JP2005329322A - Method of cleaning carrying member having cleaning function - Google Patents
Method of cleaning carrying member having cleaning function Download PDFInfo
- Publication number
- JP2005329322A JP2005329322A JP2004149858A JP2004149858A JP2005329322A JP 2005329322 A JP2005329322 A JP 2005329322A JP 2004149858 A JP2004149858 A JP 2004149858A JP 2004149858 A JP2004149858 A JP 2004149858A JP 2005329322 A JP2005329322 A JP 2005329322A
- Authority
- JP
- Japan
- Prior art keywords
- cleaning
- back surface
- protective material
- cleaning function
- transport member
- 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.)
- Pending
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- 238000000034 method Methods 0.000 title claims abstract description 60
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Abstract
Description
本発明は、基板処理装置をクリーニングするために用いられるクリーニング機能付き搬送部材の清浄化方法に関するものである。
The present invention relates to a cleaning method for a conveying member with a cleaning function used for cleaning a substrate processing apparatus.
半導体、プラットパネルディスプレイ、プリント基板などの製造装置や検査装置など、異物を嫌う各種の基板処理装置では、各搬送系と基板とを物理的に接触させながら搬送する。その際、基板や搬送系に異物が付着していると、後続の基板をつぎつぎに汚染することになるため、定期的に装置を停止して洗浄処理する必要があった。このため、稼動率の低下や多大な労力が必要となるという問題があった。
In various types of substrate processing apparatuses that dislike foreign matters, such as manufacturing apparatuses and inspection apparatuses such as semiconductors, platform panel displays, and printed circuit boards, the respective transport systems and the substrate are transported in physical contact. At that time, if foreign matter adheres to the substrate or the transport system, subsequent substrates are successively contaminated, so that it is necessary to periodically stop and clean the apparatus. For this reason, there existed a problem that the fall of an operation rate and a great effort were needed.
この問題を解決するため、クリーニング部材として、搬送部材である基板上にクリーニング層である粘着性物質を固着した、いわゆるクリーニング機能付き搬送部材を作製し、これを基板処理装置内に搬送して、装置内に付着する異物をクリーニング除去する方法が提案されている（特許文献１参照）。
上記の提案方法は、装置を停止して洗浄する必要がなく、稼動率の低下や多大な労力を回避するのに有効な方法である。しかし、クリーニング部材として使用するクリーニング機能付き搬送部材の作製に際し、以下のような問題があった。
上記作製では、搬送部材を搬入してこの上にクリーニング層を設けるための適宜の製造装置（たとえば、クリーニングシートの貼り合わせ装置やクリーニング塗料の塗布装置）が用いられるが、その際、搬送部材のクリーニング層形成面（主面）とは反対側の裏面が製造装置と接触し、この接触部位から上記背面にパーティクル、メタル不純物、シリコーン不純物などが付着し、作製されるクリーニング部材が汚染される。
The above proposed method is effective in avoiding a reduction in operating rate and a great amount of labor without having to stop and clean the apparatus. However, there are the following problems in producing a transport member with a cleaning function used as a cleaning member.
In the above production, an appropriate manufacturing apparatus (for example, a cleaning sheet laminating apparatus or a cleaning paint applying apparatus) for carrying a conveying member and providing a cleaning layer thereon is used. The back surface opposite to the cleaning layer forming surface (main surface) comes into contact with the manufacturing apparatus, and particles, metal impurities, silicone impurities, and the like adhere to the back surface from this contact portion, and the manufactured cleaning member is contaminated.
このように汚染されたクリーニング部材を基板処理装置内に搬送すると、装置内で上記パーティクルやメタル不純物などが飛散したり、装置接触部にシリコーン不純物などが転写し、処理装置が汚染される。その結果、製品ウエハが二次汚染され、デバイス特性の低下による不良が多発し、製品ウエハの歩留り低下の原因となる。
したがって、クリーニング部材として使用するクリーニング機能付き搬送部材は、クリーニング層が設けられる主面とは反対側の裏面の汚染管理も重要である。
When the contaminated cleaning member is transported into the substrate processing apparatus, the particles, metal impurities, and the like are scattered in the apparatus, or silicone impurities are transferred to the apparatus contact portion, thereby contaminating the processing apparatus. As a result, the product wafer is secondarily contaminated, frequent defects due to the deterioration of device characteristics occur, and the yield of the product wafer is reduced.
Therefore, it is also important for the transport member with a cleaning function to be used as a cleaning member to manage contamination on the back surface opposite to the main surface on which the cleaning layer is provided.
本発明は、上記の事情に照らし、クリーニング機能付き搬送部材の作製におけるパーティクル、メタル不純物、シリコーン不純物などによる汚染を回避し、基板処理装置内に搬送したときにこの装置を汚染させることなく、装置内に付着している異物を簡便かつ確実に除去できるクリーニング機能付き搬送部材を得ることを目的とする。
In light of the above circumstances, the present invention avoids contamination due to particles, metal impurities, silicone impurities, etc. in the production of a conveying member with a cleaning function, and does not contaminate this apparatus when conveyed into a substrate processing apparatus. It is an object of the present invention to obtain a conveying member with a cleaning function that can easily and reliably remove foreign matter adhering to the inside.
本発明者らは、上記の目的を達成するため、鋭意検討した結果、搬送部材の主面にクリーニング層を設けるあたり、搬送部材の裏面をあらかじめ保護材で保護し、この状態でクリーニング層を設けたのち、上記裏面に対して、その保護材の一部または全部を除去して清浄化処理するか、保護材を除去しないまま清浄化処理することにより、搬送部材裏面のパーティクル、メタル不純物、シリコーン不純物などによる汚染が著しく低減されたクリーニング部材が得られることを見出し、本発明を完成するに至った。
As a result of intensive studies to achieve the above object, the present inventors have previously protected the back surface of the transport member with a protective material when providing the cleaning layer on the main surface of the transport member, and provided the cleaning layer in this state. After that, a part of or all of the protective material is removed from the back surface for cleaning, or the protective material is removed without removing the protective material to remove particles, metal impurities, silicone on the back surface of the conveying member. The present inventors have found that a cleaning member in which contamination due to impurities or the like is remarkably reduced can be obtained, and the present invention has been completed.
すなわち、本発明は、搬送部材上にクリーニング層を有するクリーニング機能付き搬送部材を得るにあたり、搬送部材の裏面をあらかじめ保護材で保護し、この状態で搬送部材の主面にクリーニング層を設け、その後、上記の裏面を清浄化処理することを特徴とするクリーニング機能付き搬送部材の清浄化方法に係るのである。
とくに、本発明は、上記裏面の清浄化処理が、保護材の一部または全部を除去する工程を含むか、あるいは保護材を残したまま、清浄化する工程からなる上記構成のクリーニング機能付き搬送部材の清浄化方法に係るものである。
That is, in the present invention, in order to obtain a transport member with a cleaning function having a cleaning layer on the transport member, the back surface of the transport member is protected in advance with a protective material, and in this state, a cleaning layer is provided on the main surface of the transport member, and then The present invention relates to a cleaning method for a conveying member with a cleaning function, characterized in that the back surface is cleaned.
In particular, the present invention provides the transport with a cleaning function having the above-described configuration, in which the cleaning process of the back surface includes a process of removing a part or all of the protective material, or a process of cleaning while leaving the protective material. The present invention relates to a member cleaning method.
また、本発明は、上記構成のクリーニング機能付き搬送部材の清浄化方法として、清浄化処理後の裏面が、清浄化の程度として、下記の（ａ）〜（ｃ）；
（ａ）０．２００μｍ以上のパーティクル数が６．３７個／cm2 以下
（ｂ）全反射蛍光エックス線分析装置で測定されるＦｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各検出量が１．０×１０11ａｔｏｍｓ／cm2 未満
（ｃ）飛行時間型２次イオン質量分析で測定されるＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）が０．１未満
のうちのいずれか少なくともひとつを満足するクリーニング機能付き搬送部材の清浄化方法を提供できるものである。
さらに、本発明は、上記方法で清浄化された上記低汚染性のクリーニング機能付き搬送部材を提供できるものである。また、本発明は、この低汚染性のクリーニング機能付き搬送部材を、基板処理装置内に搬送することを特徴とする基板処理装置のクリーニング方法を提供できるものである。
Moreover, this invention is the following (a)-(c) as a cleaning method of the conveyance member with a cleaning function of the said structure, and the back surface after a cleaning process is as a cleaning degree.
(A) The number of particles of 0.200 μm or more is 6.37 / cm 2 or less
(B) Each detected amount of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti measured by a total reflection fluorescent X-ray analyzer is less than 1.0 × 10 11 atoms / cm 2.
(C) are measured by time-of-flight secondary ion mass spectrometry CH 3 Si +, C 3 H 9 Si +, C 5 H 15 Si 2 O +, C 5 H 15 Si 3 O 3 +, C 7 H 21 The relative intensity of each fragment ion of Si 3 O 2 + , Si + , CH 3 SiO − , and CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) is less than 0.1
It is possible to provide a method for cleaning a conveying member with a cleaning function that satisfies at least one of the above.
Furthermore, the present invention can provide the low-contamination transport member with a cleaning function cleaned by the above method. Further, the present invention can provide a cleaning method for a substrate processing apparatus, characterized in that the transport member with a cleaning function with low contamination is transported into the substrate processing apparatus.
このように、本発明は、搬送部材の裏面を保護材で保護した状態で、搬送部材の主面にクリーニング層を設け、その後上記裏面を清浄化処理することにより、裏面のパーティクル、メタル不純物、シリコーン不純物などによる汚染が低減された、低汚染性のクリーニング機能付き搬送部材を提供でき、この搬送部材を基板処理装置に搬送することにより、処理装置を汚染させることなく、したがって製品ウエハの歩留り低下をきたすことなく、処理装置内に付着する異物を簡便かつ確実にクリーニング除去できる。
As described above, the present invention provides a cleaning layer on the main surface of the transport member in a state where the back surface of the transport member is protected by a protective material, and then cleans the back surface, whereby particles on the back surface, metal impurities, It is possible to provide a transfer member with a cleaning function that is less contaminated with reduced contamination due to silicone impurities and the like. By transferring this transfer member to the substrate processing apparatus, the processing apparatus is not contaminated, and thus the yield of product wafers is reduced. The foreign matter adhering to the inside of the processing apparatus can be removed easily and reliably without causing any trouble.
本発明において、クリーニング層を設ける搬送部材としては、とくに限定はなく、異物除去の対象となる基板処理装置の種類に応じて、各種の基板が用いられる。具体的には、半導体ウエハ，ＬＣＤ，ＰＤＰなどのフラットパネルディスプレイ用基板，その他、コンパクトディスク，ＭＲヘッドなどの基板などが挙げられる。
In the present invention, the transport member provided with the cleaning layer is not particularly limited, and various substrates are used according to the type of the substrate processing apparatus to be subjected to foreign matter removal. Specific examples include semiconductor wafers, substrates for flat panel displays such as LCD and PDP, and other substrates such as compact disks and MR heads.
本発明においては、このような搬送部材の裏面に、つまりクリーニング層を設ける主面とは反対側の面に、あらかじめ、保護材を設ける。保護材の厚さは、とくに限定されないが、通常は１〜１００μｍであるのがよい。この保護材としては、たとえば、テープ材（シート材）やコーティング材などが用いられる。
テープ材（シート材）としては、半導体製造工程で使用されているダイシングテープ、バックグラインドテープ、クリーニング用テープ、フィルムレジストなどが用いられる。また、コーティング材としては、ポリアミック酸、ポリイミド、フッ素樹脂、紫外線や熱などにより硬化する粘着剤、液状レジストなどが用いられる。
In the present invention, a protective material is provided in advance on the back surface of such a conveying member, that is, on the surface opposite to the main surface on which the cleaning layer is provided. Although the thickness of a protective material is not specifically limited, Usually, it is good that it is 1-100 micrometers. As this protective material, for example, a tape material (sheet material) or a coating material is used.
As the tape material (sheet material), a dicing tape, a back grind tape, a cleaning tape, a film resist or the like used in the semiconductor manufacturing process is used. As the coating material, polyamic acid, polyimide, fluororesin, an adhesive that is cured by ultraviolet rays or heat, a liquid resist, or the like is used.
このような保護材の中でも、搬送部材の主面側にクリーニング層を設けたのち、最終的に保護材を除去する場合は、テープ剥離、ウェットエッチング、ドライエッチングなどにより、容易に除去できるものであることが望ましい。また、とくに、テープ材（フィルム材）では、容易に剥離除去できるように、シリコンウエハ（ミラー面）に対する１８０度引き剥がし粘着力（ＪＩＳ Ｚ０２３７に準じて測定）が０．２Ｎ／１０mm幅以下、好ましくは０．００１〜０．１Ｎ／１０mm幅であるのがよい。
Among these protective materials, after the cleaning layer is provided on the main surface side of the conveying member, when the protective material is finally removed, it can be easily removed by tape peeling, wet etching, dry etching, etc. It is desirable to be. In particular, in the case of a tape material (film material), the 180 degree peeling adhesive force (measured according to JIS Z0237) to a silicon wafer (mirror surface) is 0.2 N / 10 mm width or less so that it can be easily peeled and removed. Preferably, the width is 0.001 to 0.1 N / 10 mm.
一方、クリーニング層の形成中に保護材表面に付着するパーティクル、メタル不純物、シリコーン不純物などの汚染物を、これ単独で除去可能であるときは、クリーニング層の形成後、保護材をあえて除去しなくてもよい。よって、この場合、上記のような容易に除去できる保護材を使用する必要はない。このように保護材を除去しない態様では、最終的に裏面保護材付きクリーニング機能付き搬送部材が得られる。
On the other hand, if contaminants such as particles, metal impurities, and silicone impurities that adhere to the surface of the protective material during the formation of the cleaning layer can be removed alone, do not remove the protective material after forming the cleaning layer. May be. Therefore, in this case, there is no need to use a protective material that can be easily removed as described above. Thus, in the aspect which does not remove a protective material, the conveyance member with a cleaning function with a back surface protective material is finally obtained.
本発明においては、このように搬送部材の裏面を保護した状態で、この搬送部材の主面にクリーニング層を設ける。この方法は、常法に準じ、たとえば、クリーニングシートの貼り合わせ装置やクリーニング塗料の塗布装置などの適宜の製造装置を使用し、この装置内に上記裏面を保護した搬送部材を搬入し、その主面にクリーニングシートの貼り合わせやクリーニング塗料の塗布を行うことにより、実施される。
In the present invention, a cleaning layer is provided on the main surface of the transport member in such a state that the back surface of the transport member is protected as described above. According to a conventional method, for example, an appropriate manufacturing apparatus such as a cleaning sheet laminating apparatus or a cleaning paint applying apparatus is used, and the conveying member with the back surface protected is carried into the apparatus, It is carried out by laminating a cleaning sheet on the surface and applying a cleaning paint.
上記のクリーニングシートとは、支持体の片面にクリーニング層を、反対面に粘着剤層を有するもので、上記粘着剤層を介して、搬送部材の主面に貼り合わされるものである。ここで、上記のクリーニング層は、支持体の片面にクリーニング塗料を塗布し所要の工程を経て、形成される。この目的で使用するクリーニング塗料や、搬送部材の主面に直接塗布するクリーニング塗料としては、本発明の目的上、シリコーン変性していないものが好ましく、また重金属を含まないものであるのが好ましい。
The cleaning sheet has a cleaning layer on one side of the support and an adhesive layer on the opposite side, and is bonded to the main surface of the transport member via the adhesive layer. Here, the cleaning layer is formed by applying a cleaning paint on one side of the support and performing a required process. For the purpose of the present invention, the cleaning paint used for this purpose and the cleaning paint directly applied to the main surface of the conveying member are preferably those not modified with silicone, and preferably do not contain heavy metals.
このようなクリーニング塗料には、（イ）ポリイミド樹脂やフッ素系樹脂などの耐熱性樹脂を用いたものが好ましい。また、（ロ）紫外線や熱などの活性エネルギー源により硬化し、分子構造が三次元網状化して粘着力が低下または消失する硬化型の粘着剤が、好ましい。このようなクリーニング塗料を用いてクリーニング層を形成すると、基板処理装置内への搬送時にクリーニング層が装置接触部と強く接着することがなく、装置内を支障なく搬送できるクリーニング機能付き搬送部材が得られる。
As such a cleaning paint, (a) a heat-resistant resin such as a polyimide resin or a fluorine resin is preferably used. Further, (b) a curable pressure-sensitive adhesive that is cured by an active energy source such as ultraviolet rays or heat and has a three-dimensional network structure and a decrease or disappearance of the adhesive strength is preferable. When the cleaning layer is formed using such a cleaning paint, the cleaning layer does not adhere strongly to the apparatus contact portion during conveyance into the substrate processing apparatus, and a conveyance member with a cleaning function that can be conveyed without trouble in the apparatus is obtained. It is done.
上記（イ）の耐熱性樹脂は、どのような分子構造を持つものでもかまわないが、基板処理装置を汚染する物質を含まないものが望ましい。代表的な耐熱性樹脂としては、たとえば、ブタジエン−アクリロニトリル共重合体骨格を主鎖中に有するポリアミック酸樹脂を加熱イミド化して得られるポリイミド樹脂が挙げられる。
上記のポリアミック酸樹脂は、テトラカルボン酸二無水物成分とジアミン成分とを、実質的に等モル比にて、適宜の有機溶剤中で反応させて得ることができる。
The heat-resistant resin (a) may have any molecular structure, but preferably does not contain a substance that contaminates the substrate processing apparatus. As a typical heat resistant resin, for example, a polyimide resin obtained by heating and imidizing a polyamic acid resin having a butadiene-acrylonitrile copolymer skeleton in the main chain can be mentioned.
The polyamic acid resin can be obtained by reacting a tetracarboxylic dianhydride component and a diamine component in an appropriate organic solvent at a substantially equimolar ratio.
上記のテトラカルボン酸二無水物成分としては、たとえば、３，３′，４，４′−ビフェニルテトラカルボン酸二無水物、２，２′，３，３′−ビフェニルテトラカルボン酸二無水物、３，３′，４，４′−ベンゾフェノンテトラカルボン酸二無水物、２，２′，３，３′−ベンゾフェノンテトラカルボン酸二無水物、４，４′−オキシジフタル酸二無水物、２，２−ビス（２，３−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物、２，２−ビス（３，４−ジカルボキシフェニル）ヘキサフルオロプロパン二無水物（６ＦＤＡ）、ビス（２，３−ジカルボキシフェニル）メタン二無水物、ビス（３，４−ジカルボキシフェニル）メタン二無水物、ビス（２，３−ジカルボキシフェニル）スルホン二無水物、ビス（３，４−ジカルボキシフェニル）スルホン二無水物、ピロメリット酸二無水物、エチレングリコールビストリメリット酸二無水物などが挙げられ、これらは、単独で用いてもよいし、２種以上を併用してもよい。
Examples of the tetracarboxylic dianhydride component include 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 4,4'-oxydiphthalic dianhydride, 2,2 -Bis (2,3-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), bis (2,3-dicarboxy Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) sulfone dianhydride, bis (3,4-dicarbo) Shifeniru) sulfone dianhydride, pyromellitic dianhydride, include ethylene glycol bis trimellitic acid dianhydride, these may be used alone or in combination of two or more.
上記のジアミン成分としては、ブタジエン−アクリロニトリル共重合体骨格を有するジアミン、たとえば、下記の式（１）または式（２）で示される脂肪族ジアミン（両式中、ｍ1 ，ｍ2 は０以上の整数、ｎは１以上の整数、Ｒは単結合または有機基である）が用いられ、これらのジアミンは単独で用いてもよいし、他のジアミンと併用してもよい。
Examples of the diamine component include diamines having a butadiene-acrylonitrile copolymer skeleton, such as aliphatic diamines represented by the following formula (1) or formula (2) (where m 1 and m 2 are 0 or more). , N is an integer of 1 or more, and R is a single bond or an organic group. These diamines may be used alone or in combination with other diamines.
＜式（１）で示される脂肪族ジアミン＞
＜式（２）で示される脂肪族ジアミン＞
上記の併用されるジアミンとしては、たとえば、４，４′−ジアミノジフェニルエーテル、３，４′−ジアミノジフェニルエーテル、３，３′−ジアミノジフェニルエーテル、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４′−ジアミノジフェニルプロパン、３，３′−ジアミノジフェニルプロパン、４，４′−ジアミノジフェニルメタン、３，３′−ジアミノジフェニルメタン、４，４′−ジアミノジフェニルスルフィド、３，３′−ジアミノジフェニルスルフィド、４，４′−ジアミノジフェニルスルホン、３，３′−ジアミノジフェニルスルホン、１，４−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）−２，２−ジメチルプロパン、ヘキサメチレンジアミン、１，８−ジアミノオクタン、１，１２−ジアミノドデカン、４，４′−ジアミノベンゾフェノン、１，３−ビス（３−アミノプロピル）−１，１，３，３−テトラメチルジシロキサンなどのジアミンが挙げられる。
Examples of the diamine used in combination include 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, m-phenylenediamine, p-phenylenediamine, 4,4'- Diaminodiphenylpropane, 3,3'-diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3-amino Phenoxy) benzene, 1,3-bis (4- Minophenoxy) -2,2-dimethylpropane, hexamethylenediamine, 1,8-diaminooctane, 1,12-diaminododecane, 4,4'-diaminobenzophenone, 1,3-bis (3-aminopropyl) -1 1,3,3-tetramethyldisiloxane and other diamines.
上記のテトラカルボン酸二無水物とジアミンとは、実質的に等モル比にて、適宜の有機溶媒中で反応させることができるが、ブタジエン−アクリロニトリル共重合体骨格を有するジアミンを用いる場合には、１００℃以上の温度で反応させることにより、ゲル化を防止することができる。すなわち、これ以下の温度で重合させた場合には、上記ジアミンの使用量によっては、ゲル分が系中に残存し、目詰まりによって、ろ過による異物の除去が困難となる場合がある。また、反応が不均一となることにより、樹脂の特性にばらつきを生じる原因となる場合がある。
また、上記のテトラカルボン酸二無水物とジアミンを反応させる適宜の溶剤としては、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ−メチル−２−ピロリドン、Ｎ，Ｎ−ジメチルホルムアミドなどが挙げられるが、原材料や樹脂の溶解性を調整するため、トルエンやキシレンなどの非極性の溶剤を適宜、混合して用いることができる。
The tetracarboxylic dianhydride and diamine can be reacted in an appropriate organic solvent at a substantially equimolar ratio, but when a diamine having a butadiene-acrylonitrile copolymer skeleton is used. The gelation can be prevented by reacting at a temperature of 100 ° C. or higher. That is, when polymerized at a temperature lower than this, depending on the amount of the diamine used, the gel content may remain in the system and clogging may make it difficult to remove foreign matter by filtration. In addition, non-uniform reaction may cause variations in resin characteristics.
Examples of suitable solvents for reacting the tetracarboxylic dianhydride with diamine include N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, and the like. In order to adjust the solubility of the resin, a nonpolar solvent such as toluene or xylene can be appropriately mixed and used.
本発明で用いられるポリイミド樹脂としては、上記の方法により得られるポリアミック酸樹脂を、不活性雰囲気下、高温で加熱処理することにより、得ることができる。溶剤の乾燥後、高温で加熱処理する温度しては、１５０℃以上がよく、樹脂の酸化劣化を防ぐため、窒素雰囲気や真空中などの不活性雰囲気下で処理することが望ましい。これにより、樹脂中に残った揮発成分を除去することができる。
The polyimide resin used in the present invention can be obtained by heat-treating the polyamic acid resin obtained by the above method at a high temperature in an inert atmosphere. After drying the solvent, the temperature for the heat treatment is preferably 150 ° C. or higher, and it is desirable to perform the treatment under an inert atmosphere such as a nitrogen atmosphere or a vacuum in order to prevent oxidative degradation of the resin. Thereby, the volatile component remaining in the resin can be removed.
また、上記（ロ）の硬化型の粘着剤としては、たとえば、感圧接着性ポリマーに、分子内に不飽和二重結合を１個以上有する化合物（以下、重合性不飽和化合物という）および重合開始剤と、必要により架橋剤などを含ませたものが挙げられる。
感圧接着性ポリマーとしては、（メタ）アクリル酸および／または（メタ）アクリル酸エステルを主モノマーとしたアクリル系ポリマーが好ましい。重合性不飽和化合物は、重量平均分子量が１０，０００以下の低分子量体が好ましく、たとえば、ポリエチレングリコールジ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ウレタン（メタ）アクリレート、エポキシ（メタ）アクリレートなどが挙げられる。重合開始剤としては、ベンゾイルパーオキサイドなどの熱重合開始剤や、ベンジルジメチルケタール、ベンゾインエチルエーテルなどの光重合開始剤などがある。
Examples of the (b) curable pressure-sensitive adhesive include, for example, a compound having at least one unsaturated double bond in the molecule (hereinafter referred to as a polymerizable unsaturated compound) and polymerization in a pressure-sensitive adhesive polymer. Examples include an initiator and, if necessary, a crosslinking agent.
As the pressure-sensitive adhesive polymer, an acrylic polymer having (meth) acrylic acid and / or (meth) acrylic acid ester as a main monomer is preferable. The polymerizable unsaturated compound is preferably a low molecular weight material having a weight average molecular weight of 10,000 or less. For example, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, epoxy (meth) ) Acrylate and the like. Examples of the polymerization initiator include thermal polymerization initiators such as benzoyl peroxide and photopolymerization initiators such as benzyldimethyl ketal and benzoin ethyl ether.
クリーニングシートにおいて、支持体としては、ポリオレフィン、塩化ビニル系樹脂、ポリエステル樹脂、アクリル樹脂、ポリスチレン、ポリカーボネートなどの各種樹脂からなる、厚さが通常１０〜１００μｍのプラスチックフィルムが用いられる。また、支持体のクリーニング層とは反対側に設ける粘着剤層には、アクリル系やゴム系などの通常の粘着剤からなるものが使用できるが、重量平均分子量が１０万以下の成分が１０重量％以下であるアクリル系ポリマーを主剤としたものがとくに好ましい。この粘着剤層の厚さは、通常１〜１００μｍ程度であるのが望ましい。
In the cleaning sheet, a plastic film having a thickness of usually 10 to 100 μm made of various resins such as polyolefin, vinyl chloride resin, polyester resin, acrylic resin, polystyrene, and polycarbonate is used as the support. The pressure-sensitive adhesive layer provided on the opposite side of the support from the cleaning layer can be made of a normal pressure-sensitive adhesive such as acrylic or rubber, but 10% by weight of the component having a weight average molecular weight of 100,000 or less. It is particularly preferable to use an acrylic polymer that is not more than% as a main ingredient. The thickness of the pressure-sensitive adhesive layer is usually preferably about 1 to 100 μm.
このように搬送部材の主面に設けるクリーニング層は、その厚さに関して、とくに限定はないが、通常は０．１〜２００μｍであり、好ましくは１〜５０μｍであるのがよい。また、シリコンウエハ（ミラー面）に対する１８０度引き剥がし粘着力（ＪＩＳ Ｚ０２３７に準じて測定）は、通常０．２Ｎ／１０mm幅以下、好ましくは０．００１〜０．１Ｎ／１０mm幅であるのがよい。粘着力が０．２Ｎ／１０mm幅を超えると、搬送時に装置内の接触部と強く接着して、搬送トラブルとなるおそれがある。
As described above, the thickness of the cleaning layer provided on the main surface of the conveying member is not particularly limited, but is usually 0.1 to 200 μm, preferably 1 to 50 μm. Further, the 180-degree peeling adhesion to the silicon wafer (mirror surface) (measured according to JIS Z0237) is usually 0.2 N / 10 mm or less, preferably 0.001 to 0.1 N / 10 mm. Good. When the adhesive strength exceeds 0.2 N / 10 mm width, it may adhere strongly to the contact portion in the apparatus during transportation, which may cause transportation trouble.
本発明においては、上記のように搬送部材の主面にクリーニング層を設けたのち、搬送部材の裏面を清浄化処理する。すなわち、クリーニングシートの貼り合わせ装置やクリーニング塗料の塗布装置などの製造装置を用いて、上記のように搬送部材の主面にクリーニング層を設ける間に、搬送部材の裏面に設けた保護材の表面には、上記製造装置との接触により、パーティクル、メタル不純物、シリコーン不純物などの汚染物が付着するため、この不純物を除去する清浄化処理を施すものである。
In the present invention, after the cleaning layer is provided on the main surface of the conveying member as described above, the back surface of the conveying member is cleaned. That is, the surface of the protective material provided on the back surface of the transport member while the cleaning layer is provided on the main surface of the transport member as described above using a manufacturing apparatus such as a cleaning sheet bonding device or a cleaning paint application device. In this case, contaminants such as particles, metal impurities, and silicone impurities adhere due to contact with the manufacturing apparatus. Therefore, a cleaning process is performed to remove the impurities.
上記の清浄化処理には、裏面に設けた保護材の一部または全部を除去する工程を含んでいてよく、この場合、上記保護材の除去工程と同時に、裏面の清浄化処理を完結させてもよいし、上記保護材の除去工程の後に、再度、裏面の清浄化処理を施してもよい。また、裏面に設けた保護材を除去することなく、搬送部材上に残したまま、保護材の表面に付着する汚染物のみを除去する清浄化処理を施してもよい。
The cleaning process may include a step of removing a part or all of the protective material provided on the back surface. In this case, the back surface cleaning process is completed simultaneously with the protective material removing step. Alternatively, after the protective material removing step, the back surface may be cleaned again. Moreover, you may perform the cleaning process which removes only the contaminant which adheres to the surface of a protective material, leaving it on a conveyance member, without removing the protective material provided in the back surface.
保護材の一部または全部を除去する方法としては、たとえば、保護材がテープ状物（シート状物）からなる場合、それ自体の剥離性を利用して剥離除去する方法があり、また、他の接着テープなどを用いて剥離除去する方法、適宜の薬剤を用いたウェットエッチングやドライエッチングなどの方法が採用される。保護材の除去と同時に、裏面の清浄化処理が達成される場合は、その後に清浄化処理を施す必要はない。
As a method of removing a part or all of the protective material, for example, when the protective material is made of a tape-like material (sheet-like material), there is a method of peeling and removing using its own peelability. A method of peeling and removing using an adhesive tape or the like, or a method such as wet etching or dry etching using an appropriate agent is employed. When the back surface cleaning process is achieved simultaneously with the removal of the protective material, it is not necessary to perform the cleaning process thereafter.
保護材の除去と同時に清浄化処理が達成されない場合、その後にさらに清浄化処理を施す必要があるが、この清浄化処理の方法は、保護材を残したまま施す場合の清浄化処理と本質的に同じである。たとえば、ウエハ両面洗浄装置を用いて、ウエハを回転させ、また洗浄水（薬剤を含む）を供給しながら、ブラシを接触させて洗浄処理する、いわゆるブラシ洗浄が挙げられる。この方法において、ウエハの回転数、洗浄水の供給圧力、ブラシの接触圧力などを調節することで、洗浄の程度を容易に調整できる。
If the cleaning process is not achieved simultaneously with the removal of the protective material, it is necessary to perform a further cleaning process after that. This cleaning process is essentially the same as the cleaning process when the protective material is left as it is. Is the same. For example, there is a so-called brush cleaning in which a wafer is rotated by using a wafer double-side cleaning apparatus and a cleaning process is performed by contacting a brush while supplying cleaning water (including a chemical). In this method, the degree of cleaning can be easily adjusted by adjusting the number of rotations of the wafer, the supply pressure of the cleaning water, the contact pressure of the brush, and the like.
本発明においては、このような清浄化処理を施すことにより、搬送部材の裏面に付着するパーティクル、メタル不純物、シリコーン不純物などの汚染物が低減された低汚染性のクリーニング機能付き搬送部材が得られる。ここで、清浄化の程度としては、下記（ａ）〜（ｃ）のうちのいずれか少なくともひとつを満足すればよい。
In the present invention, by carrying out such a cleaning process, a conveying member with a cleaning function having a low contamination property in which contaminants such as particles, metal impurities, and silicone impurities adhering to the back surface of the conveying member are reduced can be obtained. . Here, as the degree of cleaning, at least one of the following (a) to (c) may be satisfied.
まず、パーティクルに関し、（ａ）０．２００μｍ以上のパーティクル数が６．３７個／cm2 以下であり、好ましくは１．５９個／cm2 以下である。
なお、上記のパーティクル数は、パーティクルカウンター（ＫＬＡ Ｔｅｎｃｏｒ製の「ＳｕｒｆＳｃａｎ６２００」）で測定し、測定した搬送部材の面積より、単位面積あたりのパーティクル数を計算したものである。
First, regarding the particles, (a) the number of particles of 0.200 μm or more is 6.37 / cm 2 or less, preferably 1.59 / cm 2 or less.
The number of particles is measured by a particle counter (“SurfScan 6200” manufactured by KLA Tencor), and the number of particles per unit area is calculated from the measured area of the conveying member.
また、メタル不純物に関し、（ｂ）全反射蛍光エックス線分析装置で測定されるＦｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各検出量が１．０×１０11ａｔｏｍｓ／cm2 未満、好ましくは５．０×１０10ａｔｏｍｓ／cm2 以下である。
なお、これら金属の検出量は、上記分析装置（ＴＸＲＦ）としてテクノス社製の「ＴＲＥＸ６１０Ｔ」を使用し、搬送部材の裏面に付着する各金属の量を、直接または間接的に測定したものである。
In addition, regarding metal impurities, (b) each detected amount of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, Ti measured by a total reflection X-ray fluorescence spectrometer is 1.0 × 10 11 atoms. / Cm 2 or less, preferably 5.0 × 10 10 atoms / cm 2 or less.
The detected amounts of these metals are obtained by directly or indirectly measuring the amount of each metal adhering to the back surface of the conveying member using “TREX610T” manufactured by Technos as the analyzer (TXRF). .
さらに、シリコーン不純物に関し、（ｃ）飛行時間型２次イオン質量分析で測定されるＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）が０．１未満であり、好ましくは０．０９以下である。
これらの測定は、上記質量分析（ＴＯＦ−ＳＩＭＳ）として、ＵＬＶＡＣ−ＰＨＩ製の「ＴＲＩＦＴ−II」を用い、測定条件として、試料サイズ：１０mm×５mm、１次イオン：69Ｇａ+ 、加速電圧：１５ｋＶ、測定範囲：１００μｍとし、搬送部材の裏面に対して、帯電補正用電子銃を用い、上記各フラグメントイオンのイオン強度を測定し、正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比として、相対強度を求めたものである。
Further, regarding silicone impurities, (c) CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 measured by time-of-flight secondary ion mass spectrometry. Relative intensity of each fragment ion of + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − , CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) Is less than 0.1, and preferably 0.09 or less.
In these measurements, “TRIFT-II” manufactured by ULVAC-PHI is used as the above-mentioned mass spectrometry (TOF-SIMS), and measurement conditions are as follows: sample size: 10 mm × 5 mm, primary ion: 69 Ga + , acceleration voltage: 15 kV, measurement range: 100 μm, and using a charge correcting electron gun on the back surface of the transport member, the ion intensity of each of the fragment ions is measured. The positive ions are C 2 H 3 + ratio, and the negative ions are O −. As a ratio, the relative strength is obtained.
なお、上記の方法により、裏面が低汚染性のクリーニング機能付き搬送部材が得られるが、裏面の保護材を完全に除去する態様においては、この除去した裏面に、上記と同様の手法により、クリーニング層を設けることも可能であり、これにより、両面クリーニング機能付き搬送部材が得られる。この場合、主面側に設けたクリーニング層が保護材としての役割を果たし、裏面にクリーニング層を形成したのち、主面側のクリーニング層に対してこれを残したまま清浄化処理を施せばよい。
In addition, a transport member with a cleaning function having a low contamination on the back surface can be obtained by the above method. However, in a mode in which the protective material on the back surface is completely removed, the removed back surface is cleaned by the same method as described above. It is also possible to provide a layer, whereby a conveying member with a double-sided cleaning function is obtained. In this case, the cleaning layer provided on the main surface side serves as a protective material, and after forming the cleaning layer on the back surface, the cleaning process may be performed with the cleaning layer remaining on the main surface side. .
本発明においては、このようにして得られる低汚染性のクリーニング機能付き搬送部材を用い、これを基板処理装置内に搬送して、そのクリーニング層を装置の被接触部位に接触させることにより、上記部位に付着する異物を簡便かつ確実にクリーニング除去する。その際、搬送部材の裏面が低汚染性であるため、処理装置を汚染させる心配がなく、従来のように製品ウエハが二次汚染されてデバイス特性の低下による不良が多発し、製品ウエハの歩留りが低下するといった問題を引き起こすことはない。
In the present invention, the transporting member with a cleaning function with low contamination obtained in this way is used, transported into the substrate processing apparatus, and the cleaning layer is brought into contact with the contacted part of the apparatus. Foreign matter adhering to the site is easily and reliably removed by cleaning. At this time, since the back surface of the transfer member is low-contamination, there is no concern of contaminating the processing apparatus, and the product wafer is secondarily contaminated as in the conventional case, resulting in frequent failures due to deterioration of device characteristics, and the yield of product wafers. Will not cause problems such as lowering.
本発明において、クリーニングが行われる基板処理装置としては、とくに限定されず、たとえば、露光装置、レジスト塗布装置、現像装置、アッシング装置、ドライエッチング装置、イオン注入装置、ＰＶＤ装置、ＣＶＤ装置、外観検査装置、ウエハプローバなどが挙げられる。本発明においては、上記の方法によりクリーニングされた上記の各基板処理装置を提供できるものである。
以下に、本発明の実施例を記載して、より具体的に説明する。ただし、本発明は以下の実施例にのみ限定されるものではない。なお、以下において、部とあるのは重量部を意味するものとする。
In the present invention, the substrate processing apparatus to be cleaned is not particularly limited. For example, an exposure apparatus, a resist coating apparatus, a developing apparatus, an ashing apparatus, a dry etching apparatus, an ion implantation apparatus, a PVD apparatus, a CVD apparatus, and an appearance inspection. Examples thereof include an apparatus and a wafer prober. In the present invention, each substrate processing apparatus cleaned by the above method can be provided.
Examples of the present invention will be described below in more detail. However, the present invention is not limited only to the following examples. In the following, “parts” means parts by weight.
アクリル酸２−エチルヘキシル７５部、アクリル酸メチル２０部およびアクリル酸５部からなるモノマー混合物から得たアクリル系ポリマー（重量平均分子量７０万）１００部に、ポリエチレングリコール２００ジメタクリレート（新中村化学社製の商品名「ＮＫエステル４Ｇ」）２００部、ポリイソシアネート化合物（日本ポリウレタン工業社製の商品名「コロネートＬ」）３部および光重合開始剤としてベンジルジメチルケタール（チバ・スペシャリティケミカルズ社製の商品名「イルガキュアー６５1 」）３部を、均一に混合して、紫外線硬化型の粘着剤溶液を調製した。
Polyethylene glycol 200 dimethacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.) was added to 100 parts of an acrylic polymer (weight average molecular weight 700,000) obtained from a monomer mixture consisting of 75 parts of 2-ethylhexyl acrylate, 20 parts of methyl acrylate and 5 parts of acrylic acid. Product name “NK Ester 4G”) 200 parts, polyisocyanate compound (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) 3 parts, and benzyldimethyl ketal (product name manufactured by Ciba Specialty Chemicals Co., Ltd.) as a photopolymerization initiator 3 parts of “Irgacure 651”) were uniformly mixed to prepare an ultraviolet curable adhesive solution.
これとは別に、温度計、撹拌機、窒素導入管および還流冷却管を備えた内容量が５００ｍｌの３つ口フラスコ型反応器内に、アクリル酸２−エチルへキシル７３部、アクリル酸ｎ−ブチル１０部、Ｎ，Ｎ−ジメチルアクリルアミド１５部およびアクリル酸５部からなる単量体混合物、重合開始剤として２，２′−アゾビスイソブチロニトリル０．１５部、溶剤として酢酸エチル１００部を、全体が２００ｇになるように配合して投入し、窒素ガスを約１時間導入しながら撹拌し、内部の空気を窒素で置換した。その後、内部の温度を５８℃にし、この状態で約４時間保持して重合を行い、粘着剤ポリマー溶液を得た。この粘着剤ポリマー溶液１００部に、ポリイソシアネート化合物（日本ポリウレタン工業社製の商品名「コロネートＬ」）３部を、均一に混合して、粘着剤溶液を得た。
Separately, in a 500 ml three-necked flask reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube and a reflux condenser, 73 parts of 2-ethylhexyl acrylate, n-acrylic acid n- Monomer mixture consisting of 10 parts of butyl, 15 parts of N, N-dimethylacrylamide and 5 parts of acrylic acid, 0.15 part of 2,2'-azobisisobutyronitrile as a polymerization initiator, 100 parts of ethyl acetate as a solvent Were mixed and introduced so that the whole became 200 g, and stirred while introducing nitrogen gas for about 1 hour, and the air inside was replaced with nitrogen. Thereafter, the internal temperature was set to 58 ° C., and the polymerization was carried out in this state for about 4 hours to obtain an adhesive polymer solution. To 100 parts of this pressure-sensitive adhesive polymer solution, 3 parts of a polyisocyanate compound (trade name “Coronate L” manufactured by Nippon Polyurethane Industry Co., Ltd.) was uniformly mixed to obtain a pressure-sensitive adhesive solution.
片面が剥離処理されたポリプロピレンフィルムからなるセパレータ（厚さ３０μｍ、幅２５０mm）の剥離処理面に、上記の粘着剤溶液を、乾燥後の厚さが７μｍとなるように、塗布し、乾燥して、粘着剤層を形成した。この粘着剤層上に、支持体として長尺ポリエステルフィルム（厚さ２５μｍ、幅２５０mm）を積層し、さらにそのフィルム上に、上記の紫外線硬化型の粘着剤溶液を、乾燥後の厚さが１５μｍとなるように、塗布し、乾燥して、紫外線硬化型の粘着剤層を設けた。その表面に、片面が非シリコーン系剥離剤で剥離処理された長鎖ポリエステルフィルムからなる保護フィルム（厚さ２５μｍ、幅２５０mm）の剥離処理面を貼り合わせ、積層シートとした。この積層シートに、中心波長３６５ｎｍの紫外線を積算光量１，０００ｍＪ／cm2 照射して、紫外線硬化した粘着剤層からなるクリーニング層を有するクリーニングシートＡを作製した。
The above pressure-sensitive adhesive solution is applied on the release-treated surface of a separator (thickness 30 μm, width 250 mm) made of a polypropylene film with one side peel-treated so that the thickness after drying is 7 μm, and dried. A pressure-sensitive adhesive layer was formed. On this pressure-sensitive adhesive layer, a long polyester film (thickness 25 μm, width 250 mm) is laminated as a support, and the above UV-curable pressure-sensitive adhesive solution is further dried on the film to a thickness of 15 μm. Then, it was coated and dried to provide an ultraviolet curable pressure-sensitive adhesive layer. On the surface, a release-treated surface of a protective film (thickness 25 μm, width 250 mm) made of a long-chain polyester film, one side of which was peeled with a non-silicone release agent, was bonded to obtain a laminated sheet. The laminated sheet was irradiated with ultraviolet rays having a central wavelength of 365 nm and an integrated light amount of 1,000 mJ / cm 2 to prepare a cleaning sheet A having a cleaning layer composed of an ultraviolet-cured adhesive layer.
また、片面が剥離処理されたポリプロピレンフィルムからなるセパレータ（厚さ３０μｍ、幅２５０mm）の剥離処理面に、上記の紫外線硬化型の粘着剤溶液を、乾燥後の厚さが１５μｍとなるように、塗布し、乾燥して、紫外線硬化型の粘着剤層を設けた。その表面に、片面が非シリコーン系剥離剤で剥離処理された長鎖ポリエステルフィルムからなる保護フィルム（厚さ２５μｍ、幅２５０mm）の剥離処理面を貼り合わせ、積層シートとした。この積層シートに、中心波長３６５ｎｍの紫外線を積算光量１，０００ｍＪ／cm2 照射して、紫外線硬化した粘着剤層からなる保護材を有する保護シートＡを作製した。
In addition, on the release-treated surface of a separator (thickness 30 μm, width 250 mm) made of a polypropylene film on which one side is peeled, the above-mentioned UV-curable adhesive solution is dried to a thickness of 15 μm. It was applied and dried to provide an ultraviolet curable pressure-sensitive adhesive layer. On the surface, a release-treated surface of a protective film (thickness 25 μm, width 250 mm) made of a long-chain polyester film, one side of which was peeled with a non-silicone release agent, was bonded to obtain a laminated sheet. The laminated sheet was irradiated with ultraviolet light having a central wavelength of 365 nm and an integrated light quantity of 1,000 mJ / cm 2 to prepare a protective sheet A having a protective material comprising an ultraviolet-cured adhesive layer.
この保護シートＡをそのセパレータを剥がして、搬送部材である８インチシリコンウエハの裏面（ミラー面）にハンドローラーで貼り付け、裏面保護材付き搬送部材Ａを作製した。つぎに、この裏面保護材付き搬送部材Ａの主面（エッチング面）に、上記のクリーニングシートＡをその粘着剤層側のセパレータを剥がして、ハンドローラーで貼り付け、裏面保護材付きクリーニング機能付き搬送部材Ａを作製した。なお、これら一連の作業は、常用の貼り合わせ装置を使用し、これに搬入して流れ作業的に行った。
ついで、上記の裏面保護材付きクリーニング機能付き搬送部材Ａの保護材を、セパレータ剥離装置（ＮＥＬ社製の「ＨＲ３００−ＣＷ」）を用いて剥離し、この剥離により裏面が清浄化されたクリーニング機能付き搬送部材Ａを得た。
The separator was peeled off from the protective sheet A, and the sheet was attached to the back surface (mirror surface) of an 8-inch silicon wafer serving as a conveying member with a hand roller to prepare a conveying member A with a back surface protective material. Next, the cleaning sheet A is peeled off the adhesive layer side separator on the main surface (etching surface) of the transport member A with the back surface protective material, and attached with a hand roller, with a cleaning function with the back surface protective material. The conveyance member A was produced. These series of operations were carried out in a flow manner using a conventional laminating apparatus, which was carried into the apparatus.
Next, the protective material of the transport member A with the cleaning function with the back surface protective material is peeled off using a separator peeling device ("HR300-CW" manufactured by NEL), and the back surface is cleaned by this peeling function. Attached conveyance member A was obtained.
このようにして得られたクリーニング機能付き搬送部材Ａについて、裏面（ミラー面）のパーティクル数に関し、パーティクルカウンター（ＫＬＡ Ｔｅｎｃｏｒ製の「ＳｕｒｆＳｃａｎ６２００」）により、０．２００μｍ以上のパーティクルを測定した。その結果、０．４７個／cm2 のパーティクルが付着していた。
また、裏面（ミラー面）のメタル不純物に関し、全反射蛍光エックス線分析装置（ＴＸＲＦ）としてテクノス社製の「ＴＲＥＸ６１０Ｔ」を使用して、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の量を検出した。その結果、各元素とも、検出量は１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、裏面（ミラー面）のシリコーン不純物に関し、飛行時間型２次イオン質量分析（ＴＯＦ−ＳＩＭＳ）として、ＵＬＶＡＣ−ＰＨＩ製の「ＴＲＩＦＴ−II」を使用して、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）を、本文詳記の条件で測定した。その結果、検出量は、最大のＳｉ+ で８．５×１０-3であった。
With respect to the transport member A with a cleaning function thus obtained, particles of 0.200 μm or more were measured with a particle counter (“SurfScan 6200” manufactured by KLA Tencor) regarding the number of particles on the back surface (mirror surface). As a result, 0.47 particles / cm 2 particles were adhered.
Further, regarding the metal impurities on the back surface (mirror surface), using “TREX610T” manufactured by Technos as a total reflection X-ray fluorescence spectrometer (TXRF), Fe, Ni, Cr, Cu, Zn, Co, Mn, K, The amount of each element of Ca and Ti was detected. As a result, the detected amount of each element was less than 1.0 × 10 10 atoms / cm 2 .
Furthermore, with respect to silicone impurities on the back surface (mirror surface), CH 3 Si + , C 3 H is used by using “TRIFT-II” manufactured by ULVAC-PHI as time-of-flight secondary ion mass spectrometry (TOF-SIMS). 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − , CH 3 SiO 2 − fragment ions The relative intensity of the positive ions (C 2 H 3 + ratio for positive ions and O − ratio for negative ions) was measured under the conditions detailed in the text. As a result, the detected amount was 8.5 × 10 −3 at the maximum Si + .
エチレン−１，２−ビストリメリテート，テトラカルボン酸二無水物（ＴＭＥＧ）３０．０ｇを、窒素気流下、１１０ｇのＮ−メチル−２−ピロリドン（ＮＭＰ）中で、前記の式（１）で示される脂肪族ジアミン（宇部興産社製の「ＡＴＢＮ１３００×１６」、アミン当量９００、アクリロニトリル含有量１８％）６５．８ｇおよび２，２′−ビス〔４−（４−アミノフェノキシ）フェニル〕プロパン（ＢＡＰＰ）１５．０ｇと、１２０℃で混合して、反応させた。この反応後、冷却して、ポリアミック酸溶液を得た。
このポリアミック酸溶液を使用して、以下のように、搬送部材の主面（エッチング面）にクリーニング層を形成するようにした以外は、実施例１の方法に準じて、クリーニング機能付き搬送部材Ｂを得た。
30.0 g of ethylene-1,2-bistrimellitate, tetracarboxylic dianhydride (TMEG) in 110 g of N-methyl-2-pyrrolidone (NMP) under a nitrogen stream, according to the above formula (1) 65.8 g of an aliphatic diamine (“ATBN 1300 × 16” manufactured by Ube Industries, Ltd., amine equivalent 900, acrylonitrile content 18%) and 2,2′-bis [4- (4-aminophenoxy) phenyl] propane ( (BAPP) 15.0 g and mixed at 120 ° C. to react. After this reaction, the reaction mixture was cooled to obtain a polyamic acid solution.
Conveying member B with a cleaning function according to the method of Example 1 except that this polyamic acid solution was used to form a cleaning layer on the main surface (etching surface) of the conveying member as follows. Got.
すなわち、まず、実施例１と同様に作製した裏面保護材付き搬送部材Ａを、裏面（ミラー面）を下にしてスピンコーターに設置し、その主面（エッチング面）側に上記のポリアミック酸溶液を１，０００ｒｐｍの回転数で１０秒間塗布し、９０℃で２０分乾燥して、裏面保護材付きクリーニング機能付き搬送部材Ｂを作製した。
つぎに、この裏面保護材付きクリーニング機能付き搬送部材Ｂの保護材を、実施例１と同様のセパレータ剥離装置により剥離し、窒素雰囲気下、３００℃で２時間熱処理して、裏面が清浄化されたクリーニング機能付き搬送部材Ｂを得た。
That is, first, the transport member A with the back surface protective material produced in the same manner as in Example 1 was placed on the spin coater with the back surface (mirror surface) facing down, and the above polyamic acid solution was placed on the main surface (etching surface) side. Was applied for 10 seconds at a rotation speed of 1,000 rpm, and dried at 90 ° C. for 20 minutes to prepare a conveying member B having a cleaning function with a back surface protective material.
Next, the protective material of the conveying member B with the cleaning function with the back surface protective material is peeled off by the same separator peeling apparatus as in Example 1, and heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to clean the back surface. A transport member B with a cleaning function was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｂについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．３４個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、４．２×１０-2であった。
With respect to the transport member B with a cleaning function thus obtained, in the same manner as in Example 1, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured. As a result, the number of particles of 0.200 μm or more was 0.34 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 4.2 × 10 −2 at the maximum Si + .
ビロメリット酸無水物３０．０ｇと１，４−ジアミノジフェニルエーテル２７．５ｇとを、ＮＭＰ中で、実施例２に準じて反応させ、ポリアミック酸溶液を得た。
つぎに、搬送部材である８インチシリコンウエハの裏面（ミラー面）に、上記のポリアミック酸溶液を塗布し、窒素雰囲気下、３００℃以上で２時間熱処理して、裏面保護材付き搬送部材Ｃを作製した。
つぎに、この裏面保護材付き搬送部材Ｃを使用した以外は、実施例１と同様にして、裏面保護材付きクリーニング機能付き搬送部材Ｃを作製した。すなわち、上記の裏面保護材付き搬送部材Ｃの主面（エッチング面）に、実施例１と同様に作製したクリーニングシートＡをその粘着剤層側のセパレータを剥がして、ハンドローラーで貼り付け、裏面保護材付きクリーニング機能付き搬送部材Ｃを作製した。
30.0 g of pyromellitic anhydride and 27.5 g of 1,4-diaminodiphenyl ether were reacted in NMP according to Example 2 to obtain a polyamic acid solution.
Next, the polyamic acid solution is applied to the back surface (mirror surface) of an 8-inch silicon wafer that is a transport member, and heat-treated at 300 ° C. or higher for 2 hours in a nitrogen atmosphere. Produced.
Next, a conveyance member C with a cleaning function with a back surface protective material was produced in the same manner as in Example 1 except that this conveyance member C with a back surface protection material was used. That is, the cleaning sheet A produced in the same manner as in Example 1 is peeled off the adhesive layer side separator on the main surface (etching surface) of the transport member C with the back surface protective material, and the back surface is pasted with a hand roller. A conveying member C having a cleaning function with a protective material was produced.
ついで、上記の裏面保護材付きクリーニング機能付き搬送部材Ｃに対して、下記の方法により、裏面保護材をすべてエッチング除去し、これにより裏面が清浄化処理されたクリーニング機能付き搬送部材Ｃを得た。
すなわち、裏面保護材付きクリーニング機能付き搬送部材Ｃを、ウエハ両面洗浄装置（リックス社製の「ＪＳ−１０００Ｍ」）を用い、回転数１，０００ｒｐｍ、供給圧力０．５ＭＰａ、ブラシ接触圧力０．２kg／cm2 の条件で、ＮＭＰとモノエタノールアミン混合水溶液９０秒、純水洗浄３０秒を行い、乾燥６０秒として、清浄化処理した。その結果、裏面保護材がすべてエッチングされたクリーニング機能付き搬送部材Ｃが得られた。
Next, with respect to the transport member C with the cleaning function with the back surface protective material, the back surface protective material was completely etched away by the following method, thereby obtaining the transport member C with the cleaning function in which the back surface was cleaned. .
That is, using a wafer double-side cleaning device (“JS-1000M” manufactured by Rix Co., Ltd.), the conveyance member C with the cleaning function with the back surface protective material is rotated at 1,000 rpm, the supply pressure is 0.5 MPa, and the brush contact pressure is 0.2 kg. Under the condition of / cm 2 , NMP and monoethanolamine mixed aqueous solution 90 seconds, pure water washing 30 seconds were performed, and drying was performed for 60 seconds to carry out cleaning treatment. As a result, a conveying member C with a cleaning function in which the back surface protective material was entirely etched was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｃについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．０９個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、３．８×１０-3であった。
With respect to the transport member C with a cleaning function thus obtained, the back surface (mirror surface) particles, metal impurities, and silicone impurities were measured in the same manner as in Example 1. As a result, the number of particles of 0.200 μm or more was 0.09 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 3.8 × 10 −3 at the maximum Si + .
実施例３と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｃに対して、下記の方法により、裏面保護材を一部エッチング除去し、これにより裏面が清浄化処理された裏面保護材付きのクリーニング機能付き搬送部材Ｄを得た。
すなわち、裏面保護材付きクリーニング機能付き搬送部材Ｃを、実施例３と同様のウエハ両面洗浄装置を用い、回転数１，０００ｒｐｍ、供給圧力０．５ＭＰａ、ブラシ接触圧力０．２kg／cm2 の条件で、ＮＭＰとモノエタノールアミン混合水溶液３０秒、純水洗浄３０秒を行い、乾燥６０秒として、清浄化処理した。その結果、裏面保護材がわずかにエッチングされた、裏面保護材付きのクリーニング機能付き搬送部材Ｄが得られた。
For the transport member C with the cleaning function with the back surface protection material produced in the same manner as in Example 3, the back surface protection material was partially etched away by the following method, and the back surface was cleaned by this. A conveying member D with a cleaning function was obtained.
That is, the conveyance member C with the cleaning function with the back surface protective material was subjected to the same conditions as in Example 3 using a wafer double-side cleaning apparatus, with a rotation speed of 1,000 rpm, a supply pressure of 0.5 MPa, and a brush contact pressure of 0.2 kg / cm 2 . Then, NMP and monoethanolamine mixed aqueous solution for 30 seconds and pure water washing for 30 seconds were performed, and drying was performed for 60 seconds for purification treatment. As a result, a transport member D having a cleaning function with a back surface protection material, in which the back surface protection material was slightly etched, was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｄについて、その保護材が一部付いた裏面（ミラー面）を、測定用ウエハ（三益半導体製の「ファーネスモニタ」）のミラー面に外周が重なり合うように接触させ、１Ｋｇのハンドローラーで貼り付けたのち、１分間保持させた。その後、両ウエハ同士がずれないように剥離したのち、測定用ウエハのミラー面に対して、実施例１と同様にして、パーティクル、メタル不純物およびシリコーン不純物の測定を行った。
その結果、０．２００μｍ以上のパーティクル数は０．０９個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、３．８×１０-3であった。
About the conveyance member D with the cleaning function obtained in this way, the outer periphery is placed on the mirror surface of the wafer for measurement (“Furness Monitor” made by Sanmichi Semiconductor) with a part of the protective material attached. After making contact with each other and pasting with a 1 kg hand roller, it was held for 1 minute. Then, after peeling so that both wafers may not shift | deviate, it carried out similarly to Example 1, and measured the particle, the metal impurity, and the silicone impurity with respect to the mirror surface of the wafer for a measurement.
As a result, the number of particles of 0.200 μm or more was 0.09 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 3.8 × 10 −3 at the maximum Si + .
実施例３と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｃに対して、下記の方法により、裏面保護材を残したまま清浄化処理することにより、裏面保護材付きのクリーニング機能付き搬送部材Ｅを得た。
すなわち、裏面保護材付きクリーニング機能付き搬送部材Ｃを、実施例３と同様のウエハ両面洗浄装置を用い、ＮＭＰとモノエタノールアミン混合水溶液洗浄をやめて純水洗浄のみとし、回転数１，０００ｒｐｍ、供給圧力０．５ＭＰａ、ブラシ接触圧力０．２kg／cm2 の条件で、純水温度５０℃の純水洗浄９０秒を行い、乾燥６０秒として、清浄化処理した。その結果、裏面保護材が清浄化処理された、裏面保護材付きのクリーニング機能付き搬送部材Ｅが得られた。
The transport member C with the cleaning function with the back surface protective material is subjected to the cleaning process with the back surface protection material left by the following method with respect to the transport member C with the back surface protection material manufactured in the same manner as in Example 3. Member E was obtained.
That is, the conveying member C with the cleaning function with the back surface protective material is used only for cleaning with pure water by using the same wafer double-side cleaning apparatus as in Example 3 and cleaning with a mixed aqueous solution of NMP and monoethanolamine. Under the conditions of a pressure of 0.5 MPa and a brush contact pressure of 0.2 kg / cm 2 , pure water washing at a pure water temperature of 50 ° C. was performed for 90 seconds, and drying was performed for 60 seconds for cleaning treatment. As a result, a transport member E having a cleaning function with a back surface protection material, in which the back surface protection material was cleaned, was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｅについて、実施例４と同様にして、裏面接触後の測定用ウエハのミラー面のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は１．３５個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、８．６×１０-2であった。
For the transport member E with the cleaning function thus obtained, in the same manner as in Example 4, particles, metal impurities, and silicone impurities on the mirror surface of the measurement wafer after contact with the back surface were measured. As a result, the number of particles of 0.200 μm or more was 1.35 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 8.6 × 10 −2 at the maximum Si + .
実施例３と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｃに対して、セパレータ剥離装置（ＮＥＬ社製の「ＨＲ３００−ＣＷ」）を使用して、裏面保護材を剥離除去したのち、さらに下記の方法により、清浄化処理することにより、クリーニング機能付き搬送部材Ｆを得た。
すなわち、上記のように裏面保護材を剥離除去したのち、実施例３と同様のウエハ両面洗浄装置を用い、ＮＭＰとモノエタノールアミン混合水溶液洗浄をやめて純水洗浄のみとし、回転数１，０００ｒｐｍ、供給圧力０．５ＭＰａ、ブラシ接触圧力０．２kg／cm2 の条件で、純水温度５０℃の純水洗浄９０秒を行い、乾燥６０秒として、清浄化処理した。その結果、裏面保護材を持たないクリーニング機能付き搬送部材Ｆが得られた。
For the transport member C having a cleaning function with a back surface protection material produced in the same manner as in Example 3, using a separator peeling device ("HR300-CW" manufactured by NEL), the back surface protection material was peeled and removed, Furthermore, the conveyance member F with a cleaning function was obtained by carrying out the cleaning process by the following method.
That is, after peeling off and removing the back surface protective material as described above, using the same wafer double-side cleaning apparatus as in Example 3, the NMP and monoethanolamine mixed aqueous solution cleaning was stopped, and only pure water cleaning was performed. Under the conditions of a supply pressure of 0.5 MPa and a brush contact pressure of 0.2 kg / cm 2 , pure water was washed at a pure water temperature of 50 ° C. for 90 seconds and dried for 60 seconds for cleaning. As a result, a conveyance member F with a cleaning function having no back surface protective material was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｆについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．１３個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、７．４×１０-3であった。
The transport member F with the cleaning function thus obtained was measured for particles, metal impurities, and silicone impurities on the back surface (mirror surface) in the same manner as in Example 1. As a result, the number of particles of 0.200 μm or more was 0.13 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 7.4 × 10 −3 at the maximum Si + .
実施例３と同様に作製した裏面保護材付き搬送部材Ｃを使用し、この搬送部材Ｃの主面（エッチング面）に、実施例２で得たポリアミック酸溶液を用いて、１，０００ｒｐｍの回転数で１０秒間塗布し、９０℃で２０分乾燥し、窒素雰囲気下、３００℃で２時間熱処理して、裏面保護材付きクリーニング機能付き搬送部材Ｇを作製した。
ついで、上記の裏面保護材付きクリーニング機能付き搬送部材Ｃに対して、実施例３と同様にして、裏面保護材を完全にエッチング除去し、これにより裏面が清浄化されたクリーニング機能付き搬送部材Ｇを得た。
Using the conveyance member C with the back surface protective material produced in the same manner as in Example 3, using the polyamic acid solution obtained in Example 2 on the main surface (etching surface) of the conveyance member C, rotation at 1,000 rpm The film was applied for 10 seconds, dried at 90 ° C. for 20 minutes, and heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to prepare a conveying member G having a cleaning function with a back surface protective material.
Next, in the same manner as in Example 3, the back surface protective material was completely removed by etching with respect to the transport member C having a cleaning function with the back surface protective material, and the back surface was cleaned thereby, thereby transporting member G with a cleaning function. Got.
このようにして得られたクリーニング機能付き搬送部材Ｇについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．０９個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、４．４×１０-3であった。
With respect to the transport member G with a cleaning function thus obtained, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured in the same manner as in Example 1. As a result, the number of particles of 0.200 μm or more was 0.09 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 4.4 × 10 −3 at the maximum Si + .
実施例７と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｇに対して、実施例４と同様にして、裏面保護材を一部エッチング除去し、これにより裏面が清浄化処理された裏面保護材付きのクリーニング機能付き搬送部材Ｈを得た。
For the transport member G with the cleaning function with the back surface protection material manufactured in the same manner as in Example 7, the back surface protection material was partially removed by etching in the same manner as in Example 4 so that the back surface was cleaned. A conveying member H with a protective function and a cleaning function was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｈについて、実施例４と同様にして、裏面へ接触させたのちの測定用ウエハのミラー面のパーティクル、メタル不純物およびシリコーン不純物を測定した。
その結果、０．２００μｍ以上のパーティクル数は０．８０個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、８．２×１０-3であった。
The transport member H with a cleaning function thus obtained was measured in the same manner as in Example 4 for particles, metal impurities, and silicone impurities on the mirror surface of the measurement wafer after contacting the back surface.
As a result, the number of particles of 0.200 μm or more was 0.80 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 8.2 × 10 −3 at the maximum Si + .
実施例７と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｇに対して、実施例５と同様に、裏面保護材を残したまま清浄化処理することにより、裏面保護材付きのクリーニング機能付き搬送部材Ｉを得た。
A cleaning function with a back surface protection material is obtained by cleaning the transport member G with a back surface protection material manufactured in the same manner as in Example 7 while leaving the back surface protection material in the same manner as in Example 5. The attached conveying member I was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｉについて、実施例４と同様にして、裏面へ接触させたのちの測定用ウエハのミラー面のパーティクル、メタル不純物およびシリコーン不純物を測定した。
その結果、０．２００μｍ以上のパーティクル数は１．２０個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、６．７×１０-2であった。
The transport member I with a cleaning function thus obtained was measured in the same manner as in Example 4 for particles, metal impurities, and silicone impurities on the mirror surface of the measurement wafer after contacting the back surface.
As a result, the number of particles of 0.200 μm or more was 1.20 particles / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 6.7 × 10 −2 at maximum Si + .
実施例７と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｇに対して、実施例６と同様に、裏面保護材をセパレータ剥離装置にて剥離除去し、さらに清浄化処理して、クリーニング機能付き搬送部材Ｊを得た。
In the same manner as in Example 6, the back surface protective material was peeled and removed by the separator peeling device, and the cleaning member was cleaned in the same manner as in Example 6, with respect to the transport member G with the cleaning function with the back surface protection material manufactured in the same manner as in Example 7. A carrying member J with a function was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｊについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．０８個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、７．７×１０-3であった。
With respect to the transport member J with the cleaning function thus obtained, in the same manner as in Example 1, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured. As a result, the number of particles of 0.200 μm or more was 0.08 particles / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 7.7 × 10 −3 at the maximum Si + .
実施例７と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｇに対して、バッチ洗浄装置（プレテック社製）により、ＳＣ−１洗浄液に５分間浸漬して、裏面保護材を剥離し、純水洗浄を５分、湯煎洗浄を１分行い、引き上げて、自然乾燥した。これにより、裏面が清浄化処理されたクリーニング機能付き搬送部材Ｋを得た。
For the transport member G with the cleaning function with the back surface protective material produced in the same manner as in Example 7, it was immersed in the SC-1 cleaning solution for 5 minutes by a batch cleaning device (manufactured by Pretec), and the back surface protective material was peeled off. Washing with pure water was performed for 5 minutes, washing with hot water bath was performed for 1 minute, and it was pulled up and dried naturally. Thereby, the conveyance member K with the cleaning function in which the back surface was cleaned was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｋについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は１．５０個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、９．２×１０-3であった。
For the transport member K with a cleaning function thus obtained, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured in the same manner as in Example 1. As a result, the number of particles of 0.200 μm or more was 1.50 particles / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 9.2 × 10 −3 at the maximum Si + .
実施例３と同様に作製した裏面保護材付きクリーニング機能付き搬送部材Ｃに対して、下記の方法により、裏面保護材を完全にエッチング除去し、これにより裏面が清浄化されたクリーニング機能付き搬送部材Ｌを得た。
すなわち、上記の裏面保護材付きクリーニング機能付き搬送部材Ｃを、実施例３と同様のウエハ両面洗浄装置により、２．３８重量％に希釈した東洋合成工業社製の「ＴＭＡＨ−１０」（水酸化テトラメチルアンモニウム）を用い、回転数１，０００ｒｐｍ、供給圧力０．５ＭＰａ、ブラシ接触圧力０．２kg／cm2 の条件で、裏面保護材を完全にエッチングし、純水洗浄９０秒を行ったのち、乾燥６０秒を行い、清浄化処理した。これにより裏面が清浄化されたクリーニング機能付き搬送部材Ｌが得られた。
With respect to the transport member C with the cleaning function with the back surface protection material manufactured in the same manner as in Example 3, the back surface protection material was completely etched away by the following method, and the transport surface with the cleaning function was thereby cleaned. L was obtained.
That is, “TMAH-10” (hydroxylized) manufactured by Toyo Gosei Kogyo Co., Ltd. was prepared by diluting the transport member C with a cleaning function with a back surface protective material to 2.38% by weight using the same wafer double-side cleaning apparatus as in Example 3. Tetramethylammonium) was used, and the back surface protective material was completely etched under the conditions of a rotation speed of 1,000 rpm, a supply pressure of 0.5 MPa, and a brush contact pressure of 0.2 kg / cm 2. Then, drying was performed for 60 seconds to perform a cleaning process. Thereby, the conveyance member L with the cleaning function in which the back surface was cleaned was obtained.
このようにして得られたクリーニング機能付き搬送部材Ｌについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．１３個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、９．５×１０-3であった。
For the transport member L with a cleaning function thus obtained, particles, metal impurities and silicone impurities on the back surface (mirror surface) were measured in the same manner as in Example 1. As a result, the number of particles of 0.200 μm or more was 0.13 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 9.5 × 10 −3 at the maximum Si + .
実施例３と同様に作製した裏面保護材付き搬送部材Ｃの主面（エッチング面）側に、実施例２と同様にして、スピンコーターにより実施例２で得たポリアミック酸溶液を塗布し乾燥して、裏面保護材付きクリーニング機能付き搬送部材Ｍを作製した。
つぎに、上記の裏面保護材付きクリーニング機能付き搬送部材Ｍに対して、実施例１２と同様に、裏面保護材を完全にエッチング除去し、これにより裏面が清浄化されたクリーニング機能付き搬送部材Ｍを得た。
In the same manner as in Example 2, the polyamic acid solution obtained in Example 2 was applied to the main surface (etching surface) side of the conveyance member C with the back surface protective material prepared in the same manner as in Example 3 and dried. Thus, a conveying member M having a cleaning function with a back surface protective material was produced.
Next, in the same manner as in Example 12, the back surface protective material was completely etched away from the transport member M with the cleaning function with the back surface protective material, and the back surface was cleaned thereby, so that the back surface was cleaned. Got.
このようにして得られたクリーニング機能付き搬送部材Ｍについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．０９個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、８．２×１０-3であった。
With respect to the transport member M with a cleaning function thus obtained, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured in the same manner as in Example 1. As a result, the number of particles of 0.200 μm or more was 0.09 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 8.2 × 10 −3 at the maximum Si + .
搬送部材である８インチシリコンウエハの裏面（ミラー面）に、液状レジスト（ＪＳＲ社製の「ＭＥＳ ＥＰ３０Ｇ」）を、スピンコーターにより１，０００ｒｐｍの回転数で３０秒間塗布し、１３０℃で９０秒乾燥したのち、露光機（日立製作所製の「ＨＬ７００Ｄ」）にて、Ｖａｃｃ＝５０ｋｅＶ、Ｃｕｒｅｎｔ Ｄｅｎｓｉｔｙ＝５Ａ／cm2 で全面露光し、裏面保護材付き搬送部材Ｎを作製した。
A liquid resist (“MES EP30G” manufactured by JSR) is applied to the back surface (mirror surface) of an 8-inch silicon wafer, which is a transfer member, by a spin coater at a rotation speed of 1,000 rpm for 30 seconds, and at 130 ° C. for 90 seconds. After drying, the entire surface was exposed with an exposure machine (“HL700D” manufactured by Hitachi, Ltd.) at Vacc = 50 keV and Current Density = 5 A / cm 2 to prepare a transport member N with a back surface protective material.
つぎに、この裏面保護材付き搬送部材Ｎの主面（エッチング面）側に、実施例２と同様にして、スピンコーターにより実施例２で得たポリアミック酸溶液を塗布し乾燥して、裏面保護材付きクリーニング機能付き搬送部材Ｎを作製した。
ついで、上記の裏面保護材付きクリーニング機能付き搬送部材Ｎに対して、実施例１２と同様に、裏面保護材を完全にエッチング除去し、これにより裏面が清浄化されたクリーニング機能付き搬送部材Ｎを得た。
Next, on the main surface (etching surface) side of the transport member N with the back surface protective material, the polyamic acid solution obtained in Example 2 was applied by a spin coater and dried in the same manner as in Example 2 to protect the back surface. The conveyance member N with a cleaning function with a material was produced.
Next, as in Example 12, the back surface protective material was completely removed by etching with respect to the transport member N with the cleaning function with the back surface protective material, and thus the transport member N with the cleaning function was cleaned. Obtained.
このようにして得られたクリーニング機能付き搬送部材Ｎについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．０９個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、８．２×１０-3であった。
For the transport member N with a cleaning function thus obtained, in the same manner as in Example 1, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured. As a result, the number of particles of 0.200 μm or more was 0.09 / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 8.2 × 10 −3 at the maximum Si + .
実施例１４と同様に作製した裏面保護材付き搬送部材Ｎを使用し、実施例１と同様にして、裏面保護材付きクリーニング機能付き搬送部材Ｏを作製した。すなわち、上記の裏面保護材付き搬送部材Ｎの主面（エッチング面）に、実施例１と同様に作製したクリーニングシートＡをその粘着剤層側のセパレータを剥がして、ハンドローラーで貼り付け、裏面保護材付きクリーニング機能付き搬送部材Ｏを作製した。
ついで、上記の裏面保護材付きクリーニング機能付き搬送部材Ｏに対して、実施例１２と同様に、裏面保護材を完全にエッチング除去し、これにより裏面が清浄化されたクリーニング機能付き搬送部材Ｏを得た。
Using the transport member N with the back surface protective material prepared in the same manner as in Example 14, the transport member O with the cleaning function with the back surface protective material was manufactured in the same manner as in Example 1. That is, the cleaning sheet A produced in the same manner as in Example 1 is peeled off the pressure-sensitive adhesive layer separator on the main surface (etching surface) of the transport member N with the back surface protective material, and the back surface is pasted with a hand roller. A transport member O having a cleaning function with a protective material was produced.
Next, the back surface protective material is completely removed by etching with respect to the transport member O with the cleaning function with the back surface protective material, as in Example 12, and the transport member O with the cleaning function whose back surface is thereby cleaned is obtained. Obtained.
このようにして得られたクリーニング機能付き搬送部材Ｏについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は０．０８個／cm2 であった。また、Ｆｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各元素の検出量は、いずれも、１．０×１０10ａｔｏｍｓ／cm2 未満であった。
さらに、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、４．２×１０-3であった。
With respect to the transport member O with the cleaning function thus obtained, in the same manner as in Example 1, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured. As a result, the number of particles of 0.200 μm or more was 0.08 particles / cm 2 . In addition, the detected amount of each element of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti was less than 1.0 × 10 10 atoms / cm 2 .
Further, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , CH 3 SiO − The relative intensity of each fragment ion of CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) was 4.2 × 10 −3 at the maximum Si + .
比較例１
搬送部材である８インチシリコンウエハの裏面（ミラー面）に保護材を全く設けずに、主面（エッチング面）に対して、実施例１と同様に作製したクリーニングシートＡをその粘着剤層側のセパレータを剥がして、ハンドローラーで貼り付け、クリーニング機能付き搬送部材Ｐを得た。なお、これら一連の作業は、常用の貼り合わせ装置を使用し、これに搬入して流れ作業的に行った。
Comparative Example 1
Without providing any protective material on the back surface (mirror surface) of the 8-inch silicon wafer as the conveying member, the cleaning sheet A produced in the same manner as in Example 1 is applied to the main surface (etching surface) on the adhesive layer side. The separator was peeled off and pasted with a hand roller to obtain a conveying member P with a cleaning function. These series of operations were carried out in a flow manner using a conventional laminating apparatus, which was carried into the apparatus.
このようにして得られたクリーニング機能付き搬送部材Ｐについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は１０．２個／cm2 であった。
また、メタル不純物については、Ｆｅ、Ｎｉ、Ｃｒ、Ｚｎ、Ｔｉは、下記のとおり、ＣｕはＮＤ（検出限界値０．１６×１０10ａｔｏｍｓ／cm2 未満）、ＣｏはＮＤ（検出限界値０．２３×１０10ａｔｏｍｓ／cm2 未満）、ＭｎはＮＤ（検出限界値０．３８×１０10ａｔｏｍｓ／cm2 未満）、ＫはＮＤ（検出限界値２．４０×１０10ａｔｏｍｓ／cm2 未満）、ＣａはＮＤ（検出限界値１．７０×１０10ａｔｏｍｓ／cm2 未満）であった。
Ｆｅ： １．２×１０11ａｔｏｍｓ／cm2
Ｎｉ： ７．４×１０11ａｔｏｍｓ／cm2
Ｃｒ： ３．２×１０11ａｔｏｍｓ／cm2
Ｚｎ： １．３×１０10ａｔｏｍｓ／cm2
Ｔｉ： ８．４×１０10ａｔｏｍｓ／cm2
さらに、シリコーン不純物について、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、０．３７であった。
For the transport member P with a cleaning function thus obtained, in the same manner as in Example 1, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured. As a result, the number of particles of 0.200 μm or more was 10.2 particles / cm 2 .
As for metal impurities, Fe, Ni, Cr, Zn, and Ti are as follows: Cu is ND (detection limit value less than 0.16 × 10 10 atoms / cm 2 ), Co is ND (detection limit value 0 .23 × 10 10 atoms / cm 2 ), Mn is ND (detection limit value is less than 0.38 × 10 10 atoms / cm 2 ), K is ND (detection limit value is less than 2.40 × 10 10 atoms / cm 2) ), Ca was ND (detection limit value less than 1.70 × 10 10 atoms / cm 2 ).
Fe: 1.2 × 10 11 atoms / cm 2
Ni: 7.4 × 10 11 atoms / cm 2
Cr: 3.2 × 10 11 atoms / cm 2
Zn: 1.3 × 10 10 atoms / cm 2
Ti: 8.4 × 10 10 atoms / cm 2
Further, regarding silicone impurities, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , The relative intensity of each fragment ion of CH 3 SiO − and CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) is 0.37, which is the maximum Si + .
比較例２
搬送部材である８インチシリコンウエハの裏面（ミラー面）に保護材を全く設けずに、主面（エッチング面）に対し、実施例２と同様にして、クリーニング層を形成した。すなわち、上記シリコンウエハを裏面（ミラー面）を下にしてスピンコーターに設置し、その主面（エッチング面）に実施例２で得たポリアミック酸溶液を１，０００ｒｐｍの回転数で１０秒間塗布し、９０℃で２０分乾燥し、窒素雰囲気下３００℃で２時間熱処理して、クリーニング機能付き搬送部材Ｑを得た。
Comparative Example 2
A cleaning layer was formed on the main surface (etching surface) in the same manner as in Example 2 without providing any protective material on the back surface (mirror surface) of the 8-inch silicon wafer serving as the transfer member. That is, the silicon wafer was placed on a spin coater with the back surface (mirror surface) facing down, and the polyamic acid solution obtained in Example 2 was applied to the main surface (etching surface) at 1,000 rpm for 10 seconds. , Dried at 90 ° C. for 20 minutes, and heat-treated at 300 ° C. for 2 hours in a nitrogen atmosphere to obtain a transport member Q with a cleaning function.
このようにして得られたクリーニング機能付き搬送部材Ｑについて、実施例１と同様にして、裏面（ミラー面）のパーティクル、メタル不純物およびシリコーン不純物を測定した。その結果、０．２００μｍ以上のパーティクル数は８．２個／cm2 であった。
また、メタル不純物については、Ｆｅ、Ｎｉ、Ｃｒ、Ｔｉは、下記のとおり、Ｃｕ、Ｃｏ、Ｍｎ、Ｋ、ＣａはＮＤであり、また、ＺｎもＮＤ（検出限界値０．１３×１０10ａｔｏｍｓ／cm2 未満）であった。
Ｆｅ： ２．３×１０11ａｔｏｍｓ／cm2
Ｎｉ： １．４×１０11ａｔｏｍｓ／cm2
Ｃｒ： ８．６×１０10ａｔｏｍｓ／cm2
Ｔｉ： ９．２×１０10ａｔｏｍｓ／cm2
さらに、シリコーン不純物について、ＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）は、最大のＳｉ+ で、０．２４であった。
For the transport member Q with the cleaning function thus obtained, in the same manner as in Example 1, particles on the back surface (mirror surface), metal impurities, and silicone impurities were measured. As a result, the number of particles of 0.200 μm or more was 8.2 particles / cm 2 .
As for metal impurities, Fe, Ni, Cr, and Ti are ND as follows, and Cu, Co, Mn, K, and Ca are ND, and Zn is also ND (detection limit value 0.13 × 10 10 atoms). / Cm 2 ).
Fe: 2.3 × 10 11 atoms / cm 2
Ni: 1.4 × 10 11 atoms / cm 2
Cr: 8.6 × 10 10 atoms / cm 2
Ti: 9.2 × 10 10 atoms / cm 2
Further, regarding silicone impurities, CH 3 Si + , C 3 H 9 Si + , C 5 H 15 Si 2 O + , C 5 H 15 Si 3 O 3 + , C 7 H 21 Si 3 O 2 + , Si + , The relative intensity of each fragment ion of CH 3 SiO − and CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) is 0.24, which is the maximum Si + .
つぎに、実施例１〜１５および比較例１，２の各クリーニング機能付き搬送部材について、下記の方法で、ドライエッチング処理装置の異物除去試験を行った。
すなわち、クリーニング機能付き搬送部材を、異物が付着しているドライエッチング処理装置内に搬送し、装置内の異物をクリーニング除去した。この操作を５回繰り返した。新品の８インチシリコンウエハを用い、レーザー表面検査装置によりクリーニング前後の０．２００μｍ以上の異物の数を測定し、異物除去率を算出した。
Next, the foreign substance removal test of the dry etching processing apparatus was done with the following method about each conveyance member with a cleaning function of Examples 1-15 and Comparative Examples 1 and 2.
That is, the transport member with a cleaning function was transported into a dry etching processing apparatus to which foreign matter had adhered, and the foreign matter in the apparatus was removed by cleaning. This operation was repeated 5 times. Using a new 8-inch silicon wafer, the number of foreign matters of 0.200 μm or more before and after cleaning was measured by a laser surface inspection apparatus, and the foreign matter removal rate was calculated.
その結果は、実施例１〜１５の各クリーニング機能付き搬送部材では、いずれも、９０％以上の異物除去率が得られていた。これに対して、比較例１，２の両クリーニング機能付き搬送部材では、異物除去率が約７０％程度と低かった。
また、実施例１〜１５の各クリーニング機能付き搬送部材は、裏面が低汚染性のため、これらを上記ドライエッチング処理装置内に搬送したときに、処理装置を汚染させる心配はほとんどなかった。これに対し、比較例１，２の両クリーニング機能付き搬送部材は、裏面の汚染度合いが高いため、これらを上記のドライエッチング処理装置内に搬送したときに、処理装置を著しく汚染させ、製品ウエハが二次汚染されて、デバイス特性の低下による不良が多発し、製品ウエハの歩留りが低下した。
As a result, in each of the conveyance members with a cleaning function in Examples 1 to 15, a foreign matter removal rate of 90% or more was obtained. In contrast, in the conveyance members with both cleaning functions of Comparative Examples 1 and 2, the foreign matter removal rate was as low as about 70%.
Moreover, since the back surface of each conveyance member with a cleaning function of Examples 1-15 was low-contamination, there was almost no worry which contaminates a processing apparatus when these were conveyed in the said dry etching processing apparatus. On the other hand, since the conveyance members with both cleaning functions of Comparative Examples 1 and 2 have a high degree of contamination on the back surface, when these are conveyed into the dry etching processing apparatus, the processing apparatus is significantly contaminated, and the product wafer As a result of secondary contamination, defects due to degradation of device characteristics frequently occurred, and the yield of product wafers decreased.
Claims (6)
In obtaining a transport member with a cleaning function having a cleaning layer on the transport member, the back surface of the transport member is protected in advance with a protective material, and in this state, a cleaning layer is provided on the main surface of the transport member, and then the above back surface is cleaned. The cleaning method of the conveyance member with a cleaning function characterized by carrying out the conversion process.
The method for cleaning a transport member with a cleaning function according to claim 1, wherein the back surface cleaning process includes a step of removing a part or all of the protective material.
The method for cleaning a transport member with a cleaning function according to claim 1, wherein the cleaning process of the back surface includes a process of cleaning while leaving the protective material.
（ａ）０．２００μｍ以上のパーティクル数が６．３７個／cm2 以下
（ｂ）全反射蛍光エックス線分析装置で測定されるＦｅ，Ｎｉ，Ｃｒ，Ｃｕ，Ｚｎ，Ｃｏ ，Ｍｎ，Ｋ，Ｃａ，Ｔｉの各検出量が１．０×１０11ａｔｏｍｓ／cm2 未満
（ｃ）飛行時間型２次イオン質量分析で測定されるＣＨ3 Ｓｉ+ 、Ｃ3 Ｈ9 Ｓｉ+ 、Ｃ5 Ｈ15Ｓｉ2 Ｏ+ 、Ｃ5 Ｈ15Ｓｉ3 Ｏ3 + 、Ｃ7 Ｈ21Ｓｉ3 Ｏ2 + 、Ｓｉ+ 、ＣＨ3 ＳｉＯ- 、ＣＨ3 ＳｉＯ2 - の各フラグメントイオンの相対強度（正イオンはＣ2 Ｈ3 + 比、負イオンはＯ- 比）が０．１未満
のうちのいずれか少なくともひとつを満足する請求項１〜３のいずれかに記載のクリーニング機能付き搬送部材の清浄化方法。
The back surface after the cleaning treatment is as the degree of cleaning described below (a) to (c);
(A) The number of particles of 0.200 μm or more is 6.37 / cm 2 or less
(B) Each detected amount of Fe, Ni, Cr, Cu, Zn, Co, Mn, K, Ca, and Ti measured by a total reflection fluorescent X-ray analyzer is less than 1.0 × 10 11 atoms / cm 2.
(C) are measured by time-of-flight secondary ion mass spectrometry CH 3 Si +, C 3 H 9 Si +, C 5 H 15 Si 2 O +, C 5 H 15 Si 3 O 3 +, C 7 H 21 The relative intensity of each fragment ion of Si 3 O 2 + , Si + , CH 3 SiO − , and CH 3 SiO 2 − (positive ion is C 2 H 3 + ratio, negative ion is O − ratio) is less than 0.1
The method for cleaning a transport member with a cleaning function according to claim 1, wherein at least one of the conditions is satisfied.
A conveying member with a cleaning function cleaned by the method according to claim 4.
6. A method for cleaning a substrate processing apparatus, comprising transporting the transport member with a cleaning function according to claim 5 into the substrate processing apparatus.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004149858A JP2005329322A (en) | 2004-05-20 | 2004-05-20 | Method of cleaning carrying member having cleaning function |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004149858A JP2005329322A (en) | 2004-05-20 | 2004-05-20 | Method of cleaning carrying member having cleaning function |
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| JP2005329322A true JP2005329322A (en) | 2005-12-02 |
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