JP4452127B2 - Semiconductor wafer surface protecting adhesive film and semiconductor wafer protecting method using the adhesive film - Google Patents
Semiconductor wafer surface protecting adhesive film and semiconductor wafer protecting method using the adhesive film Download PDFInfo
- Publication number
- JP4452127B2 JP4452127B2 JP2004163052A JP2004163052A JP4452127B2 JP 4452127 B2 JP4452127 B2 JP 4452127B2 JP 2004163052 A JP2004163052 A JP 2004163052A JP 2004163052 A JP2004163052 A JP 2004163052A JP 4452127 B2 JP4452127 B2 JP 4452127B2
- Authority
- JP
- Japan
- Prior art keywords
- semiconductor wafer
- film
- protecting
- adhesive film
- pressure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000004065 semiconductor Substances 0.000 title claims description 147
- 238000000034 method Methods 0.000 title claims description 88
- 239000002313 adhesive film Substances 0.000 title claims description 68
- 239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 83
- 239000010410 layer Substances 0.000 claims description 66
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- 229920005989 resin Polymers 0.000 claims description 32
- 239000011347 resin Substances 0.000 claims description 32
- 238000012545 processing Methods 0.000 claims description 12
- 229920000728 polyester Polymers 0.000 claims description 10
- 238000003860 storage Methods 0.000 claims description 10
- 239000002390 adhesive tape Substances 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 6
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 238000007654 immersion Methods 0.000 claims description 2
- 235000012431 wafers Nutrition 0.000 description 176
- 238000000227 grinding Methods 0.000 description 29
- 230000008569 process Effects 0.000 description 26
- 230000001070 adhesive effect Effects 0.000 description 23
- 239000000853 adhesive Substances 0.000 description 21
- 239000003431 cross linking reagent Substances 0.000 description 21
- -1 polyethylene terephthalate Polymers 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 19
- 238000004519 manufacturing process Methods 0.000 description 18
- 239000012790 adhesive layer Substances 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 15
- 239000000178 monomer Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 10
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- 230000000052 comparative effect Effects 0.000 description 8
- 238000003851 corona treatment Methods 0.000 description 8
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- 238000005259 measurement Methods 0.000 description 8
- 230000001681 protective effect Effects 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 7
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 6
- 238000003486 chemical etching Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
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- 239000005020 polyethylene terephthalate Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
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- 239000004593 Epoxy Substances 0.000 description 2
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- 239000002998 adhesive polymer Substances 0.000 description 2
- 125000005250 alkyl acrylate group Chemical group 0.000 description 2
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
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Description
本発明は、半導体ウェハ表面保護用粘着フィルム、及び該半導体ウェハ表面保護用粘着フィルムを用いる半導体ウェハの裏面加工方法に関する。詳しくは、シリコン、ガリウム−砒素等の半導体ウェハの集積回路が形成された側の面に粘着フィルムを貼着して該ウエハの他の面を加工する際に用いる半導体ウェハ表面保護用粘着フィルム、及び該半導体ウェハ表面保護用粘着フィルムを用いる半導体ウエハの裏面加工方法に関する。更に詳しくは、薄層化した半導体チップの製造工程、特に、粘着フィルム剥離工程において、半導体ウェハの破損防止、生産性向上のために好適である半導体ウェハ表面保護用粘着フィルム及びそれを用いる半導体ウェハの裏面加工方法に関する。 The present invention relates to an adhesive film for protecting a semiconductor wafer surface, and a method for processing a back surface of a semiconductor wafer using the adhesive film for protecting a semiconductor wafer surface. Specifically, a pressure-sensitive adhesive film for protecting a semiconductor wafer surface used for processing the other surface of the wafer by sticking a pressure-sensitive adhesive film to the surface on which the integrated circuit of the semiconductor wafer such as silicon or gallium-arsenide is formed, The present invention also relates to a semiconductor wafer back surface processing method using the semiconductor wafer surface protecting adhesive film. More specifically, in the manufacturing process of a thinned semiconductor chip, in particular, in the adhesive film peeling process, a semiconductor wafer surface protecting adhesive film suitable for preventing damage to the semiconductor wafer and improving productivity, and a semiconductor wafer using the same It is related with the back surface processing method.
半導体ウェハを加工する工程は、半導体ウェハの回路形成面に半導体ウェハ表面保護用粘着フィルムを貼着する工程、半導体ウェハの回路非形成面を加工する工程、半導体ウェハ表面保護用粘着フィルムを剥離する工程、半導体ウェハを分割切断するダイシング工程、分割された半導体チップをリードフレームへ接合するダイボンディング工程を経た後、半導体チップを外部保護の為に樹脂で封止するモールド工程、等により構成されている。
特に、厚みが１５０μｍ以下に薄層化された半導体チップを製造する工程において、ウェハの裏面加工は、従来行なわれている研削工程において２００〜１５０μｍ程度まで薄層化し、次いで、研磨加工、エッチング加工等により更に薄層化する場合がある。薄層化されたウェハは、剛性が低下しており、半導体ウェハ表面保護用粘着フィルムを剥離する際に、割れ、クラック等が発生する等、重大な支障が発生することがある。
The process of processing a semiconductor wafer includes the steps of attaching a semiconductor wafer surface protective adhesive film to the circuit forming surface of the semiconductor wafer, processing the circuit non-forming surface of the semiconductor wafer, and peeling the semiconductor wafer surface protective adhesive film. After the process, the dicing process for dividing and cutting the semiconductor wafer, the die bonding process for bonding the divided semiconductor chip to the lead frame, and the molding process for sealing the semiconductor chip with resin for external protection, etc. Yes.
In particular, in the process of manufacturing a semiconductor chip having a thickness of 150 μm or less, the back surface processing of the wafer is thinned to about 200 to 150 μm in a conventional grinding process, and then polishing and etching processes are performed. In some cases, the thickness may be further reduced. The thinned wafer has a reduced rigidity, and when the semiconductor wafer surface protecting adhesive film is peeled off, a serious trouble such as a crack or a crack may occur.
従来、半導体ウェハ表面保護用粘着フィルムを剥離する工程では、２５〜５０ｍｍ幅の剥離用テープをプレスローラを用いて、半導体ウェハの表面に貼付けられた半導体ウェハ表面保護用粘着フィルム上に貼付け、この剥離用テープを引っ張ることにより、半導体ウェハ表面から表面保護用粘着フィルムを剥離する方法が採られている。 Conventionally, in the process of peeling the adhesive film for protecting the semiconductor wafer surface, a 25 to 50 mm wide peeling tape is stuck on the adhesive film for protecting the semiconductor wafer surface stuck on the surface of the semiconductor wafer using a press roller. A method of peeling the surface protecting adhesive film from the surface of the semiconductor wafer by pulling the peeling tape is employed.
例えば、特開平１１−１６８６２号公報には、半導体ウェハ等の板状部材に貼付されたシートを接着テープを用いて剥離するシート剥離装置において、前記接着テープを前記シートの端部に接着し、前記テープを引っ張って前記シートを剥離するシートの剥離装置、及び剥離方法が開示されている。この剥離装置には、ポリエチレンテレフタレート等の耐熱性フィルムに感熱性接着剤層を設けた感熱性接着テープ、又は基材自体に感熱性接着性を有する感熱性接着テープが使用されることが記載されている。上記剥離方法は、板状部材に接着されたシートの端部に接着テープを接着することにより、板状部材の全面を押圧することを回避することに特徴がある。そのため、例えば、板状部材が半導体ウェハ等である場合、その破損を防止できるとしている。 For example, in JP-A-11-16862, in a sheet peeling apparatus that peels off a sheet affixed to a plate-shaped member such as a semiconductor wafer using an adhesive tape, the adhesive tape is bonded to an end of the sheet, A sheet peeling apparatus and a peeling method for peeling the sheet by pulling the tape are disclosed. In this peeling apparatus, it is described that a heat-sensitive adhesive tape in which a heat-sensitive adhesive layer is provided on a heat-resistant film such as polyethylene terephthalate, or a heat-sensitive adhesive tape having a heat-sensitive adhesive property on the substrate itself is used. ing. The peeling method is characterized by avoiding pressing the entire surface of the plate-like member by adhering an adhesive tape to the end portion of the sheet bonded to the plate-like member. Therefore, for example, when the plate-like member is a semiconductor wafer or the like, the damage can be prevented.
しかし、近年益々半導体チップの薄層化の要求が高まっており、厚みが３０〜１５０μｍ程度のチップも望まれている。このように薄層化された半導体ウェハの場合、半導体ウェハ表面保護用粘着フィルムの剥離の際、半導体ウェハに割れが発生することがある。また半導体ウェハに割れが生じることなく剥離できた場合であっても、剥離速度が従来手法の剥離に比べ遅くする必要があり、半導体製造工程の製造効率が低下するという重大な欠点がある。従って、このように薄層化された半導体ウェハであっても破損することなく、且つ従来手法の剥離時間と同程度の時間で、半導体ウェハ表面保護用粘着フィルムを剥離できる半導体ウェハの保護方法が望まれている。
本発明の目的は、上記問題に鑑み、半導体ウェハが厚み１５０μｍ以下程度に薄層化された場合であっても、半導体ウェハが破損することなく、且つ従来手法の剥離時間と同程度の時間で、半導体ウェハから剥離できる半導体ウェハ表面保護用粘着フィルム、及び該粘着フィルムを用いる半導体ウェハの保護方法を提供することにある。 In view of the above problems, the object of the present invention is to prevent the semiconductor wafer from being damaged even when the semiconductor wafer is thinned to a thickness of about 150 μm or less, and in a time comparable to the peeling time of the conventional method. Another object of the present invention is to provide a semiconductor wafer surface protecting adhesive film that can be peeled off from a semiconductor wafer, and a semiconductor wafer protecting method using the adhesive film.
本発明者らは鋭意検討した結果、半導体ウェハ表面保護用粘着フィルムの基材フィルムに着目し、基材フィルムの少なくとも一層に５０℃でのＭＤ方向及び、ＴＤ方向の収縮率がそれぞれ５％未満であり、且つ７０〜１００℃の温水及び雰囲気下に１秒以上加熱した時のＭＤ方向、若しくはＴＤ方向の少なくとも一方の収縮率が５〜９９％であり、厚みが１０〜２００μｍである樹脂層（Ａ）を用いることにより、上記課題が解決できることを見出し本発明に到った。 As a result of intensive studies, the inventors focused on the base film of the adhesive film for protecting a semiconductor wafer surface, and the shrinkage in the MD direction and the TD direction at 50 ° C. is less than 5%, respectively, on at least one layer of the base film. And a resin layer having a shrinkage ratio of at least one of MD and TD of 5 to 99% and a thickness of 10 to 200 μm when heated at 70 to 100 ° C. for 1 second or more in an atmosphere. It has been found that the above-mentioned problems can be solved by using (A), and the present invention has been reached.
すなわち、本発明は、基材フィルムの片表面に粘着剤層が形成された半導体ウェハ表面保護用粘着フィルムであって、基材フィルムの少なくとも一層に５０℃でのＭＤ方向及び、ＴＤ方向の収縮率がそれぞれ５％未満であり、且つ７０〜１００℃の温水若しくは雰囲気下に１秒以上加熱した時のＭＤ方向、若しくはＴＤ方向の少なくとも一方の収縮率が５〜９９％であり、厚みが１０〜２００μｍである樹脂層（Ａ）を用いることを特徴とする半導体ウエハ表面保護用粘着フィルムに関する。
前記樹脂層（Ａ）が、ポリエステル系延伸フィルムであることは好ましい態様である。
That is, the present invention is an adhesive film for protecting a semiconductor wafer surface in which an adhesive layer is formed on one surface of a substrate film, and shrinks in the MD direction and TD direction at 50 ° C. on at least one layer of the substrate film. Each rate is less than 5%, and at least one shrinkage in the MD direction or TD direction is 5 to 99% when heated at 70 to 100 ° C. in warm water or atmosphere for 1 second or more, and the thickness is 10 It is related with the adhesive film for semiconductor wafer surface protection characterized by using the resin layer (A) which is -200 micrometers.
It is a preferred embodiment that the resin layer (A) is a polyester stretched film.
また、本発明の他の発明は、半導体ウェハの回路形成面に前記の半導体ウェハ表面保護用粘着フィルムを貼着する第一工程、半導体ウェハの回路非形成面を加工する第二工程を順次実施し、７０〜１００℃の温水に浸漬若しくは、該温水を接射、或いは同温度の雰囲気で加熱し、該半導体ウエハ表面から該半導体ウエハ表面保護用粘着テープを剥離する第三工程を実施することを特徴とする半導体ウエハ表面保護方法である。
本発明に係わる半導体ウエハ表面保護用粘着フィルムを用いることにより、半導体ウェハの裏面研削加工において、ウェハ厚みが１５０μｍ以下になるまで薄層化された場合であっても、７０〜１００℃の温水に浸漬若しくは、該温水を接射、或いは同温度の雰囲気で加熱し、該半導体ウエハ表面から該半導体ウエハ表面保護用粘着テープを容易に剥離することができ、ウェハの破損を防止できる。
In another aspect of the present invention, the first step of attaching the above-mentioned adhesive film for protecting the surface of a semiconductor wafer to the circuit forming surface of the semiconductor wafer and the second step of processing the non-circuit forming surface of the semiconductor wafer are sequentially performed. And performing a third step of detaching the adhesive tape for protecting the semiconductor wafer surface from the surface of the semiconductor wafer by immersing it in warm water of 70 to 100 ° C., spraying the hot water or heating it in an atmosphere of the same temperature. A method for protecting a surface of a semiconductor wafer.
By using the adhesive film for protecting the surface of a semiconductor wafer according to the present invention, even in the case where the wafer thickness is reduced to 150 μm or less in the back grinding process of the semiconductor wafer, The adhesive tape for protecting the surface of the semiconductor wafer can be easily peeled off from the surface of the semiconductor wafer by dipping or by spraying the hot water or heating in an atmosphere of the same temperature, and damage of the wafer can be prevented.
本発明の粘着フィルムは、半導体ウェハが厚み１５０μｍ以下程度に薄層化された場合であっても、半導体ウェハが破損することなく、且つ従来手法の剥離時間と同程度の時間で、半導体ウェハから剥離できるので、該粘着フィルムを用いる半導体ウェハの保護方法は、産業上極めて有用な方法である。 The pressure-sensitive adhesive film of the present invention does not break the semiconductor wafer even when the semiconductor wafer is thinned to a thickness of about 150 μm or less, and can be removed from the semiconductor wafer in the same time as the conventional peeling time. Since it can peel, the protection method of the semiconductor wafer using this adhesive film is a very useful method industrially.
以下、本発明について詳細に説明する。
先ず、本発明に係わる半導体ウェハ表面保護用粘着フィルムについて説明する。本発明に係わる半導体ウェハ表面保護用粘着フィルムは、基材フィルムの片表面に粘着剤層を形成することにより製造される。通常、粘着剤層を保護するために、粘着剤層の表面に剥離フィルムが貼着される。剥離フィルムを剥離したときに露出する粘着剤層の表面を介して半導体ウェハ表面に貼着することを考慮し、粘着剤層による半導体ウェハ表面の汚染防止を図るためには、剥離フィルムの片面に、粘着剤塗布液を塗布、乾燥して粘着剤層を形成した後、得られた粘着剤層を基材フィルムの片面に転写する方法が好ましい。
Hereinafter, the present invention will be described in detail.
First, the adhesive film for protecting the surface of a semiconductor wafer according to the present invention will be described. The adhesive film for protecting a semiconductor wafer surface according to the present invention is produced by forming an adhesive layer on one surface of a base film. Usually, in order to protect an adhesive layer, a peeling film is stuck on the surface of an adhesive layer. In consideration of sticking to the surface of the semiconductor wafer through the surface of the adhesive layer exposed when the release film is peeled off, in order to prevent contamination of the semiconductor wafer surface by the adhesive layer, on one side of the release film A method is preferred in which a pressure-sensitive adhesive coating solution is applied and dried to form a pressure-sensitive adhesive layer, and then the resulting pressure-sensitive adhesive layer is transferred to one side of a substrate film.
本発明に係わる粘着フィルムに用いる基材フィルムの特徴は、基材フィルムの少なくとも一層が、５０℃でのＭＤ方向及び、ＴＤ方向の収縮率がそれぞれ５％未満、且つ７０〜１００℃の温水に浸漬、若しくは雰囲気下において、１秒以上好ましくは１０秒以上加熱した時のＭＤ方向、若しくはＴＤ方向の少なくとも一方の収縮率が５〜９９％、好ましくは１０〜９９％であり、厚みが１０〜２００μｍ、好ましくは２０〜１５０μｍである樹脂層（Ａ）を有することにある。基材フィルム全体の厚みは５０〜３５０μｍが好ましく、更に好ましくは５０〜３００μｍである。
更に、基材フィルムの少なくとも１層の２３〜６０℃における貯蔵弾性率が少なくとも１×１０７Ｐａ以上であることが好ましい。更に好ましくは、少なくとも１×１０８Ｐa以上である。
The characteristic of the base film used for the adhesive film according to the present invention is that at least one layer of the base film has a shrinkage rate of less than 5% in MD direction and TD direction at 50 ° C., respectively, and warm water of 70 to 100 ° C. In the immersion or atmosphere, the shrinkage of at least one of the MD direction or the TD direction when heated for 1 second or more, preferably 10 seconds or more is 5 to 99%, preferably 10 to 99%, and the thickness is 10 to 10%. There exists in having a resin layer (A) which is 200 micrometers, Preferably it is 20-150 micrometers. The thickness of the entire base film is preferably 50 to 350 μm, more preferably 50 to 300 μm.
Furthermore, it is preferable that the storage elastic modulus in 23-60 degreeC of at least 1 layer of a base film is at least 1 * 10 < 7 > Pa or more. More preferably, it is at least 1 × 10 8 Pa or more.
基材フィルムの少なくとも１層の２３〜６０℃における貯蔵弾性率が１×１０６Ｐａ未満である場合は、半導体ウェハの回路非形成面を加工する第二工程おいて、加工時に発生する熱により、粘着フィルムが破壊され、半導体ウェハに破損が生じることがある。
樹脂層（Ａ）を形成する樹脂として、ポリエステル系延伸フィルムが好ましく使用できる。ポリエステル系延伸フィルムの代表的市販品としては、東洋紡績（株）製、商品名：スペースクリーン、三菱樹脂（株）製、商品名：ヒシペットが挙げられる。
本発明に用いるポリエステル系延伸フィルムは、一般に食品包装、ラベル、結束等として用いられ、機械的、光学的、熱的性質、気体透過性、耐薬品性、安全衛生性で優れた性能を持っている。ポリエステル系延伸フィルムの代表的なものは、ポリエチレンテレフタレートフィルムがあり、ポリエチレンテレフタレートはテレフタル酸とエチレングリコールの縮合物である。テレフタル酸はキシレンから得られるｐ−キシレンを分離精製し、酸化して得られる。他にフタル酸、トルエンなどからも得られる。エチレングリコールはエチレンを銀触媒等を用いて直接酸化してエチレンオキサイドを作り、加水分解して得られる。エチレン、塩素、水よりエチレンクロルヒドリンを経て製造する方法も行われている。ポリエチレンテレフタレートの製造法としては、エステル交換法が用いられ、ジメチルテレフタレートとエチレングリコールとの交換反応により製造される。また、テレフタル酸の一部を他のジカルボン酸に置き換え、ポリメチレングリコールや多価アルコールを組合わせたポリエステルも製造されている。成形法はＴダイ法、インフレーション法、カレンダー法等が用いられているが、厚み偏差、加工速度等の利点より、Ｔダイ法が多く用いられている。Ｔダイ法は大きく２軸延伸法と、１軸延伸法の２種類に分類されるが、本願はそのどちらでも構わない。
When the storage elastic modulus at 23 to 60 ° C. of at least one layer of the base film is less than 1 × 10 6 Pa, in the second step of processing the circuit non-formed surface of the semiconductor wafer, heat generated during processing The adhesive film is destroyed, and the semiconductor wafer may be damaged.
A polyester stretched film can be preferably used as the resin for forming the resin layer (A). Representative commercial products of the polyester stretched film include Toyobo Co., Ltd., trade name: Space Clean, Mitsubishi Plastics Co., Ltd., trade name: HISHIPET.
The polyester stretched film used in the present invention is generally used for food packaging, labels, binding, etc., and has excellent performance in mechanical, optical, thermal properties, gas permeability, chemical resistance, safety and hygiene. Yes. A typical polyester stretched film is a polyethylene terephthalate film, which is a condensate of terephthalic acid and ethylene glycol. Terephthalic acid is obtained by separating and purifying p-xylene obtained from xylene and oxidizing it. It can also be obtained from phthalic acid, toluene, etc. Ethylene glycol is obtained by directly oxidizing ethylene using a silver catalyst or the like to produce ethylene oxide and hydrolyzing it. A method for producing ethylene, chlorine, and water via ethylene chlorohydrin is also performed. As a method for producing polyethylene terephthalate, an ester exchange method is used, which is produced by an exchange reaction between dimethyl terephthalate and ethylene glycol. In addition, polyesters in which a part of terephthalic acid is replaced with other dicarboxylic acids and polymethylene glycol or polyhydric alcohol is combined are also produced. As the forming method, a T-die method, an inflation method, a calendar method, or the like is used, but the T-die method is often used because of advantages such as thickness deviation and processing speed. The T-die method is roughly classified into two types, that is, a biaxial stretching method and a uniaxial stretching method.
本発明の半導体ウエハ表面保護用粘着フィルムに用いる基材フィルムは、上記特性を有する樹脂層（Ａ）に、裏面加工時の振動吸収、半導体ウエハ表面の段差吸収等を目的として低弾性率樹脂層を積層することが好ましい。低弾性率樹脂層を形成する樹脂について例示すると、エチレン−酢酸ビニル共重合体、エチレン−アルキルアクリレート共重合体（アルキル基の炭素数１〜４）、アクリルゴム等が挙げられる。これらの内、エチレン−酢酸ビニル共重合体を用いることが好ましい。更に好ましくは、酢酸ビニル単位の含有量が５〜５０重量％程度のエチレン−酢酸ビニル共重合体である。 The base film used in the adhesive film for protecting a semiconductor wafer surface of the present invention is a low elastic modulus resin layer for the purpose of absorbing vibration during back surface processing, absorbing the level difference of the semiconductor wafer surface, etc. in the resin layer (A) having the above characteristics. Are preferably laminated. Examples of the resin forming the low elastic modulus resin layer include ethylene-vinyl acetate copolymer, ethylene-alkyl acrylate copolymer (alkyl group having 1 to 4 carbon atoms), acrylic rubber and the like. Among these, it is preferable to use an ethylene-vinyl acetate copolymer. More preferably, it is an ethylene-vinyl acetate copolymer having a vinyl acetate unit content of about 5 to 50% by weight.
低弾性率樹脂層の厚みは３０〜２５０μｍであることが好ましい。より好ましくは３０〜１５０μｍである。厚みが３０μｍ未満であるとウエハ表面の段差を充分に吸収できない場合がある。また、２５０μｍを超えるとウエハの裏面加工後の半導体ウエハの厚みが大きくばらつき、半導体ウエハの品質に悪影響を及ぼす場合がある。 The thickness of the low elastic modulus resin layer is preferably 30 to 250 μm. More preferably, it is 30-150 micrometers. If the thickness is less than 30 μm, the step on the wafer surface may not be sufficiently absorbed. On the other hand, if the thickness exceeds 250 μm, the thickness of the semiconductor wafer after the backside processing of the wafer varies greatly, which may adversely affect the quality of the semiconductor wafer.
基材フィルムの代表的な製造方法として、Ｔダイ押出法、インフレーション法、カレンダー法等が挙げられる。上記特性を有する樹脂層（Ａ）を少なくとも１層含む多層フィルムを製造する方法としては、例えば、低弾性率樹脂を押出機で押出成形しながら、予め用意しておいた上記フィルムとラミネートする方法や、予め溶液又はエマルション液とした低弾性率樹脂を、ロールコーター、コンマコーター、ダイコーター、メイヤーバーコーター、リバースロールコーター、グラビアコーター等の公知の方法に従って塗布、乾燥して、予め用意しておいたフィルム上に低弾性率樹脂層を形成する方法が用いられる。この場合、低弾性率樹脂層を直接フィルム上に塗布、乾燥してもよいし、表面にシリコーン処理等の離型処理を施した工程フィルム上に塗布、乾燥した後、ドライラミネート法等の慣用の方法を用いて、低弾性率樹脂層を基材フィルムに転写させる方法等が挙げられる。これら多層フィルムの層間における接着力を高めるために、両層の間に新たに接着層を設けてもよいし、コロナ放電処理または化学処理等を施しても良い。粘着剤層を設ける面にはコロナ放電処理または化学処理等を施すことが好ましい。 As a typical method for producing a base film, a T-die extrusion method, an inflation method, a calendar method, and the like can be given. As a method for producing a multilayer film including at least one resin layer (A) having the above characteristics, for example, a method of laminating with a previously prepared film while extruding a low elastic modulus resin with an extruder Alternatively, a low elastic modulus resin previously prepared as a solution or emulsion is applied and dried according to a known method such as a roll coater, comma coater, die coater, Mayer bar coater, reverse roll coater, gravure coater, etc. A method of forming a low elastic modulus resin layer on the placed film is used. In this case, the low elastic modulus resin layer may be applied directly on the film and dried, or applied to the process film whose surface has been subjected to a release treatment such as silicone treatment, dried, and then commonly used for dry laminating and the like. And a method of transferring the low elastic modulus resin layer to the base film using the above method. In order to increase the adhesive force between the layers of these multilayer films, a new adhesive layer may be provided between the two layers, or corona discharge treatment or chemical treatment may be performed. The surface on which the pressure-sensitive adhesive layer is provided is preferably subjected to corona discharge treatment or chemical treatment.
本発明の半導体ウエハ表面保護用粘着フィルム（以下、粘着フィルムと略称する）に用いる粘着剤層は、半導体ウエハ表面に対し極めて低汚染性であることが好ましい。粘着フィルムを剥離した後、ウエハ表面に汚染が多い場合は洗浄する必要があるが、薄層化したウエハにおいては、洗浄工程において破損する頻度が高くなる。 The pressure-sensitive adhesive layer used for the semiconductor wafer surface protecting pressure-sensitive adhesive film (hereinafter abbreviated as pressure-sensitive adhesive film) of the present invention preferably has extremely low contamination to the semiconductor wafer surface. After the adhesive film is peeled off, the wafer surface needs to be cleaned if there is a lot of contamination. However, the thinned wafer is more frequently damaged in the cleaning process.
本発明において、粘着剤層は、通常、架橋剤と反応し得る官能基を有する粘着剤ポリマー１００重量部、及び、１分子中に２個以上の架橋反応性官能基を有する架橋剤０．１〜３０重量部を含む。このような粘着剤としては、例えば、放射線硬化型、熱硬化型、加熱発泡型等の粘着力スイッチング機能を有する粘着剤、スイッチング機能を有しない通常の粘着剤等が挙げられる。
スイッチング機能を有しない通常の粘着剤としては、天然ゴム系、合成ゴム系、シリコーンゴム系、アクリル酸アルキルエステル、メタクリル酸アルキルエステル等のアクリル系粘着剤等が挙げられる。これらの粘着剤の中でも、粘着剤物性の制御、再現性等を考慮するとアクリル系の粘着剤が好ましい。
In the present invention, the pressure-sensitive adhesive layer usually comprises 100 parts by weight of a pressure-sensitive adhesive polymer having a functional group capable of reacting with a cross-linking agent, and a cross-linking agent 0.1 having two or more cross-linking reactive functional groups in one molecule. Contains 30 parts by weight. Examples of such an adhesive include an adhesive having an adhesive force switching function such as a radiation curing type, a thermosetting type, and a heating foam type, and an ordinary adhesive having no switching function.
Examples of normal pressure-sensitive adhesives that do not have a switching function include natural rubber-based, synthetic rubber-based, silicone rubber-based, acrylic pressure-sensitive adhesives such as alkyl acrylates and alkyl methacrylates. Among these pressure-sensitive adhesives, an acrylic pressure-sensitive adhesive is preferable in consideration of control of physical properties of the pressure-sensitive adhesive, reproducibility, and the like.
粘着剤がアクリル系である場合、粘着剤ポリマーを構成する主モノマーは、アクリル酸アルキルエステル及びメタクリル酸アルキルエステルを含むものが好ましい。アクリル酸アルキルエステル及びメタクリル酸アルキルエステルの例としては、アクリル酸メチル、メタクリル酸メチル、アクリル酸エチル、メタクリル酸エチル、アクリル酸ブチル、メタクリル酸ブチル、アクリル酸−２−エチルヘキシル等が挙げられる。これらは単独で使用しても、又、２種以上を混合して使用してもよい。主モノマーの使用量は、粘着剤ポリマーの原料となる全モノマーの総量中に、６０〜９９重量％の範囲で含まれていることが好ましい。かかる組成のモノマー混合物を用いることにより、ほぼ同組成のアクリル酸アルキルエステル単位、メタクリル酸アルキルエステル単位、又はこれらの混合単位を含むポリマーが得られる。 When the pressure-sensitive adhesive is acrylic, it is preferable that the main monomer constituting the pressure-sensitive adhesive polymer includes an acrylic acid alkyl ester and a methacrylic acid alkyl ester. Examples of the alkyl acrylate ester and the alkyl methacrylate ester include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, and 2-ethylhexyl acrylate. These may be used alone or in combination of two or more. It is preferable that the usage-amount of a main monomer is contained in the range of 60 to 99 weight% in the total amount of all the monomers used as the raw material of an adhesive polymer. By using a monomer mixture having such a composition, an alkyl acrylate unit, a methacrylic acid alkyl ester unit, or a polymer containing these mixed units having substantially the same composition can be obtained.
粘着剤ポリマーは、架橋剤と反応し得る官能基を有していることが好ましい。架橋剤と反応し得る官能基としては、水酸基、カルボキシル基、エポキシ基、アミノ基等が挙げられる。粘着剤ポリマー中にこれらの架橋剤と反応しうる官能基を導入する方法としては、粘着剤ポリマーを重合する際にこれらの官能基を有するコモノマーを共重合させる方法が一般に用いられる。 The pressure-sensitive adhesive polymer preferably has a functional group capable of reacting with the crosslinking agent. Examples of the functional group capable of reacting with the crosslinking agent include a hydroxyl group, a carboxyl group, an epoxy group, and an amino group. As a method for introducing functional groups capable of reacting with these crosslinking agents into the pressure-sensitive adhesive polymer, a method of copolymerizing comonomers having these functional groups when the pressure-sensitive adhesive polymer is polymerized is generally used.
例えば、アクリル酸、メタクリル酸、イタコン酸、メサコン酸、シトラコン酸、フマル酸、マレイン酸、イタコン酸モノアルキルエステル、メサコン酸モノアルキルエステル、シトラコン酸モノアルキルエステル、フマル酸モノアルキルエステル、マレイン酸モノアルキルエステル、アクリル酸−２−ヒドロキシエチル、メタクリル酸−２−ヒドロキシエチル、アクリルアミド、メタクリルアミド、ターシャル−ブチルアミノエチルアクリレート、ターシャル−ブチルアミノエチルメタクリレート等が挙げられる。これらのコモノマーの内の１種を上記主モノマーと共重合させてもよいし、又２種以上を共重合させてもよい。上記の架橋剤と反応しうる官能基を有するコモノマーの使用量（共重合量）は、粘着剤ポリマーの原料となる全モノマーの総量中に、１〜４０重量％の範囲内で含まれていることが好ましい。かかる組成のモノマー混合物を用いることにより、ほぼ同組成のコモノマー単位を含むポリマーが得られる。 For example, acrylic acid, methacrylic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, maleic acid, itaconic acid monoalkyl ester, mesaconic acid monoalkyl ester, citraconic acid monoalkyl ester, fumaric acid monoalkyl ester, maleic acid mono Examples thereof include alkyl esters, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, acrylamide, methacrylamide, tertiary-butylaminoethyl acrylate, and tertiary-butylaminoethyl methacrylate. One of these comonomers may be copolymerized with the main monomer, or two or more may be copolymerized. The use amount (copolymerization amount) of the comonomer having a functional group capable of reacting with the cross-linking agent is included in the range of 1 to 40% by weight in the total amount of all monomers used as the raw material of the pressure-sensitive adhesive polymer. It is preferable. By using a monomer mixture having such a composition, a polymer containing comonomer units having almost the same composition can be obtained.
本発明において、上記粘着剤ポリマーを構成する主モノマー単位及び架橋剤と反応し得る官能基を有するコモノマー単位の他に、界面活性剤としての性質を有する特定のコモノマー（以下、重合性界面活性剤と称する）を共重合してもよい。重合性界面活性剤は、主モノマー及びコモノマーと共重合する性質を有しており、万一粘着剤層に起因する汚染がウエハ表面に生じたとしても、水洗により容易に除去することが可能となる。 In the present invention, in addition to the main monomer unit constituting the pressure-sensitive adhesive polymer and the comonomer unit having a functional group capable of reacting with the crosslinking agent, a specific comonomer having a property as a surfactant (hereinafter referred to as a polymerizable surfactant). May be copolymerized. The polymerizable surfactant has the property of copolymerizing with the main monomer and comonomer, and even if contamination due to the pressure-sensitive adhesive layer occurs on the wafer surface, it can be easily removed by washing with water. Become.
このような重合性界面活性剤の例としては、例えば、ポリオキシエチレンノニルフェニルエーテルのベンゼン環に重合性の１−プロペニル基を導入したもの〔第一工業製薬（株）製；商品名：アクアロンＲＮ−１０、同ＲＮ−２０、同ＲＮ−３０、同ＲＮ−５０等〕、ポリオキシエチレンノニルフェニルエーテルの硫酸エステルのアンモニウム塩のベンゼン環に重合性の１−プロペニル基を導入したもの〔第一工業製薬（株）製；商品名：アクアロンＨＳ−１０、同ＨＳ−２０等〕、及び分子内に重合性二重結合を持つ、スルホコハク酸ジエステル系のもの〔花王（株）製；商品名：ラテムルＳ−１２０Ａ、同Ｓ−１８０Ａ等〕等が挙げられる。 Examples of such polymerizable surfactants include, for example, those obtained by introducing a polymerizable 1-propenyl group into the benzene ring of polyoxyethylene nonylphenyl ether [Daiichi Kogyo Seiyaku Co., Ltd .; trade name: Aqualon RN-10, RN-20, RN-30, RN-50, etc.], a polyoxyethylene nonylphenyl ether sulfate ester ammonium salt introduced with a polymerizable 1-propenyl group in the benzene ring Manufactured by Ichi Kogyo Seiyaku Co., Ltd .; trade names: Aqualon HS-10, HS-20, etc.] and sulfosuccinic acid diesters having a polymerizable double bond in the molecule [produced by Kao Corporation; : Latemulu S-120A, S-180A, etc.].
さらに必要に応じて、アクリル酸グリシジル、メタクリル酸グリシジル、イソシアネートエチルアクリレート、イソシアネートエチルメタクリレート、２−（１−アジリジニル）エチルアクリレート、２−（１−アジリジニル）エチルメタクリレート等の自己架橋性の官能基を持ったモノマー、酢酸ビニル、アクリロニトリル、スチレン等の重合性二重結合を持ったモノマー、ジビニルベンゼン、アクリル酸ビニル、メタクリル酸ビニル、アクリル酸アリル、メタクリル酸アリル等の多官能性のモノマー等を共重合してもよい。 If necessary, self-crosslinkable functional groups such as glycidyl acrylate, glycidyl methacrylate, isocyanate ethyl acrylate, isocyanate ethyl methacrylate, 2- (1-aziridinyl) ethyl acrylate, 2- (1-aziridinyl) ethyl methacrylate, etc. Monomers with polymerizable double bonds such as vinyl acetate, acrylonitrile and styrene, and polyfunctional monomers such as divinylbenzene, vinyl acrylate, vinyl methacrylate, allyl acrylate and allyl methacrylate. Polymerization may be performed.
粘着剤ポリマーの重合反応機構としては、ラジカル重合、アニオン重合、カチオン重合等が挙げられる。粘着剤の製造コスト、モノマーの官能基の影響及び半導体ウエハ表面へのイオンの影響、等を等慮すれば、ラジカル重合によって重合することが好ましい。ラジカル重合反応によって重合する際、ラジカル重合開始剤として、ベンゾイルパーオキサイド、アセチルパーオキサイド、イソブチリルパーオキサイド、オクタノイルパーオキサイド、ジ−ターシャル−ブチルパーオキサイド、ジ−ターシャル−アミルパーオキサイド等の有機過酸化物、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物、２，２’−アゾビスイソブチロニトリル、２，２’−アゾビス−２−メチルブチロニトリル、４，４’−アゾビス−４−シアノバレリックアシッド等のアゾ化合物、等が挙げられる。 Examples of the polymerization reaction mechanism of the pressure-sensitive adhesive polymer include radical polymerization, anionic polymerization, and cationic polymerization. In consideration of the production cost of the pressure-sensitive adhesive, the influence of the functional group of the monomer, the influence of ions on the surface of the semiconductor wafer, etc., it is preferable to polymerize by radical polymerization. When polymerizing by radical polymerization reaction, organic compounds such as benzoyl peroxide, acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, di-tertiary-butyl peroxide, di-tertiary-amyl peroxide as radical polymerization initiators Inorganic peroxides such as peroxide, ammonium persulfate, potassium persulfate, sodium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 4,4 And azo compounds such as' -azobis-4-cyanovaleric acid.
粘着剤ポリマーの重合法としては、乳化重合法、懸濁重合法、溶液重合法等の公知の重合法を適宜選択して用いることができる。粘着剤ポリマーを乳化重合法により重合する場合には、前記したラジカル重合開始剤の中で、水溶性の過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物、同じく水溶性の４，４’−アゾビス−４−シアノバレリックアシッド等の分子内にカルボキシル基を持ったアゾ化合物が好ましく用いられる。半導体ウエハ表面へのイオンの影響を考慮すれば、過硫酸アンモニウム、４，４’−アゾビス−４−シアノバレリックアシッド等の分子内にカルボキシル基を持ったアゾ化合物がさらに好ましい。４，４’−アゾビス−４−シアノバレリックアシッド等の分子内にカルボキシル基を持ったアゾ化合物が特に好ましい。 As a method for polymerizing the pressure-sensitive adhesive polymer, a known polymerization method such as an emulsion polymerization method, a suspension polymerization method, or a solution polymerization method can be appropriately selected and used. When the pressure-sensitive adhesive polymer is polymerized by an emulsion polymerization method, among the radical polymerization initiators described above, water-soluble ammonium persulfate, potassium persulfate, inorganic peroxides such as sodium persulfate, and water-soluble 4, An azo compound having a carboxyl group in the molecule such as 4′-azobis-4-cyanovaleric acid is preferably used. Considering the influence of ions on the surface of the semiconductor wafer, azo compounds having a carboxyl group in the molecule such as ammonium persulfate and 4,4'-azobis-4-cyanovaleric acid are more preferable. An azo compound having a carboxyl group in the molecule such as 4,4'-azobis-4-cyanovaleric acid is particularly preferred.
本発明に用いる１分子中に２個以上の架橋反応性官能基を有する架橋剤は、粘着剤ポリマーが有する官能基と反応させて、架橋密度、粘着力及び凝集力を調整する為に用いる。架橋剤としては、ソルビトールポリグリシジルエーテル、ポリグリセロールポリグリシジルエーテル、ペンタエリスリトールポリグリシジルエーテル、ジグリセロールポリグリシジルエーテル、グリセロールポリグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテル、レソルシンジグリシジルエーテル等のエポキシ系架橋剤、トリメチロールプロパン−トリ−β−アジリジニルプロピオネート、テトラメチロールメタン−トリ−β−アジリジニルプロピオネート、Ｎ，Ｎ’−ジフェニルメタン−４，４’−ビス（１−アジリジンカルボキシアミド）、Ｎ，Ｎ’−ヘキサメチレン−１，６−ビス（１−アジリジンカルボキシアミド）、Ｎ，Ｎ’−トルエン−２，４−ビス（１−アジリジンカルボキシアミド）、トリメチロールプロパン−トリ−β−（２−メチルアジリジン）プロピオネート等のアジリジン系架橋剤、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トリメチロールプロパンのトルエンジイソシアネート３付加物、ポリイソシアネート等のイソシアネート系架橋剤等が挙げられる。これらの架橋剤は単独で使用してもよいし、２種以上を併用してもよい。 The cross-linking agent having two or more cross-linking reactive functional groups in one molecule used in the present invention is used to adjust the cross-linking density, adhesive force and cohesive force by reacting with the functional group of the pressure-sensitive adhesive polymer. As the crosslinking agent, epoxy-based crosslinking such as sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether, glycerol polyglycidyl ether, neopentyl glycol diglycidyl ether, resorcin diglycidyl ether, etc. Agent, trimethylolpropane-tri-β-aziridinylpropionate, tetramethylolmethane-tri-β-aziridinylpropionate, N, N′-diphenylmethane-4,4′-bis (1-aziridinecarboxyl Amide), N, N′-hexamethylene-1,6-bis (1-aziridinecarboxamide), N, N′-toluene-2,4-bis (1-aziridinecarboxyamide), trimethylolpro Aziridine-based crosslinking agents such as pan-tri-β- (2-methylaziridine) propionate, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate 3-adduct of trimethylolpropane, isocyanate-based crosslinking agents such as polyisocyanate, etc. . These crosslinking agents may be used alone or in combination of two or more.
又、粘着剤が水系（エマルションを含む）である場合には、イソシアネート系架橋剤は水との副反応による失活速度が速い為、粘着剤ポリマーとの架橋反応が十分に進行しない場合がある。従って、この場合には上記の架橋剤の中でアジリジン系もしくはエポキシ系の架橋剤を用いることが好ましい。 When the pressure-sensitive adhesive is water-based (including emulsion), the crosslinking reaction with the pressure-sensitive adhesive polymer may not sufficiently proceed because the isocyanate-based cross-linking agent has a high deactivation rate due to side reaction with water. . Therefore, in this case, it is preferable to use an aziridine-based or epoxy-based crosslinking agent among the above-mentioned crosslinking agents.
本発明における１分子中に２個以上の架橋反応性官能基を有する架橋剤の含有量は、粘着剤ポリマー１００重量部に対し架橋剤０．１〜３０重量部、特に好ましくは０．５〜２５重量部である。架橋剤の含有量が少ないと、粘着剤層の凝集力が不十分となり、ウエハ表面に汚染を生じることがある。多過ぎると、粘着剤層とウエハ表面との密着力が弱くなり、研削加工中に水や研削屑が浸入し、ウエハを破損したり、研削屑によるウエハ表面の汚染が生じることがある。 In the present invention, the content of the crosslinking agent having two or more crosslinking reactive functional groups in one molecule is 0.1 to 30 parts by weight, particularly preferably 0.5 to 100 parts by weight of the pressure-sensitive adhesive polymer. 25 parts by weight. When the content of the crosslinking agent is small, the cohesive force of the pressure-sensitive adhesive layer becomes insufficient, and the wafer surface may be contaminated. When the amount is too large, the adhesive force between the pressure-sensitive adhesive layer and the wafer surface is weakened, and water and grinding debris may enter during the grinding process, resulting in damage to the wafer and contamination of the wafer surface with the grinding debris.
本発明における粘着剤層を構成する粘着剤には、上記の架橋剤と反応しうる官能基を有する粘着剤ポリマー、一分子中に２個以上の架橋反応性官能基を有する架橋剤の他に、粘着特性を調整する為に、ロジン系、テルペン樹脂系等のタッキファイヤー、各種界面活性剤等を適宜含有してもよい。又、粘着剤ポリマーがエマルション液である場合は、ジエチレングリコールモノブチルエーテル等の増膜助剤を本発明の目的に影響しない程度に適宜含有してよい。 The pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer in the present invention includes a pressure-sensitive adhesive polymer having a functional group capable of reacting with the above-mentioned cross-linking agent, and a cross-linking agent having two or more cross-linking reactive functional groups in one molecule. In order to adjust the adhesive properties, rosin-based and terpene resin-based tackifiers, various surfactants and the like may be appropriately contained. Further, when the pressure-sensitive adhesive polymer is an emulsion liquid, a film-forming auxiliary such as diethylene glycol monobutyl ether may be appropriately contained so as not to affect the object of the present invention.
また、粘着剤中に放射性硬化性のモノマー成分やオリゴマー成分、放射線重合開始剤を加えることにより、粘着剤層を放射線硬化型の粘着剤とすることもできる。この放射線硬化型の粘着剤を用いた場合、半導体ウエハ表面から粘着フィルムを剥離する前に紫外線等の放射線を照射することで、該粘着剤を硬化させ、粘着力を低減することができる。 In addition, the pressure-sensitive adhesive layer can be made into a radiation-curable pressure-sensitive adhesive by adding a radiation-curable monomer component or oligomer component or a radiation polymerization initiator to the pressure-sensitive adhesive. When this radiation curable pressure-sensitive adhesive is used, the pressure-sensitive adhesive can be cured and the pressure-sensitive adhesive force can be reduced by irradiating radiation such as ultraviolet rays before peeling the pressure-sensitive adhesive film from the surface of the semiconductor wafer.
粘着剤層の厚みは、半導体ウエハ表面の汚染性、粘着力等に影響を及ぼす。粘着剤層の厚みが薄くなると、ウエハ表面に残留することがある。粘着剤層の厚みが厚すぎると粘着力が高くなり、剥離の際の作業性が低下することがある。かかる観点から、粘着剤層の厚みは１〜１００μｍであることが好ましい。 The thickness of the pressure-sensitive adhesive layer affects the contamination properties, adhesive strength, and the like of the semiconductor wafer surface. When the thickness of the pressure-sensitive adhesive layer is reduced, it may remain on the wafer surface. If the thickness of the pressure-sensitive adhesive layer is too thick, the adhesive strength increases, and the workability during peeling may be reduced. From this viewpoint, the thickness of the pressure-sensitive adhesive layer is preferably 1 to 100 μm.
本発明において、基材フィルムの片表面に粘着剤層を形成する際には、上記粘着剤を溶液又はエマルション液（以下、これらを総称して粘着剤塗布液と称する）として、ロールコーター、コンマコーター、ダイコーター、メイヤーバーコーター、リバースロールコーター、グラビアコーター等の公知の方法に従って塗布、乾燥して粘着剤層を形成する方法を用いることができる。この際、塗布した粘着剤層を環境に起因する汚染等から保護する為に、塗布した粘着剤層の表面に剥離フィルムを貼着することが好ましい。あるいは、剥離フィルムの片表面に、上記の公知の方法に従って粘着剤塗布液を塗布、乾燥して粘着剤層を形成した後、ドライラミネート法等の慣用の方法を用いて粘着剤層を基材フィルムに転写させる方法（以下、転写法という）をとってもよい。 In the present invention, when the pressure-sensitive adhesive layer is formed on one surface of the base film, the pressure-sensitive adhesive is used as a solution or an emulsion liquid (hereinafter collectively referred to as a pressure-sensitive adhesive coating liquid), a roll coater, a comma A method of forming an adhesive layer by coating and drying according to a known method such as a coater, a die coater, a Mayer bar coater, a reverse roll coater, or a gravure coater can be used. At this time, in order to protect the applied pressure-sensitive adhesive layer from contamination caused by the environment, it is preferable to attach a release film to the surface of the applied pressure-sensitive adhesive layer. Alternatively, a pressure-sensitive adhesive coating solution is applied to one surface of the release film according to the above-mentioned known method and dried to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive layer is formed into a substrate using a conventional method such as a dry laminating method. A method of transferring to a film (hereinafter referred to as transfer method) may be used.
粘着剤を乾燥する際の乾燥条件には特に制限はないが、一般的には、８０〜３００℃の温度範囲において、１０秒〜１０分間乾燥することが好ましい。さらに好ましくは、８０〜２００℃の温度範囲において１５秒〜５分間乾燥する。本発明においては、架橋剤と粘着剤ポリマーとの架橋反応を十分に促進させる為に、粘着剤塗布液の乾燥が終了した後に、粘着フィルムを４０〜８０℃において５〜３００時間程度加熱してもよい。
粘着フィルムの粘着力は、ウエハ裏面の研削加工、薬液処理時等におけるウエハの保護性と、ウエハから剥離する際の作業性との双方に影響する為、ウエハ裏面の研削加工、薬液処理時等におけるウエハの保護性（研削水、研削屑及び薬液等の浸入防止）を考慮して決定される。具体的には、ＪＩＳ Ｚ−０２３７に規定される方法に準拠して、被着体としてＳＵＳ３０４−ＢＡ板を用い、剥離速度３００ｍｍ／ｍｉｎ、剥離角度１８０度の条件下で測定した粘着力が、０．０５〜２．５Ｎ／２５ｍｍであることが好ましい。より好ましくは０．０５〜２．０Ｎ／２５ｍｍである。なお、粘着剤が粘着力スイッチング機能を有する粘着剤である場合には、加熱硬化、放射線硬化、熱発泡等により粘着力を低下させた状態での粘着力が前記の範囲にあることが好ましい。
Although there is no restriction | limiting in particular in the drying conditions at the time of drying an adhesive, Generally, it is preferable to dry for 10 second-10 minutes in a 80-300 degreeC temperature range. More preferably, it is dried for 15 seconds to 5 minutes in a temperature range of 80 to 200 ° C. In the present invention, in order to sufficiently accelerate the crosslinking reaction between the crosslinking agent and the pressure-sensitive adhesive polymer, after the drying of the pressure-sensitive adhesive coating solution is completed, the pressure-sensitive adhesive film is heated at 40 to 80 ° C. for about 5 to 300 hours. Also good.
The adhesive strength of the adhesive film affects both the wafer's protection during grinding and chemical treatment of the wafer and the workability when peeling from the wafer. Is determined in consideration of the protection of the wafer (preventing the ingress of grinding water, grinding debris, chemicals, etc.). Specifically, in accordance with the method defined in JIS Z-0237, using an SUS304-BA plate as an adherend, the adhesive force measured under conditions of a peeling speed of 300 mm / min and a peeling angle of 180 degrees, It is preferable that it is 0.05-2.5N / 25mm. More preferably, it is 0.05-2.0N / 25mm. In addition, when an adhesive is an adhesive which has an adhesive force switching function, it is preferable that the adhesive force in the state which reduced adhesive force by heat hardening, radiation curing, thermal foaming, etc. exists in the said range.
本発明の粘着フィルムの製造方法は上記のとおりであるが、半導体ウエハ表面の汚染防止の観点から、基材フィルム、剥離フィルム、粘着剤等、全ての原料及び資材の製造環境、粘着剤塗布液の調整、保存、塗布及び乾燥環境は、米国連邦規格２０９ｂに規定されるクラス１，０００以下のクリーン度に維持されていることが好ましい。 The production method of the pressure-sensitive adhesive film of the present invention is as described above. From the viewpoint of preventing contamination of the semiconductor wafer surface, the production environment for all raw materials and materials, such as a base film, a release film, and a pressure-sensitive adhesive, a pressure-sensitive adhesive coating solution The adjustment, storage, application, and drying environment are preferably maintained at a clean level of class 1,000 or less as defined in US Federal Standard 209b.
次に、本発明の半導体ウエハの裏面加工方法について説明する。本発明の半導体ウエハの裏面加工方法は、半導体ウエハの裏面を研削加工、化学エッチング加工、またはこれらの操作を共に実施する際に、上記半導体ウエハ表面保護粘着フィルムを用いることに特徴がある。その詳細は、通常、温度が１８〜３０℃に管理された室内近傍の温度において上記粘着フィルムの粘着剤層から剥離フィルムを剥離し、粘着剤層の表面を露出させ、粘着剤層を介して、半導体ウエハの表面に貼着する。次いで、研削機のチャックテーブル等に粘着フィルムの基材フィルム層を介して半導体ウエハを固定し、半導体ウエハの裏面に対し、研削加工、研磨加工、化学エッチング加工等を実施する。本発明においては、研削加工、研磨加工、化学エッチング加工等の何れかを単独で行ってもよいし、複数の加工を組み合わせて行ってもよい。複数の加工を組み合わせて行う場合、その順番は特に規定しないが、通常、研削加工の後に、研磨加工または化学エッチング加工等を行う。 Next, the back surface processing method of the semiconductor wafer of this invention is demonstrated. The semiconductor wafer back surface processing method of the present invention is characterized in that the semiconductor wafer surface protective adhesive film is used when the back surface of the semiconductor wafer is ground, chemically etched, or when these operations are performed together. In detail, the release film is usually peeled off from the pressure-sensitive adhesive layer of the pressure-sensitive adhesive film at a temperature in the vicinity of the room where the temperature is controlled at 18 to 30 ° C., the surface of the pressure-sensitive adhesive layer is exposed, and the pressure-sensitive adhesive layer is interposed. Affixed to the surface of the semiconductor wafer. Next, a semiconductor wafer is fixed to a chuck table or the like of a grinding machine via a base film layer of an adhesive film, and grinding, polishing, chemical etching, or the like is performed on the back surface of the semiconductor wafer. In the present invention, any one of grinding, polishing, chemical etching and the like may be performed alone, or a plurality of processes may be combined. In the case of performing a combination of a plurality of processes, the order is not particularly defined, but usually a polishing process or a chemical etching process is performed after the grinding process.
研削加工、化学エッチング加工等が終了した後、該粘着フィルムを剥離する。いずれの裏面加工方法においても、必要に応じて、粘着フィルムを剥離した後の半導体ウエハ表面に対して、水洗、プラズマ洗浄等の処理を施してもよい。この様な一連の工程中の、半導体ウエハ裏面の研削加工、化学エッチング等の操作によって、半導体ウエハは研削前の厚みが、通常、５００〜１０００μｍであるのに対して、本発明の方法を適用することにより、１５０μｍ以下になるまで、破損等のトラブルを生じることなしに薄層化することができる。半導体チップの種類等に応じ、１００μｍ以下まで、時には５０μｍ程度まで薄層化することができる。裏面の研削加工後のウエハの厚みと化学エッチング後のウエハの厚みは、半導体ウエハの種類、目標最終厚み等により適宜決められる。裏面を研削する前の半導体ウエハの厚みは、半導体ウエハの直径、種類等により適宜決められ、裏面研削後のウエハ厚みは、得られる集積回路の種類、用途等により適宜決められる。 After the grinding process, chemical etching process and the like are completed, the adhesive film is peeled off. In any of the back surface processing methods, if necessary, the surface of the semiconductor wafer after peeling off the adhesive film may be subjected to treatment such as water washing or plasma washing. The semiconductor wafer has a thickness of 500 to 1000 μm before grinding by operations such as grinding of the back surface of the semiconductor wafer and chemical etching during a series of such processes, and the method of the present invention is applied. By doing so, the thickness can be reduced without causing trouble such as breakage until it becomes 150 μm or less. Depending on the type of semiconductor chip, etc., it can be thinned to 100 μm or less, and sometimes to about 50 μm. The thickness of the wafer after grinding the back surface and the thickness of the wafer after chemical etching are appropriately determined depending on the type of semiconductor wafer, the target final thickness, and the like. The thickness of the semiconductor wafer before grinding the back surface is appropriately determined depending on the diameter and type of the semiconductor wafer, and the wafer thickness after the back surface grinding is appropriately determined depending on the type of integrated circuit to be obtained and the application.
表面保護用粘着フィルムを半導体ウェハの表面に貼着する操作は、人手により行われる場合もあるが、一般に、ロール状の表面保護用粘着フィルムを取り付けた自動貼り機と称される装置によって行われる。このような自動貼り機として、例えばタカトリ（株）製、形式：ＡＴＭ−１０００Ｂ、同ＡＴＭ−１１００、同ＴＥＡＭ−１００、帝国精機（株）製、形式：ＳＴＬシリーズ等が挙げられる。 The operation of adhering the surface protective adhesive film to the surface of the semiconductor wafer may be performed manually, but is generally performed by an apparatus called an automatic attaching machine equipped with a roll-shaped surface protective adhesive film. . Examples of such an automatic pasting machine include Takatori Co., Ltd., model: ATM-1000B, ATM-1100, TEAM-100, Teikoku Seiki Co., Ltd., model: STL series.
裏面研削方式としては、スルーフィード方式、インフィード方式等の公知の研削方式が採用される。通常、いずれの方法においても、半導体ウェハと砥石に水を供給して冷却しながら裏面研削が行われる。裏面研削終了後、必要に応じて、ウェットエッチング、ポリッシングが行われる。ウェットエッチング工程及びポリッシング工程は、半導体ウェハ裏面に生じた歪の除去、半導体ウェハのさらなる薄層化、酸化膜等の除去、電極を裏面に形成する際の前処理等を目的として行われる。エッチング液は、上記の目的に応じて適宜選択される。 As the back surface grinding method, a known grinding method such as a through-feed method or an in-feed method is employed. In either method, back surface grinding is usually performed while supplying water to the semiconductor wafer and the grindstone and cooling. After the back surface grinding, wet etching and polishing are performed as necessary. The wet etching process and the polishing process are performed for the purpose of removing strain generated on the back surface of the semiconductor wafer, further thinning the semiconductor wafer, removing an oxide film, etc., pretreatment when forming electrodes on the back surface. The etching solution is appropriately selected according to the above purpose.
裏面研削工程、及びエッチング工程がそれぞれ終了した後、半導体ウェハ表面から表面保護用粘着フィルムが剥離される。これらの一連の操作は、人手により行われる場合もあるが、一般的に自動剥がし機と称される装置を用いて行われる。このような自動剥がし機としては、タカトリ（株）製、形式：ＡＴＲＭ−２０００Ｂ、同ＡＴＲＭ−２１００、帝国精機（株）製、形式：ＳＴＰシリーズ等が挙げられる。但し、ウェハ厚みが１５０μｍ以下になるまで薄層化された場合には、粘着フィルム剥離時のウェハ破損、及びウェハ反りによる搬送時の搬送不良等が心配される。 After the back grinding step and the etching step are finished, the surface protecting adhesive film is peeled off from the semiconductor wafer surface. Although a series of these operations may be performed manually, it is generally performed using an apparatus called an automatic peeling machine. Examples of such an automatic peeling machine include Takatori Co., Ltd., model: ATRM-2000B, ATRM-2100, Teikoku Seiki Co., Ltd., model: STP series. However, when the wafer is thinned to a thickness of 150 μm or less, there is a concern about wafer breakage when the adhesive film is peeled off, conveyance failure due to wafer warpage, and the like.
本発明に係わる半導体ウエハ表面保護用粘着フィルムを用いることにより、半導体ウェハの裏面研削加工において、ウェハ厚みが１５０μｍ以下になるまで薄層化された場合であっても、７０〜１００℃の温水に浸漬若しくは、該温水を接射、或いは同温度の雰囲気で加熱し、該半導体ウエハ表面から該半導体ウエハ表面保護用粘着テープを容易に剥離することができ、ウェハの破損を防止できる。 By using the adhesive film for protecting the surface of a semiconductor wafer according to the present invention, even in the case where the wafer thickness is reduced to 150 μm or less in the back grinding process of the semiconductor wafer, The adhesive tape for protecting the surface of the semiconductor wafer can be easily peeled off from the surface of the semiconductor wafer by dipping or by spraying the hot water or heating in an atmosphere of the same temperature, and damage of the wafer can be prevented.
表面保護用粘着フィルムを剥離した後の半導体ウェハ表面は、必要に応じて洗浄される。洗浄方法としては、水洗浄、溶剤洗浄等の湿式洗浄、プラズマ洗浄等の乾式洗浄等が挙げられる。湿式洗浄の場合、超音波洗浄を併用してもよい。これらの洗浄方法は、半導体ウェハ表面の汚染状況により適宜選択される。
本発明の半導体ウェハ保護方法が適用できる半導体ウェハとして、シリコンウェハに限らず、ゲルマニウム、ガリウム−ヒ素、ガリウム−リン、ガリウム−ヒ素−アルミニウム等のウェハが挙げられる。
The surface of the semiconductor wafer after peeling off the surface protective adhesive film is cleaned as necessary. Examples of the cleaning method include wet cleaning such as water cleaning and solvent cleaning, and dry cleaning such as plasma cleaning. In the case of wet cleaning, ultrasonic cleaning may be used in combination. These cleaning methods are appropriately selected depending on the contamination state of the semiconductor wafer surface.
Semiconductor wafers to which the semiconductor wafer protection method of the present invention can be applied are not limited to silicon wafers, but include wafers of germanium, gallium-arsenic, gallium-phosphorus, gallium-arsenic-aluminum, and the like.
以下、実施例を示して本発明についてさらに詳細に説明する。以下に示す全ての実施例及び比較例において、米国連邦規格２０９ｂに規定されるクラス１，０００以下のクリーン度に維持された環境において粘着剤塗布液の調製及び塗布、半導体シリコンウエハの裏面研削、並びに半導体ウエハ表面保護用粘着フィルムの剥離評価等を実施した。本発明はこれら実施例に限定されるものではない。尚、実施例に示した各種特性値は下記の方法で測定した。 Hereinafter, the present invention will be described in more detail with reference to examples. In all the examples and comparative examples shown below, preparation and application of an adhesive coating solution in an environment maintained at a cleanness of class 1,000 or less as defined in US Federal Standard 209b, back grinding of a semiconductor silicon wafer, In addition, peeling evaluation of the adhesive film for protecting the semiconductor wafer surface was performed. The present invention is not limited to these examples. Various characteristic values shown in the examples were measured by the following methods.
１．各種特性の測定方法
１−１．粘着力測定（ｇ／２５ｍｍ）
下記に規定した条件以外は、全てＪＩＳ Ｚ０２３７−１９９１に規定される方法に準じて測定する。２３℃の雰囲気下において、実施例または比較例で得られた粘着フィルムをその粘着剤層を介して、２０ｃｍ×５ｃｍの長方形のＳＵＳ３０４−ＢＡ板（ＪＩＳ Ｇ４３０５−１９９１規定）の表面に貼着し、同サイズに粘着フィルムをカットし、６０分放置する。但し、粘着フィルムはＭＤ方向がＳＵＳ３０４−ＢＡ板の２０ｃｍの辺に、ＴＤ方向がＳＵＳ３０４−ＢＡ板の５ｃｍの辺に対するように粘着フィルムを貼着する。試料のＭＤ方向の一端を挟持し、剥離角度１８０度、剥離速度３００ｍｍ／ｍｉｎ．でＳＵＳ３０４−ＢＡ板の表面から試料を剥離する際の応力を測定し、２５ｍｍ幅に換算する。
1. Measuring method of various characteristics 1-1. Adhesive strength measurement (g / 25mm)
Except for the conditions specified below, all measurements are performed in accordance with the method specified in JIS Z0237-1991. In an atmosphere of 23 ° C., the adhesive film obtained in Example or Comparative Example was stuck to the surface of a 20 cm × 5 cm rectangular SUS304-BA plate (JIS G4305-1991 regulation) through the adhesive layer. Cut the adhesive film to the same size and leave it for 60 minutes. However, the adhesive film is adhered so that the MD direction is on the 20 cm side of the SUS304-BA plate and the TD direction is on the 5 cm side of the SUS304-BA plate. One end of the sample in the MD direction is sandwiched, the peeling angle is 180 degrees, and the peeling speed is 300 mm / min. Then, the stress at the time of peeling the sample from the surface of the SUS304-BA plate is measured and converted to a width of 25 mm.
１−２．貯蔵弾性率（Ｐａ）
１）粘着剤層
半導体ウェハ表面保護用粘着フィルムの粘着剤層の部分を厚さ１ｍｍになるように積層し、直径８ｍｍの粘弾性測定用試料を作製する。動的粘弾性測定装置（レオメトリックス社製：形式：ＲＭＳ−８００）を用いて、１５０℃及び２００℃において貯蔵弾性率を測定する。測定周波数は１Ｈｚとし、歪みは０．１〜３％とする。
２）基材フィルム層
半導体ウェハ表面保護用粘着フィルムの基材フィルム層部分を切断し、長方形（ＭＤ方向：３０ｍｍ、ＴＤ方向：１０ｍｍ）の試料を作製する。動的粘弾性測定装置（レオメトリックス社製：形式：ＲＳＡ−ＩＩ）を用いて、０〜３００℃までの貯蔵弾性率（機械方向）を測定する。測定周波数は、１Ｈｚとし、歪みは０．０１〜０．１％とする。但し、積層基材フィルムの場合は、各層独立で測定を行った。
1-2. Storage modulus (Pa)
1) Adhesive layer The adhesive layer portion of the adhesive film for protecting a semiconductor wafer surface is laminated to a thickness of 1 mm to produce a viscoelasticity measurement sample having a diameter of 8 mm. The storage elastic modulus is measured at 150 ° C. and 200 ° C. using a dynamic viscoelasticity measuring device (Rheometrics: model: RMS-800). The measurement frequency is 1 Hz and the distortion is 0.1 to 3%.
2) Base film layer The base film layer portion of the adhesive film for protecting a semiconductor wafer surface is cut to prepare a rectangular (MD direction: 30 mm, TD direction: 10 mm) sample. The storage elastic modulus (machine direction) from 0 to 300 ° C. is measured using a dynamic viscoelasticity measuring device (Rheometrics: model: RSA-II). The measurement frequency is 1 Hz, and the distortion is 0.01 to 0.1%. However, in the case of a laminated substrate film, the measurement was performed independently for each layer.
１−３．基材フィルムの寸法変化率（％）
基材フィルムを正方形（ＭＤ方向：３０ｃｍ、ＴＤ方向：３０ｃｍ）に切断し、パンチでスポット（ＭＤ方向：２５ｃｍ、ＴＤ方向：２５ｃｍ）を基材フィルムに開け、試料を作製する。２次元測定機（（株）ミツトヨ製：形式：ＣＲＹＳＴＡＬ＊μＶ６０６）を用いて、基材フィルムに開けられたスポット間隔を測定する。測定後、試料を５０℃のオーブン内にサンプルを静置する。２分後に該サンプルをオーブンから取り出し、スポット間隔を測定し、加熱前後での寸法変化率を計算する。試料１０枚について測定し、その平均値で示す。
1-3. Dimensional change rate of base film (%)
A base film is cut into a square (MD direction: 30 cm, TD direction: 30 cm), and a spot (MD direction: 25 cm, TD direction: 25 cm) is opened on the base film with a punch to prepare a sample. Using a two-dimensional measuring machine (manufactured by Mitutoyo Corporation: Model: CRYSTAL * μV606), the spot interval opened in the base film is measured. After the measurement, the sample is placed in a 50 ° C. oven. After 2 minutes, the sample is removed from the oven, the spot spacing is measured, and the dimensional change rate before and after heating is calculated. Measurements are made on 10 samples and the average value is shown.
１−４．半導体ウエハ表面保護用粘着フィルムの剥離評価（１）
半導体ウェハ表面保護用粘着フィルム貼着工程後、半導体ウェハ裏面研削工程で75μmまで研削したウェハを、ウォーターバスにおいて、８０℃の温水に10秒間浸漬し、半導体ウエハ表面保護用フィルムが自然に剥離するかを確認した。１０枚のミラーウェハについて評価し、自然に剥離した枚数を示す。
1-4. Evaluation of peeling of adhesive film for semiconductor wafer surface protection (1)
After attaching the adhesive film for semiconductor wafer surface protection, the wafer ground to 75μm in the semiconductor wafer back surface grinding process is immersed in warm water at 80 ° C for 10 seconds in a water bath, and the semiconductor wafer surface protection film peels naturally. I confirmed. 10 mirror wafers were evaluated and the number of sheets naturally peeled off is shown.
１−５．半導体ウエハ表面保護用粘着フィルムの剥離評価（２）
半導体ウェハ表面保護用粘着フィルム貼着工程後、半導体ウェハ裏面研削工程で75μmまで研削したウェハを、剥離機（日東精機（株）製、形式：ＨＲ８５００ＩＩ）を用いて、ウェハ表面から半導体ウェハ表面保護用粘着フィルムを剥離する。１０枚のミラーウェハについて評価し、剥離の際にウェハの割れが発生するかを確認した。
1-5. Evaluation of peeling of adhesive film for semiconductor wafer surface protection (2)
After attaching the adhesive film for semiconductor wafer surface protection, the wafer ground to 75μm in the semiconductor wafer backside grinding process is used to protect the semiconductor wafer surface from the wafer surface using a peeling machine (manufactured by Nitto Seiki Co., Ltd., model: HR8500II). Remove the adhesive film. Ten mirror wafers were evaluated, and it was confirmed whether or not the wafer was cracked during peeling.
２．表面保護用粘着フィルムの製造例
２−１．基材フィルムの製造例１
樹脂層（Ａ）として、ポリエステル系延伸フィルム[（株）東洋紡績製、商品名：東洋紡スペースクリーン 、厚み：６０μm]を選定した。粘着剤層を形成する側の表面にコロナ処理を施し、基材フィルム１とした。尚、ウォーターバスに於いて、８０℃×１秒の収縮率はＭＤ方向が６５％、ＴＤ方向の収縮率０％であった。５０℃での収縮率は、ＭＤ方向、ＴＤ方向共に収縮率０％。貯蔵弾性率は、２３℃において１．５ＧＰａ、６０℃において１．２ＧＰａであった。
2. 2. Production example of surface protective adhesive film 2-1. Production example 1 of base film
As the resin layer (A), a polyester stretched film [manufactured by Toyobo Co., Ltd., trade name: Toyobo Space Clean, thickness: 60 μm] was selected. The surface on the side where the pressure-sensitive adhesive layer is formed was subjected to corona treatment to obtain a base film 1. In the water bath, the shrinkage rate at 80 ° C. × 1 second was 65% in the MD direction and 0% in the TD direction. The shrinkage rate at 50 ° C. is 0% in both the MD direction and the TD direction. The storage elastic modulus was 1.5 GPa at 23 ° C. and 1.2 GPa at 60 ° C.
２−２．基材フィルムの製造例２
樹脂層（Ａ）として、ポリエステル系延伸フィルム[（株）三菱樹脂製、商品名：ヒシペット 、厚み：６０μm]を選定した。粘着剤層を形成する側の表面にコロナ処理を施し、基材フィルム２とした。尚、ウォーターバスに於いて、８０℃×１秒の収縮率はＭＤ方向が７２％、ＴＤ方向の収縮率５％であった。５０℃での収縮率は、ＭＤ方向、ＴＤ方向共に収縮率０％。貯蔵弾性率は、２３℃において２．０ＧＰａ、６０℃において１．７ＧＰａであった。
2-2. Production example 2 of base film
As the resin layer (A), a polyester stretched film [manufactured by Mitsubishi Plastics, Inc., trade name: HISHIPET, thickness: 60 μm] was selected. The surface on the side where the pressure-sensitive adhesive layer is formed was subjected to corona treatment to obtain a base film 2. In the water bath, the shrinkage rate at 80 ° C. × 1 second was 72% in the MD direction and 5% in the TD direction. The shrinkage rate at 50 ° C. is 0% in both the MD direction and the TD direction. The storage elastic modulus was 2.0 GPa at 23 ° C. and 1.7 GPa at 60 ° C.
２−３．基材フィルムの製造例３
樹脂層（Ａ）として、ポリエステル系延伸フィルム[（株）東洋紡績製、商品名：東洋紡スペースクリーン 、厚み：６０μm]を選定し、その片表面に、低弾性率樹脂層として厚さ１２０μｍのエチレン−酢酸ビニル共重合体（三井・デュポンポリケミカル（株）製、銘柄：エバフレックスＰ−１９０５（ＥＶ４６０）フィルムを積層した。この際、エチレン−酢酸ビニル共重合体フィルムの粘着剤層を形成する側の面にコロナ放電処理を施し、基材フィルム３とした。
2-3. Production example 3 of base film
As the resin layer (A), a polyester stretched film [manufactured by Toyobo Co., Ltd., trade name: Toyobo Space Clean, thickness: 60 μm] is selected, and ethylene having a thickness of 120 μm as a low elastic modulus resin layer is formed on one surface thereof. -Vinyl acetate copolymer (Mitsui / DuPont Polychemical Co., Ltd., brand: EVAFLEX P-1905 (EV460) film was laminated. At this time, an adhesive layer of the ethylene-vinyl acetate copolymer film was formed. The side surface was subjected to corona discharge treatment to obtain a base film 3.
２−４．基材フィルムの比較製造例１
５０℃におけるフィルムＭＤ方向及び、ＴＤ方向の収縮率が其々、０．０％であり、８０℃の温水に１秒浸漬した時のＭＤ方向、ＴＤ方向の収縮率が其々、０．１％以下、０．０％である、２軸延伸ポリエチレンテレフタレート[帝人デュポンフィルム（株）製、商品名：テイジンテトロンフィルム 、厚み：５０μm]を選定し、粘着剤層を形成する側の表面にコロナ処理を施し、基材フィルム４とした。尚、貯蔵弾性率は、２３℃において２．０ＧＰａ、６０℃において１．５ＭＰａであった。
2-4. Comparative production example 1 of base film
The shrinkage in the MD and TD directions at 50 ° C. is 0.0%, respectively, and the shrinkage in the MD and TD directions is 0.1% when immersed in warm water at 80 ° C. for 1 second. %, 0.0%, biaxially stretched polyethylene terephthalate [manufactured by Teijin DuPont Films, trade name: Teijin Tetron Film, thickness: 50 μm] is selected, and the corona is formed on the surface on which the adhesive layer is formed. It processed and it was set as the base film 4. The storage elastic modulus was 2.0 GPa at 23 ° C. and 1.5 MPa at 60 ° C.
２−５．基材フィルムの比較製造例２
５０℃におけるフィルムＭＤ方向及び、ＴＤ方向の収縮率が其々、０．０％であり、８０℃の温水に１秒浸漬した時のＭＤ方向、ＴＤ方向の収縮率が其々、０．１％以下、０．０％である、２軸延伸ポリエチレンテレフタレート[帝人デュポンフィルム（株）製、商品名：テイジンテトロンフィルム 、厚み：５０μm] を選定し、その片表面に、低弾性率樹脂層として、Ｔダイ押出法にて成形した厚さ１２０μｍのエチレン−酢酸ビニル共重合体（三井・デュポンポリケミカル（株）製、銘柄：エバフレックスＰ−１９０５（ＥＶ４６０）フィルムを積層した。この際、エチレン−酢酸ビニル共重合体フィルムの粘着剤層を形成する側の面にコロナ放電処理を施し、基材フィルム５とした。
2-5. Comparative production example 2 of base film
The shrinkage in the MD and TD directions at 50 ° C. is 0.0%, respectively, and the shrinkage in the MD and TD directions is 0.1% when immersed in warm water at 80 ° C. for 1 second. %, 0.0%, biaxially stretched polyethylene terephthalate [manufactured by Teijin DuPont Films, trade name: Teijin Tetron Film, thickness: 50 μm] is selected as a low elastic modulus resin layer on one surface A 120 μm-thick ethylene-vinyl acetate copolymer (Mitsui / DuPont Polychemical Co., Ltd., brand: EVAFLEX P-1905 (EV460) film formed by T-die extrusion method was laminated. -Corona discharge treatment was performed on the surface of the vinyl acetate copolymer film on the side where the pressure-sensitive adhesive layer is to be formed, and a base film 5 was obtained.
２−６． 粘着剤層を構成する粘着剤塗布液の調製
重合反応機に脱イオン水１５０重量部、重合開始剤として４，４’−アゾビス−４−シアノバレリックアシッド〔大塚化学（株）製、商品名：ＡＣＶＡ〕を０．５重量部、アクリル酸ブチル５２．２５重量部、メタクリル酸メチル２５重量部、メタクリル酸−２−ヒドロキシエチル１５重量部、メタクリル酸６重量部、アクリルアミド１重量部、水溶性コモノマーとしてポリオキシエチレンノニルフェニルエーテル（エチレンオキサイドの付加モル数の平均値；約２０）の硫酸エステルのアンモニウム塩のベンゼン環に重合性の１−プロペニル基を導入したもの〔第一工業製薬（株）製：商品名：アクアロンＨＳ−２０〕０．７５重量部を添加し、攪拌下で７０℃において９時間乳化重合を実施し、アクリル樹脂系水エマルジョンを得た。これを１４重量％アンモニア水で中和し、固形分４０重量％を含有する粘着剤ポリマーエマルジョン（粘着剤主剤）を得た。得られた粘着剤主剤エマルジョン１００重量部（粘着剤ポリマー濃度：４０重量％）を採取し、さらに１４重量％アンモニア水を加えてｐＨ９．３に調整した。次いで、アジリジン系架橋剤〔日本触媒化学工業（株）製、商品名：ケミタイトＰＺ−３３〕４.０重量部、及びジエチレングリコールモノブチルエーテル５重量部を添加して粘着剤層を構成する粘着剤塗布液を得た。
2-6. Preparation of pressure-sensitive adhesive coating solution constituting pressure-sensitive adhesive layer 150 parts by weight of deionized water in a polymerization reactor, 4,4′-azobis-4-cyanovaleric acid as a polymerization initiator [trade name, manufactured by Otsuka Chemical Co., Ltd. : ACVA] 0.5 parts by weight, butyl acrylate 52.25 parts by weight, methyl methacrylate 25 parts by weight, methacrylate-2-hydroxyethyl 15 parts by weight, methacrylic acid 6 parts by weight, acrylamide 1 part by weight, water-soluble As a comonomer, a polymerizable 1-propenyl group is introduced into the benzene ring of an ammonium sulfate salt of polyoxyethylene nonylphenyl ether (average value of the number of added moles of ethylene oxide; about 20) [Daiichi Kogyo Seiyaku Co., Ltd. ) Product: Trade name: Aqualon HS-20] 0.75 part by weight was added, and emulsion polymerization was carried out at 70 ° C. for 9 hours under stirring. It was obtained Lil resin water emulsions. This was neutralized with 14 wt% aqueous ammonia to obtain an adhesive polymer emulsion (adhesive main ingredient) containing 40 wt% solid content. 100 parts by weight of the resulting pressure-sensitive adhesive main agent emulsion (pressure-sensitive adhesive polymer concentration: 40% by weight) was collected, and further adjusted to pH 9.3 by adding 14% by weight aqueous ammonia. Next, a pressure-sensitive adhesive coating is prepared by adding 4.0 parts by weight of an aziridine-based crosslinking agent [manufactured by Nippon Shokubai Chemical Industry Co., Ltd., trade name: Chemitite PZ-33] and 5 parts by weight of diethylene glycol monobutyl ether. A liquid was obtained.
２−７ 粘着フィルムの製造
片表面にシリコーン処理（離型処理）が施された厚み３８μｍのポリエチレンテレフタレートフィルム（剥離フィルム）の離型処理が施された側の面に、前述の粘着剤塗布液をロールコーターにより塗布し、１２０℃で1分間乾燥し、厚み１０μｍの粘着剤層を形成した。これに、前項で得られた基材フィルム１〜５のコロナ処理が施された側の面を、それぞれドライラミネーターにより貼り合わせて押圧して、粘着剤層をそれぞれのコロナ処理が施された側の面に転写させた。転写後、６０℃において４８時間加熱した後、室温まで冷却することにより、半導体ウエハ表面保護用粘着フィルム１〜５を得た。基材フィルム１〜５を用いて作製された粘着フィルム１〜５それぞれ半導体ウエハ表面保護フィルム１〜５とした。得られた半導体ウエハ表面保護用粘着フィルム１〜５の粘着力は、順番に０．６Ｎ/２５ｍｍ、０．６Ｎ/２５ｍｍ、０．７Ｎ/２５ｍｍ、０．６Ｎ/２５ｍｍ、０．７Ｎ/２５ｍｍであった。
2-7 Manufacture of pressure-sensitive adhesive film The pressure-sensitive adhesive coating solution described above is applied to the surface on which the release treatment of a 38 μm-thick polyethylene terephthalate film (release film) having a silicone treatment (release treatment) on one surface is performed. Was applied with a roll coater and dried at 120 ° C. for 1 minute to form an adhesive layer having a thickness of 10 μm. The surface on which the corona treatment of the base films 1 to 5 obtained in the previous section was applied to each of them by a dry laminator and pressed, and the pressure-sensitive adhesive layer was subjected to the corona treatment. It was transferred to the surface. After the transfer, the film was heated at 60 ° C. for 48 hours, and then cooled to room temperature to obtain adhesive films 1 to 5 for protecting a semiconductor wafer surface. The pressure-sensitive adhesive films 1 to 5 prepared using the base films 1 to 5 were respectively semiconductor wafer surface protective films 1 to 5. The adhesive strength of the obtained semiconductor wafer surface protecting adhesive films 1 to 5 is 0.6 N / 25 mm, 0.6 N / 25 mm, 0.7 N / 25 mm, 0.6 N / 25 mm, 0.7 N / 25 mm in order. there were.
３−１．実施例１
半導体ウェハ（ミラーウェハ）に対する、半導体ウェハ表面保護用粘着フィルム１の剥離性能を評価した。半導体ウェハ表面保護用粘着フィルム１を１０枚のミラーウェハ（直径：８インチ、厚み：７５０μｍ）の全表面に貼着した状態で、裏面研削機（（株）ディスコ製、形式：ＤＦＧ８６０）を用いて、厚みが７５μｍになるまでウェハ裏面を研削した。次いで、ウォーターバスにおいて、８０℃の温水に10秒間浸漬し、半導体ウエハ表面保護用フィルム剥離評価を実施した。１０枚のミラーウェハで実施し、１０枚とも自然に剥離した。得られた結果を表１に示す。
3-1. Example 1
The peeling performance of the semiconductor wafer surface protecting adhesive film 1 with respect to the semiconductor wafer (mirror wafer) was evaluated. Using a back surface grinding machine (manufactured by DISCO Corporation, model: DFG860) with the adhesive film 1 for protecting the surface of a semiconductor wafer adhered to the entire surface of 10 mirror wafers (diameter: 8 inches, thickness: 750 μm) Then, the back surface of the wafer was ground until the thickness became 75 μm. Subsequently, it was immersed in 80 degreeC warm water for 10 second in the water bath, and film peeling evaluation for semiconductor wafer surface protection was implemented. The test was carried out with 10 mirror wafers, and all 10 sheets were naturally peeled off. The obtained results are shown in Table 1.
３−２．実施例２
半導体ウェハ表面保護用粘着フィルム２を用いた以外、保護方法の実施例１と同様の方法を実施した。その結果、全ての評価で実施例１と同様の結果が得られた。得られた結果を表１に示す。
3-2. Example 2
A method similar to Example 1 of the protection method was carried out except that the semiconductor wafer surface protecting adhesive film 2 was used. As a result, the same results as in Example 1 were obtained in all evaluations. The obtained results are shown in Table 1.
３−３．実施例３
半導体ウェハ表面保護用粘着フィルム３を用いた以外、保護方法の実施例１と同様の方法を実施した。その結果、全ての評価で実施例１と同様の結果が得られた。得られた結果を表１に示す。
3-3. Example 3
The same method as Example 1 of the protection method was carried out except that the semiconductor wafer surface protecting adhesive film 3 was used. As a result, the same results as in Example 1 were obtained in all evaluations. The obtained results are shown in Table 1.
３−４．比較例１
半導体ウェハ表面保護用粘着フィルム４を用いた以外、保護方法の実施例１と同様の方法を実施した。その結果、ウォーターバスにおいて、８０℃の温水に10秒間浸漬し、半導体ウエハ表面保護用フィルム剥離評価を実施した。１０枚のミラーウェハで実施したところ、１０枚とも剥離することが出来なかった。得られた結果を表１に示す。
3-4. Comparative Example 1
A method similar to Example 1 of the protection method was carried out except that the semiconductor wafer surface protecting adhesive film 4 was used. As a result, the film was immersed in warm water at 80 ° C. for 10 seconds in a water bath, and the film peeling evaluation for protecting the semiconductor wafer surface was performed. When implemented with 10 mirror wafers, none of the 10 wafers could be peeled off. The obtained results are shown in Table 1.
３−５．比較例２
半導体ウェハ表面保護用粘着フィルム５を用いた以外、保護方法の実施例１と同様の方法を実施した。その結果、ウォーターバスにおいて、８０℃の温水に10秒間浸漬し、半導体ウエハ表面保護用フィルム剥離評価を実施した。１０枚のミラーウェハで実施したところ、１０枚とも剥離することが出来なかった。得られた結果を表１に示す。
3-5. Comparative Example 2
A method similar to Example 1 of the protection method was carried out except that the semiconductor wafer surface protecting adhesive film 5 was used. As a result, the film was immersed in warm water at 80 ° C. for 10 seconds in a water bath, and the film peeling evaluation for protecting the semiconductor wafer surface was performed. When implemented with 10 mirror wafers, none of the 10 wafers could be peeled off. The obtained results are shown in Table 1.
３−６．比較例３
半導体ウェハ表面保護用粘着フィルム１を貼着した後、半導体ウェハ裏面研削工程で７５μmまで研削したウェハを、剥離機（日東精機（株）製、形式：ＨＲ８５００ＩＩ）を用いて、ウェハ表面から半導体ウェハ表面保護用粘着フィルムを剥離した。１０枚のミラーウェハについて評価し、４枚のウェハで搬送時にロボットアームとウェハとで吸着不良が発生し、４枚のウェハで剥離の際にウェハの割れが発生した。得られた結果を表１に示す。
3-6. Comparative Example 3
After sticking the adhesive film 1 for protecting the semiconductor wafer surface, the wafer that has been ground to 75 μm in the semiconductor wafer back grinding process is removed from the wafer surface using a peeling machine (manufactured by Nitto Seiki Co., Ltd., model: HR8500II). The adhesive film for surface protection was peeled off. Ten mirror wafers were evaluated, and adsorption failure occurred between the robot arm and the wafer when the four wafers were transferred, and cracking of the wafer occurred when the four wafers were peeled off. The obtained results are shown in Table 1.
３−７．比較例４
半導体ウェハ表面保護用粘着フィルム１を用い、ウォーターバスの湯水温度を５０℃とする以外は、保護方法の実施例１と同様の半導体ウエハ表面保護用フィルム剥離評価を実施した。１０枚のミラーウェハで実施したところ、１０枚とも剥離することが出来なかった。得られた結果を表１に示す。
3-7. Comparative Example 4
Using the adhesive film 1 for protecting a semiconductor wafer surface, the film peeling evaluation for protecting the semiconductor wafer surface was carried out in the same manner as in Example 1 of the protection method, except that the hot water temperature of the water bath was 50 ° C. When implemented with 10 mirror wafers, none of the 10 wafers could be peeled off. The obtained results are shown in Table 1.
Claims (7)
基材フィルムの少なくとも一層に、
ポリエステル系延伸フィルムであり、
５０℃での機械方向（以下、ＭＤ方向という）及び、機械方向と直交する方向（以下、ＴＤ方向という）の収縮率がいずれも５％未満であり、
７０〜１００℃の温水、若しくは雰囲気下において、１秒以上加熱したとき、ＭＤ方向、若しくはＴＤ方向の少なくとも一方の収縮率が５〜９９％であり、
厚みが１０〜２００μｍである
樹脂層（Ａ）を含むことを特徴とする、半導体ウェハ表面保護用粘着フィルム。 A pressure-sensitive adhesive film for protecting a semiconductor wafer surface having a pressure-sensitive adhesive layer formed on one surface of a base film,
In at least one layer of the base film,
A polyester stretched film,
The shrinkage in the machine direction at 50 ° C. (hereinafter referred to as MD direction) and the direction orthogonal to the machine direction (hereinafter referred to as TD direction) are both less than 5% ,
When heated for 1 second or more in warm water at 70 to 100 ° C. or in an atmosphere, the shrinkage rate of at least one of MD direction or TD direction is 5 to 99%,
Thickness and comprising a resin layer (A) is 10 to 200 [mu] m, the adhesive film for protecting semiconductor wafer surface.
半導体ウェハの回路非形成面を加工する第二工程、および
７０〜１００℃の温水に浸漬、若しくは該温水を接射させ、該半導体ウエハ表面から該半導体ウエハ表面保護用粘着テープを剥離する第三工程、を含むことを特徴とする半導体ウエハ表面保護方法。 A first step of adhering the adhesive film for protecting a semiconductor wafer surface according to any one of claims 1 to 5 , to a circuit forming surface of the semiconductor wafer,
A second step of processing the non-circuit-formed surface of the semiconductor wafer; and
Immersion in hot water at 70 to 100 ° C., or was Isa contact the hot water, a third step, the semiconductor wafer surface protection method characterized by comprising the of peeling the semiconductor wafer surface protecting adhesive tape from the semiconductor wafer surface.
The semiconductor wafer protection method according to claim 6 , wherein the thickness of the semiconductor wafer after the second step is 150 μm or less.
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| JP5008340B2 (en) * | 2006-06-01 | 2012-08-22 | 東京応化工業株式会社 | Substrate thinning method, bonding system, and thinning system |
| TWI553083B (en) * | 2008-04-21 | 2016-10-11 | Ｌｇ化學股份有限公司 | Pressure-sensitive adhesive film and backgrinding method using the same |
| WO2010147356A2 (en) * | 2009-06-15 | 2010-12-23 | (주)Lg화학 | Wafer processing base |
| CN102763211B (en) | 2010-06-02 | 2014-11-05 | 三井化学东赛璐株式会社 | Sheet for protecting surface of semiconductor wafer, semiconductor device manufacturing method and semiconductor wafer protection method using sheet |
| JP5367903B2 (en) * | 2012-03-19 | 2013-12-11 | 古河電気工業株式会社 | Adhesive tape for semiconductor wafer surface protection |
| JP6577341B2 (en) * | 2015-11-13 | 2019-09-18 | 日東電工株式会社 | LAMINATE AND SEMICONDUCTOR DEVICE MANUFACTURING METHOD |
| JP2018100423A (en) * | 2018-03-20 | 2018-06-28 | リンテック株式会社 | Adhesive tape and method of manufacturing semiconductor device |
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