JP3262674B2 - Quartz glass surface treatment liquid and method of using the same - Google Patents
Quartz glass surface treatment liquid and method of using the sameInfo
- Publication number
- JP3262674B2 JP3262674B2 JP08357894A JP8357894A JP3262674B2 JP 3262674 B2 JP3262674 B2 JP 3262674B2 JP 08357894 A JP08357894 A JP 08357894A JP 8357894 A JP8357894 A JP 8357894A JP 3262674 B2 JP3262674 B2 JP 3262674B2
- Authority
- JP
- Japan
- Prior art keywords
- quartz glass
- surface treatment
- hydrogen fluoride
- treatment liquid
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims description 57
- 238000004381 surface treatment Methods 0.000 title claims description 26
- 239000007788 liquid Substances 0.000 title claims description 19
- 238000000034 method Methods 0.000 title claims description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 30
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 23
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 26
- 238000005530 etching Methods 0.000 description 11
- 239000002244 precipitate Substances 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003486 chemical etching Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000007788 roughening Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000010587 phase diagram Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004518 low pressure chemical vapour deposition Methods 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 229920005591 polysilicon Polymers 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UOACKFBJUYNSLK-XRKIENNPSA-N Estradiol Cypionate Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H](C4=CC=C(O)C=C4CC3)CC[C@@]21C)C(=O)CCC1CCCC1 UOACKFBJUYNSLK-XRKIENNPSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- LDDQLRUQCUTJBB-UHFFFAOYSA-O azanium;hydrofluoride Chemical compound [NH4+].F LDDQLRUQCUTJBB-UHFFFAOYSA-O 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000009972 noncorrosive effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、石英ガラスの表面、特
に半導体の製造用石英ガラス治具の表面に凹凸のある粗
面を形成するための石英ガラス表面処理液、及びそれを
使用した表面処理方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a quartz glass surface treating solution for forming a roughened surface having irregularities on the surface of quartz glass, in particular, the surface of a quartz glass jig for manufacturing semiconductors, and a surface using the same. Regarding the processing method.
【０００２】[0002]
【従来の技術】石英ガラスは、高純度で溶融温度が高
く、しかも耐化学薬品性に優れているところから熱処理
治具として、特に半導体製造用治具として用いられてき
た。しかしながら、石英ガラスからなる半導体製造用治
具は、その使用目的により、例えば赤外線等の輻射線が
炉芯管やボート保持具内を伝搬しその端部のシール部材
や連結用の有機物材料を劣化させたり（特開昭６３ー５
８８２２号公報）、また、ＬＰＣＶＤ（Ｌｏｗ Ｐｒｅ
ｓｓｕｒｅ Ｃｈｅｍｉｃａｌ ｖａｐｏｒ Ｄｅｐｏ
ｓｉｔｉｏｎ）法によるポリシリコン膜の成長時に炉芯
管内表面にも堆積が起こり、それがウエハの熱処理時に
剥離して汚染したり（実開昭６１ー８８２３３号公
報）、あるいは前記処理時にボートにウエハを癒着させ
たり（特開平１ー１７００１９号公報）する等の不都合
があり、その不都合を解決するため、石英ガラス表面に
凹凸を設けることが行われている。前記凹凸の形成には
サンドブラスト法が一般的に採用され、化学的エッチン
グ処理による形成は特開平１ー１７００１９号公報等に
その可能性が示唆されているにとどまる。2. Description of the Related Art Quartz glass has been used as a heat treatment jig, particularly as a jig for semiconductor production, because of its high purity, high melting temperature and excellent chemical resistance. However, semiconductor manufacturing jigs made of quartz glass, depending on the purpose of use, cause radiation such as infrared rays to propagate inside the furnace core tube or boat holder and degrade the sealing members at the ends and the organic material for connection. (See JP-A-63-5
No. 8822) and LPCVD (Low Pre
sure Chemical vapor Depo
During the growth of the polysilicon film by the position method, deposition also occurs on the inner surface of the furnace core tube, which is separated and contaminated during the heat treatment of the wafer (Japanese Utility Model Laid-Open No. 88233/1986), or the wafer is attached to the boat during the processing. For example, there is a problem that the surface is fused (Japanese Unexamined Patent Publication No. 1-170019). In order to solve the problem, irregularities are provided on the surface of quartz glass. The sand blast method is generally adopted for the formation of the unevenness, and the formation by the chemical etching treatment is suggested only in Japanese Patent Application Laid-Open No. 1-1170019.
【０００３】ところが、上記サンドブラスト法による凹
凸の形成は、その凹凸が浅いといっても機械的に表面を
破壊するため、凹凸面の下にマイクロクラックを持った
層が形成されその深さが１００μｍにも達することがあ
る。このように深いクラックが発生するとその中にシリ
コンウエーハを汚染する物質が取り込まれたり、あるい
は前記クラックが破壊開始クラックとなり製品の強度劣
化をもたらす。そのため通常行われているサンドブラス
ト法では凹凸を形成した後、フッ化水素の水溶液である
フッ化水素酸、いわゆるフッ酸でエッチング処理して、
マイクロクラックの除去を行っている。しかしながら、
深いマイクロクラックをフッ酸で除去すると治具の寸法
精度に狂が生じたり、あるいは形成した凸面が少なくな
って所期の目的を達成できなくなるという欠点があっ
た。そのため、従来法は、なるべくクラックが深くなら
ないようにサンドブラストをかけて、クラックが多く、
汚染の大きい層を取り除く程度にフッ酸エッチング処理
を行い、次いで腐食性のない洗浄液や純水で十分洗浄し
ていた。こうした処理方法によっても、サンドブラスト
法で凹凸を形成した石英ガラス治具にはそのマイクロク
ラック内に不純物が残存したり、あるいは機械的強度が
低下したりして、近年、高純度化が一段と進み、かつそ
の生産性が要求されるようになった半導体工業において
満足のいく石英ガラス治具を提供するものではなかっ
た。However, the formation of the irregularities by the sand blast method mechanically destroys the surface even if the irregularities are shallow, so that a layer having microcracks is formed under the irregularities and the depth is 100 μm. Can also reach. When such a deep crack is generated, a substance contaminating the silicon wafer is taken into the crack, or the crack becomes a fracture initiation crack, thereby deteriorating the strength of the product. Therefore, in the sand blast method that is usually performed, after forming irregularities, etching treatment is performed with hydrofluoric acid, which is an aqueous solution of hydrogen fluoride, so-called hydrofluoric acid,
Micro cracks are removed. However,
When deep microcracks are removed with hydrofluoric acid, the dimensional accuracy of the jig is deviated, or the formed convex surface is reduced, so that the intended purpose cannot be achieved. For this reason, in the conventional method, sandblasting is performed so that cracks do not deepen as much as possible,
Hydrofluoric acid etching was performed to the extent that highly contaminated layers were removed, and then sufficiently cleaned with a non-corrosive cleaning solution or pure water. Even with such a processing method, the quartz glass jig with the irregularities formed by the sandblast method has impurities remaining in its micro cracks, or the mechanical strength is reduced, and in recent years, higher purification has been further advanced, Moreover, it has not been possible to provide a satisfactory quartz glass jig in the semiconductor industry where the productivity is required.
【０００４】上記欠点はすべて機械的処理に起因すると
ころから、化学的エッチング処理による凹凸面の形成が
考えられ、例えばガラス工業ハンドブック（森谷太郎等
編、朝倉書店昭和４６年８月１０日発行）第４７１頁に
記載のフロスト加工液を用いて石英ガラスをエッチング
することが考えられるが、石英ガラスが高純度のＳｉＯ
2からなるため、ソーダガラスやカリウムガラス等の通
常の多成分系ガラスに有効な前記処理液も十分に作用せ
ず、満足のいく凹凸の形成および半導体製品の要求され
る清浄な表面の形成ができなかった。Since all of the above-mentioned drawbacks are caused by mechanical treatment, it is conceivable to form an uneven surface by a chemical etching treatment. For example, a glass industry handbook (edited by Taro Moriya, published by Asakura Shoten on August 10, 1976) It is conceivable to etch quartz glass using a frost processing liquid described on page 471, but quartz glass is made of high-purity SiO2.
2, the processing solution effective for ordinary multi-component glasses such as soda glass and potassium glass does not sufficiently act, and the formation of satisfactory unevenness and the formation of the required clean surface of semiconductor products are prevented. could not.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、上記化
学的エッチング処理は機械的エッチング処理に比べて石
英ガラス表面にダメージを与えることが少ないところか
ら、半導体工業で要求される凹凸の形成には最適である
と思料し、本発明者等は、半導体用治具の処理液として
十分な清浄を維持でき、しかも凹凸面の形成が良好な化
学的エッチング処理液の開発について、鋭意研究を重ね
た結果、フッ化水素とフッ化アンモニウムからなる処理
液に酢酸を含有させた水溶液を用いることにより前記問
題点が解決できることを見出し、本発明を完成したもの
である。すなわちHowever, the above chemical etching treatment is less suitable for forming irregularities required in the semiconductor industry because the chemical etching treatment causes less damage to the quartz glass surface than the mechanical etching treatment. Considering that there is, the present inventors have conducted intensive research on the development of a chemical etching treatment solution that can maintain sufficient cleaning as a treatment solution for a semiconductor jig, and also has a good formation of uneven surface, The present inventors have found that the above problem can be solved by using an aqueous solution containing acetic acid in a treatment solution comprising hydrogen fluoride and ammonium fluoride, and have completed the present invention. Ie
【０００６】本発明は、石英ガラス表面に清浄な凹凸を
形成する石英ガラス表面処理液を提供することを目的と
する。An object of the present invention is to provide a surface treatment liquid for quartz glass which forms clean irregularities on the surface of quartz glass.
【０００７】また、本発明は、石英ガラスの強度劣化を
惹起しない石英ガラス表面処理液を提供することを目的
とする。Another object of the present invention is to provide a surface treatment liquid for quartz glass which does not cause deterioration in the strength of quartz glass.
【０００８】さらに、本発明は、上記表面処理液を使用
して石英ガラス表面に粗面を形成する表面処理方法を提
供することを目的とする。Another object of the present invention is to provide a surface treatment method for forming a rough surface on the surface of quartz glass using the above surface treatment solution.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成する本発
明は、フッ化水素とフッ化アンモニウムと酢酸を水に混
合する石英ガラス表面処理液、及び該表面処理液を使用
する表面処理方法に係る。SUMMARY OF THE INVENTION The present invention, which achieves the above object, comprises a quartz glass surface treatment solution in which hydrogen fluoride, ammonium fluoride and acetic acid are mixed with water, and a surface treatment method using the surface treatment solution. Related.
【００１０】本発明の石英ガラス表面処理液の各成分と
して電子工業薬品として市販されている化学薬品を使用
することができる。これによりコストを下げることがで
き、工業用処理液として十分利用が可能である。前記石
英ガラス表面処理液の組成割合は表面処理液全重量に対
して、酢酸の含有量が１０重量％以上、水の含有量が５
０重量％以下、フッ化水素とフッ化アンモニウムの合計
含有量が２５％以上、及びフッ化アンモニウム１モルに
対してフッ化水素の含有量が０．２〜１５モルの比率
で、かつフッ化水素７０部に対して水が３０部以上の範
囲が選ばれる。前記表面処理液は必ずしも均一な溶液に
ならずに沈殿物を含んだ混合体の場合もあるがこのこと
は妨げにならず、液の劣化を沈殿物の再溶解で補うため
かむしろ好ましい結果が得られる。この処理液の成分
中、フッ化アンモニウムは他の化学薬品に比して高価で
あるので、処理液のコスト上からその使用量はできるだ
け少なくするのが好ましい。この意味でフッ化アンモニ
ウムに対するフッ化水素の使用量は多い方が宜しい。し
かしながら、フッ化アンモニウム１モルに対してフッ化
水素が１５モルを超えるような場合は粗面化が起こらな
い。０．２モル未満の場合はエッチングの進行が遅くて
粗面化が起こるといっても凹凸が浅過ぎて実用上その効
果が出てこない。フッ化アンモニウムとフッ化水素の合
計含有量が２５重量％未満では実用的に採用しやすい時
間、例えば２時間程度では粗面化が起こらず透明のまま
である。経済的な理由からは水が多い方がよいが５０重
量％以上では粗面の成長が遅く、また処理液中の沈殿物
の量も少なくなる。理由は解らないが水が５０重量％以
下の時現れる沈殿物を含んだ混合状態の方が液寿命も長
くて石英ガラスの処理状態も良好である。また、本発明
の表面処理液において酢酸は必須の成分であり、その量
が１０重量％に満たないと、石英ガラス表面への凹凸の
形成が悪く、粗面化が十分でない。As each component of the quartz glass surface treating solution of the present invention, a chemical commercially available as an electronic industrial chemical can be used. As a result, the cost can be reduced, and it can be sufficiently used as an industrial treatment liquid. The composition ratio of the quartz glass surface treatment liquid is such that the acetic acid content is 10% by weight or more and the water content is 5% based on the total weight of the surface treatment liquid.
0% by weight or less, the total content of hydrogen fluoride and ammonium fluoride is at least 25%, and the content of hydrogen fluoride is 0.2 to 15 mol per 1 mol of ammonium fluoride; The range of 30 parts or more of water to 70 parts of hydrogen is selected. The surface treatment solution may not necessarily be a homogeneous solution but may be a mixture containing a precipitate, but this is not a hindrance, and rather preferable results are obtained to compensate for the deterioration of the solution by re-dissolving the precipitate. can get. Among the components of this processing solution, ammonium fluoride is more expensive than other chemicals, so it is preferable to use as little as possible in view of the cost of the processing solution. In this sense, it is preferable to use a large amount of hydrogen fluoride with respect to ammonium fluoride. However, when the amount of hydrogen fluoride exceeds 15 moles per 1 mole of ammonium fluoride, surface roughening does not occur. If the amount is less than 0.2 mol, the progress of the etching is slow and the surface is roughened, but the unevenness is too shallow and the effect cannot be obtained in practical use. If the total content of ammonium fluoride and hydrogen fluoride is less than 25% by weight, the surface is transparent without any roughening for a time that can be practically used, for example, about 2 hours. For economic reasons, more water is better, but if it is 50% by weight or more, the growth of the rough surface is slow, and the amount of the precipitate in the processing solution is also reduced. Although the reason is not understood, the mixed state containing the precipitate which appears when the water content is 50% by weight or less has a longer liquid life and a better treatment state of the quartz glass. Further, acetic acid is an essential component in the surface treatment liquid of the present invention, and if the amount is less than 10% by weight, the formation of irregularities on the quartz glass surface is poor, and the surface roughening is not sufficient.
【００１１】 本発明の表面処理液の組成割合を状態図
で示すと図１本発明の表面処理液の組成割合を状態図で
示すと図１のとおりとなる。図１において、酢酸の１０
重量％以上はＦＪＫＧの右、水の５０重量％以下はＥＦ
ＧＨの下、（フッ化水素＋フッ化アンモニウム）の２５
重量％以上はＥＩＬＨの手前、フッ化アンモニウム１モ
ルに対してフッ化水素の含有量が０．２モル以上１５モ
ル以下はＨＧＫＬの左奥及びＥＦＪＩの右手前、フッ化
水素７０部に対して水が３０部以上はＩＪＫＬの上をそ
れぞれ意味するから、本発明の組成範囲は線で囲まれた
部分に該当する。FIG. 1 is a phase diagram showing the composition ratio of the surface treatment solution of the present invention, and FIG. 1 is a phase diagram showing the composition ratio of the surface treatment solution of the present invention. In FIG.
More than 50% by weight of water is EF on the right of FJKG
Under GH, 25 of (hydrogen fluoride + ammonium fluoride)
Weight percent or more is before EILH, and the content of hydrogen fluoride is 0.2 mol or more and 15 mol or less per 1 mol of ammonium fluoride. Since the water content of 30 parts or more means above IJKL, the composition range of the present invention corresponds to the portion surrounded by the line.
【００１２】本発明の石英ガラス表面処理液の作用は明
らかでないが、フッ化水素によるエッチング作用と、ガ
ラス表面に何らかの析出物が付着成長してエッチングを
妨げる作用とのバランスで粗面化が達成されるようであ
る。フッ酸エッチングは通常凹曲面（ディンプル面）を
形成し、他方析出物は多面体なので石英ガラス表面に小
さな平面で構成される凹凸を形成することが解った。こ
の二つの凹凸の複合状態を発生させると良好な粗面状態
が得られる。Although the function of the quartz glass surface treating solution of the present invention is not clear, roughening is achieved by a balance between the etching action by hydrogen fluoride and the action of preventing some precipitates from adhering to and growing on the glass surface. It seems to be done. It was found that hydrofluoric acid etching usually forms a concave curved surface (dimple surface), while the precipitates are polyhedral, so that irregularities composed of small flat surfaces are formed on the quartz glass surface. When a composite state of these two irregularities is generated, a good rough surface state can be obtained.
【００１３】また、本発明の石英ガラス表面処理液は水
の存在を必須とする。水の存在により、各化学物質の配
合で決まる作用のバランスを更に綿密に調整できる。す
なわち、析出物の大きさや数や成長速度を変え、同時に
それにつれてエッチング速度も変わる。種々試行検討し
たところ水の含有量が５０重量％を超えない前記範囲の
組成物が目的とする処理に好適であることが解った。も
っとも、試薬のフッ化水素には最小でも約３０重量％の
水が、また酢酸にも水が含まれている場合もあるので上
記水の配合にはこれらの水をも計算した上で、決める必
要がある。The quartz glass surface treatment liquid of the present invention requires the presence of water. The balance of the action determined by the composition of each chemical substance can be more precisely adjusted by the presence of water. That is, the size, number, and growth rate of the precipitates are changed, and at the same time, the etching rate is changed accordingly. After conducting various trials, it was found that compositions in the above-mentioned range where the water content did not exceed 50% by weight were suitable for the intended treatment. However, at least about 30% by weight of water is contained in hydrogen fluoride as a reagent, and water may be contained in acetic acid in some cases. There is a need.
【００１４】フッ化水素とフッ化アンモニウムの１：１
モル比の試薬であるフッ化水素アンモニウムを用いて結
果として上記組成にしても作用は変わらないので、経済
的理由や取り扱いの簡便さから好適に使用される。1: 1 of hydrogen fluoride and ammonium fluoride
Even if the above composition is used as a result by using ammonium hydrogen fluoride which is a molar ratio reagent, the effect is not changed, so that it is preferably used for economic reasons and easy handling.
【００１５】本発明の石英ガラス表面処理液による石英
ガラスの処理は、表面処理液に石英ガラスを浸漬するだ
けで十分である。表面処理液の下部に沈殿を認めること
があるが、沈殿層に浸けても上澄み層に浸けても良い。
前記浸漬により石英ガラス表面に自形をもった多面体結
晶が析出し、石英ガラスの表面が保護され、その部分の
エッチング作用が遅れ、結果として突起が形成される。
一方、前記突起とならない部分はフッ化水素のエッチン
グ作用で凹曲面となり、石英ガラス表面に凹凸が形成さ
れる。すなわち、石英ガラス表面には多面体表面である
平面的凹凸とフッ化水素エッチングによるディンプル面
とが形成され、それらの複合状態で石英ガラス表面に白
色の均一な粗面が生じる。In the treatment of the quartz glass with the quartz glass surface treating solution of the present invention, it is sufficient to immerse the quartz glass in the surface treating solution. Precipitation may be observed at the lower part of the surface treatment solution, but may be immersed in the precipitation layer or the supernatant layer.
The immersion precipitates a polyhedral crystal having a self-form on the surface of the quartz glass, protects the surface of the quartz glass, delays the etching action of the portion, and as a result, forms a projection.
On the other hand, the portions that do not become the protrusions become concave curved surfaces due to the etching action of hydrogen fluoride, and irregularities are formed on the surface of the quartz glass. That is, on the quartz glass surface, planar irregularities, which are polyhedral surfaces, and dimple surfaces formed by hydrogen fluoride etching are formed, and a white uniform rough surface is generated on the quartz glass surface in a composite state thereof.
【００１６】上記自形を持った多面体結晶の析出が石英
ガラス表面の凹凸に影響を及ぼし、その大きさが表面処
理液の組成に依存するところから、石英ガラスの使用目
的に応じて前記組成の割合を変えることで任意の凹凸を
形成できる。例えば白さを優先して熱の遮断効果を最大
にするには各成分の配合割合を上記にみた最適な組成比
にすればよく、また、洗浄し易いように粗目の凹凸にす
るには水の量を多くすればよく、さらに、エッチング量
を少なくして寸法変化を極力抑えるにはフッ化水素の量
を少なくすれば良い等である。前記に加えて、本発明の
表面処理液は、石英ガラス表面を機械的に処理しないた
め、石英ガラスの強度低下が少なく、例えばＬＰＣＶＤ
法によりポリシリコン膜を成長させるボートに応用する
と、サンドブラスト法で処理したボートよりその使用す
る材料の直径を小さくできる。ＬＰＣＶＤにおいてはこ
のことが炉内雰囲気の均一性に大きく影響するので結果
としてウエハ面内の支持部近傍のロスが少なく出来る。The precipitation of the polyhedral crystals having the above-mentioned automorphism affects the roughness of the quartz glass surface, and the size thereof depends on the composition of the surface treatment solution. Arbitrary irregularities can be formed by changing the ratio. For example, in order to maximize the heat blocking effect by giving priority to whiteness, the mixing ratio of each component may be set to the optimum composition ratio as seen above. In order to minimize the amount of etching and minimize the dimensional change, the amount of hydrogen fluoride may be reduced. In addition to the above, the surface treatment liquid of the present invention does not mechanically treat the surface of quartz glass, so that the strength of quartz glass is less reduced.
When applied to a boat for growing a polysilicon film by the method, the diameter of the material used can be smaller than that of a boat treated by the sandblast method. In LPCVD, this greatly affects the uniformity of the atmosphere in the furnace, and as a result, loss near the support portion in the wafer surface can be reduced.
【００１７】[0017]
実施例１〜２６ フッ化水素（フッ化水素酸５０％溶液として）、フッ化
アンモニウム（関東化学株式会社製、純度９７．０％以
上）及び酢酸（純度９９．７％以上、沸点１１８．１
℃）を表１に示す組成割合で配合し、石英ガラス表面処
理液を得た。これに半導体工業用透明石英ガラスＨＥＲ
ＡＬＵＸ（商品名、信越石英株式会社製）を２時間浸漬
し、その時の石英ガラスの表面を観察した。その結果を
表１に示す。Examples 1-26 Hydrogen fluoride (as a 50% solution of hydrofluoric acid), ammonium fluoride (manufactured by Kanto Chemical Co., Ltd., purity 97.0% or more) and acetic acid (purity 99.7% or more, boiling point 118.1)
° C) at the composition ratio shown in Table 1 to obtain a quartz glass surface treatment liquid. This is a transparent quartz glass HER for semiconductor industry
ALUX (trade name, manufactured by Shin-Etsu Quartz Co., Ltd.) was immersed for 2 hours, and the surface of the quartz glass at that time was observed. Table 1 shows the results.
【００１８】[0018]
【表１】 [Table 1]
【００１９】比較例１〜１４ 一方、石英ガラス処理液に酢酸を配合しない処理液、及
び配合しても水の量が過剰量である処理液で上記と同様
に２時間浸漬し、その表面を調べた。その結果を表２に
示す。Comparative Examples 1 to 14 On the other hand, the surface was immersed for 2 hours in the same manner as described above in a treatment solution in which acetic acid was not added to the quartz glass treatment solution, and a treatment solution in which the amount of water was excessive even if it was added. Examined. Table 2 shows the results.
【００２０】[0020]
【表２】 [Table 2]
【００２１】上記表１、２の結果を配合比を示す正四面
体の状態図に記入し、実施例と比較例の範囲の境界をみ
ると、酢酸の量、水の量、フッ化水素とフッ化アンモニ
ウムの含有量の合計、及びフッ化水素とフッ化アンモニ
ウムのモル比で実施例を定義するのが良いことが解る。
上記実施例において実施例１７及び２０が最適な白色の
凹凸面を形成する。The results shown in Tables 1 and 2 are plotted on a tetrahedral phase diagram showing the blending ratio. The boundaries between the ranges of the Examples and Comparative Examples are shown. It can be seen that it is better to define the embodiment based on the total content of ammonium fluoride and the molar ratio between hydrogen fluoride and ammonium fluoride.
In the above embodiment, Embodiments 17 and 20 form an optimum white uneven surface.
【００２２】実施例２７ 上記実施例１７の処理をした石英ガラス治具について、
強度試験を行った。その結果は、表３のとおりである。
同強度試験は１２ｍｍ直径の丸棒で構成したウエハーボ
ートのウエハー支持部材を実験対象とした。表中の記載
の数値は部材の２点を支持して中央に荷重を印加する３
点曲げ法にて測定した曲げ破断強度である。Embodiment 27 With respect to the quartz glass jig treated in the above Embodiment 17,
A strength test was performed. Table 3 shows the results.
The strength test was performed on a wafer support member of a wafer boat composed of a round bar having a diameter of 12 mm. The numerical values in the table indicate that a load is applied to the center while supporting two points of the member.
It is a bending rupture strength measured by a point bending method.
【００２３】[0023]
【表３】 [Table 3]
【００２４】同表から明らかなように本発明の表面処理
を行った石英ガラス治具はサンドブラスト法で処理した
石英ガラス治具に比べて強度の低下が少ないことがわか
る。As is clear from the table, the quartz glass jig subjected to the surface treatment of the present invention has a smaller decrease in strength than the quartz glass jig treated by the sandblast method.
【００２５】[0025]
【発明の効果】本発明の石英ガラス表面処理液は、石英
ガラス表面に均一な、任意の大きさの凹凸を形成でき、
しかも石英ガラスにダメージを与えて強度劣化を起させ
ることがない。しかも該処理液で処理された石英ガラス
表面から洗浄により前記処理液を除去でき清浄な凹凸面
を形成できるので清浄な表面を得ることができる。The quartz glass surface treatment liquid of the present invention can form a uniform and irregular surface of any size on the quartz glass surface.
In addition, the quartz glass is not damaged and the strength is not deteriorated. Moreover, since the treatment liquid can be removed from the surface of the quartz glass treated with the treatment liquid by washing and a clean uneven surface can be formed, a clean surface can be obtained.
【図１】本発明の表面処理液の組成割合図である。FIG. 1 is a composition ratio diagram of a surface treatment liquid of the present invention.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C03C 15/00 - 23/00 H01L 21/203 H01L 21/22 H01L 21/302 H01L 21/3065 ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────続 き Continued on the front page (58) Fields surveyed (Int. Cl. 7 , DB name) C03C 15/00-23/00 H01L 21/203 H01L 21/22 H01L 21/302 H01L 21/3065 JICST file ( JOIS)
Claims (3)
を水に混合することを特徴とする石英ガラス表面処理
液。1. A quartz glass surface treatment liquid comprising a mixture of hydrogen fluoride, ammonium fluoride and acetic acid in water.
が１０重量％以上、水の含有量が５０重量％以下、フッ
化水素とフッ化アンモニウムの含有量の合計が２５重量
％以上、及びフッ化アンモニウム１モルに対してフッ化
水素の含有量が０．２モル以上１５モル以下の比率であ
り、かつフッ化水素７０部に対して水が３０部以上であ
ることを特徴とする請求項１記載の石英ガラス表面処理
液。2. The acetic acid content is 10% by weight or more, the water content is 50% by weight or less, and the total content of hydrogen fluoride and ammonium fluoride is 25% by weight or more based on the total weight of the surface treatment liquid. And the content of hydrogen fluoride is in a ratio of 0.2 mol or more and 15 mol or less with respect to 1 mol of ammonium fluoride, and water is 30 parts or more with respect to 70 parts of hydrogen fluoride. The surface treatment liquid for quartz glass according to claim 1.
ンモニウムと酢酸を水に混合した石英ガラス表面処理液
で不均一に腐食させ、その表面を粗面化することを特徴
とする石英ガラスの表面処理方法。3. A quartz glass surface characterized in that the surface of the quartz glass is unevenly corroded with a quartz glass surface treating solution obtained by mixing hydrogen fluoride, ammonium fluoride and acetic acid in water, and the surface is roughened. Surface treatment method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08357894A JP3262674B2 (en) | 1994-03-31 | 1994-03-31 | Quartz glass surface treatment liquid and method of using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP08357894A JP3262674B2 (en) | 1994-03-31 | 1994-03-31 | Quartz glass surface treatment liquid and method of using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07267679A JPH07267679A (en) | 1995-10-17 |
| JP3262674B2 true JP3262674B2 (en) | 2002-03-04 |
Family
ID=13806387
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP08357894A Expired - Fee Related JP3262674B2 (en) | 1994-03-31 | 1994-03-31 | Quartz glass surface treatment liquid and method of using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3262674B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19713014C2 (en) * | 1997-03-27 | 1999-01-21 | Heraeus Quarzglas | Quartz glass component for use in semiconductor manufacture |
| JP4539794B2 (en) * | 2000-09-28 | 2010-09-08 | 信越石英株式会社 | Silica glass jig for semiconductor industry and manufacturing method thereof |
| KR100547743B1 (en) * | 2000-09-28 | 2006-01-31 | 신에쯔 세끼에이 가부시키가이샤 | Silica Glass Jig for Semiconductor Industry and Manufacturing Method Thereof |
| JP4453995B2 (en) | 2000-12-05 | 2010-04-21 | 信越石英株式会社 | Carrier boat made of fluororesin-coated quartz glass |
| JP6191154B2 (en) * | 2013-02-19 | 2017-09-06 | 信越化学工業株式会社 | Manufacturing method of SOI substrate |
| WO2022270576A1 (en) * | 2021-06-25 | 2022-12-29 | 信越石英株式会社 | Method for manufacturing fused quartz jig and fused quartz jig |
| CN118007243B (en) * | 2024-02-04 | 2025-01-28 | 内蒙古大全半导体有限公司 | A chemical cleaning process for electronic grade polysilicon |
-
1994
- 1994-03-31 JP JP08357894A patent/JP3262674B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07267679A (en) | 1995-10-17 |
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