TWI540194B - Followed by the following method, followed by the later peeling method - Google Patents
Followed by the following method, followed by the later peeling method Download PDFInfo
- Publication number
- TWI540194B TWI540194B TW102125624A TW102125624A TWI540194B TW I540194 B TWI540194 B TW I540194B TW 102125624 A TW102125624 A TW 102125624A TW 102125624 A TW102125624 A TW 102125624A TW I540194 B TWI540194 B TW I540194B
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive composition
- group
- substrate
- glass substrate
- peeling
- Prior art date
Links
Landscapes
- Adhesives Or Adhesive Processes (AREA)
Description
本發明係關於一種接著性組合物與其接著方法、及接著後之剝離方法。尤其是關於形成有積體電路(Integrated Circuit，以下有時稱為IC)圖案之半導體元件製造用之接著性組合物與其接著方法、及接著後之剝離方法，進而，係關於對使半導體晶片積層於厚度方向而謀求半導體元件之高積體化之三維安裝技術有用之接著性組合物與其接著方法、及接著後之剝離方法。特佳為關於在使用用以電性連接所積層之半導體晶片間之矽貫通電極(Through Silicon Via，以下有時稱為TSV)的半導體元件之製造中，於研磨形成有半導體晶片之矽基板時，為了支持矽基板而與玻璃基板貼合之接著性組合物與其接著方法、及接著後之剝離方法。 The present invention is directed to an adhesive composition and its subsequent process, and subsequent peeling methods. In particular, the adhesive composition for forming a semiconductor device in which an integrated circuit (hereinafter referred to as an IC) pattern is formed, a method for bonding the same, and a subsequent peeling method, and further, for laminating a semiconductor wafer An adhesive composition useful in a three-dimensional mounting technique for achieving a high integration of semiconductor elements in the thickness direction, a method of bonding the same, and a subsequent peeling method. Particularly, in the manufacture of a semiconductor element using a through-silicon (hereinafter referred to as TSV) between the semiconductor wafers for electrically connecting the stacked layers, when the germanium substrate on which the semiconductor wafer is formed is polished An adhesive composition bonded to a glass substrate in order to support the ruthenium substrate, a method of annealing the same, and a subsequent peeling method.
於半導體元件中，藉由使IC圖案微細化，變得趨於小型化、多功能化及高速化等高性能化。然而，IC圖案之微細化存在有技術極限之擔憂，藉由使二維配置之半導體晶片積層於厚度方向成為三維配置而三維安裝半導體晶片，可無關於微細化而謀求半導體元件之高積體化之三維安裝技術受到關注，例如，於非專利文獻1中報告有用以安裝三維大型積體電路(Large Scale Integration，以下有時稱為LSI)之TSV技術之研究開發動向。 In the semiconductor device, by miniaturizing the IC pattern, it is becoming more compact, multi-functional, and high-speed. However, there is a technical limit in the miniaturization of the IC pattern. By stacking the semiconductor wafers which are two-dimensionally arranged in a three-dimensional arrangement in the thickness direction and mounting the semiconductor wafer three-dimensionally, it is possible to achieve high integration of semiconductor elements without miniaturization. The three-dimensional mounting technique has been attracting attention. For example, Non-Patent Document 1 reports on research and development trends for installing a TSV technology of a three-dimensional large scale integrated circuit (Large Scale Integration, hereinafter sometimes referred to as LSI).
於三維安裝中，在LSI等積體度較高之半導體元件中，使複數個半導體晶片藉由金屬細線之打線結合電性連接而封裝成為1個半導體 元件之被稱為系統級封裝(System in Package，以下有時稱為SiP)之三維安裝技術正實用化。然而，於藉由SiP之半導體晶片之三維安裝中，於半導體晶片之外側必需用以進行打線結合之空間。必需空間對半導體晶片之小型化不利。作為去除該空間而進一步提高積體度之技術，存在使用縱向貫通半導體晶片內部之矽貫通電極(TSV)之三維安裝技術。 In a three-dimensional mounting, in a semiconductor element having a high degree of integration such as an LSI, a plurality of semiconductor wafers are electrically connected by a metal thin wire and electrically connected to form a semiconductor. A three-dimensional mounting technique called a system in package (hereinafter sometimes referred to as SiP) is being put to practical use. However, in the three-dimensional mounting of a semiconductor wafer by SiP, a space for bonding a wire must be provided on the outer side of the semiconductor wafer. The necessary space is detrimental to the miniaturization of semiconductor wafers. As a technique for further removing the space and further improving the integrated body, there is a three-dimensional mounting technique using a through-via electrode (TSV) that penetrates the inside of the semiconductor wafer in the longitudinal direction.
於使用TSV之三維安裝技術中，用以於使半導體晶片積層而成之半導體元件中獲得TSV之基板加工例如包括：於形成有IC圖案之矽基板上挖掘孔槽之步驟，繼而將矽基板之背面研磨得較薄而獲得孔槽貫通而成之貫通孔之步驟，其後獲得將已獲得貫通孔之矽基板貼合併積層而成之半導體元件之步驟。其後，於貫通孔中形成矽貫通電極(TSV)。其中，於將矽基板之背面研磨得較薄而獲得貫通孔之步驟中，必須將形成有IC圖案之矽基板於以接著劑貼附於被稱為支持基板之支持體上之狀態下進行研磨。通常，因獲取容易且廉價，而使用玻璃基板作為支持基板。將研磨背面而變薄之矽基板自支持基板卸除並使之積層，於貫通孔中加工TSV而三維安裝半導體晶片。如此可獲得使形成有IC圖案之半導體晶片積層而成之半導體元件。 In the three-dimensional mounting technique using the TSV, the substrate processing for obtaining the TSV in the semiconductor device in which the semiconductor wafer is laminated includes, for example, the step of digging the hole on the germanium substrate on which the IC pattern is formed, and then the germanium substrate The step of polishing the back surface to be thin and obtaining the through hole through which the hole is formed, and then obtaining the semiconductor element in which the tantalum substrate having the through hole is laminated and laminated is obtained. Thereafter, a tantalum through electrode (TSV) is formed in the through hole. In the step of polishing the back surface of the ruthenium substrate to obtain a through-hole, it is necessary to polish the ruthenium substrate on which the IC pattern is formed in a state in which an adhesive is attached to a support called a support substrate. . Generally, a glass substrate is used as a support substrate because it is easy to obtain and inexpensive. The ruthenium substrate which is polished and polished on the back surface is removed from the support substrate and laminated, and the TSV is processed in the through hole to mount the semiconductor wafer three-dimensionally. Thus, a semiconductor element in which a semiconductor wafer in which an IC pattern is formed is laminated can be obtained.
作為上述步驟中使用之接著劑所要求之特性，可列舉：使矽基板與支持基板良好地接著；具有耐熱性；及研磨矽基板而使孔槽加工部成為貫通孔後，自矽基板剝離支持基板後，於矽基板側無附著有接著劑之接著殘渣，或即使有亦能容易地去除。此時，自矽基板剝離支持基板之剝離方法較簡便為宜。 The properties required for the adhesive used in the above-mentioned step include a good adhesion between the ruthenium substrate and the support substrate, heat resistance, and polishing of the ruthenium substrate to make the hole processed portion a through hole. After the substrate, the subsequent residue of the adhesive agent is not adhered to the side of the substrate, or can be easily removed even if it is present. At this time, the method of peeling off the support substrate from the substrate is relatively simple.
於專利文獻1~3中揭示有可用於形成TSV之接著劑。 Patent Documents 1 to 3 disclose an adhesive which can be used to form a TSV.
例如，於專利文獻1中揭示有接合用組合物之使用方法，其係使特定之熱塑性組合物分散或溶解於溶劑者，且將活性晶圓接合於載體晶圓或基板上，對在其後之處理或操作中保護活性晶圓或其活性部位 有用。該文獻中指出，接著性組合物形成接合層，該接合層具有耐化學品性及耐熱性，於製造步驟之適當階段可使之軟化以可使晶圓滑動並分開。於分開(剝離)時，在以高溫使接著劑軟化之狀態下，藉由機械之力使兩片基板剝離，最後以溶劑將附著於矽基板之接著殘渣洗淨。 For example, Patent Document 1 discloses a method of using a composition for bonding, in which a specific thermoplastic composition is dispersed or dissolved in a solvent, and the active wafer is bonded to a carrier wafer or a substrate, and thereafter Protecting active wafers or their active sites during processing or operation it works. It is pointed out in this document that the adhesive composition forms a bonding layer which has chemical resistance and heat resistance which can be softened at appropriate stages of the manufacturing step to allow the wafer to slide and separate. At the time of separation (peeling), the two substrates are peeled off by mechanical force in a state where the adhesive is softened at a high temperature, and finally the subsequent residue adhering to the ruthenium substrate is washed with a solvent.
於專利文獻2中揭示有接著劑組合物，其特徵在於：其係以使包含具有馬來醯亞胺基之單體之單體組合物共聚合而成之聚合物為主成分者，且進而包含熱聚合抑制劑。於剝離時使兩片基板浸漬於有機溶劑中，在進行剝離之同時使接著劑溶解。 Patent Document 2 discloses an adhesive composition characterized in that a polymer obtained by copolymerizing a monomer composition containing a monomer having a maleimide group as a main component, and further Contains a thermal polymerization inhibitor. At the time of peeling, two sheets of the substrate were immersed in an organic solvent, and the adhesive was dissolved while being peeled off.
又，於專利文獻3中揭示有相反將被安裝之元件晶圓自載體基板分離之方法及裝置。本方法僅於作為晶圓之矽基板之外周部分使用接著劑，於矽基板之內側使用不表現接著力之樹脂而支持，以使內側不產生接著殘渣。 Further, Patent Document 3 discloses a method and an apparatus for separating an element wafer to be mounted from a carrier substrate. This method uses an adhesive only on the outer peripheral portion of the substrate as a wafer, and supports the resin on the inner side of the tantalum substrate without using an adhesive force so that no residue remains on the inner side.
專利文獻1：日本專利特表2010-531385號公報 Patent Document 1: Japanese Patent Laid-Open Publication No. 2010-531385
專利文獻2：日本專利特開2010-24435號公報 Patent Document 2: Japanese Patent Laid-Open Publication No. 2010-24435
專利文獻3：日本專利特開2012-4522號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2012-4522
非專利文獻1：吉永孝司，Science & Technology Trends, April, 2010, p.23~p.34 Non-Patent Document 1: Ji Yongxiao, Science & Technology Trends, April, 2010, p.23~p.34
於半導體元件製造時，尤其於TSV加工時，將矽基板接著於支持基板並於特定之加工後使之剝離之情形時，存在接著殘渣殘留於矽基板上，而產生去除接著殘渣之必要之情況。對於接著劑，要求可迅速 進行接著且可承受接著後之基板研磨等機械處理之接著力及耐熱性、及於特定之加工後可容易地剝離。 When manufacturing a semiconductor device, especially in the case of TSV processing, when the germanium substrate is attached to the support substrate and is peeled off after the specific processing, there is a case where the residue remains on the germanium substrate, and the necessity of removing the residue is generated. . For adhesives, the requirements can be quickly The adhesion and heat resistance of the mechanical treatment such as subsequent substrate polishing can be carried out, and the film can be easily peeled off after the specific processing.
本發明之目的在於提供滿足上述要求之接著性組合物與其接著方法、及接著後之剝離方法。 It is an object of the present invention to provide an adhesive composition that satisfies the above requirements, a method of continuation thereof, and a subsequent peeling method.
本發明包括以下之發明1~6。 The present invention includes the following inventions 1 to 6.
[發明1] [Invention 1]
一種接著性組合物，其包含：具有光聚合性基之矽氧烷化合物、光聚合起始劑、及發泡劑。 An adhesive composition comprising: a siloxane compound having a photopolymerizable group, a photopolymerization initiator, and a foaming agent.
[發明2] [Invention 2]
如發明1之接著性組合物，其中光聚合性基係包含選自由丙烯醯基、甲基丙烯醯基、乙烯基、環氧基、氧雜環丁烷基及乙烯醚基所組成之群中之至少一種基者。 An adhesive composition according to Invention 1, wherein the photopolymerizable group comprises a group selected from the group consisting of an acrylonitrile group, a methacryl group, a vinyl group, an epoxy group, an oxetanyl group, and a vinyl ether group. At least one of the basics.
[發明3] [Invention 3]
如發明1或2之接著性組合物，其中矽氧烷化合物係烷氧基矽烷之水解縮合物。 The adhesive composition according to Invention 1 or 2, wherein the oxoxane compound is a hydrolysis condensate of alkoxy decane.
[發明4] [Invention 4]
如發明1或2之接著性組合物，其中矽氧烷化合物係籠型倍半矽氧烷。 An adhesive composition according to Invention 1 or 2, wherein the siloxane compound is a cage sesquioxane.
[發明5] [Invention 5]
一種接著方法，其係將如發明1至4中任一項之接著性組合物夾持於基板間，並對接著性組合物照射光使接著性組合物硬化而使基板彼此接著。 An adhesive method in which the adhesive composition according to any one of Inventions 1 to 4 is sandwiched between substrates, and the adhesive composition is irradiated with light to harden the adhesive composition to cause the substrates to adhere to each other.
[發明6] [Invention 6]
如發明5之接著方法，其中使基板彼此接著係使矽基板與玻璃基板接著。 A method according to Invention 5, wherein the substrates are bonded to each other to cause the ruthenium substrate to follow the glass substrate.
[發明7] [Invention 7]
如發明5或6之接著方法，其包括將具有光聚合性基之烷氧基矽烷之水解縮合物塗佈於玻璃基板之接著面之步驟。 The method according to Invention 5 or 6, which comprises the step of applying a hydrolysis condensate of alkoxysilane having a photopolymerizable group to the back surface of the glass substrate.
[發明8] [Invention 8]
一種剝離方法，其係將使用如發明1至4中任一項之接著性組合物而接著之基板加熱而剝離。 A peeling method by using the adhesive composition according to any one of Inventions 1 to 4, followed by heating and peeling off the substrate.
利用本發明之接著性組合物之接著可藉由光照射迅速進行。例如，於將接著性組合物配置於玻璃基板與矽基板之間後，自玻璃基板側照射光使接著性組合物硬化，藉此使玻璃基板與矽基板接著。藉由本發明之接著性組合物接著而成之接著物具有可藉由加熱使接著性組合物中之發泡劑發泡而將矽基板與接著劑層分開(剝離)，且於剝離後接著殘渣不殘留於矽基板上之效果。又，本發明之接著性組合物具有可承受接著後之基板研磨等機械處理之接著力及耐熱性，並於特定之加工後可容易地剝離。 The subsequent use of the adhesive composition of the present invention can be rapidly carried out by light irradiation. For example, after the adhesive composition is disposed between the glass substrate and the ruthenium substrate, light is irradiated from the glass substrate side to cure the adhesive composition, thereby adhering the glass substrate to the ruthenium substrate. The subsequent composition obtained by the adhesive composition of the present invention has a structure in which the foaming agent in the adhesive composition can be foamed by heating to separate (peel) the tantalum substrate from the adhesive layer, and after the peeling, the residue is removed. The effect of not remaining on the ruthenium substrate. Further, the adhesive composition of the present invention has an adhesive force and heat resistance which can withstand mechanical processing such as subsequent substrate polishing, and can be easily peeled off after specific processing.
1‧‧‧塗佈層 1‧‧‧ coating layer
2‧‧‧接著性組合物層(接著性組合物) 2‧‧‧Adhesive composition layer (adhesive composition)
G‧‧‧玻璃基板 G‧‧‧glass substrate
S‧‧‧矽基板 S‧‧‧矽 substrate
圖1係玻璃基板與矽基板之接著及剝離步驟之說明圖，(A)係接著前之概略圖，(B)係接著後之概略圖，(C)係剝離後之概略圖。 Fig. 1 is an explanatory view showing a step of peeling off and peeling off a glass substrate and a tantalum substrate, (A) is a schematic view immediately before, (B) is a schematic view after that, and (C) is a schematic view after peeling.
本發明之接著性組合物與其使用方法、及接著後之剝離方法由於可藉由光照射進行迅速接著，且具有可承受接著後之基板研磨等之接著力及耐熱性，進而於不需要時可剝離，因此例如適用於半導體元件製造用途，較佳為被採用於半導體元件製造用之接著性組合物與其接著方法、及接著後之剝離方法。進而較佳為被採用於具有矽貫通電極(TSV)之半導體元件製造用之接著性組合物與其使用方法、及接著後之剝離方法。以下，對本發明之接著性組合物與其使用方法、及接著後之剝離方法進行說明。 The adhesive composition of the present invention, the method of using the same, and the subsequent peeling method can be quickly followed by light irradiation, and have an adhesive force and heat resistance which can withstand subsequent polishing of the substrate, and the like, and can be used when not needed. Since it is peeled, it is suitable, for example, for the semiconductor element manufacturing use, and is preferably used for the adhesive composition for manufacturing a semiconductor element, the following method, and the subsequent peeling method. Further, it is preferably an adhesive composition for use in the manufacture of a semiconductor element having a tantalum through electrode (TSV), a method of using the same, and a subsequent peeling method. Hereinafter, the adhesive composition of the present invention, the method of using the same, and the subsequent peeling method will be described.
本發明之接著性組合物包含具有光聚合性基之矽氧烷化合物。矽氧烷化合物之光聚合性基較佳為包含選自由丙烯醯基、甲基丙烯醯基、乙烯基、環氧基、氧雜環丁烷基及乙烯醚基所組成之群中之至少一種基之光聚合性基。又，本發明之接著性組合物包含用以藉由光照射開始聚合之光聚合起始劑、及藉由加熱產生氣體之發泡劑。再者，根據本發明，所謂矽氧烷化合物，係以矽與氧為骨架之化合物，且係具有矽氧鍵(-Si-O-Si-)者，亦包含環狀矽氧烷化合物。 The adhesive composition of the present invention contains a siloxane compound having a photopolymerizable group. The photopolymerizable group of the oxoxane compound preferably contains at least one selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an epoxy group, an oxetanyl group, and a vinyl ether group. A photopolymerizable group. Further, the adhesive composition of the present invention comprises a photopolymerization initiator for starting polymerization by light irradiation, and a foaming agent for generating a gas by heating. Further, according to the present invention, the oxime compound is a compound having ruthenium and oxygen as a skeleton, and has a oxime bond (-Si-O-Si-), and also contains a cyclic siloxane compound.
以下，對本發明之接著性組合物之要素分別進行說明。 Hereinafter, the elements of the adhesive composition of the present invention will be separately described.
作為具有光聚合性基之矽氧烷化合物，可藉由先前已知之溶膠凝膠法製造，就原料化合物易獲取之方面而言，可較佳地使用具有光聚合性基之烷氧基矽烷之水解縮合物。所謂具有光聚合性基之烷氧基矽烷之水解縮合物，係分別使用至少一種以上之以下通式(1)或通式(2)所表示之烷氧基矽烷，使其水解縮合而獲得之縮合物。 The siloxane compound having a photopolymerizable group can be produced by a previously known sol-gel method, and an alkoxy decane having a photopolymerizable group can be preferably used in terms of easy availability of a raw material compound. Hydrolyzed condensate. The hydrolysis condensate of the alkoxy decane having a photopolymerizable group is obtained by hydrolyzing and condensing at least one or more alkoxy decane represented by the following general formula (1) or (2). Condensate.
[化1](R1)xSi(OR2)4-x (1) ( 1 )(R 1 ) x Si(OR 2 ) 4-x (1)
(式(1)中，R1分別獨立為甲基或苯基，R2分別獨立為甲基或乙基，x係0~3之整數) (In the formula (1), R 1 is independently a methyl group or a phenyl group, and R 2 is independently a methyl group or an ethyl group, and x is an integer of 0 to 3)
[化2](R3)xSi(OR4)4-x (2) (R 2 ) x Si(OR 4 ) 4-x (2)
(式(2)中，R3係光聚合性基，R4分別獨立為甲基或乙基，R3分別獨立為包含選自由丙烯醯基、甲基丙烯醯基、乙烯基、環氧基、氧雜環丁烷基及乙烯醚基所組成之群中之至少1種基之光聚合性基，x係1~3之整數) (In the formula (2), R 3 is a photopolymerizable group, and each of R 4 is independently a methyl group or an ethyl group, and each of R 3 is independently selected from the group consisting of an acryloyl group, a methacryl group, a vinyl group, and an epoxy group. a photopolymerizable group of at least one of the group consisting of an oxetanyl group and a vinyl ether group, and x is an integer of 1 to 3)
例如，由作為式(1)所表示之烷氧基矽烷之苯基三甲氧基矽烷(R1=苯基，R2=甲基，x=1)或二甲基二乙氧基矽烷(R1=甲基，R2=乙基，x=2)、及作為式(2)所表示之烷氧基矽烷之3-甲基丙烯酸丙酯基(三甲氧基矽烷)(R3=甲基丙烯酸丙酯基，R4=甲基，x=1)所獲得之水解縮合物被認為具有以下所示之部分結構。再者，圖中之波形線係指其前端亦有鍵連續。 For example, phenyltrimethoxydecane (R 1 =phenyl, R 2 =methyl, x=1) or dimethyldiethoxydecane (R) represented by the alkoxydecane represented by the formula (1) 1 = methyl, R 2 = ethyl, x = 2), and 3-propyl methacrylate (trimethoxydecane) as the alkoxydecane represented by the formula (2) (R 3 = methyl group) The hydrolysis condensate obtained by the propyl acrylate group, R 4 = methyl group, x = 1) is considered to have a partial structure shown below. Furthermore, the wavy line in the figure means that the front end also has a key continuous.
又，亦可較佳地使用具有光聚合基之籠型倍半矽氧烷作為具有光聚合性基之矽氧烷化合物。籠型倍半矽氧烷係亦可稱為球狀矽酸鹽(Spherosilicate)之化合物。具有光聚合基之籠型倍半矽氧烷可藉由使具有以下結構之八(二甲基矽烷基)八倍半矽氧烷發生矽氫化反應而獲得。 Further, a cage type sesquiterpene oxide having a photopolymerizable group can be preferably used as the photopolymerizable group-containing oxane compound. The cage sesquiterpene is also known as a compound of spherosilicate. The caged sesquiterpene having a photopolymerizable group can be obtained by subjecting octa(dimethyl decyl) sesquioxane having the following structure to a hydrazine hydrogenation reaction.
[化4]
作為具有光聚合基之籠型倍半矽氧烷之一例，可列舉以下通式所表示之矽氧烷化合物。 An example of the cage sesquioxane having a photopolymerizable group is a oxoxane compound represented by the following formula.
光聚合性基包含於基B之X部位。光聚合性基係包含選自由丙烯醯基、甲基丙烯醯基、乙烯基、環氧基、氧雜環丁烷基及乙烯醚基所組成之群中之至少一種基者，作為包含此種光聚合性基之基B，例如可例示具有以下結構者。 The photopolymerizable group is contained at the X site of the group B. The photopolymerizable group contains at least one selected from the group consisting of an acryloyl group, a methacryloyl group, a vinyl group, an epoxy group, an oxetanyl group, and a vinyl ether group, and includes The base B of the photopolymerizable group can be exemplified by the following structure.
[化6]
具有該等結構之光聚合性之籠型倍半矽氧烷於室溫下為液體，可作為本發明之接著性組合物使用。 The photopolymerizable cage type sesquiterpene oxide having such a structure is liquid at room temperature and can be used as the adhesive composition of the present invention.
作為具有光聚合基之籠型倍半矽氧烷之另一例，可列舉以下通式所表示之化合物。 Another example of the cage sesquioxane having a photopolymerizable group is a compound represented by the following formula.
基L為1個以上、8個以下，基L與基M之總和為8。光聚合性基包含於基L之X部分，具體而言，其係包含選自由上述丙烯醯基、甲基丙烯醯基、乙烯基、環氧基、氧雜環丁烷基及乙烯醚基所組成之群中之至少一種基之光聚合性基。 The base L is one or more and eight or less, and the sum of the base L and the base M is 8. The photopolymerizable group is contained in the X moiety of the group L, specifically, it is selected from the group consisting of the above-mentioned acryloyl group, methacryloyl group, vinyl group, epoxy group, oxetanyl group, and vinyl ether group. A photopolymerizable group of at least one of the constituent groups.
基M係對於藉由光照射產生自由基等而發生化學變化之光聚合起始劑惰性之基，例如可列舉：於Y部位不含有氫原子或雙鍵，而含有烷基或芳基之基等。作為此種基M，例如可例示具有以下結構者。 The group M is a group which is inert to a photopolymerization initiator which chemically changes by radical irradiation or the like by light irradiation, and examples thereof include a group having an alkyl group or an aryl group which does not contain a hydrogen atom or a double bond at the Y site. Wait. As such a base M, for example, the following structure can be exemplified.
本發明之接著性組合物所包含之光聚合起始劑係藉由可見光或紫外光之照射而產生自由基或陽離子者。以產生之自由基或陽離子為起點開始聚合，將接著性組合物高分子化使之硬化，藉此可接著基板等。 The photopolymerization initiator contained in the adhesive composition of the present invention generates radicals or cations by irradiation with visible light or ultraviolet light. The polymerization is started starting from the generated radical or cation, and the adhesive composition is polymerized and cured, whereby the substrate or the like can be attached.
對於光聚合起始劑，較佳為使用光自由基聚合起始劑或光陽離子聚合起始劑。該光聚合性起始劑係根據矽氧烷化合物所含有之光聚合基之種類而選擇。於聚合性基為丙烯醯基、甲基丙烯醯基及乙烯基之情形時，較佳為使用光自由基聚合起始劑，於聚合性基為環氧基、氧雜環丁烷基及乙烯醚基之情形時，較佳為使用光陽離子聚合起始劑。 As the photopolymerization initiator, a photoradical polymerization initiator or a photocationic polymerization initiator is preferably used. The photopolymerizable initiator is selected depending on the kind of photopolymerizable group contained in the siloxane compound. When the polymerizable group is a propylene fluorenyl group, a methacryl fluorenyl group or a vinyl group, a photoradical polymerization initiator is preferably used, and the polymerizable group is an epoxy group, an oxetane group and an ethylene group. In the case of an ether group, a photocationic polymerization initiator is preferably used.
光自由基聚合起始劑有分子內之鍵藉由高能量射線之吸收而斷裂並產生自由基之分子內斷裂型、及藉由併用三級胺或醚等氫供與體而產生自由基之奪氫型等。於本發明之接著性組合物中，光自由基聚 合起始劑只要可藉由吸收光產生自由基，使具有上述光聚合性基之矽氧烷化合物聚合即可。 The photoradical polymerization initiator has an intramolecular bond which is broken by absorption of a high-energy ray and generates an intramolecular cleavage type of a radical, and generates a radical by using a hydrogen such as a tertiary amine or an ether. Hydrogen abstraction and so on. In the adhesive composition of the present invention, photoradical polymerization The initiator may be polymerized by a photocatalytic group-derived alkoxylate compound by generating a radical by absorbing light.
例如，作為分子內斷裂型之2-羥基-2-甲基-1-苯基丙烷-1-酮(Ciba Specialty Chemicals股份有限公司製，商品名Darocur 1173)藉由光照射(尤其是波長200nm以上、420nm以下之紫外線區域之光)導致碳-碳鍵斷裂，由此產生自由基。 For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Darocur 1173), which is an intramolecular cleavage type, is irradiated with light (especially at a wavelength of 200 nm or more). Light in the ultraviolet region below 420 nm) causes carbon-carbon bond cleavage, thereby generating free radicals.
又，作為奪氫型，二苯甲酮、鄰安息香苯甲酸甲酯、4-苯甲醯基-4'-甲基二苯硫醚或樟腦醌等藉由與氫供與體之雙分子反應而產生自由基。 Further, as a hydrogen abstraction type, a bimolecular reaction with a hydrogen donor such as benzophenone, methyl benzoate, methyl 4-benzylidene-4'-methyldiphenyl sulfide or camphorquinone And generate free radicals.
藉由該等自由基之作用，丙烯醯基、甲基丙烯醯基或乙烯基之雙鍵斷裂而進行聚合。 The polymerization of the double bond of the acryl fluorenyl group, the methacryl fluorenyl group or the vinyl group is carried out by the action of the radicals.
除此以外，可使用市售之光自由基聚合起始劑。例如可自Ciba Specialty Chemicals股份有限公司製之光自由基聚合起始劑Darocur系列，使用2-羥基-2-甲基-1-苯基-丙烷-1-酮(商品名Darocur 1173)；自Darocur TPO或Irgacure系列，使用2-羥基-1-{4-[4-(2-羥基-2-甲基-丙醯基)-苄基]苯基}-2-甲基-丙烷-1-酮(商品名Irgacure 127)、1-羥基-環己基-苯基-酮(商品名Irgacure 184)、1-[4-(2-羥基乙氧基)-苯基]-2-羥基-2-甲基-丙烷-1-酮(商品名Irgacure 2959)、2-苄基-2-二甲基胺基-1-(4-啉基苯基)-丁酮-1(商品名Irgacure 369、Irgacure 379)、2-(二甲基胺基)-2-[(4-甲基苯基)甲基]-1-[4-(4-啉基)苯基]-1-丁酮(商品名Irgacure 379EG)、氧基苯乙酸與2-[2-氧代-2-苯基乙醯氧基乙氧基]乙酯與氧基苯乙酸2-(2-羥基乙氧基)乙酯之混合物(商品名Irgacure 754)、2-甲基-1-(4-甲基噻吩基)-2-啉基丙烷-1-酮(商品名Irgacure 907、Irgacure 1700、Irgacure 1800、Irgacure 1850、Irgacure 1870)、雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(商品名Irgacure 819)、雙(η5-2,4-環戊二烯-1-基)-雙(2,6-二氟-3-(1H-吡咯-1-基)-苯基)鈦(商品名 Irgacure 784、Irgacure 4265)。 In addition to this, commercially available photoradical polymerization initiators can be used. For example, a photoradical polymerization initiator Darocur series manufactured by Ciba Specialty Chemicals Co., Ltd., using 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name Darocur 1173); from Darocur TPO or Irgacure series using 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propenyl)-benzyl]phenyl}-2-methyl-propan-1-one (trade name Irgacure 127), 1-hydroxy-cyclohexyl-phenyl-ketone (trade name Irgacure 184), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl Base-propan-1-one (trade name Irgacure 2959), 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)-butanone-1 (trade name Irgacure 369, Irgacure 379), 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4- (4- Phenyl)phenyl]-1-butanone (trade name Irgacure 379EG), oxyphenylacetic acid and 2-[2-oxo-2-phenylethenyloxyethoxy]ethyl ester and oxyphenylacetic acid Mixture of 2-(2-hydroxyethoxy)ethyl ester (trade name Irgacure 754), 2-methyl-1-(4-methylthienyl)-2- Lolinylpropan-1-one (trade name Irgacure 907, Irgacure 1700, Irgacure 1800, Irgacure 1850, Irgacure 1870), bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (trade name) Irgacure 819), bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium (trade name) Irgacure 784, Irgacure 4265).
光陽離子聚合起始劑係藉由高能量射線之照射產生使陽離子聚合開始之酸觸媒之化合物，尤其是具有鎓鹽之化學結構者於保存穩定性及耐熱性之方面有用。 The photocationic polymerization initiator is a compound which generates an acid catalyst which initiates cationic polymerization by irradiation with high energy rays, and in particular, a chemical structure having a phosphonium salt is useful for storage stability and heat resistance.
作為市售之光陽離子聚合起始劑，可列舉：三苯基鋶六氟銻酸鹽(Midori Kagaku股份有限公司製，商品名TPS103)或雙(4-第三丁基苯基)錪六氟銻酸鹽(Midori Kagaku股份有限公司製，商品名BBI-103)。 The commercially available photocationic polymerization initiator may, for example, be triphenylsulfonium hexafluoroantimonate (manufactured by Midori Kagaku Co., Ltd., trade name TPS103) or bis(4-tert-butylphenyl)phosphonium hexafluoride. Citrate (manufactured by Midori Kagaku Co., Ltd., trade name BBI-103).
於本發明之接著性組合物中，為了提高光聚合起始劑之光之吸收效率，亦可添加光增感劑。作為光增感劑，例如可使用蒽、2-乙基-9,10-二甲氧基蒽或2-異丙基-9-氧硫。又，作為市售之增感劑，可列舉：日本化藥股份有限公司製，商品名KAYACURE DETX-S。 In the adhesive composition of the present invention, a light sensitizer may be added in order to increase the light absorbing efficiency of the photopolymerization initiator. As the photosensitizer, for example, hydrazine, 2-ethyl-9,10-dimethoxyfluorene or 2-isopropyl-9-oxosulfurate can be used. . Moreover, as a commercially available sensitizer, the product name is KAYACURE DETX-S, manufactured by Nippon Kayaku Co., Ltd.
於本發明之接著性組合物中，較佳為使用藉由加熱而產生氣體之發泡劑。對於該發泡劑，可列舉：藉由加熱改變化學結構而產生氣體之化合物、吸附成分脫離而產生氣體之化合物、或具有熱不穩定性之化學鍵並藉由加熱分解而產生氣體之有機化合物。藉由選擇具有所需之發泡溫度之發泡劑，可將基板剝離時之溫度調整為所需之溫度。尤其可將矽基板自於TSV用貫通孔之加工中藉由本發明之接著性組合物接著而成之支持基板自發地剝離時之溫度調整為所需之溫度。 In the adhesive composition of the present invention, it is preferred to use a foaming agent which generates a gas by heating. Examples of the foaming agent include a compound which generates a gas by heating to change a chemical structure, a compound which generates a gas by removing an adsorbed component, or an organic compound which has a chemical bond which is thermally unstable and which is decomposed by heating to generate a gas. The temperature at which the substrate is peeled off can be adjusted to a desired temperature by selecting a blowing agent having a desired foaming temperature. In particular, the temperature at which the support substrate is spontaneously peeled off by the subsequent composition of the present invention can be adjusted to a desired temperature from the processing of the TSV through-hole.
藉由加熱改變化學結構而發泡之發泡劑可分為有機化合物與無機化合物。作為有機化合物之例，可列舉：於約245℃下產生氮氣及氨氣等之亞肼基二甲醯胺(三協化成股份有限公司製，商品名Cellmic 142)、於200℃附近產生氮氣及二氧化碳等之偶氮二甲醯胺(三協化成股份有限公司製，商品名Cellmic CE)、於200℃附近產生氮氣等之 N,N'-二亞硝基五亞甲基四胺(永和化成工業股份有限公司製，商品名Cellular D)、及於160℃附近產生氮氣等之4,4'-氧基雙(苯磺醯肼)(永和化成工業股份有限公司製，商品名Neocellborn)。作為無機化合物之例，可列舉：於140℃以上產生二氧化碳之碳酸氫鈉。又，作為市售之發泡劑，可列舉：於325℃附近產生氮氣之永和化成工業股份有限公司製之商品名Celltetra BHT-2NH3，或於350℃附近產生氮氣之永和化成工業股份有限公司製之商品名Celltetra BHT-PIPE。 The foaming agent which is foamed by heating to change the chemical structure can be classified into an organic compound and an inorganic compound. Examples of the organic compound include mercaptodimethylamine (manufactured by Sankyo Chemical Co., Ltd., trade name Cellmic 142) which generates nitrogen gas and ammonia gas at about 245 ° C, and nitrogen gas is generated at around 200 ° C. Azoximeamine such as carbon dioxide (manufactured by Sankyo Chemical Co., Ltd., trade name Cellmic CE), nitrogen gas generated at around 200 ° C, etc. N,N'-dinitrosopentamethylenetetramine (manufactured by Yonghe Chemical Industry Co., Ltd., trade name Cellular D), and 4,4'-oxybis (benzenesulfonate) such as nitrogen gas generated at around 160 °C醯肼) (made by Yonghe Chemical Industry Co., Ltd., trade name Neocellborn). Examples of the inorganic compound include sodium hydrogencarbonate which generates carbon dioxide at 140 ° C or higher. In addition, as a commercially available foaming agent, Celltetra BHT-2NH3, manufactured by Yonghe Chemical Industry Co., Ltd., which produces nitrogen gas at around 325 °C, or manufactured by Yonghe Chemical Industry Co., Ltd., which produces nitrogen gas at around 350 °C, may be used. The trade name Celltetra BHT-PIPE.
又，發泡劑亦可使用烷氧基矽烷之水解縮合物。該水解縮合物於組成中存在多個未反應之矽烷醇基(Si-OH)，因此藉由利用加熱之脫水縮合反應產生水。若加熱至水之沸點(100℃)以上，則水蒸發變成水蒸氣，因此水解縮合物可發揮作為發泡劑之功能。 Further, as the foaming agent, a hydrolysis condensate of alkoxysilane may also be used. The hydrolysis condensate has a plurality of unreacted stanol groups (Si-OH) in the composition, and thus water is produced by a dehydration condensation reaction by heating. When heated to the boiling point (100 ° C) or more of water, water evaporates into water vapor, and thus the hydrolyzed condensate functions as a foaming agent.
作為藉由加熱使吸附成分脫離而產生氣體之化合物，例如可列舉於約300℃下分離吸附水而產生水蒸氣之硼酸鋅(早川商事股份有限公司製，商品名FireBreak ZB)作為發泡劑使用。 As a compound which generates a gas by desorption of the adsorption component by heating, for example, zinc borate (manufactured by Hayakawa Co., Ltd., trade name FireBreak ZB) which separates the adsorbed water and generates water vapor at about 300 ° C is used as a foaming agent. .
對於具有熱不穩定性之化學鍵並藉由加熱分解而產生氣體之有機化合物，可列舉：具有半縮醛鍵、三級碳酸酯鍵、三級羧酸酯鍵、縮醛鍵或磺酸酯之化合物。具有該等鍵之有機化合物於特定之溫度下熱分解，因此可將其熱分解產物用作發泡劑。所謂該有機化合物，例如係按照以下所示之反應式(1)~(5)進行熱分解之有機化合物。再者，R5、R6分別獨立地表示烷基或芳基。 Examples of the organic compound having a thermally unstable chemical bond and generating a gas by decomposition by heating include a hemiacetal bond, a tertiary carbonate bond, a tertiary carboxylate bond, an acetal bond or a sulfonate. Compound. The organic compound having these bonds is thermally decomposed at a specific temperature, and thus its thermal decomposition product can be used as a foaming agent. The organic compound is, for example, an organic compound which is thermally decomposed according to the reaction formulas (1) to (5) shown below. Further, R 5 and R 6 each independently represent an alkyl group or an aryl group.
[化10]
於本發明之接著性組合物中，亦可以提高矽基板與接著性組合物之接著力等控制接著力為目的，添加具有極性基之化合物。例如藉由添加甲基丙烯酸(2-羥基乙基)酯、季戊四醇三丙烯酸酯(大阪有機化學工業股份有限公司製，商品名Viscoat#300)、環氧丙烯酸酯(大阪有機化學工業股份有限公司製，商品名Viscoat#540)、磷酸三(2-丙烯醯氧基乙基)酯(大阪有機化學工業股份有限公司製，商品名Viscoat 3PA)或磷酸雙(2-甲基丙烯醯氧乙基)酯(日本化藥股份有限公司製，商品名 KAYAMER PM-2)等具有極性基之化合物，可使接著變得更牢固。 In the adhesive composition of the present invention, a compound having a polar group may be added for the purpose of controlling the adhesion of the tantalum substrate and the adhesive composition. For example, by adding (2-hydroxyethyl) methacrylate, pentaerythritol triacrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Viscoat #300), epoxy acrylate (made by Osaka Organic Chemical Industry Co., Ltd.) , trade name Viscoat #540), tris(2-propenyloxyethyl) phosphate (manufactured by Osaka Organic Chemical Industry Co., Ltd., trade name Viscoat 3PA) or bis(2-methylpropenyloxyethyl) phosphate Ester (made by Nippon Kayaku Co., Ltd., trade name A compound having a polar group such as KAYAMER PM-2) can be made stronger later.
該化合物較佳為相對於接著性組合物之總質量，以1質量%以上、40質量%以下添加。若少於1質量%則無提高接著力之效果，而添加超過40質量%則無必要，且存在阻礙具有光聚合性基之矽氧烷化合物、光聚合起始劑、及發泡劑之作用之虞。 The compound is preferably added in an amount of 1% by mass or more and 40% by mass or less based on the total mass of the adhesive composition. If it is less than 1% by mass, the effect of improving the adhesion is not obtained, and when it is added in an amount of more than 40% by mass, it is not necessary, and the action of the siloxane compound having a photopolymerizable group, a photopolymerization initiator, and a foaming agent is hindered. After that.
本發明之接著性組合物含有具有光聚合性基之矽氧烷化合物、光聚合起始劑及發泡劑，且以質量比表示，烷氧基矽烷之具有光聚合性基之水解縮合物、光聚合起始劑及發泡劑較佳為水解縮合物：光聚合起始劑：發泡劑=50質量%~98%質量：1質量%~10質量%：1質量%~質量49%之範圍內。若於該範圍外，則易產生接著力較弱、過度發泡等不良情形。 The adhesive composition of the present invention contains a photopolymerizable group-containing oxoxane compound, a photopolymerization initiator, and a foaming agent, and is represented by a mass ratio of a hydrolyzed condensate having a photopolymerizable group of alkoxydecane. The photopolymerization initiator and the foaming agent are preferably hydrolyzed condensates: photopolymerization initiator: foaming agent = 50% by mass to 98% by mass: 1% by mass to 10% by mass: 1% by mass to 49% by mass Within the scope. If it is outside this range, it is easy to produce a bad situation such as weak adhesion and excessive foaming.
作為本發明之接著性組合物之用途，可列舉使基板彼此接著之接著方法。於將該接著方法用於利用TSV之三維安裝技術中之貫通孔加工之情形時，所謂接著之基板彼此，係用於IC圖案加工之矽基板與用於研磨矽基板時之支持之支持基板，支持基板較佳為使用易獲取且廉價之玻璃基板。較佳為對配置於該等基板間之接著性組合物照射光使接著性組合物硬化，而使基板彼此接著。此時，為了提高與接著性組合物之接著強度，較佳為將具有光聚合性基之烷氧基矽烷之水解縮合物預先塗佈於玻璃基板之接著面上。 The use of the adhesive composition of the present invention includes a method of bringing the substrates to each other. When the bonding method is used for the through hole processing in the three-dimensional mounting technique of the TSV, the substrates to be bonded are used for the substrate for IC pattern processing and the supporting substrate for polishing the substrate. The support substrate is preferably a glass substrate that is easy to obtain and inexpensive. Preferably, the adhesive composition disposed between the substrates is irradiated with light to cure the adhesive composition, and the substrates are bonded to each other. In this case, in order to increase the adhesion strength to the adhesive composition, it is preferred to apply a hydrolysis condensate of alkoxysilane having a photopolymerizable group to the subsequent surface of the glass substrate.
以下，使用圖1，對利用TSV之半導體晶片之三維安裝技術中的使用本發明之接著性組合物之接著方法進行說明，但使用本發明之接著性組合物之接著方法的實施形態並不限定於圖1。 Hereinafter, an adhesive method using the adhesive composition of the present invention in the three-dimensional mounting technique of a semiconductor wafer using TSV will be described with reference to FIG. 1. However, the embodiment of the adhesive method using the adhesive composition of the present invention is not limited. In Figure 1.
圖1係玻璃基板與矽基板之接著及剝離步驟之說明圖，(A)係接著前之概略圖，(B)係接著後之概略圖，(C)係剝離後之概略圖。利用 TSV之半導體晶片之三維安裝技術中的使用本發明之接著性組合物之接著方法的較佳實施形態係如圖1(A)所示，使將具有光聚合性基之烷氧基矽烷之水解縮合物預先塗佈於單面而成為塗佈層1的作為支持基板之玻璃基板G之塗佈面、與包含本發明之接著性組合物之塗佈層(以下稱為接著性組合物層)2之矽基板S重合，成為圖1(B)所示之積層狀態後，對塗佈層1及接著性組合物2照射光而將玻璃基板G與矽基板S接著之接著方法。再者，於接著中，較佳為玻璃基板G及矽基板S之表面潔淨。 Fig. 1 is an explanatory view showing a step of peeling off and peeling off a glass substrate and a tantalum substrate, (A) is a schematic view immediately before, (B) is a schematic view after that, and (C) is a schematic view after peeling. use A preferred embodiment of the subsequent method using the adhesive composition of the present invention in the three-dimensional mounting technique of the semiconductor wafer of TSV is as shown in Fig. 1(A) for hydrolyzing alkoxysilane having a photopolymerizable group. The condensate is applied to the coated surface of the glass substrate G as the support substrate of the coating layer 1 in advance, and the coating layer (hereinafter referred to as the adhesive composition layer) containing the adhesive composition of the present invention. After the substrate S is overlapped with each other to form a laminated state as shown in FIG. 1(B), the coating layer 1 and the adhesive composition 2 are irradiated with light, and the glass substrate G and the tantalum substrate S are subsequently adhered to each other. Further, in the following, it is preferable that the surfaces of the glass substrate G and the ruthenium substrate S are clean.
於利用TSV之三維安裝技術中，用以與矽基板S貼合之支持基板通常使用玻璃基板或石英等。作為玻璃之種類，可使用鈉鈣玻璃、無鹼玻璃、硼矽酸玻璃或石英中之任一種。若考慮不含可能滲入半導體晶片之鹼性成分、具有半導體製造之使用實績、及價格低廉等，較佳為使用無鹼玻璃。 In the three-dimensional mounting technique using TSV, a support substrate to be bonded to the ruthenium substrate S is usually a glass substrate, quartz or the like. As the kind of the glass, any of soda lime glass, alkali-free glass, borosilicate glass, or quartz can be used. It is preferable to use an alkali-free glass in consideration of the fact that it is considered that it does not contain an alkaline component which may penetrate into a semiconductor wafer, has a performance in semiconductor manufacturing, and is inexpensive.
於利用TSV之三維安裝技術中，較佳為如圖1所示，於藉由本發明之接著劑組合物接著時形成塗佈層1，其係於支持基板上，例如玻璃基板G上預先塗佈使具有光聚合性基之烷氧基矽烷之水解縮合物溶解於有機溶劑而成之澆鑄溶液而成。進而較佳為於塗佈後進行加熱將有機溶劑自塗佈層1去除，於該狀態下使該縮合物硬化，藉此於玻璃基板G之表面形成塗佈層1。 In the three-dimensional mounting technique using TSV, as shown in FIG. 1, the coating layer 1 is subsequently formed by the adhesive composition of the present invention, which is pre-coated on a support substrate, such as a glass substrate G. A casting solution obtained by dissolving a hydrolyzed condensate of alkoxysilane having a photopolymerizable group in an organic solvent. Further, it is preferable to remove the organic solvent from the coating layer 1 by heating after coating, and to cure the condensate in this state, thereby forming the coating layer 1 on the surface of the glass substrate G.
作為具有光聚合性基之烷氧基矽烷之水解縮合物，可使用自上述通式(1)或通式(2)所表示之烷氧基矽烷獲得之水解縮合物。此時之光聚合性基較佳為與接著性組合物層2中所包含之光聚合性基相同、或類似之光聚合性基。例如，於用於其後之玻璃基板G與矽基板S之接著之接著性組合物2中含有甲基丙烯醯基作為聚合性基之情形時， 較佳為於預先塗佈於玻璃基板而用於塗佈層1之具有光聚合性基之上述烷氧基矽烷的水解縮合物中包含甲基丙烯醯基或丙烯醯基。藉由如此使用與光聚合性基相同、或類似之光聚合性基，可於預先塗佈具有光聚合性基之上述烷氧基矽烷之水解縮合物而成之玻璃基板上之塗佈層1、及塗佈本發明之接著性組合物而成之矽基板之接著性組合物層2上形成化學鍵，從而更牢固地接著。上述塗佈層1具有多個之矽烷醇基，與玻璃表面極為牢固地接著，並與接著性組合物層2化學鍵結。具體而言，具有聚合性基之烷氧基矽烷之水解縮合物所含有之矽烷醇基與玻璃基板表面之矽烷醇基(-SiOH)鍵結，從而獲得較強之接著。 As the hydrolysis condensate of the alkoxysilane having a photopolymerizable group, a hydrolysis condensate obtained from the alkoxysilane represented by the above formula (1) or (2) can be used. The photopolymerizable group at this time is preferably a photopolymerizable group which is the same as or similar to the photopolymerizable group contained in the adhesive composition layer 2. For example, when a methacryl fluorenyl group is contained as a polymerizable group in the adhesive composition 2 for the subsequent glass substrate G and the ruthenium substrate S, It is preferred that the hydrolyzed condensate of the alkoxysilane having a photopolymerizable group for coating the layer 1 applied to the glass substrate in advance contains a methacryl fluorenyl group or an acrylonitrile group. By using the photopolymerizable group which is the same as or similar to the photopolymerizable group, the coating layer 1 on the glass substrate obtained by previously applying the hydrolyzed condensate of the alkoxysilane having a photopolymerizable group can be used. And a chemical bond is formed on the adhesive composition layer 2 of the substrate on which the adhesive composition of the present invention is applied, thereby adhering more firmly. The coating layer 1 has a plurality of stanol groups, which are extremely firmly adhered to the surface of the glass and chemically bonded to the layer 2 of the adhesive composition. Specifically, the stanol group contained in the hydrolysis condensate of the alkoxysilane having a polymerizable group is bonded to a stanol group (-SiOH) on the surface of the glass substrate to obtain a strong adhesion.
形成塗佈層1時，較佳為於使玻璃基板G之表面親水化後，將上述澆鑄溶液塗佈於玻璃基板G。再者，關於使玻璃基板G表面親水化之方法，可使用任意方法，例如可列舉：藉由氧化鈰之玻璃基板G表面之濕式研磨、紫外光(UV，Ultraviolet)照射、藉由臭氧或氧電漿接觸之使玻璃基板G表面之有機物分解之乾式處理、及藉由使濃硫酸與30質量%濃度之過氧化氫水以質量比成為3：1之方式混合而成之溶液使玻璃基板G表面潔淨化之食人魚(piranha)處理，只要可進行親水化處理，則可使用任意方法。 When the coating layer 1 is formed, it is preferred to apply the casting solution to the glass substrate G after hydrophilizing the surface of the glass substrate G. Further, as a method of hydrophilizing the surface of the glass substrate G, any method may be used, and examples thereof include wet grinding of the surface of the glass substrate G by cerium oxide, ultraviolet (UV) irradiation, ozone or a dry process in which the organic material on the surface of the glass substrate G is decomposed by the contact of the oxygen plasma, and a solution obtained by mixing concentrated sulfuric acid and 30% by mass of hydrogen peroxide water in a mass ratio of 3:1 to form a glass substrate. The piranha treatment in which the G surface is cleaned can be any method as long as it can be hydrophilized.
於玻璃基板G上形成塗佈層1時，作為用於澆鑄液之有機溶劑，只要為可使水解縮合物溶解之有機溶劑，則無特別限定。例如可列舉：丙二醇甲醚乙酸酯(Propylene Glycol Methyl Ether Acetate；以下有時稱為PGMEA)、及丙二醇單甲醚(Propylene Glycol Monomethyl Ether；以下有時稱為PGME)等。作為塗佈之方法，只要為可於玻璃基板G上形成平坦之薄膜之方法即可，可列舉：旋轉塗佈法、浸塗法、棒式塗佈法、輥塗法或狹縫式塗佈法。於該等方法中，較佳為使用一般使用於半導體製程中，可使塗佈面獲得良好之平坦性之旋轉塗佈法。塗佈層1之厚度並無特別限定，於以旋轉塗佈法成膜之情形 時，易形成膜厚為0.5μm~3μm之膜，故而較佳。 When the coating layer 1 is formed on the glass substrate G, the organic solvent used for the casting liquid is not particularly limited as long as it is an organic solvent capable of dissolving the hydrolysis-condensation product. For example, Propylene Glycol Methyl Ether Acetate (hereinafter sometimes referred to as PGMEA) and Propylene Glycol Monomethyl Ether (hereinafter sometimes referred to as PGME) may be mentioned. The method of coating may be a method of forming a flat film on the glass substrate G, and examples thereof include a spin coating method, a dip coating method, a bar coating method, a roll coating method, or a slit coating method. law. Among these methods, it is preferred to use a spin coating method which is generally used in a semiconductor process to obtain good flatness on a coated surface. The thickness of the coating layer 1 is not particularly limited, and is formed by a spin coating method. In this case, a film having a film thickness of 0.5 μm to 3 μm is easily formed, which is preferable.
再者，亦可於澆鑄溶液中添加光聚合起始劑，藉由接著時之紫外線照射，可於塗佈層1與接著性組合物層2之間更廣範圍地進行化學鍵之形成，可期待牢固之接著，故而較佳為添加光聚合起始劑。 Further, a photopolymerization initiator may be added to the casting solution, and by the subsequent ultraviolet irradiation, a chemical bond can be formed in a wider range between the coating layer 1 and the adhesive composition layer 2, and it is expected It is preferably followed by the addition of a photopolymerization initiator.
於玻璃基板G之塗佈面上塗佈本發明之接著性組合物而設置接著性組合物層2時之塗佈方法可列舉：旋轉塗佈法、輥塗法、狹縫式塗佈法、網版印刷法或噴墨法。 The coating method in which the adhesive composition of the present invention is applied to the coated surface of the glass substrate G and the adhesive composition layer 2 is provided includes a spin coating method, a roll coating method, a slit coating method, and the like. Screen printing or inkjet.
如圖1所示，於矽基板S與玻璃基板G之間配置接著性組合物層2，自作為接著性組合物層2之相反側之玻璃基板G之背面側照射光，藉此進行接著。接著性組合物層2藉由進行光之照射，可利用光聚合起始劑之作用進行聚合反應而硬化，從而將矽基板S與玻璃基板G接著。 As shown in FIG. 1, the adhesive composition layer 2 is disposed between the ruthenium substrate S and the glass substrate G, and light is irradiated from the back side of the glass substrate G on the opposite side of the adhesive composition layer 2, thereby performing the subsequent step. The subsequent composition layer 2 is subjected to light irradiation, and is polymerized by the action of a photopolymerization initiator to be hardened, whereby the ruthenium substrate S and the glass substrate G are bonded.
此時，光之波長只要考慮光聚合起始劑之吸收波長而選擇即可，並無特別限定，但若考慮作為光源之發光裝置之價格及獲取之容易性等，則較佳為波長200nm以上、470nm以下之光使用容易。例如，將2-羥基-2-甲基-1-苯基丙烷-1-酮(Ciba Specialty Chemicals股份有限公司，商品名Darocur 1173)用作光聚合起始劑之情形時，只要選擇波長420nm以下之紫外線即可。較佳為波長200nm以上、420nm以下之紫外線使用容易，對於該等波長區域之紫外線之光源，可列舉：高壓水銀燈、超高壓水銀燈、中壓水銀燈、低壓水銀燈、金屬鹵素燈、氙閃光燈或紫外發光二極體(LED，Light Emitting Diode)。或者於將雙(2,4,6-三甲基苯甲醯基)-苯基氧化膦(商品名Irgacure 819)用作光聚合起始劑之情形時，由於光聚合起始劑之吸收亦存在於長波長之側，因此除上述紫外線以外，亦可使用470nm之藍色LED等之光。如上所述，較佳為於玻璃基板G上預先設置用以提高接著強度之塗佈層 1。 In this case, the wavelength of the light is not particularly limited as long as it is selected in consideration of the absorption wavelength of the photopolymerization initiator. However, considering the price of the light-emitting device as a light source and the ease of acquisition, etc., the wavelength is preferably 200 nm or more. Light below 470 nm is easy to use. For example, when 2-hydroxy-2-methyl-1-phenylpropan-1-one (Ciba Specialty Chemicals Co., Ltd., trade name Darocur 1173) is used as a photopolymerization initiator, a wavelength of 420 nm or less is selected. The ultraviolet light can be. Preferably, ultraviolet rays having a wavelength of 200 nm or more and 420 nm or less are easily used. Examples of the ultraviolet light source in the wavelength regions include a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon flash lamp, or an ultraviolet light. LED (Light Emitting Diode). Or when bis(2,4,6-trimethylbenzylidene)-phenylphosphine oxide (trade name Irgacure 819) is used as a photopolymerization initiator, the absorption by the photopolymerization initiator is also Since it exists on the side of a long wavelength, it is also possible to use light of a blue LED of 470 nm other than the above-mentioned ultraviolet-ray. As described above, it is preferable to provide a coating layer for improving the bonding strength on the glass substrate G in advance. 1.
若使用本發明之接著性組合物，則於TSV加工時使矽基板S與作為支持基板之玻璃基板G接著之情形時，藉由自玻璃基板G之背面側對接著性組合物層2照射光，可使接著性組合物層2硬化而接著，因此矽基板S與玻璃基板G可於室溫(20℃)下迅速接著。 When the adhesive composition of the present invention is used, when the tantalum substrate S is bonded to the glass substrate G as the support substrate during the TSV processing, the adhesive composition layer 2 is irradiated with light from the back side of the glass substrate G. The adhesive composition layer 2 can be hardened and then the tantalum substrate S and the glass substrate G can be quickly followed at room temperature (20 ° C).
本發明之接著性組合物及使用其之接著方法之接著部位可藉由加熱發泡並剝離。本剝離係因接著性組合物所包含之發泡劑之作用而產生。 The adhesive composition of the present invention and the subsequent portion of the subsequent method using the same can be foamed by heating and peeled off. This peeling is caused by the action of the foaming agent contained in the adhesive composition.
本發明之剝離方法係使用本發明之接著性組合物使矽基板S與玻璃基板G接著後，進行加熱而將矽基板S與玻璃基板G剝離之剝離方法。本發明之接著性組合物含有發泡劑，利用加熱使接著性組合物層2中之發泡劑發泡，藉此將矽基板S與玻璃基板G剝離。 The peeling method of the present invention is a peeling method in which the tantalum substrate S and the glass substrate G are followed by heating using the adhesive composition of the present invention, and the tantalum substrate S and the glass substrate G are peeled off. The adhesive composition of the present invention contains a foaming agent, and the foaming agent in the adhesive composition layer 2 is foamed by heating, whereby the tantalum substrate S and the glass substrate G are peeled off.
本發明之接著性組合物之接著部位可藉由加熱剝離。即，使用本發明之接著性組合物接著之矽基板S與玻璃基板G之剝離方法之特徵在於接著部位之加熱。本發明之接著性組合物含有發泡劑，利用加熱使接著性組合物層2中之發泡劑發泡，藉此將矽基板S與玻璃基板G剝離。 The subsequent portion of the adhesive composition of the present invention can be peeled off by heating. That is, the method of peeling off the substrate S and the glass substrate G using the adhesive composition of the present invention is characterized by heating of the succeeding portion. The adhesive composition of the present invention contains a foaming agent, and the foaming agent in the adhesive composition layer 2 is foamed by heating, whereby the tantalum substrate S and the glass substrate G are peeled off.
具體而言，如圖1(C)所示，藉由光照射而硬化之接著性組合物層2中之發泡劑藉由加熱而發泡，並於矽基板S與接著性組合物層2之間剝離，而使矽基板S與玻璃基板G自發地剝離。此時，由於在矽基板S側未殘留接著性組合物之殘渣，因此無需將矽基板S洗淨。其原因在於，玻璃基板G與塗佈層1之接著力、及塗佈層1與接著性組合物層2之結合比接著性組合物層2與矽基板S之接著力強。與於表面具有多個矽烷醇基之玻璃基板G相比，矽基板S表面無矽烷醇基或者很少。 Specifically, as shown in FIG. 1(C), the foaming agent in the adhesive composition layer 2 which is cured by light irradiation is foamed by heating, and is applied to the tantalum substrate S and the adhesive composition layer 2 The ruthenium substrate S and the glass substrate G are spontaneously peeled off. At this time, since the residue of the adhesive composition does not remain on the side of the ruthenium substrate S, it is not necessary to wash the ruthenium substrate S. This is because the adhesion between the glass substrate G and the coating layer 1 and the bonding between the coating layer 1 and the adhesive composition layer 2 are stronger than the adhesion between the adhesive composition layer 2 and the ruthenium substrate S. Compared with the glass substrate G having a plurality of stanol groups on the surface, the surface of the ruthenium substrate S has no stanol groups or few.
例如，為了TSV之三維安裝等，於矽基板S與玻璃基板G接著之狀態下，使用加熱板或烘箱等加熱至發泡劑開始發泡之溫度以上，使本發明之接著性組合物層2發泡，而將玻璃基板G與矽基板S剝離。例如，於將亞肼基二甲醯胺(發泡溫度：245℃)用作發泡劑之情形時，剝離溫度較佳為稍微超過其發泡溫度之溫度，具體而言較佳為260℃。藉由使發泡劑發泡，可使矽基板S與玻璃基板G自發地剝離。接著性組合物層2之殘渣未殘留於矽基板S側，而全部附著於玻璃基板G側。 For example, for the three-dimensional mounting of the TSV or the like, in the state in which the substrate S and the glass substrate G are next, the laminate of the present invention is heated to a temperature at which the foaming agent starts to foam at a temperature higher than the temperature at which the foaming agent starts to foam. The glass substrate G is peeled off from the tantalum substrate S by foaming. For example, in the case where decyldimethylamine (foaming temperature: 245 ° C) is used as the foaming agent, the peeling temperature is preferably a temperature slightly exceeding the foaming temperature, and specifically, preferably 260 ° C . The tantalum substrate S and the glass substrate G can be spontaneously peeled off by foaming the foaming agent. The residue of the subsequent composition layer 2 does not remain on the side of the ruthenium substrate S, but is entirely attached to the side of the glass substrate G.
根據上述理由，剝離選擇性地發生於接著性組合物層2與矽基板S之間，接著性組合物層2之殘渣未附著於矽基板S側。 For the above reasons, the peeling selectively occurs between the adhesive composition layer 2 and the ruthenium substrate S, and the residue of the adhesive composition layer 2 does not adhere to the ruthenium substrate S side.
本發明之接著性組合物對利用TSV之半導體晶片之三維安裝技術有用，可考慮藉由本發明之接著性組合物進行之利用TSV之三維安裝技術於下一代之微處理機等邏輯半導體、Dynamic Random Access Memory(DRAM，動態隨機存取記憶體)等揮發性記憶體、快閃記憶體、或Micro Electro Mechanical Systems(MEMS，微機電系統)中之應用。 The adhesive composition of the present invention is useful for a three-dimensional mounting technique of a semiconductor wafer using TSV, and a three-dimensional mounting technique using TSV by the adhesive composition of the present invention can be considered for a logic semiconductor such as a next-generation microprocessor, Dynamic Random. Volatile memory such as Access Memory (DRAM, Dynamic Random Access Memory), flash memory, or applications in Micro Electro Mechanical Systems (MEMS).
以下，藉由實施例對本發明進行具體說明，但本發明並非由該等實施例限定者。 Hereinafter, the invention will be specifically described by way of examples, but the invention is not limited by the examples.
首先，合成用以於玻璃基板G上設置塗佈層1之烷氧基矽烷之具有光聚合基的水解縮合物。繼而，使其溶解於丙二醇甲醚乙酸酯(PGMEA)，調整澆鑄溶液後，將無鹼玻璃用作玻璃基板G並塗佈其表面。 First, a hydrolysis-condensation product having a photopolymerizable group for alkoxysilane of the coating layer 1 on the glass substrate G is synthesized. Then, it was dissolved in propylene glycol methyl ether acetate (PGMEA), and after adjusting the casting solution, alkali-free glass was used as the glass substrate G and the surface was coated.
其次，調整以下3種接著性組合物作為接著性組合物。於實施例1中，使用烷氧基矽烷之具有光聚合性基之水解縮合物作為矽氧烷化 合物，並於其中添加光聚合起始劑，藉此製成接著性組合物2。再者，實施例1中之發泡劑設為烷氧基矽烷之具有光聚合性基之水解縮合物。於實施例2中，合成具有光聚合性基之籠型倍半矽氧烷作為矽氧烷化合物，向其中添加光聚合起始劑、及於特定溫度下發泡之發泡劑而製成接著性組合物，並塗佈於矽基板S而獲得接著性組合物層2。於實施例3中，於實施例2之接著性組合物中添加有用以提高無鹼玻璃基板G與矽基板S之接著強度之具有極性基之化合物。 Next, the following three kinds of adhesive compositions were adjusted as the adhesive composition. In Example 1, a hydrolyzed condensate having a photopolymerizable group of alkoxydecane was used as the oximation. The composition was added with a photopolymerization initiator to thereby form the adhesive composition 2. Further, the foaming agent in Example 1 is a hydrolyzed condensate having a photopolymerizable group of alkoxysilane. In the second embodiment, a cage-type sesquiterpene oxide having a photopolymerizable group is synthesized as a siloxane compound, and a photopolymerization initiator and a foaming agent which is foamed at a specific temperature are added thereto to prepare a film. The composition is applied to the ruthenium substrate S to obtain the adhesive composition layer 2. In Example 3, a compound having a polar group for improving the adhesion strength between the alkali-free glass substrate G and the ruthenium substrate S was added to the adhesive composition of Example 2.
使用所獲得之接著性組合物獲得接著性組合物層2，並藉由紫外線照射接著無鹼玻璃基板G與矽基板S，其後，藉由加熱使其等剝離。以目視觀察剝離後之矽基板S之表面，將接著性組合物層2之殘渣未附著之結果判斷為良好。 The adhesive composition layer 2 was obtained using the obtained adhesive composition, and the alkali-free glass substrate G and the ruthenium substrate S were irradiated with ultraviolet rays, and thereafter, they were peeled off by heating. The surface of the ruthenium substrate S after peeling was visually observed, and the result of the adhesion of the residue of the adhesive composition layer 2 was judged to be good.
評價不在本發明之範疇內之不含發泡劑之接著性組合物作為比較例1。繼而，評價於玻璃基板上不設置塗佈層1之接著方法作為參考例1。評價不進行玻璃基板之氧化鈰研磨之接著方法作為參考例2。 The adhesive composition-free adhesive composition not in the scope of the present invention was evaluated as Comparative Example 1. Then, the following method in which the coating layer 1 was not provided on the glass substrate was evaluated as Reference Example 1. The following method of evaluating the cerium oxide polishing without the glass substrate was evaluated as Reference Example 2.
以下，對各實施例、比較例、及參考例進行詳細說明。 Hereinafter, each embodiment, comparative example, and reference example will be described in detail.
於具備戴氏冷凝器與攪拌翼之2L燒瓶內取苯基三甲氧基矽烷(信越化學工業股份有限公司製，商品名KBM-103)140.40g、二甲基二乙氧基矽烷(信越化學工業股份有限公司製，商品名KBE-22)131.14g、3-甲基丙烯酸丙酯基(三甲氧基矽烷)(東京化成股份有限公司製)48.56g、異丙醇213.32g、水160.96g、及乙酸0.10g後，於藉由油浴升溫至90℃之狀態下，以攪拌速度200rpm攪拌6小時使其等反應。變為室溫(20℃)後，添加異丙醚400ml、水400ml，藉由分液漏斗分取有機層。使用硫酸鎂脫水後，藉由蒸發器蒸餾去除有機溶劑，獲得無色透明之固形物170.68g。如此獲得具有光聚合性基之烷氧基矽烷之水解 縮合物。繼而，使該縮合物溶解於PGMEA，製成縮合物濃度為33質量%之澆鑄溶液。 Phenyltrimethoxydecane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-103), 140.40 g, dimethyldiethoxy decane (Shin-Etsu Chemical Industry) was placed in a 2 L flask equipped with a Dairy condenser and a stirring blade. Manufactured by Co., Ltd., trade name: KBE-22) 131.14g, 3-propyl methacrylate (trimethoxydecane) (manufactured by Tokyo Chemical Industry Co., Ltd.) 48.56g, isopropyl alcohol 213.32g, water 160.96g, and After 0.10 g of acetic acid, the mixture was stirred at a stirring speed of 200 rpm for 6 hours while being heated to 90 ° C in an oil bath to cause a reaction. After changing to room temperature (20 ° C), 400 ml of isopropyl ether and 400 ml of water were added, and the organic layer was separated by a separating funnel. After dehydration using magnesium sulfate, the organic solvent was distilled off by an evaporator to obtain 170.68 g of a colorless transparent solid. Hydrolysis of alkoxydecane having a photopolymerizable group Condensate. Then, this condensate was dissolved in PGMEA to prepare a casting solution having a condensate concentration of 33% by mass.
以氧化鈰之微粒子(Aldrich股份有限公司製)研磨直徑100毫米、厚度1.1毫米之無鹼玻璃基板G(Corning股份有限公司製，品名7059)之表面。繼而，使用旋轉塗佈機，於無鹼玻璃基板G表面以1000rpm旋轉塗佈上述澆鑄液10秒。繼而，於200℃之加熱板上加熱乾燥約20分鐘，於無鹼玻璃基板G之表面形成塗佈層1。藉由觸針式表面形狀測定器(美國Veeco製，形式Dektak 8)測定塗佈層1之厚度，結果為0.7μm。 The surface of an alkali-free glass substrate G (manufactured by Corning Co., Ltd., product name: 7059) having a diameter of 100 mm and a thickness of 1.1 mm was polished with cerium oxide microparticles (manufactured by Aldrich Co., Ltd.). Then, the casting liquid was spin-coated on the surface of the alkali-free glass substrate G at 1000 rpm for 10 seconds using a spin coater. Then, the coating layer 1 was formed on the surface of the alkali-free glass substrate G by heating and drying on a hot plate at 200 ° C for about 20 minutes. The thickness of the coating layer 1 was measured by a stylus type surface shape measuring device (manufactured by Veeco, USA, Form Dektak 8) and found to be 0.7 μm.
稱量1.00g上述合成之烷氧基矽烷之具有光聚合性基之水解縮合物、及0.02g作為光自由基聚合起始劑之Ciba Specialty Chemicals股份有限公司製、商品名Dacocur 1173，使其等混合而獲得接著性組合物。再者，該烷氧基矽烷之具有光聚合性基之水解縮合物亦可代用作發泡劑。 Weighed 1.00 g of the hydrolyzed condensate having a photopolymerizable group of the above-mentioned alkoxydecane synthesized, and 0.02 g of a product of a photo-radical polymerization initiator, manufactured by Ciba Specialty Chemicals Co., Ltd., trade name Dacocur 1173, etc. Mixing to obtain an adhesive composition. Further, the hydrolyzed condensate of the alkoxysilane having a photopolymerizable group may be used as a foaming agent.
將0.6g上述接著性組合物以旋轉塗佈機塗佈於直徑100毫米之矽基板S而形成接著性組合物層2。繼而，如圖1(B)所示，將該矽基板S以塗佈層1與接著性組合物層2接觸之方式與無鹼玻璃基板G重合。藉由紫外線照射機(HOYA-SCHOTT製，商品名UV LIGHT SOURCE EX250)，從自無鹼玻璃基板G觀察之接著性組合物層2之相反側照射紫外線30秒，使塗佈層1與接著性組合物層2硬化，而使矽基板S與無鹼玻璃基板G接著。繼而，使用加熱板，使已接著之矽基板S與無鹼玻璃基板G自室溫(20℃)升溫至180℃，結果達到180℃後，接著性組合物層2中之發泡劑開始發泡，20秒後，矽基板S與無鹼玻璃基板G剝 離。剝離發生於矽基板S與接著性組合物層2之間，接著性組合物層2之殘渣僅附著於玻璃基板G，未見殘留附著於矽基板S。其原因在於剝離選擇性地發生於接著性組合物層2與矽基板S之間。 0.6 g of the above-mentioned adhesive composition was applied to a substrate S having a diameter of 100 mm by a spin coater to form an adhesive composition layer 2. Then, as shown in FIG. 1(B), the tantalum substrate S is superposed on the alkali-free glass substrate G so that the coating layer 1 and the adhesive composition layer 2 are in contact with each other. Ultraviolet irradiation (product name: UV LIGHT SOURCE EX250) was used to irradiate ultraviolet rays for 30 seconds from the opposite side of the adhesive composition layer 2 observed from the alkali-free glass substrate G to form the coating layer 1 and the adhesion. The composition layer 2 is hardened, and the tantalum substrate S is followed by the alkali-free glass substrate G. Then, using a hot plate, the subsequent substrate S and the alkali-free glass substrate G are heated from room temperature (20 ° C) to 180 ° C, and as a result, after 180 ° C, the foaming agent in the adhesive composition layer 2 starts to foam. After 20 seconds, the ruthenium substrate S and the alkali-free glass substrate G are peeled off. from. The peeling occurred between the tantalum substrate S and the adhesive composition layer 2, and the residue of the adhesive composition layer 2 adhered only to the glass substrate G, and no residue adhered to the tantalum substrate S. The reason for this is that the peeling selectively occurs between the adhesive composition layer 2 and the ruthenium substrate S.
使用與實施例1相同之澆鑄液及無鹼玻璃基板G，藉由與實施例1相同之步驟於無鹼玻璃基板G之表面形成塗佈層1。 The coating layer 1 was formed on the surface of the alkali-free glass substrate G by the same procedure as in Example 1 using the same casting liquid and the alkali-free glass substrate G as in Example 1.
作為接著性組合物之要素，按照以下反應式(6)合成具有甲基丙烯醯基之籠型倍半矽氧烷，代替實施例1中之具有光聚合性基之烷氧基矽烷之水解縮合物。具體而言，於200ml茄形燒瓶內取八(二甲基矽烷基)八倍半矽氧烷(美國Hybrid Plastics公司，商品名SH1310)10.26g、甲基丙烯酸烯丙酯10.81g(東京化成股份有限公司製)、甲苯100ml、及作為鉑觸媒之1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷鉑(0)錯合物之二甲苯溶液(鉑濃度2質量%)(Aldrich股份有限公司)30mg後，於室溫(20℃)下徹夜(24hr)攪拌。其後，以蒸發器去除甲苯與未反應之甲基丙烯酸烯丙酯，獲得17.6g成為淺黃色液體之光聚合性籠型倍半矽氧烷。 As an element of the adhesive composition, a cage type sesquiterpene oxide having a methacryl fluorenyl group is synthesized according to the following reaction formula (6), instead of the hydrolytic condensation of the alkoxy decane having a photopolymerizable group in Example 1. Things. Specifically, in a 200 ml eggplant-shaped flask, 10.26 g of octadecyl octadecane oxide (Hybrid Plastics, Inc., trade name SH1310, USA) and 10.81 g of allyl methacrylate (Tokyo Chemicals Co., Ltd.) were taken. Co., Ltd.), 100 ml of toluene, and a xylene solution of platinum 1,3-divinyl-1,1,3,3-tetramethyldioxane platinum (0) complex (platinum) After 30 mg of a concentration of 2% by mass (Aldrich Co., Ltd.), the mixture was stirred at room temperature (20 ° C) overnight (24 hr). Thereafter, toluene and unreacted allyl methacrylate were removed by an evaporator to obtain 17.6 g of a photopolymerizable cage sesquiterpene oxide which became a pale yellow liquid.
於自上述光聚合性籠型倍半矽氧烷分取之1.03g中添加光自由基聚合起始劑(Ciba Specialty Chemicals股份有限公司製，商品名Darocur 1173)0.02g、及作為發泡劑之碳酸氫鈉(和光純藥股份有限公司製)0.26g，獲得接著性組合物。 0.02 g of a photoradical polymerization initiator (manufactured by Ciba Specialty Chemicals Co., Ltd., trade name: Darocur 1173) was added to 1.03 g of the photopolymerizable cage sesquiterpene gas, and as a foaming agent. 0.26 g of sodium hydrogencarbonate (manufactured by Wako Pure Chemical Industries, Ltd.) was obtained to obtain an adhesive composition.
將0.6g上述接著性組合物以旋轉塗佈機塗佈於直徑100毫米之矽基板S上而形成接著性組合物層2。將該矽基板S與實施例1同樣地以塗佈層1與接著性組合物層2接觸之方式重疊於無鹼玻璃基板G。繼而，藉由紫外線照射機(HOYA-SCHOTT製，商品名UV LIGHT SOURCE EX250)，從自無鹼玻璃基板G觀察之接著性組合物層2之相反側照射紫外線30秒，使塗佈層1與接著性組合物層2硬化，而使矽基板S與無鹼玻璃基板G接著。繼而，藉由加熱板使其等自室溫(20℃)升溫至160℃。達到160℃後，接著性組合物層2中之發泡劑開始發泡，約1分鐘後矽基板S與無鹼玻璃基板G自發地剝離。剝離發生於矽基板S與接著性組合物層2之間，接著性組合物層2之殘渣僅附著於玻璃基板G，未見殘留附著於矽基板S。其原因在於剝離選擇性地發生於接著性組合物層2與矽基板S之間。 0.6 g of the above-mentioned adhesive composition was applied onto a substrate S having a diameter of 100 mm by a spin coater to form an adhesive composition layer 2. In the same manner as in the first embodiment, the tantalum substrate S was superposed on the alkali-free glass substrate G so that the coating layer 1 and the adhesive composition layer 2 were in contact with each other. Then, ultraviolet rays were irradiated from the opposite side of the adhesive composition layer 2 observed from the alkali-free glass substrate G for 30 seconds by an ultraviolet ray irradiation machine (product name: UV LIGHT SOURCE EX250, manufactured by HOYA-SCHOTT) to coat the coating layer 1 and The subsequent composition layer 2 is cured to cause the tantalum substrate S to be followed by the alkali-free glass substrate G. Then, the temperature was raised from room temperature (20 ° C) to 160 ° C by heating the plate. After reaching 160 ° C, the foaming agent in the adhesive composition layer 2 started to foam, and after about 1 minute, the ruthenium substrate S and the alkali-free glass substrate G spontaneously peeled off. The peeling occurred between the tantalum substrate S and the adhesive composition layer 2, and the residue of the adhesive composition layer 2 adhered only to the glass substrate G, and no residue adhered to the tantalum substrate S. The reason for this is that the peeling selectively occurs between the adhesive composition layer 2 and the ruthenium substrate S.
使用與實施例1、2相同之澆鑄液及無鹼玻璃基板G，藉由與實施例1、2相同之步驟於無鹼玻璃基板G之表面形成塗佈層1。 The coating layer 1 was formed on the surface of the alkali-free glass substrate G by the same steps as in Examples 1 and 2, using the same casting liquids as in Examples 1 and 2 and the alkali-free glass substrate G.
相對於上述光聚合性倍半矽氧烷，添加20質量%之作為用以提高無鹼玻璃基板G與矽基板S之接著強度之具有極性基之化合物的季戊四醇三丙烯酸酯(大阪有機化學工業股份有限公司製，商品名 Viscoat#300)，進而，將發泡劑由碳酸氫鈉變更為亞肼基二甲醯胺，除此以外，與實施例2同樣地獲得接著性樹脂。 To the photopolymerizable sesquiterpene oxide, 20% by mass of pentaerythritol triacrylate which is a compound having a polar group for improving the adhesion strength between the alkali-free glass substrate G and the ruthenium substrate S (Osaka Organic Chemical Industry Co., Ltd.) Limited company name The adhesive resin was obtained in the same manner as in Example 2 except that the foaming agent was changed from sodium hydrogencarbonate to sulfhydryl dimethyl hydrazine.
與實施例1同樣地，將0.6g接著性組合物塗佈於矽基板S，並使之與無鹼玻璃基板G重合，照射紫外線30秒，使其等接著。繼而，為了進行剝離，使用加熱板使其等自室溫(20℃)升溫至260℃。達到260℃後，接著性組合物層2中之發泡劑開始發泡，約40秒後，矽基板S與無鹼玻璃基板G剝離。剝離發生於矽基板S與接著性組合物層2之間，接著性組合物層2之殘渣僅附著於玻璃基板G，未見殘留附著於矽基板S。其原因在於剝離選擇性地發生於接著性組合物層2與矽基板S之間。 In the same manner as in Example 1, 0.6 g of the adhesive composition was applied onto the ruthenium substrate S, and it was superposed on the alkali-free glass substrate G, and the ultraviolet ray was irradiated for 30 seconds, and the like. Then, in order to perform peeling, the heating plate was used to raise the temperature from room temperature (20 ° C) to 260 ° C. After reaching 260 ° C, the foaming agent in the adhesive composition layer 2 starts to foam, and after about 40 seconds, the ruthenium substrate S is peeled off from the alkali-free glass substrate G. The peeling occurred between the tantalum substrate S and the adhesive composition layer 2, and the residue of the adhesive composition layer 2 adhered only to the glass substrate G, and no residue adhered to the tantalum substrate S. The reason for this is that the peeling selectively occurs between the adhesive composition layer 2 and the ruthenium substrate S.
以上，根據實施例1~3確認：本發明之接著性組合物對接著矽基板S與無鹼玻璃基板G發揮有效作用，接著性組合物所含有之發泡劑於特定溫度下發泡，可不於矽基板S上殘留接著性組合物層2之殘渣而將矽基板S與接著性組合物層2剝離。 As described above, according to Examples 1 to 3, it was confirmed that the adhesive composition of the present invention has an effective effect on the succeeding ruthenium substrate S and the alkali-free glass substrate G, and the foaming agent contained in the adhesive composition is foamed at a specific temperature. The residue of the adhesive composition layer 2 remains on the tantalum substrate S, and the tantalum substrate S and the adhesive composition layer 2 are peeled off.
除於接著性組合物中不添加發泡劑以外，與實施例3同樣地進行。詳細而言，以與實施例3相同之步驟，將0.6g接著性組合物以旋轉塗佈機塗佈於矽基板S之接著面而設置接著性組合物層2，並與設置有塗佈層1之無鹼玻璃基板G貼合。以與實施例3相同之步驟，照射紫外線30秒而使矽基板S與無鹼基板G接著後，藉由加熱板使其等自室溫升溫至160℃。然而，由於未添加發泡劑，因此即便於160℃下亦未發生剝離。進而提高加熱板之溫度，結果即便於320℃下亦未發生剝離。於320℃下，於接著性組合物層2可見白濁，接著性組合物層2發生變質。如此於接著性組合物中不添加發泡劑之情形時，無法將發泡用作剝離之驅動力，因此無法使矽基板S與無鹼玻璃基板G自發地剝 離。 The same procedure as in Example 3 was carried out except that the foaming agent was not added to the adhesive composition. Specifically, in the same procedure as in Example 3, 0.6 g of the adhesive composition was applied to the back surface of the ruthenium substrate S by a spin coater to provide the adhesive composition layer 2, and a coating layer was provided. The alkali-free glass substrate G of 1 is bonded. In the same manner as in Example 3, the ultraviolet ray was irradiated for 30 seconds to bring the ruthenium substrate S and the alkali-free substrate G, and then the temperature was raised from room temperature to 160 ° C by a hot plate. However, since no foaming agent was added, peeling did not occur even at 160 °C. Further, the temperature of the hot plate was increased, and as a result, peeling did not occur even at 320 °C. At 320 ° C, white turbidity was observed in the adhesive composition layer 2, and the adhesive composition layer 2 was deteriorated. When the foaming agent is not added to the adhesive composition, foaming cannot be used as the driving force for peeling, so that the tantalum substrate S and the alkali-free glass substrate G cannot be spontaneously peeled off. from.
除使用於無鹼玻璃基板G上不設置塗佈層1而僅以氧化鈰之研磨進行表面處理之無鹼玻璃基板G以外，與實施例1同樣地進行。詳細而言，以與實施例1相同之步驟，將0.6g接著性組合物以旋轉塗佈機塗佈於矽基板S之接著面而設置接著性組合物層2，並與未設置塗佈層1之無鹼玻璃基板G貼合。以與實施例1~3相同之步驟，照射紫外線30秒而使矽基板S與無鹼基板G接著後，藉由加熱板使其等自室溫升溫至160℃。達到160℃後，約1分鐘後，矽基板S與無鹼玻璃基板G剝離。接著殘渣附著於矽基板S與玻璃基板G之兩者，未獲得良好之結果。如此於無鹼玻璃基板G不設置塗佈層1之情形時，鹼玻璃基板G與接著性組合物層2之接著力降低，於矽基板S上亦觀測到接著殘渣。 The same procedure as in Example 1 was carried out except that the alkali-free glass substrate G which was subjected to surface treatment only by polishing with cerium oxide without using the coating layer 1 on the alkali-free glass substrate G was used. Specifically, in the same procedure as in Example 1, 0.6 g of the adhesive composition was applied to the back surface of the ruthenium substrate S by a spin coater to provide the adhesive composition layer 2, and the coating layer was not provided. The alkali-free glass substrate G of 1 is bonded. In the same manner as in the first to third embodiments, the ultraviolet ray was irradiated for 30 seconds to bring the ruthenium substrate S and the alkali-free substrate G, and then the temperature was raised from room temperature to 160 ° C by a hot plate. After reaching 160 ° C, the ruthenium substrate S was peeled off from the alkali-free glass substrate G after about 1 minute. Then, the residue adhered to both the ruthenium substrate S and the glass substrate G, and good results were not obtained. When the coating layer 1 is not provided in the alkali-free glass substrate G, the adhesion between the alkali glass substrate G and the adhesive composition layer 2 is lowered, and the subsequent residue is also observed on the ruthenium substrate S.
除使用不進行接著面之氧化鈰研磨而設置有塗佈層1之無鹼玻璃G以外，與實施例1同樣地進行。詳細而言，以與實施例1相同之步驟，將0.6g接著性組合物以旋轉塗佈機塗佈於矽基板S之接著面而設置接著性組合物層2，並與設置有塗佈層1之無鹼玻璃基板G貼合。以與實施例1相同之步驟，照射紫外線30秒，使矽基板S與無鹼玻璃基板G接著後，藉由加熱板使其等自室溫升溫至160℃。達到160℃後，約1分鐘後，矽基板S與無鹼玻璃基板剝離。接著殘渣附著於矽基板與玻璃基板之兩者，未獲得良好之結果。如此於不對無鹼玻璃基板G進行氧化鈰研磨處理之情形時，鹼玻璃基板G與塗佈層1之接著力降低，於矽基板S上亦觀測到接著殘渣。 The same procedure as in Example 1 was carried out except that the alkali-free glass G provided with the coating layer 1 was not subjected to cerium oxide polishing. Specifically, in the same procedure as in Example 1, 0.6 g of the adhesive composition was applied to the back surface of the ruthenium substrate S by a spin coater to provide the adhesive composition layer 2, and a coating layer was provided. The alkali-free glass substrate G of 1 is bonded. In the same manner as in Example 1, ultraviolet rays were irradiated for 30 seconds, and then the ruthenium substrate S and the alkali-free glass substrate G were placed, and then the temperature was raised from room temperature to 160 ° C by a hot plate. After reaching 160 ° C, the ruthenium substrate S was peeled off from the alkali-free glass substrate after about 1 minute. Then, the residue adhered to both the ruthenium substrate and the glass substrate, and good results were not obtained. When the cerium oxide-free polishing treatment is not performed on the alkali-free glass substrate G as described above, the adhesion between the alkali glass substrate G and the coating layer 1 is lowered, and the subsequent residue is also observed on the ruthenium substrate S.
將實施例1~3之結果匯總於表1，將比較例1、及參考例1、2之結果匯總於表2。 The results of Examples 1 to 3 are summarized in Table 1, and the results of Comparative Example 1 and Reference Examples 1 and 2 are summarized in Table 2.
如表1所示，於實施例1~3中，對無鹼玻璃基板G進行氧化鈰研磨後，以水解縮合物進行塗佈。實驗結果是將無鹼玻璃基板G之該塗佈面與矽基板S藉由本發明之接著性組合物接著後，其等因發泡劑之作用而剝離。無論何種結果，均係於所需之溫度下剝離，於矽基板S未見接著殘渣，均為良好之結果。 As shown in Table 1, in Examples 1 to 3, the alkali-free glass substrate G was subjected to cerium oxide polishing, and then coated with a hydrolysis condensate. As a result of the experiment, the coated surface of the alkali-free glass substrate G and the tantalum substrate S are separated by the adhesive composition by the action of the foaming agent. Regardless of the result, it was peeled off at the desired temperature, and no residue was observed on the substrate S, which was a good result.
於表2中表示比較例1之未使用發泡劑之情形之實驗結果、參考例1之未進行水解縮合物之塗佈之情形的實驗結果、及參考例2之未進行鹼玻璃G接著面之氧化鈰研磨之情形的實驗結果。於比較例1之未使用發泡劑之情形時，矽基板S與無鹼玻璃基板G即使加熱亦未發生剝離。於參考例1之未進行水解縮合物之塗佈的情形時、及參考例2之未進行無鹼玻璃G接著面之氧化鈰研磨的情形時，均於矽基板S見到接著殘渣而未獲得所需之結果。 Table 2 shows the results of the experiment in the case where the foaming agent was not used in Comparative Example 1, the experimental results in the case where the hydrolysis condensate was not applied in Reference Example 1, and the case where the alkali glass G was not subjected to the reference example 2. The experimental results of the cerium oxide grinding. In the case where the foaming agent was not used in Comparative Example 1, the ruthenium substrate S and the alkali-free glass substrate G did not peel off even when heated. In the case where the application of the hydrolysis condensate was not carried out in Reference Example 1, and the case where the cerium oxide was not subjected to the cerium oxide polishing of the alkali-free glass G in the reference example 2, the residue was not observed on the ruthenium substrate S. The desired result.
1‧‧‧塗佈層 1‧‧‧ coating layer
2‧‧‧接著性組合物層(接著性組合物) 2‧‧‧Adhesive composition layer (adhesive composition)
G‧‧‧玻璃基板 G‧‧‧glass substrate
S‧‧‧矽基板 S‧‧‧矽 substrate
Claims (8)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012162420 | 2012-07-23 | ||
| JP2012162431 | 2012-07-23 | ||
| JP2013142538A JP6277617B2 (en) | 2012-07-23 | 2013-07-08 | Adhesive composition, adhesion method thereof, and peeling method after adhesion |
| JP2013142537A JP6277616B2 (en) | 2012-07-23 | 2013-07-08 | Adhesive composition, adhesion method thereof, and peeling method after adhesion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201406901A TW201406901A (en) | 2014-02-16 |
| TWI540194B true TWI540194B (en) | 2016-07-01 |
Family
ID=50550361
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW102125624A TWI540194B (en) | 2012-07-23 | 2013-07-17 | Followed by the following method, followed by the later peeling method |
Country Status (1)
| Country | Link |
|---|---|
| TW (1) | TWI540194B (en) |
-
2013
- 2013-07-17 TW TW102125624A patent/TWI540194B/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TW201406901A (en) | 2014-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101553962B1 (en) | Adhesive composition and adhesive method thereof and separating method after adhesion | |
| JP6213127B2 (en) | Adhesive composition, adhesion method thereof, and peeling method after adhesion | |
| JP6277617B2 (en) | Adhesive composition, adhesion method thereof, and peeling method after adhesion | |
| JP5958262B2 (en) | Wafer processing body, wafer processing member, wafer processing temporary adhesive, and thin wafer manufacturing method | |
| KR101908630B1 (en) | Wafer processing laminate, wafer processing member, temporary bonding arrangement, and thin wafer manufacturing method | |
| JP2016086158A (en) | Laminate for wafer processing, temporary adhesive material for wafer processing and method of manufacturing thin wafer | |
| US10796939B2 (en) | Temporary adhesive film roll for substrate processing, method for manufacturing thin wafer | |
| JP6090547B2 (en) | Curable composition, resist material and resist film | |
| TWI566042B (en) | A hardening composition, a temporary bonding material, and a temporary method of using the member and the substrate | |
| TW201726866A (en) | Wafer processing bonding material, wafer laminate, and thin wafer manufacturing method | |
| TW201500517A (en) | Aqueous detergent soluble coating and adhesive and methods of temporary bonding for manufacturing | |
| TW201540782A (en) | Etch resistant material for oxygen plasma etching, etch resistant film, and a laminate using the same | |
| KR20160137386A (en) | Method of preparing laminate, and method of separating support | |
| TW201423853A (en) | Method for manufacturing semiconductor device | |
| US11299653B2 (en) | Composition, adhesive film, laminate, method for producing cured product pattern, and method for manufacturing circuit substrate | |
| JP6213126B2 (en) | Adhesive composition, adhesion method thereof, and peeling method after adhesion | |
| JP6277616B2 (en) | Adhesive composition, adhesion method thereof, and peeling method after adhesion | |
| TWI714725B (en) | Method for manufacturing pattern laminate, method for manufacturing reverse pattern, and pattern laminate | |
| TWI540194B (en) | Followed by the following method, followed by the later peeling method | |
| TWI507497B (en) | Followed by the following method, followed by the later peeling method | |
| WO2014017294A1 (en) | Adhesive composition, bonding method thereof, and separation method after bonding | |
| JP2017220622A (en) | Processing method of semiconductor wafer | |
| US11441053B2 (en) | Composition for forming adhesive film for imprinting, adhesive film, laminate, method for producing cured product pattern, and method for manufacturing circuit substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |