JP2018002548A - Method of manufacturing quartz glass member for ultraviolet led - Google Patents
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Abstract
Description
本発明は、波長２００ｎｍから４００ｎｍにおける紫外線ＬＥＤ用石英ガラス部材の製造方法に関する。 The present invention relates to a method for producing a quartz glass member for an ultraviolet LED having a wavelength of 200 nm to 400 nm.
深紫外波長帯で発光する紫外線ＬＥＤは、ウィルスの殺菌や飲料水、空気の浄化、樹脂硬化、環境汚染物質の分解、食品分野、各種医療機器など、幅広い分野で、その応用が期待されている。 Ultraviolet LEDs that emit light in the deep ultraviolet wavelength band are expected to be applied in a wide range of fields such as virus sterilization, drinking water, air purification, resin curing, decomposition of environmental pollutants, food, and various medical devices. .
既存の深紫外光源としては、水銀ランプなどのガス光源が用いられていたが、ガス光源は寿命が短く、発光波長がガスの輝線のみに限定され、水銀などの人体・環境に有害な物質を含み、また、光源のサイズ、消費電力も極めて大きいことから、その利用範囲は制限されており、代替技術実現への要請が高まっていた。このような背景の下、水銀フリー、低環境負荷で小型、高出力な紫外線ＬＥＤの開発が強く望まれ、窒化物系半導体（ＡｌＧａＮ）を用いた紫外線ＬＥＤの開発が活発化している。 As an existing deep ultraviolet light source, a gas light source such as a mercury lamp has been used. However, the gas light source has a short lifetime, the emission wavelength is limited to only the emission line of the gas, and mercury and other substances harmful to the human body and the environment are used. In addition, since the size and power consumption of the light source are extremely large, the range of use of the light source is limited, and there is an increasing demand for the realization of alternative technologies. Against this background, development of mercury-free, low environmental load, small size, high output ultraviolet LEDs is strongly desired, and development of ultraviolet LEDs using nitride semiconductors (AlGaN) has been activated.
紫外線ＬＥＤは２００ｎｍから４００ｎｍの波長の光であり、これまで可視光ＬＥＤで使用されてきたシリコーン樹脂製レンズでは樹脂の劣化もしくは光が透過しないという問題があった。 The ultraviolet LED has a wavelength of 200 nm to 400 nm, and the silicone resin lens that has been used in the visible light LED has a problem that the resin is deteriorated or light is not transmitted.
また、紫外線ＬＥＤ素子からの光取出し効率が極めて低いという問題もあり、窓材もしくはレンズ材料にも光の吸収が極力少ない材料が求められ、石英ガラス製光学部材の使用が検討されてきた（特許文献１および２）。 In addition, there is a problem that the light extraction efficiency from the ultraviolet LED element is extremely low, and a material that absorbs as little light as possible is required for the window material or lens material, and the use of an optical member made of quartz glass has been studied (patent) References 1 and 2).
しかし、石英ガラス製の窓板では光が拡散して所望の光強度が得られず、また半球状のレンズはパッケージへの実装が難しいという問題があった。 However, a quartz glass window plate has a problem that light is diffused and a desired light intensity cannot be obtained, and a hemispherical lens is difficult to mount on a package.
一方、高精度な寸法形状にて石英ガラス部材を製造する方法として射出成形法がある（特許文献３および４）。 On the other hand, there is an injection molding method as a method for producing a quartz glass member with a highly accurate dimensional shape (Patent Documents 3 and 4).
この方法は成形体を脱脂および純化後に焼成を行うことで透明石英ガラス体を得ることができるが、塩素もしくは塩化水素による純化処理で波長約２５０ｎｍ（５．０ｅＶ）に酸素欠乏欠陥による光の吸収帯が生じてしまうという問題があった（非特許文献１）。 In this method, a transparent quartz glass body can be obtained by degreasing and purifying the molded body and then firing, but light absorption due to oxygen deficiency defects at a wavelength of about 250 nm (5.0 eV) by purification with chlorine or hydrogen chloride. There was a problem that a band would occur (Non-patent Document 1).
また、ガラス化後に酸素を含む雰囲気もしくは水蒸気を含む雰囲気により酸素欠乏欠陥の修復を行う方法が提案されているが、その効果が石英ガラス表面に限られることや高温での処理を要することから不純物汚染の影響により透過率が低下する懸念があった（特許文献５および６）。 In addition, a method for repairing oxygen deficiency defects in an atmosphere containing oxygen or water vapor after vitrification has been proposed, but the effect is limited to the surface of quartz glass and impurities at high temperatures are required. There was a concern that the transmittance would decrease due to the influence of contamination (Patent Documents 5 and 6).
本発明は、酸素欠乏欠陥の修復を行い、波長約２５０ｎｍの光吸収が改善され、波長２００ｎｍから４００ｎｍにおいて構造欠陥による吸収のない紫外線ＬＥＤ用石英ガラス部材を得ることができるようにした紫外線ＬＥＤ用石英ガラス部材の製造方法を提供することを目的とする。 The present invention repairs an oxygen deficiency defect, improves light absorption at a wavelength of about 250 nm, and can obtain a quartz glass member for ultraviolet LED having no absorption due to a structural defect at a wavelength of 200 nm to 400 nm. It aims at providing the manufacturing method of a quartz glass member.
上記課題を解決するため、本発明の紫外線ＬＥＤ用石英ガラス部材の製造方法は、シリカ粉とバインダー成分を混合し、成形して所定形状の成形体を得る成形工程、前記成形体を各種ガスにより加熱処理を行う熱処理工程、及び前記熱処理工程後、熱処理された成形体を透明ガラス化するガラス化工程、を含む紫外線ＬＥＤ用石英ガラス部材の製造方法であって、前記熱処理工程が、酸素を含む雰囲気による１，０００℃以下での有機物の脱脂工程、前記脱脂工程後、塩化水素を含む雰囲気による１，２００℃以下での金属不純物の純化工程、及び前記純化工程後、酸化性雰囲気による１，１５０℃以下での波長約２５０ｎｍの酸素欠乏欠陥の修復を促す工程、である紫外線ＬＥＤ用石英ガラス部材の製造方法である。 In order to solve the above-described problems, the method for producing a quartz glass member for an ultraviolet LED of the present invention comprises a molding step of mixing silica powder and a binder component and molding to obtain a molded body having a predetermined shape, and the molded body using various gases. A method for producing a quartz glass member for an ultraviolet LED, comprising: a heat treatment step for performing heat treatment; and a vitrification step for converting the heat-treated molded body into a transparent glass after the heat treatment step, wherein the heat treatment step includes oxygen. Organic substance degreasing step at 1,000 ° C. or less in an atmosphere, after the degreasing step, metal impurity purifying step at 1,200 ° C. or less in an atmosphere containing hydrogen chloride, and after the purifying step, an oxidizing atmosphere 1, This is a method for producing a quartz glass member for an ultraviolet LED, which is a step for promoting the repair of oxygen-deficient defects having a wavelength of about 250 nm at 150 ° C. or lower.
前記成形工程が金型による成形工程であるのが好適である。 It is preferable that the molding step is a molding step using a mold.
前記酸化性雰囲気が酸素及び／または水蒸気を含む雰囲気であるのが好適である。 The oxidizing atmosphere is preferably an atmosphere containing oxygen and / or water vapor.
前記ガラス化工程が１，７００℃以下で行われるのが好適である。 It is preferable that the vitrification step is performed at 1,700 ° C. or lower.
前記シリカ粉に少なくとも１種類以上の球状シリカを含み、シリカ粉のＡｌ濃度が７０ｐｐｍ以下であるのが好適である。 The silica powder preferably contains at least one kind of spherical silica, and the Al concentration of the silica powder is preferably 70 ppm or less.
前記ガラス化工程後に水素雰囲気による加熱処理を行うのが好適である。 It is preferable to perform heat treatment in a hydrogen atmosphere after the vitrification step.
前記紫外線ＬＥＤが放出する紫外線の波長が２００ｎｍ〜４００ｎｍであるのが好適である。 It is preferable that the wavelength of ultraviolet rays emitted from the ultraviolet LED is 200 nm to 400 nm.
本発明によれば、酸素欠乏欠陥の修復を行い、波長約２５０ｎｍの光吸収が改善され、波長２００ｎｍから４００ｎｍにおいて構造欠陥による吸収のない紫外線ＬＥＤ用石英ガラス部材を得ることができるようにした紫外線ＬＥＤ用石英ガラス部材の製造方法を提供することができるという著大な効果を奏する。 According to the present invention, an ultraviolet ray which repairs an oxygen deficiency defect, improves light absorption at a wavelength of about 250 nm, and can obtain a quartz glass member for ultraviolet LED having no absorption due to a structural defect at a wavelength of 200 nm to 400 nm. There is a remarkable effect that a method for producing a quartz glass member for LED can be provided.
以下に本発明の実施の形態を説明するが、これら実施の形態は例示的に示されるもので、本発明の技術思想から逸脱しない限り種々の変形が可能なことはいうまでもない。 Embodiments of the present invention will be described below, but these embodiments are exemplarily shown, and it goes without saying that various modifications can be made without departing from the technical idea of the present invention.
本発明の製造方法では、金属不純物の除去を目的とした純化処理に用いる塩素系ガスにより酸素欠乏欠陥が生成されるが、それを修復するために酸化性の雰囲気による熱処理を行うことで、酸素欠乏欠陥の修復を行い、波長約２５０ｎｍの光吸収が改善され、波長２００ｎｍから４００ｎｍにおいて構造欠陥による吸収のない紫外線ＬＥＤ用石英ガラス部材を得ることができる。前記酸化性の雰囲気としては、酸素及び／または水蒸気を含んだ雰囲気を用いるのが好適である。 In the manufacturing method of the present invention, oxygen-deficient defects are generated by the chlorine-based gas used for the purification treatment for the purpose of removing metal impurities. By repairing the oxygen-deficient defects, oxygen treatment is performed by performing a heat treatment in an oxidizing atmosphere. By repairing the deficiency defect, light absorption at a wavelength of about 250 nm is improved, and a quartz glass member for an ultraviolet LED having no absorption due to a structural defect at a wavelength of 200 nm to 400 nm can be obtained. As the oxidizing atmosphere, it is preferable to use an atmosphere containing oxygen and / or water vapor.
また、紫外線ＬＥＤ用光学部材として使用するための必要特性である透過率や泡、表面形状など、バルクの石英ガラスを研削加工により作成した石英ガラスと同等以上の特性が必要になるが、以下の方法により紫外線ＬＥＤ用光学部材に好適に用いられる石英ガラスを得ることができる。 In addition, characteristics such as transmittance, foam, and surface shape, which are necessary characteristics for use as an optical member for an ultraviolet LED, are required to be equal to or better than quartz glass prepared by grinding a bulk quartz glass. Quartz glass suitably used for the optical member for ultraviolet LED can be obtained by the method.
成形工程ではシリカ粉とバインダー成分とを混合後に脱泡処理をともなう混練を行った原料を金型によって成形を行うことができる。熱処理工程では、酸素を含む雰囲気による１，０００℃以下での脱脂工程、塩化水素を含む雰囲気での１，２００℃以下での金属不純物の純化工程、酸化性雰囲気での１，１５０℃以下での酸素欠乏欠陥の波長約２５０ｎｍの修復工程を行う。熱処理工程後のガラス化工程は１，７００℃以下で行なうのが好適である。主原料であるシリカ粉中のＡｌ濃度が７０ｐｐｍ以下であるのが好適である。さらに好ましくはガラス化工程後に水素雰囲気による加熱処理を行うことにより、紫外線ＬＥＤ用光学部材に好適に用いられる石英ガラスを得ることができる。 In the molding step, the raw material kneaded with defoaming after mixing the silica powder and the binder component can be molded with a mold. In the heat treatment process, a degreasing process at 1,000 ° C. or less in an atmosphere containing oxygen, a metal impurity purification process at 1,200 ° C. or less in an atmosphere containing hydrogen chloride, and a 1,150 ° C. or less in an oxidizing atmosphere A repair process of a wavelength of about 250 nm of the oxygen deficiency defect is performed. The vitrification step after the heat treatment step is preferably performed at 1,700 ° C. or lower. It is preferable that the Al concentration in the silica powder as the main raw material is 70 ppm or less. More preferably, the quartz glass used suitably for the optical member for ultraviolet LED can be obtained by performing the heat processing by hydrogen atmosphere after a vitrification process.
原料の脱泡処理は、ガラス化工程時の泡発生を抑制する効果がある。 The defoaming treatment of the raw material has an effect of suppressing bubble generation during the vitrification process.
前記バインダー成分としては、例えば、セルロース系（メチルセルロース、カルボキシメチルセルロース、ヒドロキシエチルアルコール）、寒天、ビニル系（ポリビニルアルコール、ポリビニルピロリドン）、デンプン系（ジアルデヒドデンプン、デキストリン、ポリ乳酸）、アクリル系（ポリアクリル酸ナトリウム、メタクリル酸メチル）、植物性粘性物質などが挙げられ、ポリビニルアルコール又はメチルセルロースが好適である。 Examples of the binder component include cellulose (methyl cellulose, carboxymethyl cellulose, hydroxyethyl alcohol), agar, vinyl (polyvinyl alcohol, polyvinyl pyrrolidone), starch (dialdehyde starch, dextrin, polylactic acid), acrylic (poly Examples thereof include sodium acrylate and methyl methacrylate) and vegetable viscous substances, and polyvinyl alcohol or methyl cellulose is preferred.
脱脂工程は、その温度が１，０００℃を超えてしまうと、この工程中に結晶化が進んでしまい、後工程では再度透明ガラス化することが困難になる。そのため、脱脂工程は、１，０００℃以下４００℃以上、より好ましくは、１，０００℃以下６００℃以上で行うのが好適である。 If the temperature of the degreasing step exceeds 1,000 ° C., crystallization proceeds during this step, and it becomes difficult to form a transparent glass again in the subsequent step. Therefore, the degreasing step is preferably performed at 1,000 ° C. or lower and 400 ° C. or higher, more preferably 1,000 ° C. or lower and 600 ° C. or higher.
純化工程は、その温度が高温であればあるほど効果的ではあるが、１，２００℃を超えてしまうと成形体の収縮が進み、次工程での酸素およびまたは水蒸気を含んだ雰囲気での処理において、成形体中までガスが入り込みにくくなり、酸素欠乏欠陥の修復の効果が小さくなってしまう。そのため、純化工程は、１，２００℃以下８００℃以上、より好ましくは、１，２００℃以下１，０００℃以上で行うのが好適である。 The higher the temperature, the more effective the purification process is. However, when the temperature exceeds 1,200 ° C., the shrinkage of the molded body proceeds, and treatment in an atmosphere containing oxygen and / or water vapor in the next process. In this case, it becomes difficult for gas to enter the molded body, and the effect of repairing oxygen-deficient defects becomes small. Therefore, the purification step is preferably performed at 1,200 ° C. or lower and 800 ° C. or higher, more preferably 1200 ° C. or lower and 1,000 ° C. or higher.
酸素欠乏欠陥の修復を促す工程は、その温度が１，１５０℃を超えてしまうと、やはり結晶化が進み易くなり、透明ガラス化することが困難になる。そのため、酸素欠乏欠陥の修復を促す工程は、１，１５０℃以下８００℃以上、より好ましくは、１，１００℃以下９５０℃以上で行うのが好適である。 In the process of promoting the repair of oxygen-deficient defects, if the temperature exceeds 1,150 ° C., crystallization is likely to proceed, and it becomes difficult to form a transparent glass. Therefore, the step of promoting the repair of oxygen deficiency defects is preferably performed at 1,150 ° C. or lower and 800 ° C. or higher, more preferably 1,100 ° C. or lower and 950 ° C. or higher.
主原料であるシリカ粉中や各種添加物中に不純物として金属系元素が含まれていると各種熱処理において結晶化が促進され、特に、熱処理温度が高温になればなるほど結晶化の速度が速くなることが知られており、本発明においてはシリカ粉中に７０ｐｐｍを超えるＡｌ濃度が存在すると、透明なガラス体を得ることができず、白色不透明な結晶化したものとなってしまうため、シリカ粉のＡｌ濃度が７０ｐｐｍ以下であるのが好ましい。 If metal elements are contained as impurities in the main raw material silica powder and various additives, crystallization is promoted in various heat treatments, and in particular, the higher the heat treatment temperature, the faster the crystallization speed. In the present invention, when an Al concentration exceeding 70 ppm is present in the silica powder, a transparent glass body cannot be obtained, and a white opaque crystallized product is obtained. It is preferable that the Al concentration of is 70 ppm or less.
成形工程は、金型により行うことで、従来の研削および研磨加工よりも大量にさらに安価に作成することが可能となり、紫外線ＬＥＤの普及に大いに貢献することが可能となる。成形方法としては、射出成形、プレス成形、トランスファー成形、等が好適に用いることができる。 By performing the molding process using a mold, it can be produced in a larger amount and at a lower cost than conventional grinding and polishing processes, and can greatly contribute to the spread of ultraviolet LEDs. As a molding method, injection molding, press molding, transfer molding, or the like can be suitably used.
また、ガラス部材を水素雰囲気による熱処理を行うことで、ガラス中に水素分子を含有することができ、紫外線ＬＥＤにより発する光によりガラス中に構造欠陥が生じてもそれを修復する効果が期待できる。 Further, by performing heat treatment on the glass member in a hydrogen atmosphere, hydrogen molecules can be contained in the glass, and even if a structural defect occurs in the glass due to light emitted from the ultraviolet LED, an effect of repairing it can be expected.
以下に実施例をあげて本発明をさらに具体的に説明するが、これらの実施例は例示的に示されるもので限定的に解釈されるべきでないことはいうまでもない。 The present invention will be described more specifically with reference to the following examples. However, it is needless to say that these examples are shown by way of illustration and should not be construed in a limited manner.
＜実施例１＞
（成形工程）
平均粒径１．０μｍ（（株）アドマテックス製アドマファインＳＯ−Ｅ３）と平均粒径２．０μｍ（（株）アドマテックス製アドマファインＳＯ−Ｅ５）を重量比１：１で混合した混合粉７９重量部と７．８％メチルセルロース（信越化学工業（株）製メトローズＳＭ−４０００）水溶液２０重量部、１重量部の潤滑剤（日油（株）製ユニルーブ５０ＭＢ−２）を混合した後、３本ロールミルで混練し、真空押出成形機を用いて脱泡を行い、０．１ＭＰａの減圧下、混練押出を行った。
脱泡処理を施したシリカ粉およびバインダーの混合物を金属型内に１２０ＭＰａの加圧で射出成形し、所定の形状を有する成形体を得た。ここで、金属型に関して、面内の面粗度はＲａ値で０．１μｍ以下、好ましくは、０．０５μm以下で仕上られていることが必要である。
このようにして作成した成形体をクリーン度１０，０００程度の清浄な雰囲気で室温にて１２時間程度風乾した。
<Example 1>
(Molding process)
An average particle diameter of 1.0 μm (Admatechs Admafine SO-E3) and an average particle diameter of 2.0 μm (Admatechs Admafine SO-E5) mixed at a weight ratio of 1: 1. After mixing 79 parts by weight and 20 parts by weight of an aqueous solution of 7.8% methylcellulose (Shin-Etsu Chemical Co., Ltd. Metroles SM-4000) and 1 part by weight of a lubricant (Unilube 50MB-2 manufactured by NOF Corporation), The mixture was kneaded with a three-roll mill, defoamed using a vacuum extruder, and kneaded and extruded under a reduced pressure of 0.1 MPa.
A mixture of the silica powder and the binder subjected to the defoaming treatment was injection-molded in a metal mold under a pressure of 120 MPa to obtain a molded body having a predetermined shape. Here, regarding the metal mold, the in-plane roughness needs to be finished with an Ra value of 0.1 μm or less, preferably 0.05 μm or less.
The molded body thus prepared was air-dried for about 12 hours at room temperature in a clean atmosphere having a cleanness of about 10,000.
（熱処理工程）
乾燥後の成形体を底部が平坦な石英ガラス容器に入れ、容器ごと石英ガラス製の炉芯管を有する横型管状炉内で雰囲気・温度を変えて熱処理を施した。熱処理工程では下記（ａ）〜（ｃ）の工程を行った。
(Heat treatment process)
The dried molded body was put into a quartz glass container having a flat bottom, and the container was subjected to heat treatment while changing the atmosphere and temperature in a horizontal tubular furnace having a quartz glass furnace core tube. In the heat treatment step, the following steps (a) to (c) were performed.
（ａ）：（脱脂工程）
炉内温度を室温から２０℃／分の昇温速度にて８００℃まで昇温し保持した。昇温時の雰囲気は窒素１００％である。８００℃に炉内温度が安定した後、窒素を停止し、酸素を１００％で流しつつ１時間保持した。これにより成形体に含まれるメトローズ等の有機物を完全に酸化除去した。
(A): (Degreasing process)
The furnace temperature was raised from room temperature to 800 ° C. at a rate of temperature rise of 20 ° C./min and held. The atmosphere during the temperature rise is 100% nitrogen. After the furnace temperature was stabilized at 800 ° C., nitrogen was stopped and kept for 1 hour while flowing oxygen at 100%. As a result, organic substances such as Metroses contained in the molded body were completely removed by oxidation.
（ｂ）：（純化工程）
酸素雰囲気による脱脂処理終了後、酸素を窒素１００％に切り替え、再び昇温速度２０℃／分にて炉内温度を１，２００℃まで昇温し保持した。窒素を１００％塩化水素に切り替え、１時間塩化水素による純化処理を行った。純化処理により石英ガラス中のアルカリ金属、銅、鉄等の金属不純物濃度が低減される。一方で塩化水素は石英ガラス中のＳｉ−ＯＨと反応してＳｉ−Ｃｌ結合を生成するため、純化処理後の成形体はそのままガラス化すると２Ｓｉ−Ｃｌ⇒Ｓｉ＝Ｓｉ＋Ｃｌ２の反応が生じる。Ｓｉ＝Ｓｉ結合は酸素欠乏欠陥と呼ばれる構造欠陥で波長約２５０ｎｍに吸収を持つと同時に紫外線に対する耐性が非常に弱く、本発明の目的に適さないため、これを治癒する必要が生じる。
(B): (Purification process)
After completion of the degreasing treatment in the oxygen atmosphere, the oxygen was switched to 100% nitrogen, and the furnace temperature was again raised to 1,200 ° C. and maintained at a temperature rising rate of 20 ° C./min. Nitrogen was switched to 100% hydrogen chloride, and purification with hydrogen chloride was performed for 1 hour. By the purification treatment, the concentration of metal impurities such as alkali metal, copper, and iron in the quartz glass is reduced. On the other hand, since hydrogen chloride reacts with Si—OH in quartz glass to produce a Si—Cl bond, if the formed product after purification is vitrified as it is, a reaction of 2Si—Cl → Si = Si + Cl 2 occurs. The Si = Si bond is a structural defect called an oxygen deficiency defect and has an absorption at a wavelength of about 250 nm, and at the same time has a very low resistance to ultraviolet rays and is not suitable for the purpose of the present invention.
（ｃ）：（酸素欠乏欠陥の修復を促す工程）
純化処理後、雰囲気ガスである塩化水素を窒素１００％に切り替え、２０℃／分の降温速度で１，０５０℃まで降温し保持した。窒素を酸素１００％に切り替え、１時間酸素による石英ガラス中の酸素欠乏欠陥の修復処理を行った。処理後、酸素を窒素１００％に切り替え、室温まで冷却し取り出した。
(C): (Step of promoting repair of oxygen deficiency defect)
After the purification treatment, hydrogen chloride as an atmosphere gas was switched to 100% nitrogen, and the temperature was lowered to 1,050 ° C. at a temperature lowering rate of 20 ° C./min. Nitrogen was switched to 100% oxygen, and oxygen deficiency defects in quartz glass were repaired with oxygen for 1 hour. After the treatment, the oxygen was switched to 100% nitrogen, cooled to room temperature and taken out.
（ガラス化工程）
取り出した成形体は平滑なカーボン板上に並べ、真空炉中に設置した。真空チャンバー内を真空度１×１０−２Ｐａに排気後、２０℃／分の昇温速度で１，６５０℃まで昇温し、１，６５０℃に到達後窒素により真空破壊して０．１ＭＰａに加圧しつつ１０分間保持し、その後通電を切り炉冷した。１０時間後に取出し、目的とする紫外線ＬＥＤ用石英ガラス部材を得た。
(Vitrification process)
The molded bodies taken out were arranged on a smooth carbon plate and placed in a vacuum furnace. After evacuating the vacuum chamber to a vacuum degree of 1 × 10 −2 Pa, the temperature was raised to 1,650 ° C. at a rate of temperature increase of 20 ° C./min. The sample was held for 10 minutes while being pressurized, and then turned off and cooled in the furnace. The product was taken out after 10 hours to obtain a target quartz glass member for ultraviolet LED.
（評価）
各物性値は次の測定方法に従った。
（１）Ａｌ濃度
得られた石英ガラス部材をフッ化水素酸にて分解し、ＩＣＰ発光分光分析法により測定を行った。
（２）外観
得られた石英ガラス部材を目視により観察を行った。透明な石英ガラスの場合には「良好」、結晶化（失透）により不透明となったものは「結晶化」、目視にて確認可能な泡が含有しているものは「泡」とした。
（３）波長２５０ｎｍの吸収
２０×２０×２ｍｍの平板を作成し、ＵＶ−ＶＩＳ分光光度計にて波長２００ｎｍから４００ｎｍの範囲において測定を行い、波長２５０ｎｍの吸収の有無を確認した。波長２５０ｎｍの吸収がないものには「なし」、吸収があるものには「あり」、結晶化して測定ができなかったものは「測定不能」とした。
各種条件および測定結果については、表１にまとめて示した。実施例１で得られた紫外線ＬＥＤ用石英ガラス部材の波長２００ｎｍから４００ｎｍにおける透過率測定結果を図１に示す。
(Evaluation)
Each physical property value followed the following measuring method.
(1) Al concentration The obtained quartz glass member was decomposed with hydrofluoric acid and measured by ICP emission spectroscopy.
(2) Appearance The obtained quartz glass member was visually observed. In the case of transparent quartz glass, “good”, those that became opaque due to crystallization (devitrification) were “crystallized”, and those that contained visually observable bubbles were “bubbles”.
(3) Absorption at a wavelength of 250 nm A 20 × 20 × 2 mm flat plate was prepared and measured with a UV-VIS spectrophotometer in the wavelength range of 200 nm to 400 nm to confirm the presence or absence of absorption at a wavelength of 250 nm. “None” indicates that there is no absorption at a wavelength of 250 nm, “Yes” indicates that there is absorption, and “No measurement” indicates that the measurement cannot be performed due to crystallization.
Various conditions and measurement results are summarized in Table 1. The transmittance | permeability measurement result in wavelength 200nm to 400nm of the quartz glass member for ultraviolet LED obtained in Example 1 is shown in FIG.
＜実施例２＞
酸素欠乏欠陥の修復処理の温度を１，０５０℃とし、３０℃に保持した純水を酸素をキャリアとしたバブリング法にて水蒸気を含む雰囲気とした以外は実施例１と同様に行い紫外線ＬＥＤ用石英ガラス部材を得た。
<Example 2>
For ultraviolet LEDs, the temperature of the oxygen deficiency defect repairing process was set to 1,050 ° C., and pure water maintained at 30 ° C. was changed to an atmosphere containing water vapor by a bubbling method using oxygen as a carrier. A quartz glass member was obtained.
＜実施例３＞
実施例１で得た紫外線ＬＥＤ用石英ガラス部材に対して、４００℃、０．８ＭＰの水素雰囲気中にて水素処理（水素雰囲気による加熱処理）を行い、ガラス中に水素分子を導入した。このようにして、紫外線ＬＥＤ用石英ガラス部材を得た。
<Example 3>
The quartz glass member for ultraviolet LED obtained in Example 1 was subjected to hydrogen treatment (heat treatment in a hydrogen atmosphere) in a hydrogen atmosphere at 400 ° C. and 0.8 MP, and hydrogen molecules were introduced into the glass. Thus, the quartz glass member for ultraviolet LED was obtained.
＜実施例４＞
平均粒径０．２５μｍ（（株）アドマテックス製アドマファインＳＯ−Ｅ１）、平均粒径１．０μｍ（（株）アドマテックス製アドマファインＳＯ−Ｅ３）、平均粒径２．０μｍ（（株）アドマテックス製アドマファインＳＯ−Ｅ５）を重量比１：１：２で混合した混合粉を原料としたこと以外は実施例１と同様の処理を行い紫外線ＬＥＤ用石英ガラス部材を得た。
<Example 4>
Average particle size 0.25 μm (Admatechs Admafine SO-E1), Average particle size 1.0 μm (Admatechs Admafine SO-E3), Average particle size 2.0 μm (Co) A quartz glass member for ultraviolet LED was obtained by performing the same treatment as in Example 1 except that a mixed powder obtained by mixing Admatech Admafine SO-E5) at a weight ratio of 1: 1: 2 was used as a raw material.
＜比較例１＞
酸素欠乏欠陥の修復を促す工程を行わなかった以外は実施例１と同様にして、石英ガラス部材を得た。比較例１で得られた石英ガラス部材の波長２００ｎｍから４００ｎｍにおける透過率測定結果を図２に示した。
<Comparative Example 1>
A quartz glass member was obtained in the same manner as in Example 1 except that the step of promoting the repair of the oxygen deficiency defect was not performed. FIG. 2 shows the transmittance measurement results of the quartz glass member obtained in Comparative Example 1 at a wavelength of 200 nm to 400 nm.
＜比較例２＞
熱処理工程における脱脂工程の脱脂温度を１，１００℃とした以外は実施例１と同様に処理を行った。熱処理工程後の状態が実施例１のサンプルと特に変わらなかったため、ガラス化を行ったが、結晶化により不透明となってしまった。
<Comparative example 2>
The treatment was performed in the same manner as in Example 1 except that the degreasing temperature in the degreasing step in the heat treatment step was 1,100 ° C. Since the state after the heat treatment step was not particularly different from the sample of Example 1, vitrification was performed, but it became opaque due to crystallization.
＜比較例３＞
熱処理工程における純化工程の純化温度を１，３５０℃としたこと以外は実施例１と同様に処理を行った。熱処理工程後の焼結体の体積が若干収縮していたが、そのままガラス化を行ったところ、非常に微細な泡が多数混入してしまった。
<Comparative Example 3>
The treatment was performed in the same manner as in Example 1 except that the purification temperature in the purification step in the heat treatment step was 1,350 ° C. Although the volume of the sintered body after the heat treatment step was slightly shrunk, when vitrification was carried out as it was, many very fine bubbles were mixed.
＜比較例４＞
熱処理工程における酸素欠乏欠陥の修復を促す工程の酸素欠陥修復温度を１，２００℃にしたこと以外は実施例１と同様に処理を行った。熱処理後の状態が実施例１のサンプルと特に変わらなかったため、ガラス化を行ったが、結晶化により不透明となってしまった。
<Comparative Example 4>
The treatment was performed in the same manner as in Example 1 except that the oxygen defect repair temperature in the step of promoting the repair of oxygen deficiency defects in the heat treatment step was set to 1,200 ° C. Since the state after the heat treatment was not particularly different from the sample of Example 1, it was vitrified but became opaque due to crystallization.
＜比較例５＞
比較例１で得たガラス部材を酸素雰囲気にて１，１００℃、１０時間保持した。得られたサンプルの透過率を測定したところ、波長２５０ｎｍの吸収は若干改善していたが、熱処理による汚染の影響で２００ｎｍから４００ｎｍの全域の透過率が低下してしまった。
<Comparative Example 5>
The glass member obtained in Comparative Example 1 was held at 1,100 ° C. for 10 hours in an oxygen atmosphere. When the transmittance of the obtained sample was measured, the absorption at a wavelength of 250 nm was slightly improved, but the transmittance in the entire region from 200 nm to 400 nm was lowered due to the influence of contamination by heat treatment.
Claims (7)
前記成形体を各種ガスにより加熱処理を行う熱処理工程、及び
前記熱処理工程後、熱処理された成形体を透明ガラス化するガラス化工程、
を含む紫外線ＬＥＤ用石英ガラス部材の製造方法であって、
前記熱処理工程が、
酸素を含む雰囲気による１，０００℃以下での有機物の脱脂工程、
前記脱脂工程後、塩化水素を含む雰囲気による１，２００℃以下での金属不純物の純化工程、及び
前記純化工程後、酸化性雰囲気による１，１５０℃以下での波長約２５０ｎｍの酸素欠乏欠陥の修復を促す工程、
である、紫外線ＬＥＤ用石英ガラス部材の製造方法。 A molding process in which silica powder and a binder component are mixed and molded to obtain a molded body having a predetermined shape,
A heat treatment step of heat-treating the molded body with various gases, and a vitrification step of converting the heat-treated molded body into a transparent glass after the heat treatment step,
A method for producing a quartz glass member for an ultraviolet LED comprising:
The heat treatment step,
An organic matter degreasing step at 1,000 ° C. or lower in an atmosphere containing oxygen;
After the degreasing step, a metal impurity purification step at 1,200 ° C. or lower in an atmosphere containing hydrogen chloride, and after the purification step, repair of an oxygen-deficient defect having a wavelength of about 250 nm at 1,150 ° C. or lower in an oxidizing atmosphere The process of encouraging
The manufacturing method of the quartz glass member for ultraviolet LED which is.
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| JP2016131887A JP6789011B2 (en) | 2016-07-01 | 2016-07-01 | Manufacturing method of quartz glass member for ultraviolet LED |
| PCT/JP2017/018817 WO2017208855A1 (en) | 2016-06-01 | 2017-05-19 | Silica glass member for hermetic sealing of ultraviolet smd led element and method for manufacturing quarts glass member for ultraviolet led |
| US16/306,185 US20210226105A1 (en) | 2016-06-01 | 2017-05-19 | Silica glass member for hermetic sealing of ultraviolet smd led element and method for manufacturing quartz glass member for ultraviolet led |
| KR1020217014098A KR102330935B1 (en) | 2016-06-01 | 2017-05-19 | Silica glass member for hermetic sealing of ultraviolet smd led element and method for manufacturing quarts glass member for ultraviolet led |
| CN201780032414.4A CN109314165B (en) | 2016-06-01 | 2017-05-19 | Quartz glass member for hermetic sealing of ultraviolet SMD type LED element and method for producing quartz glass member for ultraviolet LED |
| EP17806412.7A EP3467885A4 (en) | 2016-06-01 | 2017-05-19 | Silica glass member for hermetic sealing of ultraviolet smd led element and method for manufacturing quarts glass member for ultraviolet led |
| KR1020187034290A KR102337364B1 (en) | 2016-06-01 | 2017-05-19 | A method for manufacturing a quartz glass member for airtight sealing of an ultraviolet SMD type LLD element and a quartz glass member for an ultraviolet LED |
| TW106117681A TWI737738B (en) | 2016-06-01 | 2017-05-26 | Silica glass material for airtight sealing of ultraviolet rays smd type led element and manufacturing method of silica glass material for ultraviolet led |
| US17/559,031 US11757075B2 (en) | 2016-06-01 | 2021-12-22 | Silica glass member for hermetic sealing of ultraviolet SMD LED element and method for manufacturing quartz glass member for ultraviolet led |
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