BARRIER COATINGS AND METHODS IN DISCHARGE LAMPS RELATED APPLICATIONS [°°°ll This application claims the filing-date benefit of U. S Provisional Patent Application S. N. 60/424,714 filed November 8, 2002, and incorporates this application herein in its entirety.
BACKGROUND OF THE INVENTION [0002] The present invention relates to discharge lamps having a light emitting plasma contained within an arc tube. More particularly, the present invention relates to such discharge lamps haaring a coating applied to the inner wall of the arc tube to reduce or prevent chemical reaction between the discharge medium and the arc tube wall material or loss of fill material through the arc tube wall.
[0003] Discharge lamps such as mercury lamps, metal halide lamps, and high pressure sodium lamps include an arc tube forming a light emitting chamber containing the light emitting plasma. Typically the arc tubes are formed from a vitreous material such as fused silica and hard glass, or a ceramic material. The lamp fill material varies among the lamp types. For example, a metal halide lamp includes a fill of an inert gas, mercury, and one or more metal halides. During operation of the lamp, the fill material forms a light emitting plasma contained within the arc tube.
[0004] The useful life of such lamps is often reduced due to chemical reactions between elements in the discharge medium and the material forming the wall of the arc tube or loss of fill material through the arc tube wall. Such phenomena may cause electrode meltback, loss of fill material, and darkening of the arc tube wall which may result in a lumen loss over time, a shift in color, or a poor maintenance of light output.
100051 For example, in a metal halide lamp having a sodium halide in the fill material, the useful life of the lamp can be limited by the loss of the metallic portion of the metal halide fill during lamp operation. This loss of metallic fill can be due to reaction of the metal halides with inner wall of the fused silica (Si02) arc tube and/or sodium ion diffusion/migration through the wall of the arc tube. Both mechanisms result in an increase of free halogen in the arc tube.
The term"free halogen"generally refers to volatile forms of halogens such as iodine or mercuric iodide.
[0006] The chemical reaction of the metal halides in the fill with the silica (Si02) at the inner surface of the fused silica arc tube may produce metal silicate crystals and silicon tetraiodide. Silicon tetraiodide rapidly decomposes at the tungsten electrode tip which incorporates silicon in the tungsten electrode and releases free halogen. This results in a color shift, wall darkening, and lumen loss in the lamp.
[0007] Sodium ions of the fill material (e. g. , sodium iodide (NaI)) are very mobile and may diffuse or migrate (under the influence of an external electric field) through the silica arc tube wall. The sodium ions are neutralized at the outer wall surface and may then condense on the outer lamp envelope. The halogen (e. g. , iodine) component of the fill material does not diffuse through the arc tube wall and thus accumulates in the arc tube as free halogen. The lost sodium is thus unavailable to the discharge and can no longer contribute its characteristic emission. As a consequence of the loss of sodium and the build-up of free halogen, the light output gradually diminishes and the color shifts from white to blue. The arc becomes constricted and, in a horizontally-operating lamp particularly, may bow against the arc tube wall and soften it. Also, loss of sodium causes the operating voltage of the lamp to increase. The voltage increase brings about a rise in temperature to the point where the arc can no longer be sustained.
[0008] To counter these effects, conventional art suggests various methods. For example, U. S. Patent No. 5,742, 126 to Fuji et el. proposes coating the inner layer of the arc tube with one or more oxynitride layers of Al, Ta, Nb, V, Cr, Ti, Zr, Hf, Yb, Sc, Mg, Li and La. U. S.
Patent No. 5,668, 440 to Inukai et al. discloses forming a barrier nitride layer by replacing the oxygen atoms of the quartz (Si02) with nitrogen atoms to form silicon nitride (Si3N4). U. S.
Patent No. 5,394, 057 to Russell et al. proposes applying a coating of metal silicate on the inside surfaces of the arc tube.
[0009] However, many of the conventional methods still fail to successfully prevent substantial lumen loss with lamp usage. Thus, there remains a need for chemically-stable barrier compositions that prevent, or at the very least inhibit, the extent of detrimental chemical reactions between fill constituents and the arc tube walls or the loss of fill material through the walls.
[0010] Therefore, it is an object of the present invention to provide a barrier coating and method for arc tubes that obviates the deficiencies of the prior art.
[0011] It is another object of the present invention to provide a barrier coating for arc tubes that is chemically stable and substantially inert when exposed to the discharge medium during operation of the lamp.
[0012] It is another object of the present invention to provide a novel method for deposition of a barrier coating on the inner wall of an arc tube.
[0013] It is still another object of the present invention to provide a barrier coating that inhibits the detrimental chemical reactions between fill constituents and the arc tube walls.
[0014] It is still another object of the present invention to reduce darkening of the arc tube walls over the life of a discharge lamp.
[0015] It is yet another object of the present invention to provide a discharge lamp with reduced lumen loss and color shift over the life of the lamp.
[0016] It will be noted that although the present invention is illustrated in view of these and other objectives, the principles of the invention are not limited thereto and will include all applications of the principles set forth herein.
[0017] These and other objects can be realized by simultaneous reference with the following non-exhaustive illustrative embodiments in which like segments are numbered similarly.
DESCRIPTION OF THE DRAWINGS [0018] Figure 1 is a schematic representation of a conventional arc tube for a discharge lamp ; [0019] Figure 2 is a schematic representation of a device according to one aspect of the present invention for applying one or more barrier coatings to the interior surfaces of an arc tube chamber; and [0020] Figure 3 is a schematic representation of a device according to one aspect of the present invention for regulating the application of barrier coatings to the interior chambers of an arc tube.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS [0021] Figure 1 is a schematic representation of a conventional formed body arc tube for a high intensity discharge lamp. In the embodiment of Figure 1, the arc tube 100 is formed from light transmissive material such as fused silica. The arc tube 100 defines a bulbous light emitting chamber 110 intermediate pinch-sealed end portions 115,120. An electrode assembly comprising a tungsten electrode 125, 130 is sealed within each end portion 115,120 to provide an electrically-conducting path from the interior of the chamber 110 to the exterior of the chamber through each end portion 115,120. In a metal halide lamp, the chamber 110 is dosed with a fill material including mercury, one or more metal halides, and an inert fill gas.
[0022] In one aspect of the present invention, a barrier coating is deposited on the inner wall of the chamber 110 to reduce or prevent chemical reaction between the discharge medium and the chamber wall material. It has been discovered that coatings including a nitride layer of one or more elements selected from the group consisting of aluminum, boron, scandium, yttrium, and the lanthanides (i. e. , lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium) forms a barrier coating that is highly chemically inert and thermally stable.
[0023] In one embodiment, the barrier coating is formed from a single nitride layer of an element selected from the group consisting of aluminum, boron, scandium, yttrium, and the lanthanides. In a preferred embodiment, the coating may be formed from a single layer of boron nitride.
[0024] In another embodiment of the present invention, the barrier coating may include a nitride layer formed from one or more elements selected from the group consisting of aluminum, boron, scandium, yttrium, and the lanthanides, wherein the nitride layer is exposed to the light emitting plasma, and one or more other layers are disposed between the exposed nitride layer and the inner wall of the arc tube. The other layers may include oxynitride layers of silicon, silicon and other elements, or the element forming the exposed nitride layer. For example, the barrier coating may include an exposed layer of boron nitride, a layer of silicon oxynitride adjacent the inner wall of the arc tube, and one or more intermediate layers disposed between the exposed layer and the silicon oxynitride layer. In one embodiment, the intermediate layers may include a layer of silicon boron oxynitride adjacent the silicon oxynitride layer, and a boron oxynitride layer adjacent the exposed boron nitride layer. In another embodiment, the intermediate layer may include a layer of boron oxide.
[0025] In a preferred embodiment, the inner wall of the arc tube is coated with a barrier coating comprising the following layers SiONy, SiBOxNy, BOxNy and BN. In yet another embodiment, the barrier coating may comprise silicon, oxygen, nitrogen, and an element selected from the group consisting of aluminum, boron, scandium, yttrium, and the lanthanides, wherein the layer comprises any or all mixed phases of the elements.
[0026] Various methods of depositing the barrier coating on the inner wall of the arc tube may be used. The choice of deposition method may be determined by the specific composition of the barrier coating to be formed. For example, chemical vapor deposition may be used.
[0027] According to one aspect of the present invention, the coating may be formed by introducing precursors into the chamber and pyrolitically reacting the precursors to form a layer of material. In a preferred embodiment for forming a layer of boron nitride, a boron precursor such as boron halide, borane, borazine, or a polymer of borazine, is introduced into the arc tube chamber simultaneously with a nitrogen precursor such as ammonia, hydrazine, or hydrazoic acid, and pyrolitically reacted to form a boron nitride layer in the chamber.
[0028] Figure 2 is a schematic representation of an apparatus that may be used to form barrier coatings according to one aspect of the present invention. With reference to Figure 2, the arc tube 200 includes a bulbous chamber 202 intermediate a first tubular end portion 204 and a second tubular end portion 206. A first tubular shield 220 is positioned within the first end portion 204 thereby providing fluid communication between the interior of the chamber 202 and a first source 210 of a gaseous first reactant. A second source 212 of a gaseous second reactant is in fluid communication with the interior of the chamber 202 through the first end portion 204 but exterior to the first tubular shield 220. The first tubular shield 220 thus acts to prevent commingling of the precursors in the first tubular end portion 204 thereby preventing the formation of coating layers on the inner wall thereof. A second tubular shield 260 is positioned in the second end portion 206 and connected to a vacuum source 270 so that the interior of the chamber 202 may be evacuated. An element 250 is adapted to selectively prevent fluid communication between the interior and the exterior of the chamber 202 through the second end portion 206.
[0029] The apparatus illustrated in Figure 2 is particularly suitable for methods of forming barrier coatings on the inner wall of arc tubes by pyrolitic reaction of two or more precursors. The apparatus illustrated in Figure 2 is suitable for both continuous flow of reactants into the chamber or batch flow of the reactants into the chamber.
[0030] The same principles can be used with little modification to conduct vapor deposition through batch reaction. In this embodiment, reactants are supplied in a pulsating sequence. That is, first the reactants are supplied in spurts and allowed to react. A period of a few seconds (e. g., 0.5 to 2 seconds) is allotted for the reaction to take place and form a deposit on the inner walls of the chamber. Once the reaction is complete, the chamber is then emptied by activating the vacuum or opening an exhaust valve. These process steps can be repeated to deposit more than one layer of coating. In addition, the constituents (or precursors) of the reactants can be changed to deposit layers (or sublayers) having different composition. More importantly, by controlling the volume of the reactant gases, the thickness of the coating layer can be controlled. This process is particularly suitable for depositing multiple layers of coating where each layer has a different thickness and/or composition.
[0031] Referring again to the embodiment shown in Figure 2, in a process for forming a boron nitride layer, boron trichloride (BC13) along with an inert gas such as argon are introduced into the chamber 202 through the first tubular shield 220. Ammonia (NH3) and an inert gas such as argon are introduced into the chamber 202 through the first end portion 204 but exterior to the tubular shield 220. The reactants contained in the chamber 202 may then be pyrolitically reacted to form a boron nitride layer by the following reaction: NH3 + BC13 BN + 3HC1 The gaseous hydrochloric acid and the argon may then be evacuated from the chamber 202 through the second tubular shield 206.
[0032] Although the embodiment of Figure 2 is illustrated to form a barrier layer of boron nitride, it will be readily apparent to one of ordinary skill in the art that the principles disclosed herein can be applied to other reactants for forming layers of different composition.
For example, the first or the second reactant may be compounds of aluminum, boron, scandium, yttrium, or any one of the lanthanides (e. g. , volatile metal alkyls or acetylacetonates). Further, ammonia, hydrazine or hydrazoic acid may be used as a nitrogen precursor in the formation of nitrides.
[0033] In one aspect of the present invention, a method for coating the inner walls of an arc tube with a protective film can include the steps of providing an arc tube with a bulbous chamber and intermediate tubular end portions; positioning tubular shields in each of the tubular end portions of the arc tube so that one end of each tubular shield extends partially into the chamber and the other end extends beyond the outer ends of the tubular end portions. The interior of the chamber can then be evacuated through a first end portion and the tubular shield positioned therein. Thereafter, the vacuum source can be shut off and gaseous first reactant- containing precursor can be conveyed into the interior of the chamber through the tubular shield positioned in the second end portion of the arc tube. Further, a predefined quantity of the second reactant-containing precursor can be communicated into the interior of the chamber through a space between the inner wall of the second end portion of the arc tube and the tubular shield positioned therein while the second end portion is sealed. Optionally, heat or energy can be provided to act as a catalyst for the reactants. A pyrolytic reaction takes place between the precursors to form a protective film on the inner wall of the chamber. Finally, the chamber can be evacuated again to remove any unreacted product, by-products or remaining inert gasses.
[0034] Figure 3 is a schematic representation of a device for regulating the application of barrier coating to the interior chambers of an arc tube. The apparatus of Figure 3 is adapted to regulate the amount of reactants entering the arc tube. The controller 300 can be a programmable device or an electronic module for controlling the opening and closing of each of the solenoid valves 310,320, 330,340. The solenoid valve 310 is controlled by the controller 300 to be opened for a duration of time necessary to supply a first reactant-containing precursor. The opening and closing sequences of the solenoid valve are controlled by the controller 300 in order to provide precise amounts of the first reactant into the chamber. Thus, the controller 300 controls the solenoid valve 320 such that its opening and closing sequence can overlap or be synchronous with the opening and closing of the valve 310. In the mean time, the valve 330 can be opened to allow entry of inert gas to prevent formation of a barrier layer on the inner surface of the end portion of the arc tube. Once the desired amounts of the reactants have been introduced into the chamber 202, the controller 300 effects closing of the valves 310,320, 340 (and optionally 330) to hermetically seal the chamber from the outside. The controller can be programmed to maintain the valves closed for a desired length of time to allow sufficient reaction to occur. This duration will be referred to as the reaction time. Once the reaction is completed, the controller 300 effects opening of the exhaust valve 340 so that inert gasses, unreacted precursors, and any gaseous by-product may be evacuated from the chamber 202.
[0035] In still another embodiment of the invention, a pyrolytic reaction of the precursors has been found to be expedited by supplying energy to the reactants contained in the chamber 202. The energy applied to the reactants may include microwave, heat or RF energy.
[0036] In yet another embodiment, the invention is directed to forming a barrier layer by applying a solution of polyborazylene in a solvent such as ether or tetrahydrofuran to the inner walls of an arc tube chamber and then pyrolytically reacting the solution to affect formation of a boron nitride coating. According to this embodiment, the first reactant need not be in gaseous form and can be supplied as a liquid.
Examples [0037] A series of experiments were conducted to optimize the timing sequence for a solenoid controlled batch reaction vapor deposit. In these experiments, the timing sequence can be summarized as follows: Tl : intake closed, exhaust open (evacuate the arc tube) T2 : intake open, exhaust closed (load reactants and inert gas into the arc tube) T3 : intake closed, exhaust closed (reaction time) There was a 0.1 second delay between steps T1 and T2 to allow the exhaust valve to close.
Table 1 summarizes the results of the experiments.
TABLE 1-Summary of experiments e F- iri n "rn s B : 1 T 1' i : r 10 C an I n, ; mllwiu.. Se Sc aSec <. s 19 2. 0 2. 0 0. 5 0. 1 0. 5 250 Optically clear coating. UV absorption spectrum characteristic of BN. 21 2. 0 5. 0 0. 5 0. 1 0. 5 250 Optically clear coating. W absorption spectrum characteristic of BN. 22 2. 0 0. 7 0. 5 0. 1 0. 5 250 Optically clear coating. UV absorption spectrum characteristic of BN. 23 2. 0 0. 8 0. 5 0. 1 0. 5 250 Optically clear coating. UV absorption spectrum characteristic of BN. 24 1. 0 0. 2 0. 5 0. 1 0. 5 250 Optically clear coating. UV absorption spectrum characteristic of BN.
[0038] While preferred embodiments of the present invention have been described, it is to be understood that the embodiments described are illustrative only and the scope of the invention is to be defined solely by the appended claims when accorded the full range of equivalence, many variations and modifications naturally occurring to those of ordinary skill in the art from a perusal hereof.
