HK1095579A - Method of making high-purity (>99%) moo2 powders, products made from moo2 powders, deposition of moo2 thin films, and methods of using such materials - Google Patents

Description

Preparation of MoO2Method for producing powder from MoO2Product of powder preparation, MoO2Deposition of thin films and methods of using such materials

Background

[0001]The invention relates to a method for preparing high-purity MoO₂In particular MoO close to theoretical density₂A panel, a product comprising such a panel.

[0002] Indium Tin Oxide (ITO) and zinc doped ITO and aluminium doped ZnO are commonly used sputter target materials but their work functions (typically around 4.7eV) do not match well with the desired light emission function when used in applications such as organic light emitting diodes.

[0003] It would be desirable to provide a sputter target material that can be used to make organic light emitting diodes that does not have the problems and limitations of ITO and zinc doped ITO sputter target materials.

Disclosure of Invention

[0004]The invention relates to high-purity MoO obtained by reducing ammonium molybdate or molybdenum trioxide in a rotary or boat furnace using hydrogen as a reducing agent₂And (3) powder. Consolidation of the powder by pressing/sintering, hot pressing and/or HIP is used to prepare discs, slabs or plates, which are used as sputtering targets. The MoO is applied using a suitable sputtering method or other physical means₂In the form of a disk, slab or plate, on a substrate to provide a thin film having a desired film thickness. The film has properties such as electrical, optical, surface roughness and uniformity comparable to or better than Indium Tin Oxide (ITO), zinc doped ITO and aluminum doped ZnO in terms of transmittance, conductivity, work function, uniformity and surface roughness. The thin film may be used in Organic Light Emitting Diodes (OLEDs), Liquid Crystal Displays (LCDs), Plasma Display Panels (PDPs), Field Emission Displays (FEDs), thin film solar cells, low resistivity ohmic contacts, and other electronic and semiconductor devices.

Description of the invention

[0005] Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and the like, used in the specification and claims are to be understood as modified in all instances by the term "about". Various numerical ranges are disclosed in this patent application. Because these ranges are continuous, they include every value between the minimum and maximum values. Unless expressly stated otherwise, the various numerical ranges set forth in this application are approximations.

[0006]As used herein, the term "high purity MoO₂By "is meant containing greater than 99.95 wt.% MoO₂And at least 99 wt% MoO₂Materials and compounds of the phases.

[0007]As used herein, the term "stoichiometric MoO₂Powder "means a powder containing a defined percentage of MoO₂I.e. the ratio of Mo and O is 1: 2. As a non-limiting example, 99% stoichiometric MoO₂The powder will contain 99% MoO₂Powder and 1% other materials, one non-limiting example being MoO₃。

[0008]The present invention provides high purity MoO by reducing ammonium molybdate or molybdenum trioxide in a rotary or boat furnace, typically using hydrogen as a reducing agent₂And (3) powder. Discs, slabs or plates are prepared with consolidation of the powder by pressing/sintering, hot pressing and/or HIP, which discs, slabs or plates are used as sputtering targets. The MoO is applied using a suitable sputtering method or other physical means₂In the form of a disk, slab or plate, on a substrate to provide a thin film having a desired film thickness. The film has properties such as electrical, optical, surface roughness and uniformity comparable to or better than Indium Tin Oxide (ITO), zinc doped ITO and aluminum doped ZnO in terms of transmittance, conductivity, work function, uniformity and surface roughness. The films can be used in organic light emitting diodes and other electronic and semiconductor devices.

[0009] As used herein, the term "work function" refers to the energy required to move an electron in an atom from the fermi level to the vacuum level, i.e., out of the atom. In the present invention, the work function will vary depending on the surface conditions such as impurities.

[0010] As used herein, the term "organic light emitting diode" refers to an electronic device prepared by placing a series of organic thin films between two conductors. Intense light is typically emitted by electrophosphorescence when current is applied.

[0011]One embodiment of the present invention relates to a method for preparing high purity MoO₂A method of powdering. The method comprises the following steps:

(a) placing the molybdenum component into a furnace; and

(b) the molybdenum component is heated in a furnace containing a reducing atmosphere.

[0012]In one embodiment of the invention, any suitable molybdenum source may be used as the molybdenum component. Suitable molybdenum sources include those used in the process to provide high purity MoO₂The compound of (1). Suitable sources for the molybdenum component include, but are not limited to, ammonium dimolybdate, molybdenum trioxide, and mixtures thereof.

[0013]In one embodiment of the invention, the molybdenum component is heated to a temperature sufficiently high to convert the molybdenum component to high purity MoO₂Typically greater than 99% stoichiometric MoO₂And (3) powder. In the present process, the furnace temperature may be less than 1,250 ℃, in some cases less than 1,000 ℃, in other cases less than 800 ℃, in some cases less than 700 ℃, and in other cases less than 650 ℃. And in the present process the furnace temperature is at least 100 c, in some cases at least 250 c, and in other cases at least 500 c. The furnace temperature may be any of the temperatures described or it may vary between any of the furnace temperature values described above.

[0014]In one embodiment of the invention, the molybdenum component is heated at an oven temperature for a period sufficient to convert the molybdenum component to high purity MoO₂Typically greater than 99% stoichiometric MoO₂Time of powder. This period of time may vary depending on the furnace temperature, with higher temperatures generally resulting in shorter heating times being required. The heating time may be at least 5 minutes, in some cases at least 10 minutes, in other cases at least 15 minutes, in some cases at least 30 minutes, in other cases at least 45 minutes, in some cases at least 1 hourAnd in other cases at least 90 minutes. And the heating time may be up to 8 hours, in some cases up to 6 hours, in other cases up to 5 hours, in some cases up to 4 hours, and in other cases up to 3 hours. The period of time during which the molybdenum component is heated at the furnace temperature may be any of the described periods of time or may vary between any of the periods of time described above.

[0015] Any suitable furnace may be used in the present invention. Suitable furnaces include those that can expose the molybdenum component to a desired temperature for a desired period of time as described above under a desired environment and/or atmosphere. Suitable ovens that may be used in the present invention include, but are not limited to, stationary tube ovens, rotary tube ovens, and calciners.

[0016]Any suitable atmosphere may be used in the furnace of the present invention. Proper atmosphere promotes high-purity MoO₂Usually greater than 99% stoichiometric MoO₂And (4) forming powder. In one embodiment of the invention, a reducing atmosphere is used in the furnace. In a particular embodiment of the invention, the reducing atmosphere comprises hydrogen. In one embodiment of the invention, the molybdenum component is placed in a flat bottom boat and heated in a desired atmosphere as described above, the boat being placed in a furnace. In a particular embodiment, 6.8kg of ammonium dimolybdate was placed in a flat bottom boat and the boat was heated in a static tube furnace at a temperature range of 500 ℃ to 700 ℃ for 2 to 3 hours.

[0017]In one embodiment of the invention, the preparation of high purity MoO₂Process for providing powders containing greater than 99% by weight of stoichiometric MoO₂Of MoO₂And (3) powder.

[0018]The MoO₂The powder is characterized by having an average particle size of at least 0.1 μm, in some cases at least 0.5 μm, and in other cases at least 1 μm. And the MoO₂The powder has an average particle size of up to 50 μm, in some cases up to 100 μm. The MoO₂The average particle size of the powder can be any of the values described or can vary between any of the values described above.

[0019] Another embodiment of the present invention is directed to a method for making a panel comprising:

(A) more than 99% of stoichiometric MoO₂Isostatic pressing of the powder components into a blank;

(B) maintaining more than 99% MoO₂Sintering the blank under the stoichiometric condition in vacuum and/or pressure; and

(C) formation of a catalyst containing greater than 99% of stoichiometric MoO₂The plate of (1).

[0020]In another embodiment, the invention relates to a method for making a panel comprising contacting greater than 99% stoichiometric MoO₂Subjecting the powder component to hot pressing conditions to form a composition containing greater than 99% stoichiometric MoO₂The plate of (1). Hot pressing conditions typically occur at high pressures such that the plate is formed at a low strain rate at a temperature high enough to cause sintering and creep processes. To MoO₂In general, it requires 1000+ c to reach the desired density. In one embodiment, wherein the panel is prepared under hot pressing conditions, the hot pressing step is carried out with transient liquid phase assisted hot pressing, the pressing technique involves consolidation of the powder at a temperature at which liquid and solid phases coexist due to chemical reaction, partial melting, or formation of a eutectic liquid.

[0021]In one embodiment, the plate prepared according to the present invention is made into a sputtering target. The sputtering target is prepared by subjecting the plate containing more than 99% stoichiometric MoO to a machining process until a sputtering target having the desired properties and/or dimensions is obtained₂. The machining to which the plate is subjected may include any suitable machining for producing a sputtering target 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 can be polished to improve its surface roughness. Examples of suitable diameters for circular sputtering targets range, for example, from 1 inch (2.54cm) to 25 inches (63.5cm), preferably from 4 inches (10.2cm) to 8 inches (20.4 cm). For use in such a wayExamples of suitable thicknesses for circular sputtering targets are from 1/8 inches (0.3cm) to 2 inches, 3 inches, 4 inches, 5 inches or more, preferably less than 1 inch (less than 2.54 cm).

[0022]When MoO is added₂Any suitable pressure for forming the individual billets may be applied during isostatic pressing of the powder. The pressure is suitably allowed to be in MoO₂The pressure between the powder and the billet to form a metal-powder compact. The pressure is at least 5,000psi, in some cases at least 7,500psi, in other cases at least 10,000psi, in some cases at least 15,000psi, and in other cases at least 20,000 psi. And the pressure may be up to 100,000psi, in some cases up to 75,000psi, in other cases up to 50,000psi, in some cases up to 40,000psi, and in other cases up to 30,000 psi. The pressure in the isostatic pressing step may be any of the described pressure values or may vary between any of the pressure values described above.

[0023]Suitable sintering conditions are the MoO₂The condition under which the powder did not melt to form coherent lumps. The length of time for sintering depends on the sintering temperature. In one embodiment of the invention, the blank is sintered under vacuum or under 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 cases at least 2 hours, and in other cases at least 3 hours. And the blank may be vacuum sintered for up to 10 hours, in some cases up to 20 hours, in other cases up to 7 hours, in some cases up to 6 hours, and in other cases up to 5 hours. The period of time for which the blank is sintered in vacuum or under a suitable partial pressure of oxygen may be any of the periods described or may vary between any of the periods described above.

[0024]In another embodiment of the invention, the sintering temperature is at least 1,000 ℃, in some cases at least 1,100 ℃, in other cases at least 1,200 ℃ and in some cases at least 1,250 ℃. And is dependent on the MoO₂The precise composition of the powder and the blank, the sintering temperature can be as high as 2,500 ℃. In thatIn some cases up to 2,000 ℃, in some cases up to 1,750 ℃ and in other cases up to 1,500 ℃. The sintering temperature may be any of the values described or may vary between any of the values described above.

[0025]Any suitable pressing conditions may be used in the present invention. Suitable pressing conditions are those under which pressed and sintered MoO can be pressed₂The powder is formed into a sheet while the sheet maintains greater than 99% MoO₂And (4) stoichiometry.

[0026] In one embodiment of the invention, the plate is subjected to hot isostatic pressing.

[0027]In another embodiment of the invention, the sheet formed by the above method has at least MoO₂A density of 85% of theoretical density, in some cases at least 90%, in other cases at least 95%, and can be as high as 99%, in some cases as high as 100%. The density of the board may be any specified density value, or may vary between any of the density values described above.

[0028]Another embodiment of the present invention is directed to a method of sputtering comprising providing a sputter target as described above containing greater than 99% stoichiometric MoO₂Is subjected to sputtering conditions, thereby sputtering the plate.

[0029] Any suitable sputtering method may be used in the present invention. Suitable methods are those that can deposit a thin film on the plate. Examples of suitable sputtering methods include, but are not limited to, magnetron sputtering, pulsed laser sputtering, ion beam sputtering, triode sputtering, and combinations thereof.

[0030] In addition to sputtering, other methods of depositing a thin film on the plate can be used in the present invention. Any suitable method of depositing the thin film may be used in accordance with the present invention. Suitable methods for applying the film to the plate include, but are not limited to, electron beam evaporation and physical means such as physical vapor deposition.

[0031]The invention also relates to a method for producing a film. The method comprises sputtering a material containing more than 99% of stoichiometric MoO₂Of the plate, removing MoO from the plate₂Molecules and deposition of the MoO on a substrate₂Molecules to form a thin film.

[0032] The above-described suitable sputtering method can be used in this embodiment.

[0033] The film applied by the present method may have any desired thickness. The film thickness is at least 0.5nm, in some cases 1nm, in some cases at least 5nm, in other cases at least 10nm, in some cases at least 25nm, in other cases at least 50nm, in some cases at least 75nm, and in other cases at least 100 nm. And the film thickness can be up to 10 μm, in some cases up to 5 μm, in other cases up to 2 μm, in some cases up to 1 μm and in other cases up to 0.5 μm. The film thickness may be any predetermined value or may vary between any of the values.

[0034] The invention also relates to the above-mentioned films prepared according to the invention.

[0035] In one embodiment of the invention, the indium tin oxide film has a higher work function than that of an indium tin oxide film having the same dimensions. For example, the work function can be 5.0eV to 6.0eV, and in some cases at least 5.2eV, or any single specified value.

[0036] In one embodiment of the invention, the film has a surface roughness that is lower than the surface roughness of a film of indium tin oxide. More particularly, the surface roughness may be less than 10nm, in some cases less than 5nm, in other cases less than 4nm, and in some cases less than 3 nm. The surface roughness is typically greater than 0.1 nm. The surface roughness may be any specified value or may vary between any of the values recited above.

[0037] In another embodiment of the invention, the film has an average transmission of greater than 85% at a wavelength of 350-800 nm.

[0038] In another embodiment of the invention, the film has a resistivity of less than 500 μ Ω -cm, in some cases less than 300 μ Ω -cm, and in other cases less than 250 μ Ω -cm. The resistivity of the film is typically greater than 1 μ Ω · cm. The resistivity of the film can be any specified value or can vary between any of the values recited above. Its metal behavior is highly implemented as a function of temperature.

[0039] In a particular embodiment of the invention, a very thin film is provided. In this embodiment, the film is at least 100A, in some cases at least 250A, and in other cases at least 500A. In such embodiments, the film may be up to 5,000A, in some cases up to 3,000A, in other cases up to 2,500A, and in some cases up to 2,000A.

[0040] One embodiment of the present invention relates to an organic light emitting diode, including:

(a) a metal electrode;

(b) an electron transport layer;

(c) an emission layer;

(d) a conductive polymer (hole transport layer); and

(e) the above-described thin film on the substrate.

[0041] Any suitable substrate may be used in the present invention. Suitable substrates for the thin film for use in organic light emitting diodes include, but are not limited to, plastic substrates, glass substrates, ceramic substrates, and combinations thereof. Plastic substrates include, but are not limited to, polynorbornenes, polyimides, polyarylates, polycarbonates, polyethylene naphthalate (PEN), polyethylene terephthalate (PET), and the like. Non-limiting examples of ceramic substrates include sapphire.

[0042]The present invention includes products for use in a variety of applications. In one embodiment, the thin films prepared according to the present invention may be used in Thin Film Transistor (TFT) -Liquid Crystal Display (LCD) applications. And in another embodiment, the invention includes thin films for use in solar cells and batteries. At one endIn one embodiment, the invention is an LCD-containing device that contains both (i) common electrodes (about 1500A) and (ii) pixel electrodes (about 500A). In thin film solar cell applications, the invention includes solar cells in which MoO is present₂As front electrodes for the following exemplary device structures: MoO₂Front contact/p-layer/connection layer/n-layer/Al back contact, where when the p-layer is photo-triggered, it releases electrons, resulting in a lack of electrons, and the n-layer is negatively charged. In another embodiment, the invention includes ohmic contacts (transparent, thin oxide/metal contacts) to both reduce the overall contact resistance and allow light to be emitted from a light emitting diode (e.g., GaN LED) or diode laser.

[0043]Other embodiments of the present invention relate to optical display devices. In this embodiment, the optical display device includes a display device containing greater than 99% stoichiometric MoO₂The film of (a), disposed on at least a portion of the substrate.

[0044] In one embodiment of the present invention, the film may be formed by:

(a) sputtering containing greater than 99% stoichiometric MoO₂A plate of (a);

(b) removal of MoO from the plate₂A molecule; and

(c) subjecting the MoO to a reaction₂Molecules are deposited on the substrate to form MoO₂A film.

[0045] In another embodiment, the film may be formed by:

[0046] (a) sputtering a plate containing more than 99% of stoichiometric Mo;

(b) removing Mo molecules from the plate; and

(c) in the chamber, MoO is formed under partial pressure of oxygen₂Molecule to thereby generate MoO on a substrate₂A film.

[0047] Any suitable sputtering method may be used in the present invention. Any suitable sputtering method that may be used in accordance with the present invention includes, but is not limited to, magnetron sputtering, pulsed laser sputtering, ion beam sputtering, tripolar sputtering, and combinations thereof.

[0048] In one embodiment of the invention, the thin film has a thickness of at least 0.1nm, in some cases at least 0.5nm, in other cases at least 1nm, in some cases at least 2nm, in other cases at least 5nm, in some cases at least 8nm, in other cases at least 10nm, and in particular cases at least 25 nm. And the film may have a thickness of up to 10 μm, in some cases up to 7.5 μm, in other cases up to 5 μm, in some cases up to 2.5 μm, in other cases up to 1 μm, in some cases up to 0.5 μm, in other cases up to 0.25 μm and in particular cases up to 0.1 μm. The film thickness may be or may vary between any of the values described.

[0049] In one embodiment of the invention, the thin films in optical display devices may have a film thickness of 50A to 2,500A in certain applications and uses. In one embodiment of the invention, the 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 cases at least 500 a. And the film may 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 cases up to 1,000 a. The film thickness may be or vary between any of the values described.

[0050]In some embodiments of the present optical device, one or more suitable MoO-containing materials are included₂The film of (1). Non-limiting examples of suitable membranes include, but are not limited to, mono-MoO₂Phase film, doped MoO₂Film, MoO₂Doped tin oxide film, MoO₂Doped indium tin oxide film, MoO₂Doping of ZnO/In₂O₃Film, MoO₂Doped ZnO/SnO₂/In₂O₃Film, MoO₂Doped ZnO film, MoO₂Doped SnO₂Film, MoO₂Doped ZnO/Al₂O₃Film, MoO₂Ga/ZnO doped film, MoO₂Doped GaO/ZnO film, MoO₂Doped zinc stannate (Zn)₂SnO₄) Film and MoO₂-MoO₃A composite membrane.

[0051] The sputtering plate can be of any suitable shape and size. As a non-limiting example, the sputtering plate can be square, rectangular, circular, or oval. In a particular embodiment, the square sputtering plate can be square and have dimensions of 0.1cm by 0.1cm to 5cm by 5cm, in some cases 0.5cm by 0.5cm to 4cm by 4cm, in other cases 1cm by 1cm to 3cm by 3cm, in some cases 2cm by 2cm to 3cm by 3cm, and in other cases the square sputtering target has dimensions of about 2.5cm by about 2.5 cm.

[0052] In another particular embodiment, the shorter side of the rectangular sputtering plate has a length of at least 0.1cm, in some cases at least 0.5cm, in other cases at least 1cm, in some cases at least 2cm, in other cases at least 2.5cm, in some cases at least 3cm, in other cases at least 4cm and in particular cases at least 5 cm. And the longer side of the rectangle can be up to 6cm, in some cases up to 5cm, in other cases up to 4cm, in some cases up to 3cm, in other cases up to 2.5cm, in some cases up to 2cm, in other cases up to 1cm and in particular cases up to 0.75 cm. The size of the rectangular sputtering target can vary between any of the dimensions as long as the longer dimension is larger than the shorter dimension.

[0053]In another particular embodiment of the invention, the MoO may be₂Or contains MoO₂The sputtering target of (2) is bonded to the backing plate to form a large area sputtering target. In one particular embodiment, a segment-forming (segment-forming) sputtering method may be used.

[0054] The large area sputtering plate can be of any suitable shape and size. As a non-limiting example, the large area sputtering plate can be square, rectangular, circular, or oval. In a particular embodiment, the square sputtering plate can be square and have dimensions of 0.1m x 0.1m to 6m x 6m, in some cases 0.5m x 0.5m to 5.5m x 5.5m, in other cases 1m x 1m to 4m x 4m, in some cases 2m x 2m to 3m x 3m and in other cases the square sputtering target has dimensions of about 2.5m x about 2.5 m.

[0055] In another particular embodiment, the length of the shorter side of the large area rectangular sputtering target is at least 0.1m, in some cases at least 0.5m, in other cases at least 1m, in some cases at least 2m, in other cases at least 2.5m, in some cases at least 3m, in other cases at least 4m, in particular cases at least 5m, and in particular cases at least 5.5 m. And the longer side of the rectangle may be up to 6m, in some cases up to 5m, in other cases up to 4m, in some cases up to 3m, in other cases up to 2.5m, in some cases up to 2m, in other cases up to 1m and in particular cases up to 0.75 m. The size of the large area rectangular sputtering plate can vary between any of the above dimensions as long as the dimension of the longer side is greater than the dimension of the shorter side.

[0056] In one embodiment of the present invention, the film in the optical display device is formed using one or more methods selected from the group consisting of metal-organic chemical vapor deposition (MOCVD), metal-organic deposition (MOD), and sol-gel techniques.

[0057]MOCVD or "metal-organic chemical vapor deposition" as used herein refers to a chemical vapor deposition method of film growth in which all the substance to be deposited is present in the vapor phase on the deposition surface. In MOCVD, the source of chemical vapor deposition is a metal-organic compound having oxygen as a heteroatom to attach the metal atom to one or more organic ligands. As a non-limiting example, molybdenum ethyl hexanoate (molybdenum ethyl-hexanoate) can be used as a metal-organic precursor to prepare MoO₂A film. As a specific, non-limiting example, the precursors can be contained in a vitreous silica boat or reaction tube and the compound can be heated to near boiling point, after which an argon carrier gas is mixed with a suitable oxygenPartial pressures are introduced together to oxidize the compound under a reducing atmosphere to produce MoO₂The molecules are then deposited on the substrate in the reaction chamber.

[0058]As used herein, the "sol-gel process" refers to a process that uses a metal alkoxide that forms a network cation as a solution precursor. As a non-limiting example, the cation may be M (OR) x, where M represents a metal and R represents an alkyl group. Furthermore, MoO was used for the sol-gel₂The starting alkoxide of (a) may be molybdenum acetylacetonate (molybdenum acetyl-acetate in methanol). Hydrolysis may then be accomplished by mixing the solution with ethanol, thereby producing a polymeric solution. The precursor solution is stable for only a few days, after which the clarity disappears and gelation occurs. The precursor solution may be applied to a substrate and then spun, for example at 1000rpm, to produce a thin wet film. Another technique for preparing thin films is to dip the substrate in a precursor solution and use a discharge rate (w/w) of, for example, 580 mm/min. The wet film may then be heat-treated in a vacuum and a hydrogen atmosphere (reducing atmosphere), thereby generating MoO on the substrate₂A film.

[0059]The term "MOD process" or "metal-organic decomposition process" as used herein refers to processes similar to MOCVD and/or sol-gel processes. In the MOD process, metal-organic compounds are also used as precursors, which have oxygen as a heteroatom to attach the metal atom to one or more organic ligands. The compound is dissolved in a suitable solvent, one non-limiting example being xylene. As a non-limiting example, molybdenum ethylhexanoate or molybdenum acetylacetonate can be used as the metal-organic compound to produce MoO₂A film. After adjusting the rheology of the solution, a liquid film is formed on the substrate by spinning the precursor solution.

[0060]Typically, the final step in the MOD process is pyrolysis, which involves solvent evaporation, thermal decomposition of compounds and solid solutions to form MoO under a suitable oxidizing and reducing atmosphere₂And (3) a membrane.

[0061]In the present inventionIn one embodiment of the invention, in the MOD process, pure MoO is excluded₂In addition to phase films, MoO-containing films can also be prepared by mixing several different metal-organic solutions₂The film of (1). As a non-limiting example, molybdenum ethylhexanoate can be mixed with tin ethylhexanoate in a solvent such as xylene at a ratio whereby the desired stoichiometry is achieved. After the wet film is prepared on the substrate in a rotating way, the pyrolysis is carried out under the appropriate oxygen partial pressure to prepare the molybdenum tin oxide film (containing MoO)₂A film).

[0062] In one embodiment of the invention, the MOCVD or MOD techniques utilize metal-organic chemistries including molybdenum ethylhexanoate.

[0063] In one embodiment of the invention, the film in the optical device may have a work function of 4.5-6eV, in some cases 4-5.5eV, and in some cases 4.5-5.5 eV.

[0064] In another embodiment of the invention, the thin film may generally have a roughness of less than about 5nm, in some cases from 0.1nm to 5nm, and in other cases from 0.1 to 2.5 nm.

[0065] Under another embodiment of the present invention, the film may have an average transmission of greater than 85%, in some cases greater than 90%, and in other cases greater than 95% at wavelengths from 350nm to 800 nm.

[0066] In another embodiment of the invention, the film can have a resistivity of less than 300 μ Ω -cm, in some cases less than 250 μ Ω -cm, and in other cases less than 200 μ Ω -cm.

[0067]In a particular embodiment of the invention, the optical device is an organic light emitting diode, the MoO-containing layer₂The membrane of (a) is an anode.

[0068] Further, the organic light emitting diode includes:

(a) a metal cathode;

(b) an electron transport layer;

(c) an emission layer;

(d) a hole transport layer; and

(e) MoO-containing layer as anode layer₂And (3) a membrane.

[0069] In some aspects of this embodiment, the film can be on a substrate selected from the group consisting of a plastic substrate, a glass substrate, a ceramic substrate, and combinations thereof. As a non-limiting example, the plastic substrate may comprise one or more plastics selected from the group consisting of polynorbornene, polyimide, polyarylate, polycarbonate, polyethylene naphthalate, and polyethylene terephthalate. And as a non-limiting example, the ceramic substrate may comprise sapphire.

[0070]In another embodiment of the invention, the optical device is a light emitting diode, the MoO-containing layer₂The thin film may be an ohmic contact. Further, the light emitting diode may include:

(a) a substrate;

(b) a buffer layer;

(c) an N-type semiconductor material;

(d) a connecting layer;

(e) a P-type semiconductor material;

(f) a P-type metal contact; and

(g) an n-type metal contact.

Non-limiting examples of suitable substrates are those comprising materials selected from the group consisting of sapphire, SiC, Si, GaN, GaP, GeSi, AlN, and combinations thereof. Non-limiting examples of suitable buffer layer materials are those that include one or more compounds from group IIIB and group VB elements of the periodic table of elements. The term "periodic table of elements" as used herein refers to the periodic table format used by IUPAC. In a particular embodiment of the invention, the buffer layer comprises AlN, GaN or a combination thereof.

[0071] In another aspect of the light emitting diode embodiments of the present invention, the N-type semiconductor material can include, but is not limited to, a material containing one or more compounds doped with one or more elements selected from the group consisting of Si, Se, Te, and S. Non-limiting examples of such compounds include compounds of elements of group IIIB and elements of group VB of the periodic table of elements, and compounds selected from elements of group IIB and elements of group VIB of the periodic table of elements. Non-limiting examples of suitable group IIIB and group VB element compounds include Si-doped compounds selected from GaN, GaAs, GaAlAs, AlGaN, GaP, GaAsP, GaInN, AlGaInN, AlGaAs, AlGaInP, PbSnTe, PbSnSe, and combinations thereof. Non-limiting examples of suitable group IIB and group VIB element compounds include Si-doped compounds selected from ZnSSe, ZnSe, SiC, and combinations thereof.

[0072]In another aspect of an embodiment of the light emitting diode of the present invention, the thin film can be an n-type metal contact. In particular embodiments of the present invention, the n-type metal contact may comprise a metal selected from Ti/Au, MoO₂Conductive oxide and MoO₂A metal, wherein the metal is selected from the group consisting of Ti, Au, and combinations thereof.

[0073] In another aspect of the light emitting diode embodiments of the present invention, the p-type semiconductor material can include one or more compounds doped with one or more elements selected from the group consisting of Mg, Zn, and C. Suitable compounds for this aspect of the invention include compounds of elements from group IIIB and VB of the periodic table of elements and compounds selected from compounds of elements from group IIB and VIB of the periodic table of elements. Non-limiting examples of suitable group IIIB and group VB element compounds include Mg-doped compounds selected from GaN, GaAs, GaAlAs, AlGaN, GaP, GaAsP, GaInN, AlGaInN, AlGaAs, AlGaInP, PbSnTe, PbSnSe, and combinations thereof. Non-limiting examples of suitable group IIB and group VIB element compounds include Mg-doped compounds selected from ZnSSe, ZnSe, SiC, and combinations thereof.

[0074]In another aspect of the light emitting diode embodiments of the present invention, the thin film can be a p-type metal contact. In particular embodiments of the invention, the p-type metal contact comprises a material selected from the group consisting of MoO-containing₂Transparent conductive oxide and MoO-containing₂A material for a metal film, wherein the metal is selected from the group consisting of Ag, Au, and combinations thereof.

[0075]In one embodiment of the invention, the optical device may be a liquid crystal display, the MoO-containing₂The 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 a combination thereof. In addition, the liquid crystal display may include a thin film diode or a thin film transistor switching element.

[0076] Aspects of embodiments of liquid crystal displays of the invention include a liquid display crystal comprising:

A) a glass substrate having a plurality of glass layers,

B) a source electrode, a drain electrode and a source electrode,

C) a drain electrode formed on the substrate,

D) a gate insulator is provided on the gate electrode,

E) a gate electrode formed on the substrate and having a first electrode,

F) a layer of amorphous silicon, polycrystalline silicon or single crystal silicon,

G) an n-doped silicon layer, a silicon nitride layer,

H) a passivation layer for protecting the substrate from light,

I) a pixel transparent electrode formed on the substrate,

J) the electrodes are arranged on a common electrode, and the electrodes are arranged on a common electrode,

K) polyimide alignment layer and

l) storage capacitor electrodes.

In some aspects of this embodiment, the pixel transparent electrode and the common electrode can comprise MoO-containing₂And (3) a membrane.

[0077]Another embodiment of the present invention is directed to these cases wherein the optical device is a plasma display panel and the MoO-containing layer₂The membrane is a positive electrode or a negative electrode. In this embodiment, the plasma display panel may include:

A) a front glass plate, a rear glass plate,

B) an insulating film is formed on the surface of the substrate,

C) a layer of MgO,

D) the gas is ionized and the gas is discharged,

E) separator

F) One or more phosphors, and

G) a rear glass panel.

In some aspects of this embodiment, MoO may be used₂A film coats the rear glass.

[0078]Other embodiments of the invention are directed to cases where the optical device is a field emission display, the MoO-containing₂The film is an anode or cathode material. In this embodiment, the field emission display may include:

[0079]

A) an anode of a glass panel is provided,

B) a phosphor which is capable of emitting light,

C) the spacer is provided with a plurality of spacers,

D) the small tip is provided with a small hole,

E) cathodes in rows and columns and

F) a glass base plate.

In some aspects of this embodiment, the composition comprises MoO₂Film coating the glass panel a). In another aspect of this embodiment, at least one of the rows and columns of cathodes E) can comprise a cathode comprising MoO₂A film of (2).

[0080]In another embodiment of the invention, the optical device may be a solar cell and the MoO-containing layer₂The film may be one or more of an electrical contact, a transparent contact, and a top connection layer. In this embodiment, the solar cell may include:

A) a glass cover is arranged on the glass plate,

B) a top electrical contact layer is provided on the substrate,

C) the transparent contact is provided with a transparent contact point,

D) a top connection layer is arranged on the top of the substrate,

E) an absorption layer is arranged on the outer surface of the substrate,

F) a rear electrical contact, and

G) a substrate.

In some aspects of this embodiment, the transparent contact C) can comprise a MoO-containing material₂The film of (1). In another aspect of this embodiment, the top tie layer D) can comprise a MoO-containing layer₂The film of (1). In another aspect of this embodiment, the glass envelope a) can include an anti-reflective coating.

Examples

Example 1

Four different MoOs₂The powder was characterized for its sintering and shrinkage by dilatometer. Small specimens of approximately Φ 8 × 10mm were pressed with steel dies and compacted after Cold Isostatic Pressing (CIP). The four MoO₂The powder showed the following characteristics:

MoO for densification experiments₂Powder of

Name content of impurities ppm specific surface area m²Mineral phase/g

MoO-P1 ＞100 0.5 MoO₂

MoO-P2 ＜50 1.0 MoO₂

MoO₂Trace Mo4O11

MoO-P3 ＜50 2.3 MoO₃

MoO-P4 ＜50 2.0 MoO₂

In Ar-3H₂The mixture was heated to 1250 ℃ at a rate of 5k/min in an atmosphere. The samples prepared from MoO-P1, 2 and 4 in the dilatometer showed reduced swelling and densification and ended up with a density comparable to the "as compressed" starting density, which was about 3.5g/cm³. Despite this, the sample prepared from MoO-P3 showed an onset of shrinkage at approximately 600 ℃, which continued until a maximum temperature of 1250 ℃ was reached. The shrinkage recorded amounts to 10.3%, the density measured after expansion was 4.1g/cm³。

These results are interpreted as: in contrast to the mineral phase, neither the impurity content nor the specific surface area of the powder have a significant influence on the densification.

Example 2

A sample of approximately Φ 30 x 5mm was prepared from MoO-P1-4 in the same manner as described in test 1. The density "as pressed" was about 3.5g/cm³. In sealing Al₂O₃In a lining furnace, in Ar-3H₂These samples were sintered under an atmosphere and placed on a recrystallized SiC plate. The heating rate was 5k/min and the temperature was raised to 1100, 1150, 1200, 1250 and 1300 ℃ respectively, followed by a soaking time of 1-5 h. Up to 1200 ℃ the measured density after the sintering cycle, except for the sample prepared from MoO-P3, increased slightly to about 3.8g/cm³The density of the sample prepared from MoO-P3 reached 4.1g/cm³. Further increases in temperature lead to a further decrease in density and an increase in weight loss.

These results are again interpreted in this way: in contrast to the mineral phase, the impurity content and the specific surface area of these powders do not have a significant influence on the sintering behavior.

Example 3

Placing MoO-P powder 4 in Mo-foil lined hot press molds, made from graphite. Various hot press tests were performed at elevated temperatures, starting at 750 ℃, 1000 ℃ and ending at 1300 ℃. In order to run the hot press as a dilatometer and thus record the densification as a function of temperature, a maximum pressure of 30MPa is applied at 600 ℃. Heating and cooling at 10k/min, and applying Ar-3H again₂As an atmosphere. None of these conditions resulted in a strong, dense sample. Most of which break during ejection from the die and are soft as if scratched by the fingernails. At the 1300 ℃ test, severe reactions with the Mo foil have occurred, resulting in strong adhesion.

Thus, the powder is not suitable for densification under technically feasible hot pressing conditions.

Example 4

MoO-P4 was mixed with 2.5 wt% of fine MoO₃And (4) mixing the powder. In a plastic bottle, in the dry state, on a roller frame for 5 hours, and use Al₂O₃The ball aids in dispensing. The mixed powder was screened < 300 μm and used for further hot pressing tests. At 600 ℃, a maximum pressure of 30MPa is applied in order to run the hot press as a dilatometer and thus record the densification as a function of temperature. Heating and cooling at 10k/min, and applying Ar-3H again₂As an atmosphere. The system records the onset of densification at about 700 ℃, which continues until about 800 ℃. Further increases in temperature did not result in further densification. After ejection, the density was measured to be about 5.9g/cm³. There is no reaction with the Mo barrier foil. By XRD, only MoO could be detected₂And (4) phase(s). The presence of crystalline Mo phases with O/Mo ratios > 2 above the XRD detection limit is not shown. This supports the conclusion that: a few percent of the Mo phase allows for densification of MoO by hot pressing to theoretical density at relatively low temperatures₂Powder (within the characteristic limits indicated above), the Mo phase having an O/Mo ratio > 2.

Example 5

According to test 4, to analyze the MoO added during the hot pressing₃Amount of (d) to MoO₂Effect of powder densification MoO-P2 was compared with 2, 3 and 5 wt% MoO, respectively₃And (4) mixing the powder. Fixing the hot pressing condition at 750 deg.C, 30 min soaking time, 30MPa pressure and Ar-3H₂Under an atmosphere. Graphite was used as the isolating foil.

Under these conditions, 1 wt% MoO was added₃Sample #1 of the mixture reached 4.5g/cm³While 3 wt% MoO was added₃Sample #2 and 5 wt% MoO addition₃Sample #3 of (2) reached 6.1g/cm³The density of (c). No reaction between the sample material and the graphite separator foil is shown. These specimens were very hard and could not be scratched by fingernails. Only MoO₂The phases were detectable by XRD and did not show the presence of crystalline Mo phases with O/Mo ratios > 2, which are above the XRD detection limits.

According to the procedure described in test 4, 3% by weight of MoO were added₂And hot pressing conditions are as described above but soaking time is prolonged, a density of > 6.0g/cm can be prepared³Of phi 50-250mm and may be up to about 20mm thick. Therefore, the process is suitable for preparing high-density MoO with professional-size technology₂And (3) a plate.

The present invention and its various embodiments have been disclosed above. It will be apparent to those skilled in the art that various changes and modifications may be made herein without departing from the scope of the invention as defined in the specification and the appended claims.

Claims (94)

1. For preparing high-purity MoO₂A method of powder comprising:

(a) placing a molybdenum component in a furnace, wherein the molybdenum component is selected from the group consisting of ammonium dimolybdate, molybdenum trioxide, and mixtures thereof; and

(b) heating the molybdenum component in a furnace at a temperature below 700 ℃ in a reducing atmosphere to form high purity MoO₂And (3) powder.

2. The method of claim 1, wherein the MoO₂The powder is characterized by being greater than 99.95% purity, and has more than 99% MoO₂And (4) phase(s).

3. The method of claim 1, wherein the MoO₂The powder is more than 99% of stoichiometric MoO₂And (3) powder.

4. The method of claim 1, wherein the molybdenum component is heated for a period of time ranging from 15 minutes to about 4 hours.

5. The process of claim 1, wherein the furnace is selected from the group consisting of a stationary tube furnace, a rotary tube furnace, and a calciner.

6. The method of claim 1, wherein the reducing atmosphere comprises hydrogen.

7. The process of claim 1 wherein 6.8Kg of ammonium dimolybdate is placed in a flat bottom boat and the boat is heated in a static tube furnace for 2-3 hours at a temperature in the range of 500 ℃ to 700 ℃.

8. MoO (MoO)₂Powder comprising MoO in a stoichiometric amount of more than 99%₂。

9. A method of making a panel comprising:

(a) more than 99% of stoichiometric MoO₂Isostatic pressing of the powder components into a blank;

(b) vacuum sintering the blank under conditions to maintain greater than 99% MoO₂The stoichiometry of (a); and

(c) formation of a catalyst containing greater than 99% of stoichiometric MoO₂The plate of (1).

10. The method of claim 9, wherein the blank is vacuum sintered at a temperature of at least 1250 ℃ for 6 hours.

11. The method of claim 9, wherein the pressure is between 10,000psi and 40,000psiIsostatic pressing of the MoO over a force range₂And (3) powder.

12. The method of claim 9, wherein the plate is subjected to hot isostatic pressing.

13. The method of claim 9, wherein the plate has a MoO₂A density of 90% to 100% of theoretical density.

14. A panel made according to the method of claim 9.

15. A sputtering process comprising contacting a substrate containing greater than 99% stoichiometric MoO₂Is subjected to sputtering conditions, thereby sputtering the plate.

16. The method of claim 15, wherein sputtering is performed using a sputtering method selected from the group consisting of magnetron sputtering, pulsed laser sputtering, ion beam sputtering, tripolar sputtering, and combinations thereof.

17. A method for preparing a thin film, comprising the steps of:

(a) sputtering containing greater than 99% stoichiometric MoO₂A plate of (a);

(b) removal of MoO from the plate₂A molecule; and

(c) deposition of MoO on a substrate₂Molecules, thereby forming a thin film.

18. The method of claim 17, wherein the thin film has a thickness of 0.5nm to 10 μm.

19. The method of claim 17, wherein the sputtering method is selected from the group consisting of magnetron sputtering, pulsed laser sputtering, ion beam sputtering, tripolar sputtering, and combinations thereof.

20. A film made according to the method of claim 16.

21. The film of claim 20 wherein the film has a work function that is higher than a work function of an indium tin oxide film having the same dimensions.

22. The film of claim 20 wherein the film has a work function of from about 4.5eV to about 6 eV.

23. The film of claim 20, wherein the film has a surface roughness that is lower than the surface roughness of the indium tin oxide film.

24. The film of claim 20, wherein the film has a roughness of less than about 5 nm.

25. The film of claim 20, wherein the film has an average transmission of greater than 85% at wavelengths from 350nm to 800 nm.

26. The film of claim 20, wherein the film has a resistivity of less than 300 μ Ω -cm.

27. The film of claim 20, wherein the film has a thickness in the range of about 50 a to about 2,500 a.

28. An organic light emitting diode comprising:

(a) a metal electrode;

(b) an electron transport layer;

(c) an emission layer;

(d) a conductive polymer layer; and

(e) containing greater than about 99% stoichiometric MoO₂Wherein the film is on a substrate.

29. The organic light emitting diode of claim 28, wherein the substrate is selected from the group consisting of a plastic substrate, a glass substrate, a ceramic substrate, and combinations thereof.

30. The organic light emitting diode of claim 28, wherein the plastic substrate comprises one or more plastics selected from the group consisting of polynorbornene, polyimide, polyarylate, polycarbonate, polyethylene naphthalate, and polyethylene terephthalate.

31. The organic light emitting diode of claim 28, wherein the ceramic substrate comprises sapphire.

32. A component comprising a sputter target, wherein the sputter target comprises machined high purity MoO₂And (3) a plate.

33. The element of claim 32 wherein the plate is machined by laser cutting, milling, turning or lathe techniques.

34. The element of claim 32, wherein the sputter target is circular and has a diameter of 2.54cm to 63.5 cm.

35. The element of claim 32 wherein the target has a thickness of from about 0.15cm to about 20 cm.

36. An optical display device comprising a film comprising greater than about 99% stoichiometric MoO₂Disposed on at least a portion of the substrate.

37. The optical device of claim 36, wherein the film is formed by:

(a) sputtering containing greater than 99% stoichiometric MoO₂A plate of (a);

(b) removal of MoO from the plate₂A molecule; and

(c) adding MoO₂Molecules are deposited on the substrate to form MoO₂A film.

38. The optical device of claim 36, wherein the film is formed by:

(a) sputtering a plate containing greater than about 99% Mo;

(b) removing Mo molecules from the plate; and

(c) in the chamber, MoO is formed under partial pressure of oxygen₂Molecule to thereby generate MoO on a substrate₂A film.

39. The optical device of claim 36, wherein the thin film has a thickness of 0.5nm to 10 μm.

40. The optical device according to claim 37, wherein the sputtering method is selected from the group consisting of magnetron sputtering, pulsed laser sputtering, ion beam sputtering, tripolar sputtering, and combinations thereof.

41. The optical device according to claim 36, wherein the film has a work function of 4.5eV to 6 eV.

42. The optical device of claim 36, wherein the film has a roughness of less than about 5 nm.

43. The optical device of claim 36, wherein the film has an average transmission of greater than 85% at wavelengths of about 350nm to about 800 nm.

44. The optical device of claim 36, wherein the film has a resistivity of less than about 300 μ Ω -cm.

45. The optical device according to claim 36, wherein the film has a film thickness of about 50 a to about 2,500 a.

46. The optical device according to claim 36, wherein the optical device is an organic light emitting diode and the MoO-containing layer₂The membrane of (a) is an anode.

47. An optical device according to claim 46, wherein the organic light emitting diode comprises:

(a) a metal cathode;

(b) an electron transport layer;

(c) an emission layer;

(d) a hole transport layer; and

(e) containing MoO₂The membrane of (a) serves as the anode layer.

48. The optical device of claim 46, wherein the film is on a substrate selected from the group consisting of plastic substrates, glass substrates, ceramic substrates, and combinations thereof.

49. The optical device of claim 48, wherein the plastic substrate comprises one or more plastics selected from the group consisting of polynorbornene, polyimide, polyarylate, polycarbonate, polyethylene naphthalate, and polyethylene terephthalate.

50. The optical device of claim 48, wherein the ceramic substrate comprises sapphire.

51. The optical device according to claim 36, wherein the optical device is a light emitting diode and the MoO-containing material₂The film is an ohmic contact.

52. The optical device according to claim 51, wherein the thin film is a p-type metal contact.

53. The optical device according to claim 51, wherein the thin film is an n-type metal contact.

54. An optical device according to claim 51, wherein the light emitting diode comprises:

(a) a substrate;

(b) a buffer layer;

(c) an N-type semiconductor material;

(d) a connecting layer;

(e) a p-type semiconductor material;

(f) a p-type metal contact; and

(g) an n-type metal contact.

55. The optical device of claim 54, wherein the substrate comprises a material selected from the group consisting of sapphire, SiC, Si, GaN, GaP, GeSi, AlN, and combinations thereof.

56. The optical device of claim 54, wherein the buffer layer comprises one or more compounds of an element from group HIB and an element from group VB of the periodic Table of elements.

57. The optical device of claim 56, wherein the buffer layer comprises AlN, GaN, or a combination thereof.

58. The optical device of claim 54, wherein the N-type semiconductor material comprises one or more compounds doped with one or more elements selected from the group consisting of Si, Se, Te and S, the compounds being selected from the group consisting of compounds of elements of group IIIB and group VB of the periodic Table of elements, and compounds selected from the group consisting of compounds of elements of group IIB and group VIB of the periodic Table of elements.

59. The optical device of claim 58, wherein the compound of a group IIIB element and a group VB element is a Si-doped compound selected from the group consisting of GaN, GaAs, GaAlAs, AlGaN, GaP, GaAsP, GaInN, AlGaInN, AlGaAs, AlGaInP, PbSnTe, PbSnSe, and combinations thereof.

60. The optical device according to claim 58, wherein the compound of group IIB and VIB elements is a Si-doped compound selected from the group consisting of ZnSSe, ZnSe, SiC and combinations thereof.

61. The optical device of claim 54, wherein the n-type metal contact comprises a metal selected from the group consisting of Ti/Au, MoO₂Conductive oxide and MoO₂A material of metal, wherein the goldThe metal is selected from Ti, Au and the combination thereof.

62. The optical device of claim 54, wherein the P-type semiconductor material comprises one or more compounds doped with one or more elements selected from the group consisting of Mg, Zn, and C, the compounds being selected from the group consisting of compounds of elements from group IIIB and group VB of the periodic Table of elements, and compounds selected from the group consisting of compounds of elements from group IIB and group VIB of the periodic Table of elements.

63. The optical device of claim 62, wherein the compound of a group IIIB element and a group VB element is a Mg-doped compound selected from the group consisting of GaN, GaAs, GaAlAs, AlGaN, GaP, GaAsP, GaInN, AlGaInN, AlGaAs, AlGaInP, PbSnTe, PbSnSe, and combinations thereof.

64. The optical device according to claim 58, wherein the compound of group IIB and VIB elements is an Mg-doped compound selected from the group consisting of ZnSSe, ZnSe, SiC and combinations thereof.

65. The optical device of claim 54, wherein the P-type metal contact comprises a material selected from the group consisting of MoO-containing₂And a transparent conductive oxide containing MoO₂A material for a metal film, wherein the metal is selected from the group consisting of Ag, Au, and combinations thereof.

66. The optical device according to claim 36, wherein the optical device is a liquid crystal display and the MoO-containing layer₂The 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 a combination thereof.

67. The optical device according to claim 66, wherein the liquid crystal display comprises thin film diode or thin film transistor switching elements.

68. The optical device according to claim 66, wherein the liquid crystal display comprises:

A) a glass substrate having a plurality of glass layers,

B) a source electrode, a drain electrode and a source electrode,

C) a drain electrode formed on the substrate,

D) a gate insulator is provided on the gate electrode,

E) a gate electrode formed on the substrate and having a first electrode,

F) a layer of amorphous silicon, polycrystalline silicon or single crystal silicon,

G) an n-doped silicon layer, a silicon nitride layer,

H) a passivation layer for protecting the substrate from light,

I) a pixel transparent electrode formed on the substrate,

J) the electrodes are arranged on a common electrode, and the electrodes are arranged on a common electrode,

K) polyimide alignment layer and

l) storage capacitor electrodes.

69. The optical device according to claim 68, wherein the pixel transparent electrode and the common electrode comprise MoO-containing₂And (3) a membrane.

70. The optical device according to claim 36, wherein the optical device is a plasma display panel, the MoO-containing layer₂The membrane is a positive electrode or a negative electrode.

71. The optical device according to claim 70, wherein the plasma display panel comprises:

A) a front glass plate, a rear glass plate,

B) an insulating film is formed on the surface of the substrate,

C) a layer of MgO,

D) the gas is ionized and the gas is discharged,

E) the separation part is arranged on the bottom of the container,

F) one or more phosphors, and

G) a rear glass panel.

72. The optical device according to claim 71, wherein the rear glass is MoO coated₂And (3) a membrane.

73. The optical device according to claim 36, wherein the optical device is a field emission display and the MoO-containing layer₂The membrane is an anode or cathode material.

74. An optical device according to claim 73, wherein the field emission display comprises:

A) an anode of a glass panel is provided,

B) a phosphor which is capable of emitting light,

C) the spacer is provided with a plurality of spacers,

D) the small tip is provided with a small hole,

E) cathodes in rows and columns, and

F) a glass base plate.

75. The optical device according to claim 74, wherein the glass panel A) is coated with a coating comprising MoO₂The film of (1).

76. The optical device according to claim 74, wherein at least one of the rows and columns of cathodes E) comprises MoO-containing₂The film of (1).

77. The optical device according to claim 36, wherein the optical device is a solar cell, the MoO comprising₂The film is one or more of an electrical contact, a transparent contact, and a top connection layer.

78. The optical device of claim 77, wherein the solar cell comprises:

A) a glass cover is arranged on the glass plate,

B) a top electrical contact layer is provided on the substrate,

C) the transparent contact is provided with a transparent contact point,

D) a top connection layer is arranged on the top of the substrate,

E) an absorption layer is arranged on the outer surface of the substrate,

F) a rear electrical contact, and

G) a substrate.

79. The optical device according to claim 78, wherein the transparent contact C) comprises a material comprising MoO₂The film of (1).

80. The optical device according to claim 78, wherein the top connecting layer D) comprises a MoO-containing layer₂The film of (1).

81. An optical device according to claim 78, wherein the glass cap A) comprises an anti-reflective coating.

82. The optical device of claim 81, wherein the anti-reflective coating comprises MoO-containing₂Film, Si₃N₄A film, a titanium silicon oxide film (titania silicon), and combinations thereof.

83. The optical device according to claim 36, wherein the one or more MoO-containing materials₂The membrane comprises a material selected from the group consisting of mono MoO₂Phase film, doped MoO₂Film, MoO₂Doped tin oxide film, MoO₂Doped indium tin oxide film, MoO₂Doping of ZnO/In₂O₃、MoO₂Doped ZnO/SnO₂/In₂O₃、MoO₂Doped ZnO film, MoO₂Doped SnO₂Film, MoO₂Doped ZnO/Al₂O₃Film, MoO₂Ga/ZnO, MoO doped₂Doped GaO/ZnO, MoO₂Doped zinc stannate (Zn)₂SnO₄) Film and MoO₂-MoO₃A composite membrane.

84. The optical device according to claim 37, wherein the sputtering plate is square or rectangular in shape.

85. The optical device of claim 84, wherein the plate has dimensions of 2.5cm x 2.5cm for a square and 2.5cm x 3cm for a rectangle.

86. The optical device according to claim 37, wherein the MoO is doped with a metal oxide₂Or contains MoO₂Is bonded to the back plate, thereby forming a large area sputtering target.

87. The optical device of claim 86, wherein a segmented shaping sputtering method is used.

88. The optical device of claim 87, wherein the large area sputtering target can have dimensions of 6m x 5.5 m.

89. The optical device according to claim 37, wherein the MoO₂Or contains MoO₂The sputtering target of (1) has a thickness of 0.15cm to 20 cm.

90. The optical device of claim 36, wherein the film is formed using one or more methods selected from the group consisting of metal-organic chemical vapor deposition (MOCVD), metal-organic deposition, and sol-gel techniques.

91. The optical device according to claim 90, wherein the sol-gel technique utilizes metal-organic chemicals including molybdenum acetylacetonate.

92. The optical device of claim 90, wherein the MOCVD or MOD techniques utilize metal-organic chemistries including molybdenum ethylhexanoate.

93. A method for making a panel comprising contacting greater than 99% stoichiometric MoO₂Subjecting the powder component to hot pressing conditions to form a composition containing greater than 99% stoichiometric MoO₂The plate of (1).

94. The method of claim 93, wherein the hot pressing is carried out with an instant liquid phase assisted hot pressing.