WO2016088590A1 - 変色層として金属酸化物微粒子を使用したプラズマ処理検知インジケータ - Google Patents
変色層として金属酸化物微粒子を使用したプラズマ処理検知インジケータ Download PDFInfo
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- WO2016088590A1 WO2016088590A1 PCT/JP2015/082818 JP2015082818W WO2016088590A1 WO 2016088590 A1 WO2016088590 A1 WO 2016088590A1 JP 2015082818 W JP2015082818 W JP 2015082818W WO 2016088590 A1 WO2016088590 A1 WO 2016088590A1
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- fine particles
- oxide fine
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Images
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- H01L21/02263—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase
- H01L21/02271—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition
- H01L21/02274—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process deposition from the gas or vapour phase deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition in the presence of a plasma [PECVD]
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
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- H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
- H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
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- substantially the same means that the length of the main surface of the electronic device substrate (diameter if the main surface shape of the substrate is circular, if the main surface shape of the substrate is square, rectangular, etc.
- the difference in length of the main surface of the indicator of the present invention with respect to the vertical and horizontal lengths) is within ⁇ 5.0 mm, and the difference in thickness of the indicator of the present invention with respect to the electronic device substrate is within ⁇ 1000 ⁇ m. .
- the metal particles and the reactive gas are combined to promote the chemical reaction.
- the particles whose chemical reaction is promoted are accelerated toward the workpiece to which negative electrons are added, collide with high energy, and are deposited on the surface as a metal compound. Note that a vapor deposition method similar to ion plating is also exemplified as the film forming step.
- the circular plate electrodes face each other in parallel, the reaction gas is introduced into the reduced pressure reaction chamber (chamber), and the introduced gas is neutralized or ionized by plasma excitation. Then, the effects of both etching and physical sputtering that are generated between the electrodes and converted into volatile substances by chemical reaction between these radicals and ions and the material on the semiconductor wafer are utilized.
- the plasma etching apparatus include a barrel type (cylindrical type) in addition to the parallel plate type.
- a gas containing impurity atoms to be doped is introduced into the decompression chamber to excite the plasma by ionizing the impurities, and a negative bias voltage is applied to the semiconductor wafer to dope the impurity ions.
- FIG. 3 is a schematic cross-sectional view of a capacitively coupled plasma (capacitively coupled plasma) type plasma etching apparatus.
- Test Example 2 the discoloration of the discoloration layer of each indicator was evaluated in the case where the indicator prepared in Samples 1 to 7 was placed in this apparatus, and argon gas (Ar) was introduced as a reactive gas and plasma treatment was performed. .
- Ar argon gas
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Abstract
Description
1. プラズマ処理により変色する変色層を有するプラズマ処理検知インジケータであって、
前記変色層は、Mo、W、Sn、V、Ce、Te及びBiからなる群から選択される少なくとも一種の元素を含む平均粒子径が50μm以下の金属酸化物微粒子を含有するプラズマ処理検知インジケータ。
2. 前記金属酸化物微粒子は、酸化モリブデン微粒子(IV)、酸化モリブデン微粒子(VI)、酸化タングステン微粒子(VI)、酸化スズ微粒子(IV)、酸化バナジウム微粒子(II)、酸化バナジウム微粒子(III)、酸化バナジウム微粒子(IV)、酸化バナジウム微粒子(V)、酸化セリウム微粒子(IV)、酸化テルル微粒子(IV)、酸化ビスマス微粒子(III)、炭酸酸化ビスマス微粒子(III)及び酸化硫酸バナジウム微粒子(IV)からなる群から選択される少なくとも一種である、上記項1に記載のプラズマ処理検知インジケータ。
3. 前記金属酸化物微粒子は、酸化モリブデン微粒子(VI)、酸化タングステン微粒子(VI)、酸化バナジウム微粒子(III)、酸化バナジウム微粒子(V)及び酸化ビスマス微粒子(III)からなる群から選択される少なくとも一種である、上記項1又は2に記載のプラズマ処理検知インジケータ。
4. 前記変色層を支持する基材を有する、上記項1~3のいずれかに記載のプラズマ処理検知インジケータ。
5. 電子デバイス製造装置で使用するインジケータである、上記項1~4のいずれかに記載のプラズマ処理検知インジケータ。
6. 前記インジケータの形状が、前記電子デバイス製造装置で使用される電子デバイス基板の形状と同一である、上記項5に記載のプラズマ処理検知インジケータ。
7. 前記電子デバイス製造装置は、成膜工程、エッチング工程、アッシング工程、不純物添加工程及び洗浄工程からなる群から選択される少なくとも一種のプラズマ処理を行う、上記項5又は6のいずれかに記載のプラズマ処理検知インジケータ。
8. プラズマ処理により変色しない非変色層を有する、上記項1~7のいずれかに記載のプラズマ処理検知インジケータ。
9. 前記非変色層は、酸化チタン(IV)、酸化ジルコニウム(IV)、酸化イットリウム(III)、硫酸バリウム、酸化マグネシウム、二酸化ケイ素、アルミナ、アルミニウム、銀、イットリウム、ジルコニウム、チタン、白金からなる群から選択される少なくとも一種を含有する、上記項8に記載のプラズマ処理検知インジケータ。
10. 前記基材上に、前記非変色層及び前記変色層が順に形成されており、前記非変色層が、前記基材の主面上に隣接して形成されており、前記変色層が、前記非変色層の主面上に隣接して形成されている、上記項8又は9に記載のプラズマ処理検知インジケータ。
本発明のインジケータは、プラズマ処理により変色する変色層を有し、前記変色層は、Mo、W、Sn、V、Ce、Te及びBiからなる群から選択される少なくとも一種の元素を含む平均粒子径が50μm以下の金属酸化物微粒子を含有する。特に本発明では、プラズマ処理により金属酸化物微粒子の価数が変化することで化学的に変色が生じる。かかる金属酸化物微粒子は、有機成分とは異なり、プラズマ処理によりガス化したり微細な屑となって飛散したりすることが、電子デバイス特性に影響を及ぼさない程度に抑制されている上、電子デバイス製造時のプロセス温度に耐え得る耐熱性を有する。
本発明のインジケータは、上記変色層を支持する基材を有していてもよい。
本発明のインジケータは、変色層の視認性を高めるために下地層としてプラズマ処理により変色しない非変色層を設けてもよい。非変色層としては、耐熱性があり、且つガス化しないことも求められる。かかる非変色層としては、白色層、メタル層等が好ましい。
本発明のインジケータは、必要に応じて、裏面(インジケータをプラズマ処理装置内の底面に配置した際に当該底面と接触する面)に粘着層を有していてもよい。インジケータの裏面に粘着層を有することにより、本発明のインジケータをプラズマ処理装置内の所望部位(例えばプラズマ処理に供する対象物、装置底面等)に確実に固定することができるため好ましい。
本発明のインジケータの形状は特に限定されず、公知のプラズマ処理検知インジケータに採用されている形状を幅広く用いることができる。この中でも本発明のインジケータの形状を電子デバイス製造装置で使用される電子デバイス基板の形状と同一とする場合には、いわゆるダミー基板として、簡便にプラズマ処理が電子デバイス基板全体に対して均一に行われているかどうかを検知することが可能となる。
プラズマとしては、特に限定されず、プラズマ発生用ガスによって発生するプラズマを使用することができる。プラズマの中でも、酸素、窒素、水素、塩素、アルゴン、シラン、アンモニア、臭化硫黄、三塩化ホウ素、臭化水素、水蒸気、亜酸化窒素、テトラエトキシシラン、三フッ化窒素、四フッ化炭素、パーフルオロシクロブタン、ジフルオロメタン、トリフルオロメタン、四塩化炭素、四塩化ケイ素、六フッ化硫黄、六フッ化エタン、四塩化チタン、ジクロロシラン、トリメチルガリウム、トリメチルインジウム、及びトリメチルアルミニウムからなる群から選ばれた少なくとも一種のプラズマ発生用ガスによって発生するプラズマが好ましい。これらのプラズマ発生用ガスの中でも、特に四フッ化炭素;パーフルオロシクロブタン;トリフルオロメタン;六フッ化硫黄;アルゴンと酸素との混合ガス;からなる群から選択される少なくとも一種が好ましい。
・試料1:Bi2O3微粒子(平均粒子径0.05μm)
・試料2:Bi2O3微粒子(平均粒子径0.20μm)
・試料3:Bi2O3微粒子(平均粒子径3.20μm)
・試料4:Bi2O3微粒子(平均粒子径7.80μm)
・試料5:Bi2O3微粒子(平均粒子径12.7μm)
・試料6:Bi2O3微粒子(平均粒子径21.2μm)
・試料7:Bi2O3微粒子(平均粒子径51.8μm;比較例)
下記表1に示す組成のスラリーを用意し、それをポリイミドフィルム上に塗布することによりポリイミドフィルムに厚さ20μmのBi2O3微粒子の塗膜を印刷した。これにより、ポリイミドフィルム上に薄膜の変色層を積層したインジケータを作製した。
図1は、誘導結合プラズマ(ICP;Inductively Coupled Plasma)型のプラズマエッチング装置の概略断面図である。
図3は、容量結合プラズマ(平行平板型;Capacitively Coupled Plasma)型のプラズマエッチング装置の概略断面図である。
Claims (10)
- プラズマ処理により変色する変色層を有するプラズマ処理検知インジケータであって、前記変色層は、Mo、W、Sn、V、Ce、Te及びBiからなる群から選択される少なくとも一種の元素を含む平均粒子径が50μm以下の金属酸化物微粒子を含有するプラズマ処理検知インジケータ。
- 前記金属酸化物微粒子は、酸化モリブデン微粒子(IV)、酸化モリブデン微粒子(VI)、酸化タングステン微粒子(VI)、酸化スズ微粒子(IV)、酸化バナジウム微粒子(II)、酸化バナジウム微粒子(III)、酸化バナジウム微粒子(IV)、酸化バナジウム微粒子(V)、酸化セリウム微粒子(IV)、酸化テルル微粒子(IV)、酸化ビスマス微粒子(III)、炭酸酸化ビスマス微粒子(III)及び酸化硫酸バナジウム微粒子(IV)からなる群から選択される少なくとも一種である、請求項1に記載のプラズマ処理検知インジケータ。
- 前記金属酸化物微粒子は、酸化モリブデン微粒子(VI)、酸化タングステン微粒子(VI)、酸化バナジウム微粒子(III)、酸化バナジウム微粒子(V)及び酸化ビスマス微粒子(III)からなる群から選択される少なくとも一種である、請求項1又は2に記載のプラズマ処理検知インジケータ。
- 前記変色層を支持する基材を有する、請求項1~3のいずれかに記載のプラズマ処理検知インジケータ。
- 電子デバイス製造装置で使用するインジケータである、請求項1~4のいずれかに記載のプラズマ処理検知インジケータ。
- 前記インジケータの形状が、前記電子デバイス製造装置で使用される電子デバイス基板の形状と同一である、請求項5に記載のプラズマ処理検知インジケータ。
- 前記電子デバイス製造装置は、成膜工程、エッチング工程、アッシング工程、不純物添加工程及び洗浄工程からなる群から選択される少なくとも一種のプラズマ処理を行う、請求項5又は6のいずれかに記載のプラズマ処理検知インジケータ。
- プラズマ処理により変色しない非変色層を有する、請求項1~7のいずれかに記載のプラズマ処理検知インジケータ。
- 前記非変色層は、酸化チタン(IV)、酸化ジルコニウム(IV)、酸化イットリウム(III)、硫酸バリウム、酸化マグネシウム、二酸化ケイ素、アルミナ、アルミニウム、銀、イットリウム、ジルコニウム、チタン、白金からなる群から選択される少なくとも一種を含有する、請求項8に記載のプラズマ処理検知インジケータ。
- 前記基材上に、前記非変色層及び前記変色層が順に形成されており、前記非変色層が、前記基材の主面上に隣接して形成されており、前記変色層が、前記非変色層の主面上に隣接して形成されている、請求項8又は9に記載のプラズマ処理検知インジケータ。
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TWI624890B (zh) | 2013-08-22 | 2018-05-21 | Sakura Color Prod Corp | Indicator for electronic component manufacturing apparatus, and design and/or management method of the same |
KR102342177B1 (ko) | 2014-02-14 | 2021-12-21 | 사쿠라 컬러 프로덕츠 코포레이션 | 플라즈마 처리 감지 표시기 |
JP2015205995A (ja) | 2014-04-21 | 2015-11-19 | 株式会社サクラクレパス | プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケータ |
JP6474390B2 (ja) | 2014-05-09 | 2019-02-27 | 株式会社サクラクレパス | 変色層として無機物質を使用したプラズマ処理検知インジケータ |
JP6567863B2 (ja) | 2014-09-16 | 2019-08-28 | 株式会社サクラクレパス | プラズマ処理検知用インキ組成物及びプラズマ処理検知インジケータ |
JP6567817B2 (ja) | 2014-12-02 | 2019-08-28 | 株式会社サクラクレパス | プラズマ処理検知インキ組成物及びそれを用いたプラズマ処理検知インジケータ |
JP6889471B2 (ja) * | 2017-04-24 | 2021-06-18 | 株式会社サクラクレパス | プラズマインジケータ |
JP6842699B2 (ja) * | 2017-05-22 | 2021-03-17 | 株式会社サクラクレパス | プラズマ処理検知用組成物及びそれを用いたプラズマ処理検知インジケータ |
CN109839388A (zh) * | 2017-11-29 | 2019-06-04 | 中微半导体设备(上海)股份有限公司 | 等离子运行状态实时监控方法、晶圆监测件和监控*** |
JP7043066B2 (ja) * | 2018-05-15 | 2022-03-29 | 株式会社サクラクレパス | プラズマインジケータ |
KR102181778B1 (ko) * | 2019-08-29 | 2020-11-24 | 가부시키가이샤 이아스 | 금속 미립자의 분석방법 및 유도 결합 플라즈마 질량 분석방법 |
US11398388B2 (en) * | 2020-09-08 | 2022-07-26 | Applied Materials, Inc. | Methods for selective dry etching gallium oxide |
CN112986250B (zh) * | 2021-02-03 | 2022-03-04 | 大连理工大学 | 一种评价醇盐法氧化铝是否满足生长无色蓝宝石的方法 |
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- 2015-11-24 WO PCT/JP2015/082818 patent/WO2016088590A1/ja active Application Filing
- 2015-11-24 CN CN201580063223.5A patent/CN107078053B/zh not_active Expired - Fee Related
- 2015-11-24 KR KR1020177013404A patent/KR20170091092A/ko not_active Application Discontinuation
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JP2005142287A (ja) * | 2003-11-05 | 2005-06-02 | Sakura Color Prod Corp | 通電変色性電気回路板 |
JP2012078202A (ja) * | 2010-10-01 | 2012-04-19 | Sakura Color Products Corp | 過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーター |
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CN107078053A (zh) | 2017-08-18 |
KR20170091092A (ko) | 2017-08-08 |
TW201633401A (zh) | 2016-09-16 |
CN107078053B (zh) | 2021-02-26 |
US20170330777A1 (en) | 2017-11-16 |
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