elements and Group VIB elements include Si-doped compounds selected from ZnSSe, ZnSe, SiC, and combinations thereof.
• the thin film can be an n-type metal contact.
• the n-type metal contact can include a material selected from Ti/Au metals, a MoO 2 conducting oxide and a MoO 2 /metal where the metal is selected from Ti, Au, and combinations thereof.
• the P-type semiconductor material can include one or more compounds doped with one or more elements selected from Mg, Zn, and C.
• Suitable compounds in this aspect of the invention include compounds of Group IIIB elements and Group VB elements from the periodic table of the elements and compounds selected from compounds of Group IIB elements and Group VIB elements from the periodic table of the elements.
• Non-limiting examples of suitable compounds of Group IIIB elements and Group VB elements include Mg-doped compounds selected from GaN, GaAs, GaAIAs, AIGaN, GaP, GaAsP, GalnN, AIGalnN, AIGaAs, AIGalnP, PbSnTe, PbSnSe, and combinations thereof.
• suitable compounds of Group IIB elements and Group VIB elements include Mg-doped compounds selected from ZnSSe, ZnSe, SiC, and combinations thereof.
• the thin film can be a p-type metal contact.
• the p-type metal contact includes a material selected from a MoO 2 containing transparent conducting oxide and a MoO 2 containing /metal films where the metal is selected from Ag, Au, and combinations thereof.
• the optical device can be a liquid crystal display and the MoO 2 containing thin film is one or more of a common electrode, a pixel electrode, a gate electrode, a source electrode, a drain electrode, a storage-capacitor electrode, and combinations thereof.
• the liquid display crystal can include a thin film diode or thin film transistor switching element.
• liquid crystal display embodiment of the invention include liquid display crystals that include: A) a glass substrate, B) a source electrode, C) a drain electrode, D) a gate insulator, E) a gate electrode, F) an amorphous-silicon, polycrystalline-silicon or single crystal silicon layer, G) an n-doped silicon layer, H) a passivation layer, I) a pixel transparent electrode, J) a common electrode, K) a polyimide alignment layer, and L) a storage-capacitor electrode.
• the pixel transparent electrode and the common electrode can include the MoO 2 containing film.
• the optical device is a plasma display panel and the MoO 2 containing film is a positive or negative electrode.
• the plasma display panel can include: A) a front glass plate, B) a dielectric film, C) an MgO layer, D) an ionized gas, E) a separator, F) one or more phosphors, and G) a back glass plate.
• the back glass can be coated with the MoO 2 thin film.
• Further embodiments of the invention are directed to the situations where the optical device is a field emission display and the MoO 2 containing thin film is an anode or cathode electrode material.
• the field emission display can include: [0079] A) a glass face plate anode, B) a phosphor, C) a spacer, D) a microtip, E) row and column cathodes, and F) a glass base plate.
• the glass face plate A) is coated with the MoO 2 containing thin film.
• at least one of the row and column cathodes E) can include the MoO 2 containing thin film.
• the optical device can be a solar cell and the MoO 2 containing film can be one or more of electrical contacts, a transparent contact, and a top junction layer.
• the solar cell can include: A) a cover glass, B) a top electric contact layer, C) a transparent contact, D) a top junction layer, E) an absorber layer, F) a back electric contact, and G) a substrate.
• the transparent contact C) can include the MoO 2 containing film.
• the top junction layer D) can include the MoO 2 containing film.
• the cover glass A) can include an anti- reflective coating.
• MoO-P 1 100 0 5 MoO2
• MoO-P 2 ⁇ 50 1 ,0 MoO2 MoO2. Traces Mo4O1 1.
• MoO-P 3 ⁇ 50 2,3 MoO3
• EXAMPLE 4 MoO-P 4 was mixed with 2.5 wt.% fine MoO3-powder. Mixing occurred on a roller frame for 5 hours within a plastic bottle in the dry state using AI2O3-balls to support distribution. The mixed powder was sieved ⁇ 300 ⁇ m and used for a further hot-pressing test. Maximum pressure of 30 MPa was applied at 600°C in order to run the hot-press as a dilatometer to registrate the densification as a function of temperature. The heating and cooling rate were 10 K/min, as atmosphere, again Ar-3H2 was applied. The system registrated an onset of densification at about 700°C which continued till about 800°C. Further rise in temperature did not result in further densification.

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• 2004
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