WO2006060660A2 - Revetements en nitrure du groupe iii et procedes associes - Google Patents

Revetements en nitrure du groupe iii et procedes associes Download PDF

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WO2006060660A2
WO2006060660A2 PCT/US2005/043637 US2005043637W WO2006060660A2 WO 2006060660 A2 WO2006060660 A2 WO 2006060660A2 US 2005043637 W US2005043637 W US 2005043637W WO 2006060660 A2 WO2006060660 A2 WO 2006060660A2
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group iii
iii nitride
dispersant
composition
dispersion
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PCT/US2005/043637
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WO2006060660A3 (fr
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Huaqiang Wu
Michael G. Spencer
Emmanuel Giannelis
Athanasios Bourlinos
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Cornell Research Foundation, Inc.
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Priority to CN2005800414858A priority Critical patent/CN101068890B/zh
Publication of WO2006060660A2 publication Critical patent/WO2006060660A2/fr
Publication of WO2006060660A3 publication Critical patent/WO2006060660A3/fr
Priority to US11/809,879 priority patent/US7772288B2/en

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    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances

Definitions

  • Group III nitrides have received a great deal of attention due to the optoelectronic and electronic properties of their thin films.
  • Group III nitride thin films are typically prepared by depositing layers on sapphire, silicon carbide (SiC), and aluminum nitride (AlN) substrates using Molecular Beam Epitaxy, Metal Organic Chemical Vapor Deposition, or Hydride Vapor Phase Epitaxy techniques.
  • the most widely studied Group III nitride is gallium nitride (GaN), which has only been layered on small substrates, typically 1-4 inches in diameter. This size limitation is due to limited matching of lattice constants and thermal expansion coefficients.
  • Group III nitride thin films have yet to be deposited on large (e.g., one-meter) or flexible substrates using current techniques. Additionally, the cost of preparing Group III nitride thin films is high due to the nature of the growth techniques and substrates involved in the process. Accordingly, new techniques for preparing Group III nitride thin films are needed. Summary of the Invention
  • the invention provides novel compositions including a dispersion made from Group III nitride particles, a solvent system, and a dispersant.
  • the dispersion can be a colloidal dispersion.
  • Dispersants such as celluloses, for example methyl cellulose, have been found to successfully disaggregate Group III nitride particles in a solution or suspension.
  • the particle size of the Group III nitrides used to produce the thin films can be controlled by adjusting the centrifugation of the dispersion and selecting a desired layer of supernatant.
  • the present invention also provides a novel method for preparing high purity Group III nitride thin films.
  • the Group III nitride thin films can be prepared by a spin coating technique using the novel colloidal dispersion of Group III nitride particles.
  • the colloidal dispersion can be used to prepare Group III nitride thin films on a wide range of substrates, for example, glass, silicon, silicon carbide, aluminum nitride, sapphire, and organic polymers.
  • the technique allows for the use of larger substrates than previously used to prepare Group III nitride thin films.
  • the thin film layer thickness can be controlled by the speed and duration of the spin coating, and can be increased by repeating the spin coating process.
  • the dispersant can be removed from the thin films or otherwise modified by calcination and annealing techniques.
  • the Group III nitride thin films have highly ordered surface particles based on X-ray diffraction measurements.
  • the Group III nitride particles typically align with their c-plane parallel to the substrate surface. Strong luminescence from these layers has been evidenced by Cathodoluminescence.
  • the Group III nitride can also contain one or more dopants. Doped Group III nitride thin films can produce visible light emission upon excitation, including green, red, and yellow light, from and erbium, europium, and cerium dopants, respectively.
  • the Group III nitride thin film-covered substrates will be useful in the field of light emitting devices and laser devices. Brief Description of the Drawings
  • FIG. 1 illustrates a flowchart for the preparation of Group III nitride thin films using a spin coating technique according to one embodiment of the invention
  • FIG. 2 illustrates a flowchart for the preparation of GaN thin films using a spin coating technique according to one embodiment of the invention
  • FIG. 3 illustrates the X-ray diffraction pattern of a GaN thin film on a silicon substrate after three GaN thin films were deposited
  • FIG. 4 illustrates the stabilization of GaN particles in an aqueous suspension by adsorption of methylcellulose, according to an embodiment of the invention.
  • FIG. 5 shows Scanning Electron Microscope (SEM) images of the surface morphology of a GaN layer on a silicon substrate; (a) 20 ⁇ m resolution; (b) 2 ⁇ m resolution; FIG. 6 shows a Scanning Electron Microscope (SEM) image illustrating the surface morphology of a thrice layered GaN thin film on a silicon substrate;
  • FIG. 7 illustrates a Cathodoluminescence spectrum of a GaN layered glass substrate with three coating steps; at room temperature with electrons accelerated to 5 KeV;
  • FIG. 8 illustrates a Photoluminescence spectrum of a GaN layered silicon substrate with three coating steps; at room temperature with an argon laser at a wavelength of 496.5 nm;
  • FIG. 9 illustrates (a) contact patterns for a GaN thin film, and (b) a cross section schematic of a thin film transistor device using GaN particles; according to one embodiment of the invention.
  • FIG. 10 illustrates V measurements of GaN particles based TFT.
  • the invention provides a composition that is a dispersion made from a Group III nitride, a solvent system, and a dispersant.
  • the dispersion can be used to prepare Group III nitride thin films by spin coating on a wide range of substrates.
  • the particle size of the Group III nitride used for producing the thin films can be controlled by adjusting the centrifugation of the dispersion. By adjusting the duration and speed of the centrifugation, different sizes of become deposited at different layers of the centrifugation supernatant. By selecting a discrete layer of supernatant, a desired size range of particles can be obtained.
  • the Group III nitride can contain one or more dopants.
  • the dispersant can be removed from the thin films or otherwise modified by calcination and annealing techniques. Definitions:
  • a "dispersant” refers to an agent that aids in breaking up or separating fine particles of a solid into another medium, such as a liquid.
  • a dispersant is a material that coats or adsorbs onto the surface of solid particles and facilitates a substantially even distribution of the particles throughout an medium, typically to produce a colloidal suspension.
  • a "dispersion” refers to a colloidal suspension wherein particles of one substance (the dispersed phase) are distributed throughout another substance or solution (the continuous phase). Dispersion is also a process characterized by 1) adsorption (the interaction of a dispersant with a surface via anchoring groups), and 2) stabilization (the interaction of a dispersant with the solvent via stabilizer groups). See Wegner, Acta Mater. 2000, 48, 253.
  • a “solvent system” refers to a solvent, or a combination of solvents, used to dissolve or suspend another substance, typically a solid.
  • Group III nitride refers to a compound containing nitrogen covalently bonded to a Group III element. Examples of Group III nitrides include boron nitride (BN), aluminum nitride (AlN), gallium nitride (GaN), indium nitride (InN), and thallium nitride (TIN).
  • Group III element refers to an element that contains one electron in a p-orbital, wherein the p-orbital is the element's outermost valence orbital.
  • Group III elements include the elements boron (B), aluminum (Al), gallium (Ga), indium (hi), and thallium (Tl).
  • Group III nitride composition refers to a composition containing a Group III nitride, optionally including other elements, compounds, dopants, or combinations thereof.
  • a "powder” refers to a substance consisting of ground, pulverized, or otherwise finely dispersed solid particles.
  • a "thin film” refers to a layer or set of layers of material.
  • the layer or layers can be about one molecule thick to about 10 ⁇ m thick and are typically deposited on a substantially flat solid substrate.
  • Thin films can exhibit various electrochemical and photochemical properties.
  • a spin coating refers to a method for the application of thin, substantially uniform films to flat substrates. An excess amount of a solution or dispersion is placed on the substrate and the substrate is then rotated at high speed in order to spread the dissolved- or dispersed-particle containing fluid by centrifugal force. Rotation is continued for a time sufficient to form a substantially even layer, with fluid being spun off the edges of the substrate, until the desired film thickness of particles is achieved.
  • the solvent system can be volatile, allowing for its simultaneous or concomitant evaporation.
  • spin coating substrate refers to any surface upon which a solution, slurry, or dispersion can be placed, and that can be rotated, such as by a spin coating apparatus, to provide a thin film upon the surface.
  • Suitable examples of spin coating substrates include, but are not limited to, wafers or sheets of glass, silicon, silicon carbide (SiC), silicon nitride (Si 3 N 4 ), silicon dioxide (SiO 2 ), aluminum nitride (AlN), sapphire, rigid organic polymers, and any other substantially rigid surface that can be modified for use on a spin coating apparatus.
  • SiC silicon carbide
  • Si 3 N 4 silicon dioxide
  • AlN aluminum nitride
  • sapphire silicon organic polymers
  • rigid organic polymers can flexible, even to the point of being able to be formed into a cylinder.
  • a “dip coating” refers to a process of coating a spin coating substrate by immersing the substrate into a solution, slurry, or dispersion, followed by removing the substrate from the slurry or dispersion in a controlled manner.
  • dopant refers to a substance that is intentionally added, usually in small amounts, to a pure semiconductor material to alter its conductive properties, typically for use in semiconductors, transistors, and diodes. Suitable dopants include, e.g., beryllium (Be), magnesium (Mg), manganese (Mn), molybdenum (Mo), silicon (Si), and zinc (Zn).
  • dopants include rare earth elements, particularly cerium (Ce), samarium (Sm), dysprosium (Dy), erbium (Er), europium (Eu), promethium (Pm), thulium (Tm), and ytterbium (Yb).
  • the dopant can be employed in the form of a pure (elemental) metal.
  • the dopant employed can be in the form of a chemical compound or salt.
  • Rare earth compounds that can be used as dopants such as, e.g., europium chloride (EuCl 3 ), europium fluoride (EuF 3 ), europium nitrate
  • Suitable dopants also include, e.g., boron, aluminum, or indium, when the Group III element that is the major component of the reaction mixture is not B, Al, or In, respectively.
  • “calcination” refers to heating a thin film covered substrate to a high temperature but below the melting or fusing point of the substrate, causing loss of moisture, reduction or oxidation, decomposition, evaporation, or a combination thereof, of components of the thin film of the substrate.
  • annealing refers to a heat or laser treatment of a thin film or a thin film substrate to modify or improve physical properties or to relieve residual stresses.
  • the invention provides a composition that is a dispersion made from a Group III nitride, a solvent system, and a dispersant.
  • the dispersion can be a colloidal suspension.
  • the dispersion can be prepared by dissolving a dispersant in a solvent system to form a solution or mixture, followed by the adding a Group III nitride to the solution to form a mixture, and agitating the mixture to form a Group III nitride dispersion.
  • the Group III nitride can be in the form of a powder.
  • the particles of the powder can be crystalline.
  • the crystalline particles can be single crystals, or they can be polycrystalline.
  • the Group III nitride particles used can also be a combination of single crystals, polycrystalline particles, and amorphous particles. High purity Group III nitride particles form thin films with physical properties that are superior to thin films produced from particles of lower purity.
  • the Group III nitride employed in the dispersion can be greater than about 95% pure by weight, greater than about 99% pure by weight, greater than about 99.9% pure by weight, or greater than about 99.99% pure by weight.
  • the size of the Group III nitride particles can affect the physical properties of a thin film prepared by spin coating a substrate with a Group III nitride dispersion. A greater amount of Group III nitride particles can be absorbed into a dispersion when smaller particles sizes are employed.
  • the Group III nitride powder is composed of crystalline particles that are less than about 20 ⁇ m in diameter, or less than about 10 ⁇ m in diameter. Larger particles can be used in certain embodiments.
  • Certain Group III nitride dispersions consists mostly of, or consist entirely of, crystalline particles that are less than about 20 ⁇ m in diameter, less than about 10 ⁇ m in diameter, or less than about 5 ⁇ m in diameter.
  • Group III nitride particles that range in diameter from about 2 nm to about 20 ⁇ m in diameter, about 2 nm to about 10 ⁇ m in diameter, about 2 nm to about 5 ⁇ m in diameter, and about 2 nm to about 1 ⁇ m in diameter.
  • Group III nitrides possess different opto-electronic and electronic properties.
  • Various Group III nitrides that can be used to prepare the dispersion include boron nitride, aluminum nitride, gallium nitride, indium nitride, and thallium nitride, or combinations thereof.
  • the Group III nitride is gallium nitride.
  • the Group III nitride is not gallium nitride.
  • the 'Group III nitride' is a combination of Group III nitrides.
  • the dispersion can be prepared using any suitable solvent system that effectively dissolves the Group III nitride dispersant.
  • the solvent system can be heated to improve the dissolution of the Group III nitride dispersant.
  • the solvent system can be one or more solvents selected from the group consisting of water, methanol, ethanol, dimethyl formamide, dimethyl sulfoxide, dimethyl acetamide, tetrahydrofuran, methylene chloride, and chloroform, or combinations thereof.
  • the solvent system is deionized water.
  • a suitable dispersant for Group III nitride particles is important so that once absorbed onto the Group III nitride particle surface, the dispersant can retard agglomeration and sedimentation of the Group III nitride particles in a dispersion or slurry.
  • Any suitable dispersant that effectively adsorbs to a Group III nitride surface and disperses the Group III nitride particles in a solvent system can be used to form the Group III nitride dispersion.
  • Suitable dispersants include cellulose and cellulose derivatives, including synthetically modified cellulose or synthetically prepared cellulose derivatives.
  • dispersants include methyl cellulose (MC), hydroxymethyl cellulose, ethyl cellulose, hydroxyethyl cellulose (HEC), propyl cellulose, 2-hydroxypropyl cellulose (HPC), 2-hydroxyethyl methyl cellulose (HEMC), 2-hydroxyethyl ethyl cellulose (EHEC), 2-hydroxypropyl methyl cellulose(HPMC), 2-hydroxybutyl methyl cellulose, cellulose acetate, cellulose acetate phthalate, calcium carboxycellulose, sodium carboxymethyl cellulose (SCMC), carboxymethyl cellulose, and polyethyleneoxide, and combinations thereof.
  • the dispersant is methyl cellulose, ethyl cellulose, or polyethyleneoxide, or a combination thereof.
  • the dispersant is methyl cellulose.
  • the amount of dispersant used per volume of solvent affects the density of the dispersion. The greater the proportion of dispersant, the greater the density of the solution will be.
  • the solution of the dispersant is typically prepared to achieve about a 1% w/v solution of the dispersant. The solution can also range from about 0.05% w/v dispersant to about 10% w/v dispersant. The solution can also be about 0.5% w/v dispersant, or about 2% w/v dispersant.
  • the solvent system can optionally be heated to facilitate dissolution of the dispersant.
  • preparation of the dispersant solution can be facilitated by heating above about 20 0 C.
  • the mixture or solution can also be heated above about 30 0 C, about 40 0 C, about 50 0 C, about 70 0 C, about 90 0 C, about 120 0 C, about 150 0 C.
  • the mixture or solution can be heated up to about the boiling point of the solvent system used in the process.
  • the mixture or solution is typically not heated above the boiling point of the solvent system. For example, when water is used as the solvent, the heating is not performed at greater than about 99 0 C.
  • the dispersion can be prepared using various ratios of the Group III nitride to dispersant.
  • the ratio of Group III nitride to dispersant can range from about 1 :5 (nitride:dispersant) to about 10:1 (nitride:dispersant). Specific rations of nitride to dispersant include about 1:5, about 1:4, about 1 :3, about 1:2, about 1 :1, about 2:1, about 3:1, about 4:1, about 5:1, about 7.5:1, and about 10:1.
  • the amount of Group III nitride particles added to the dispersant solution can range from about 1 mg per niL of dispersant solution to about 50 mg per mL of dispersant solution. Typically, the concentration of the Group III nitride in the solvent system is about 10 mg per mL to about 30 mg per mL.
  • One embodiment of the invention is a dispersion that contains about 3 wt.% Group III nitride, about 1 wt.% dispersant, and about 96 wt.% solvent system.
  • the dispersion contains about 3 wt.% gallium nitride.
  • Another embodiment includes about 1 wt.% methyl cellulose as a dispersant.
  • Another embodiment employs DI water as the solvent system.
  • a specific dispersion includes about 3 wt.% gallium nitride, about 1 wt.% methyl cellulose, and about 96 wt.% DI water. The supernatant obtained after centrifuging the dispersion can be separated from the majority of the solvent system by any suitable means know to those of skill in the art.
  • the mixture can be shaken or otherwise agitated to effect a substantially uniform distribution of the Group III nitride particles.
  • the mixture is shaken by hand and then placed into an ultrasonicator for about 15-30 minutes to facilitate formation of the dispersion.
  • the mixture can be stirred over a magnetic stir plate for a suitable period of time, typically about 30-60 minutes following agitation by sonication.
  • Heating the dispersion can help to form a uniform distribution of particles in the dispersion.
  • the dispersion can be a colloid.
  • the dispersion can optionally be heated to facilitate dispersion of the Group III nitride particles and the dispersant in the dispersion.
  • preparation of the dispersion can be facilitated by heating above about 20 0 C.
  • the dispersion can also be heated to above about 30 0 C, above about 40 0 C, above about 50 0 C, above about 70 0 C, above about 90 0 C, above about 120 0 C, or above about 150 0 C.
  • the dispersion can be heated up to about the boiling point of the solvent system used in the process.
  • the dispersion is typically not heated above the boiling point of the solvent system. For example, when water is used as the solvent, the heating is not performed at greater than about 99 0 C.
  • the dispersion can be further processed by transferring it into a centrifugation tube and inserting the tube into a centrifugation apparatus. Centrifugation can provide the Group III nitride dispersion as substantially uniform-particle size layers of a supernatant in the centrifugation tube.
  • Centrifugation can be performed for any suitable and effective period of time, and at any suitable and effective rotational speed.
  • the centrifuging can be performed at up to about 10,000 revolutions per minute (rmp), or up to about 8,000 rpm.
  • the centrifuging can also be performed anywhere in the range of about 500 revolutions per minute to about 7,500 revolutions per minute.
  • the centrifuging is typically performed for up to about 60 minutes. Often the dispersant is centrifuged for about 10 minutes.
  • the supernatant Group III nitride dispersion can be separated from larger sized particles by removing a portion of the solvent system and removing a bottom layer that contains larger sized particles.
  • the top portion of the solvent system can be removed by any method well known to those of skill in the art, including decanting, pipetting, and siphoning. Relatively large sized particles can be removed from the supernatant by scooping off a top layer (smaller particles) of the supernatant to leave the larger particles behind.
  • various layers of the supernatant can contain substantially uniform ranges of Group III nitride particles. Certain ranges of particles can be separated from other different ranges of particles by methodically removing and separating layer after layer of the supernatant to achieve separated supernatants with various particle size ranges.
  • the invention provides a method for making a Group III nitride-coated substrate by, for example, preparing a dispersion comprising a Group III nitride and a dispersant; contacting a spin coating substrate with the dispersion; and rotating the substrate at a speed sufficient to form a thin film on the surface of the substrate to provide a thin film-covered substrate.
  • the thin film can then be calcinated to remove the dispersant and any remaining solvent.
  • the process can be repeated to produce thin films of greater thickness.
  • the thin film substrate can be annealed to remove stresses from its structure. Any suitable and effective spin coating substrate can be employed.
  • Suitable spin coating substrates include silicon, silicon dioxide, silicon nitride, silicon carbide, aluminum nitride, glass, sapphire, and various organic and organometallic polymer compositions.
  • the diameter of the substrate can be as small as 5 mm, or as large as 1.5 meters.
  • the thickness of the substrate can determined by several factors, including material availability and the properties desired from the resulting thin film covered substrate. The flexibility of substrate selection provides significant advantages such as lower cost compared to other thin film preparation methods.
  • the Group III nitride films produced by this technique can be used to make light-emitting devices and laser devices.
  • Treating the spin coating substrate prior to adding the Group III nitride dispersion can alter or improve the physical properties of the resulting thin films.
  • the substrates are typically cleaned or treated prior to applying the Group III nitride dispersion. Cleaning can include rinsing the surface of the substrate with a solvent, or a series of solvents.
  • the substrate can be cleaned with sequential applications of methanol, acetone, and deionized water.
  • the substrate can also be treated prior to application of the Group III nitride composition by heating or annealing, including laser annealing techniques.
  • spin coating or dip coating processes are suitable processes to deposit layers on large area substrates. These techniques have minimal substrate selection requirements and are widely used to produce ceramic thin films.
  • the spin coating substrate can be contacted with the Group III nitride dispersion by any suitable and effective means.
  • the dispersion can be contacted with the substrate by means of a pipette, sprayer, or other applicator device.
  • the spin coating substrate can be contacted with the dispersion by immersing the spin coating substrate into the dispersion, followed by removing the substrate from the dispersion in a controlled manner.
  • the rotational speed of the spin coating apparatus affects the thickness and particle orientation of the resulting thin film.
  • Spin coating at higher rpm typically produces thinner and more uniform thin films. Any suitable and effective spin speed can be employed.
  • the spin coating substrate is typically rotated at greater than about 30 rpm.
  • the substrate can also be rotated at about 100 to about 8000 revolutions per minute. Additionally, the substrate can be rotated at about 1000 to about 3000 rpm, or at about 2000 rpm.
  • the duration of the spin coating procedure also affects the thickness and particle orientation of the resulting thin film.
  • the spin coating substrate is typically spun for about 5-120 seconds. Longer durations of up to several hours can be employed for certain embodiments. Certain embodiments requiring only about 10-40 seconds of spinning. Typically, 10 seconds of spinning at the highest desired rpm produces satisfactory results.
  • thin films of various thicknesses can be prepared. Additionally, by repeating the application step, spin coating step, and optionally the calcination processes, thin films of greater thicknesses and different properties can be achieved.
  • the thin film can have a thickness of about 20 nm to about 1 ⁇ m.
  • the thin films can have a thickness of about 50-150 nm after one cycle of spin coating, and often have a thickness of about 100 nm after one spin coating process.
  • the density of the particles in the layer and the thickness of the Group III nitride thin film can be controlled by adjusting the rotation speed in centrifugation step, the spin coating step, or both.
  • the thickness of the thin films can be determined by SEM cross-section images. High temperature annealing and laser annealing techniques can be used to improve the quality and continuity of the layer. Calcination can be performed at any suitable and effective temperature.
  • Calcination can be performed under an air atmosphere, or under atmospheres of specific gases, or combinations thereof.
  • calcination can be carried out under a nitrogen atmosphere, or an argon atmosphere.
  • the dispersant effectively disintegrates by combustion and evaporation, leaving behind a pure Group III nitride thin film.
  • the calcination can be performed at above about 300 0 C, above about 400 0 C, above about 450 0 C, or above about 500 0 C.
  • the calcination can also be performed under an atmosphere of one or more specific gases.
  • Inert atmospheres include atmospheres composes of noble gases (helium, neon, argon, krypton, xenon, and radon), nitrogen gas, and combinations thereof.
  • Other specific gases include, for example, oxygen, hydrogen, vaporized liquid compounds, and combinations thereof.
  • Calcination performed under, for example, argon or nitrogen gas can chemically modify the dispersant but does not completely remove the dispersant (or modified components or derivatives thereof) from the thin film, leaving behind a residue which modifies the physical properties of the thin film.
  • Vaporized liquid atmospheres can also be used to alter the physical and chemical characteristics of a Group III nitride thin film. Dopants
  • Dopants can alter the conductive properties of a material.
  • the Group III nitride used to prepare the Group III nitride dispersion can contain one or more dopants. Suitable dopants include beryllium, magnesium, manganese, molybdenum, silicon, zinc, cerium, erbium, europium, praseodymium, promethium, thulium, terbium, ytterbium, and yttrium, and compounds thereof, and combinations thereof. Suitable dopants also include Group III nitrides. Other suitable dopants include Group III elements. In one embodiment, the dopant is erbium. In another embodiment, the dopant is europium, hi another embodiment, the dopant is cerium. In another embodiment, the dopant is beryllium.
  • Luminescence is an important property for light emitting devices or laser device applications.
  • GaN has a 3.4 eV band gap and can emit 366 nm UV light from the band edge emission.
  • Rare earth doping in GaN can produce light in the visible regionm, as well as the infrared region, from its thin films. Irradiating dopant-containing Group III nitrides can also produce various emissions from thin films, depending on the dopant and the source of irradiation.
  • Luminescence from Group III nitride thin films deposited on various substrates implies a wide range of applicability in the field of light emitting and laser devices.
  • the layer quality can be further improved by optimizing various parameters of the process and by laser annealing the substrate either before or after the thin film is formed.
  • Important advantages of the techniques disclosed herein are low cost, low temperature processes, flexible substrate types, and large substrate sizes.
  • Analysis of a GaN thin film layer shows that the GaN particles are highly ordered based on X-ray diffraction measurements. Strong luminescence from these layers has been evidenced by Cathodoluminescence (CL).
  • Methyl cellulose has been show to be a successful dispersant to disaggregate GaN particles in solution to fo ⁇ n a colloid.
  • the colloidal dispersions have been spun on various substrates, including silicon, sapphire, and glass.
  • the layer thickness can be controlled by the speed and duration of spin coating, and the layer thickness can be increased by repeating the overall spin coating process.
  • the GaN layered substrates are useful for preparing light emitting and laser devices.
  • a new spin-coating method is provided to produce Group III nitride thin films on various substrates, such as, for example, silicon, glass and sapphire, using a colloidal dispersion, such as methylcellulose coated GaN particles.
  • the methods include steps to make dispersions from Group III nitride particles, to produce Group III nitride layers on substrate by spin coating, and to optionally remove the dispersant by calcination.
  • the layer thickness can be increased by repeating spin coating and calcination steps.
  • XRD results showed strong regular orientation of GaN layers manufactured by these methods. Most GaN particles are orientated on the surface with their c-plane parallel to the substrate surface. Both CL and PL spectra showed strong luminescence from these layers.
  • Group III nitride thin films will have a wide array of applications in the field of electroluminescence devices and laser devices.
  • FIG. 2 illustrates a flowchart for the preparation of GaN thin films using a methyl cellulose dispersion and a spin coating technique. The structure, morphology, and luminescence properties of these thin films are characterized and described below.
  • Methyl cellulose (MC) was found to be an excellent dispersant for GaN particles.
  • Methyl cellulose powder was dissolved in DI water at a concentration of 10 mg/mL. A transparent solution was obtained by stirring over a magnetic plate for 2-24 hours. Finely-ground high-purity GaN powder was added to the MC solution and the mixture was agitated on an ultrasonicator for 15-30 minutes. After the GaN particles were evenly distributed throughout the dispersion, the dispersion was placed in a centrifugation facility. The dispersion was centrifuged for 10 minutes at 7500 rpm. After centrifugation, large particles that were not disaggregated or dispersed were removed from the dispersion.
  • the remaining supernatant dispersion was collected and used in the spin coating step.
  • a silicon substrate was prepared by cleaning with methanol, acetone and DI water (sequential rinses).
  • the GaN dispersion was pipetted onto the silicon substrate such that the entire surface was covered.
  • the silicon substrate was then placed on a spin coating apparatus.
  • the parameters for the spin coating step were 1500 rpm/minute acceleration, 2000 rpm for 10 seconds, followed by 10 seconds of deceleration. A uniform layer of the GaN dispersion was formed on the silicon substrate.
  • the layered substrate was calcinated at 450 0 C in air. After one hour, all methyl cellulose was eliminated from the substrate surface, leaving behind only a thin GaN layer on the surface.
  • the spin coating layer was about 100 nm thick. The spin coating and calcination steps were repeated twice to produce a thin film of about 500 nm in thickness.
  • FIG. 3 shows an XRD pattern of a sample with three GaN layers deposited on a silicon substrate.
  • the XRD patter indicates that the layer is polycrystalline GaN with wurtzite structure.
  • the (002) peak intensity is more than ten times stronger than the intensity of the other peaks, indicating highly oriented particles on the substrate surface. This phenomena was repeatable in each sample prepared using this method, including samples prepared on other substrates.
  • the SEM image in FIG. 6 shows the surface morphology of the GaN layer deposited on silicon.
  • the spin coating process was repeated three times to achieve a thick GaN layer, evenly covering the entire substrate surface.
  • the large GaN particles are about 1-2 ⁇ m in diameter.
  • Small GaN particles of about 0.1 ⁇ m in diameter fill the spaces between larger particles.
  • the density of the GaN particles in the thin film can be controlled by adjusting the rotation speed in spin coating step, the centrifugation step, or both.
  • the thickness of this film was 0.5 ⁇ m as determined by the SEM cross-section image.
  • FIG. 7 is a room temperature Cathodoluminescence (CL) spectrum of a GaN layer with three coatings deposited on glass.
  • the powder used was high-purity GaN.
  • the excitation source was a 5 KeV electron gun focused at a 5 mm diameter point.
  • the spectrum showed a strong band-edge emission at 362.2 nm without any deep level yellow emission.
  • the luminescence at 3.43 eV measured at room temperature had a full width at half maximum (FWHM) of approximately 60 me V.
  • FWHM and high intensity luminescence from this layer indicated excellent optical properties of the deposited GaN layer using this method.
  • the use of high-purity GaN (>99.99%) powder resulted in improved optical and electronic properties compared to thin films prepared using lower purity GaN.
  • Example 1 The procedure for Example 1 was followed, with the exception that erbium-doped gallium nitride (GaN: Er) was used in preparing the dispersion.
  • GaN erbium-doped gallium nitride
  • the GaN was doped with erbium during the GaN synthesis.
  • FIG. 8 illustrates the luminescence property of deposited GaN layer.
  • This sample contained three coatings of GaN:Er.
  • the photoluminescence (PL) spectrum was performed by exciting the sample with an argon laser at a wavelength of 496.5 nm at room temperature. PL excitation resulted in green emission from the erbium-doped GaN layer. Two major emissions were observed in the green region with the strongest lines at 537.8 nm and 559.5 nm, which can be attributed to transitions from each of 2 H ⁇ m and 4 S 3 ⁇ to the ground state 4 / 15/2 .
  • the full width at half maximum (FWHM) of the 537.8 nm and 559.5 nm lines were 3.5 nm and 4.5 nm, respectively, which correspond to energy widths of 14 and 18 me V, respectively.
  • To the left of 537.8 nm peak are detail peaks corresponding to other erbium excited electrons transitions.
  • the peak positions in this PL spectra of the GaN:Er layer correspond well with PL spectra obtained from MOCVD grown GaN:Er layers (H. J. Lozykowski, et al., Appl. Phys. Lett. 1999, 74(8), 1129) or MBE grown GaNiEr layers (R. H. Birkhahn, et al., MRS Internet J. Nitride Semicond. Res. 1999, 4Sl, G3.80; A. J. Steckl, and R. Birkhahn, ⁇ ?/. Phys. Lett. 1998, 73(12), 1700).
  • Methyl cellulose (150 mg) was added to DI water (15 mL) in a container, which was then covered and shaken by hand. The solution was then placed on a sonication apparatus and sonicated for 10 minutes. A magnetic stir bar was added to the container and the solution was stirred over a magnetic stir plate for 2-24 hours, until the methyl cellulose was completely dissolved. The fully dissolved solution had the appearance of a translucent gel.
  • High purity gallium nitride (450 mg, >99.9% pure by weight) was added to the solution, and the mixture was shaken by hand, followed by sonication for 15-30 minutes to form a dispersion.
  • the dispersion was further mixed by stirring over a magnetic stir plate for 30 minutes, or up to about 24 hours, until the dispersion of the particles is substantially complete.
  • the dispersion was then transferred into a centrifugation tube and placed in a centrifugation apparatus. Centrifugation was performed at 7500 rpm for 10 minutes. This process separated non-dispersed particles from the dispersed particles. The non-dispersed particles were removed upon completion of centrifugation and the supernatant dispersion was collected.
  • a silicon wafer was cleaned by rinsing with isopropanol, methanol, acetone, and then water. The dispersion was again sonicated for one minute to 'refresh' the colloid.
  • the silicon wafer was mounted on a spin coating apparatus. The dispersion was pipetted onto the silicon wafer until the entire surface was substantially covered with the dispersion. The spin coating was then performed at 2000 rpm by accelerating the wafer at 1500 rpm/second. The wafer was spun at 2000 rpm for 10 seconds, followed by deceleration. A uniform layer was formed on the silicon wafer. The wafer was allowed to air dry for 5-15 minutes. The dry wafer was then placed in a furnace with an air atmosphere.
  • the furnace was heated to about 500 0 C by increasing the temperature by about 1 0 C per minute.
  • the wafer was heated at 500 0 C for one hour, and was then allowed to cool to room temperature.
  • Second and third layers of gallium nitride were added by repeating the dispersion application, spin coating, and calcination, to produce a gallium nitride thin film-covered substrate with a thicker thin film.
  • Gallium nitride films of greater thickness can be prepared by repeating the coating and spin process several times.
  • a gallium nitride thin film was prepared according to Example 1. The application and spin processes were repeated six times to achieve a thick gallium nitride layer.
  • Gallium nitride particles evenly covered the whole surface of the silicon substrate. Most of the larger gallium nitride particles were 1 -2 ⁇ m in diameter while smaller gallium nitride particles with sizes of about 0.1 ⁇ m filled the spaces between larger particles.
  • the density of the gallium nitride particles in the layer can be controlled by adjusting the rotation speed in the spin coating step and/or the centrifuge step. The thickness of this layer was determined to be 0.5 ⁇ m as determined by an SEM cross-section image.
  • TFTs thin film transistors
  • Zinc oxide is also a transparent conductor because of its 3.2 eV bandgap.
  • Gallium nitride however, has more favorable material properties than zinc oxide based TFT in terms of transparent conductance because mobility in gallium nitride crystals is higher than in zinc oxide.
  • Thin films of gallium nitride particles can be used to prepare electronic devices and optoelectronic devices.
  • the methods described herein can be used to prepare thin films on flexible substrates, including polymers.
  • a thin film transistor (TFT) was prepared using a gallium nitride thin film according to Example 1. Current flow through the gallium nitride layer has been demonstrated.
  • FIG. 9 shows the patterns fabricated for resistivity measurements. The circle geometry was used to avoid current spreading because the device was not isolated.
  • the fabrication processes are as follows: a 40 ran thermally deposited SiO 2 layer was grown on highly doped n + Si substrate. A gallium nitride particle layer was deposited using the spin coating techniques described in Example 1.
  • a Au/Ti (200nm/20nm) layer was evaporated on top of GaN layer.
  • a lift-off technique was used to define the metal contact pattern. In the pattern, the inside circle contact was fixed with a diameter of 200 ⁇ m.
  • the lengths of the gallium nitride layer defined by two circles varied from 50 - 500 ⁇ m.
  • FIG. 10 shows the IV measurements from a device fabricated with a gallium nitride spin coated layer. The results showed that the current was higher when the two contacts are closer. The current level was about 1 nA at 10 V applied voltage. The data indicate the feasibility for TFT applications using a gallium nitride layer produced by spin coating.
  • gallium nitride particles can be layered on any suitable substrate, including silicon, polymers, and glass.
  • the gallium nitride layer can then be used directly to prepare a thin film transistor.
  • spin coating technique such as low cost, facile scale-up for large area substrates, suitability for flexible substrates, and low temperature processing.

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Abstract

L'invention concerne une composition qui est une dispersion à base de nitrure du groupe III, un système de solvant, et un dispersant. La dispersion peut servir à préparer des films minces en nitrure du groupe III sur une large gamme de substrats, par exemple, le verre, le silicium, le dioxyde de silicium, le nitrure de silicium, le carbure de silicium, le nitrure d'aluminium, le saphir, et des polymères organiques. La granulométrie du nitrure du groupe III servant à produire les films minces peut être régulée par ajustement de la centrifugation de la dispersion et sélection d'une couche recherchée du surnageant. Le dispersant peut être évacué des films minces par calcination. Le nitrure du groupe III peut contenir un dopant. Les films minces de nitrure du groupe III dopés peuvent émettre la lumière visible à la suite d'irradiation. Des émissions de lumière verte, rouge et jaune résultent de l'irradiation du nitrure de gallium dopé à l'erbium, l'europium, et au cérium, respectivement.
PCT/US2005/043637 2004-12-01 2005-12-01 Revetements en nitrure du groupe iii et procedes associes WO2006060660A2 (fr)

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CN102746025A (zh) * 2012-06-27 2012-10-24 电子科技大学 低成本GaN外延薄膜的制备方法
EP2492951A3 (fr) * 2011-02-28 2013-11-06 Semimaterials Co., Ltd. Dispositif électroluminescent à base de nitrure utilisant un substrat en silicium et son procédé de fabrication
EP2492952A3 (fr) * 2011-02-28 2014-01-15 Semi-Materials Co., Ltd Dispositif électroluminescent à base de nitrure ayant une excellente cristallinité et luminosité et son procédé de fabrication

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CN103343005B (zh) * 2013-07-13 2015-05-13 上海洞舟实业有限公司 一种高稳定碳纳米荧光染色剂
CN107429383B (zh) * 2015-03-30 2020-07-24 东曹株式会社 氮化镓系烧结体和其制造方法

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Publication number Priority date Publication date Assignee Title
EP2492951A3 (fr) * 2011-02-28 2013-11-06 Semimaterials Co., Ltd. Dispositif électroluminescent à base de nitrure utilisant un substrat en silicium et son procédé de fabrication
EP2492952A3 (fr) * 2011-02-28 2014-01-15 Semi-Materials Co., Ltd Dispositif électroluminescent à base de nitrure ayant une excellente cristallinité et luminosité et son procédé de fabrication
CN102746025A (zh) * 2012-06-27 2012-10-24 电子科技大学 低成本GaN外延薄膜的制备方法

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