TWI704649B - Material for protecting semiconductor element and semiconductor device - Google Patents
Material for protecting semiconductor element and semiconductor device Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
- H01L23/31—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the arrangement or shape
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
本發明提供一種半導體元件保護用材料，其塗佈性優異，可獲得散熱性及柔軟性優異之硬化物，可良好地保護半導體元件。 本發明之半導體元件保護用材料係用於為了保護半導體元件而塗佈於上述半導體元件之表面上，於上述半導體元件之表面上形成硬化物者，其不同於配置於半導體元件與其他連接對象構件之間，形成以不使上述半導體元件與上述其他連接對象構件剝離之方式將該等接著及固定之硬化物者，且包含：可撓性環氧化合物、與可撓性環氧化合物不同之環氧化合物、23℃下為液狀之硬化劑、硬化促進劑、及熱導率為10 W/m･K以上且為球狀之無機填料。The present invention provides a material for protecting semiconductor elements, which has excellent coating properties, can obtain a cured product with excellent heat dissipation and flexibility, and can protect semiconductor elements well. The semiconductor element protection material of the present invention is applied to the surface of the semiconductor element in order to protect the semiconductor element, and a hardened substance is formed on the surface of the semiconductor element, which is different from the semiconductor element and other connection object members. In the meantime, a cured product that is adhered and fixed so that the semiconductor element and the other connection object member are not peeled off is formed, and includes: a flexible epoxy compound and a ring different from the flexible epoxy compound Oxygen compound, liquid curing agent at 23℃, curing accelerator, and spherical inorganic filler with thermal conductivity of 10 W/m･K or more.
Description
本發明係關於一種為了保護半導體元件而塗佈於上述半導體元件之表面上使用之半導體元件保護用材料。又，本發明係關於一種使用上述半導體元件保護用材料之半導體裝置。 The present invention relates to a semiconductor element protection material applied on the surface of the above-mentioned semiconductor element in order to protect the semiconductor element. Furthermore, the present invention relates to a semiconductor device using the above-mentioned semiconductor element protection material.
半導體裝置之高性能化不斷發展。伴隨於此，散發自半導體裝置所產生之熱之需要不斷提高。又，於半導體裝置中，半導體元件之電極例如與表面具有電極之其他連接對象構件之電極電性連接。 The high performance of semiconductor devices continues to develop. Along with this, the need to dissipate heat generated from semiconductor devices has continued to increase. Furthermore, in a semiconductor device, the electrode of the semiconductor element is electrically connected to, for example, the electrode of another connection object member having an electrode on the surface.
於半導體裝置中，例如，於半導體元件與其他連接對象構件之間配置環氧樹脂組合物後，藉由使該環氧樹脂組合物硬化而將半導體元件與其他連接對象構件接著及固定。再者，配置於半導體元件與其他連接對象構件之間的上述環氧樹脂組合物之硬化物不同於用以保護半導體元件之表面之材料。 In a semiconductor device, for example, after an epoxy resin composition is arranged between a semiconductor element and another connection object member, the semiconductor element and the other connection object member are bonded and fixed by curing the epoxy resin composition. Furthermore, the cured product of the above-mentioned epoxy resin composition arranged between the semiconductor element and other connection object members is different from the material used to protect the surface of the semiconductor element.
又，於半導體裝置中，有為了密封半導體元件而使用環氧樹脂組合物之情況。 In addition, in semiconductor devices, epoxy resin compositions may be used for sealing semiconductor elements.
例如，下述專利文獻1~4中揭示有如上所述之環氧樹脂組合物。
For example, the following
下述專利文獻1中揭示有包含環氧樹脂、酚系硬化劑、作為三(2,6-二甲氧基苯基)膦或三(2,4,6-三甲氧基苯基)膦之硬化促進劑、及氧化鋁之環氧樹脂組合物。專利文獻1之實施例中記載有作為粉體之環氧樹脂組合物。關於上述環氧樹脂組合物之用途，專利文獻1中記載有較佳用於IC(Integrated Circuit，積體電路)、LSI(Large Scale Integration，大型積
體電路)、電晶體、閘流體、二極體等半導體裝置之密封用、印刷電路板之製造等。
The following
下述專利文獻2中揭示有包含環氧樹脂、酚樹脂硬化劑、硬化促進劑、及無機填充劑之密封用環氧樹脂組合物。專利文獻2之實施例中記載有作為粉體之密封用環氧樹脂組合物。關於上述環氧樹脂組合物之用途，專利文獻2中記載有可用作普通成形材料，但亦可用作半導體裝置之密封材料，特別是可較佳用作薄型、多接腳、長導線、窄焊墊間距、或在有機基板或有機膜等安裝基板上配置有半導體晶片之半導體裝置之密封材料。
The following
下述專利文獻3中揭示有包含雙酚F型液狀環氧樹脂、硬化劑、及無機質填充劑之環氧樹脂組合物。專利文獻3之實施例中記載有作為固體之環氧樹脂組合物(熔融黏度為75℃以上)。關於上述環氧樹脂組合物之用途，專利文獻3中記載有雖亦可用作普通成形材料，但可較佳用作半導體裝置、例如TQFP(Thin Quad Flat Package，薄塑封方型扁平封裝)、TSOP(Thin Small Outline Package，薄型小尺寸封裝)、QFP(Quad Flat Package，方型扁平封裝)等多接腳薄型封裝、特別是使用矩陣框架之半導體裝置之密封材料。
The following
下述專利文獻4中揭示有包含環氧樹脂、酚樹脂硬化劑、高導熱性填充劑、及無機質填充劑之半導體密封用環氧樹脂組合物。專利文獻4之實施例中記載有作為粉體之半導體密封用環氧樹脂組合物。關於上述半導體密封用環氧樹脂組合物之用途，專利文獻4中記載有用作半導體元件等電子零件之密封材料。
又，下述專利文獻5中揭示有一種2液型環氧樹脂組合物，其具有：包含雙酚A型環氧樹脂、骨架內具有可撓性之環氧樹脂之第1劑，及包含酸酐化合物及硬化促進劑之第2劑。關於2液型環氧樹脂組合物之用途，專
利文獻5中記載有可用作殼體內填充材料。
In addition, the following
[專利文獻1]日本專利特開平5-86169號公報 [Patent Document 1] Japanese Patent Laid-Open No. 5-86169
[專利文獻2]日本專利特開2007-217469號公報 [Patent Document 2] Japanese Patent Laid-Open No. 2007-217469
[專利文獻3]日本專利特開平10-176100號公報 [Patent Document 3] Japanese Patent Laid-Open No. 10-176100
[專利文獻4]日本專利特開2005-200533號公報 [Patent Document 4] Japanese Patent Laid-Open No. 2005-200533
[專利文獻5]日本專利特開2014-40538號公報 [Patent Document 5] Japanese Patent Laid-Open No. 2014-40538
具體而言，專利文獻1~4中揭示有作為粉體或固體之環氧樹脂組合物。此種作為粉體或固體之環氧樹脂組合物之塗佈性較低，難以精度良好地配置於特定區域。
Specifically,
又，先前之環氧樹脂組合物之硬化物存在散熱性較低之情況。進而，先前之環氧樹脂組合物之硬化物存在柔軟性較低之情況。若硬化物之柔軟性較低，則存在例如因半導體元件之變形應力，而產生硬化物之剝離之情況。 In addition, the cured product of the conventional epoxy resin composition may have low heat dissipation properties. Furthermore, the cured product of the previous epoxy resin composition may have low flexibility. If the flexibility of the cured product is low, for example, the deformation stress of the semiconductor device may cause peeling of the cured product.
又，專利文獻1~4中，作為環氧樹脂組合物之具體之用途，主要記載有密封用途。專利文獻5中，作為環氧樹脂組合物之具體之用途，主要記載有殼體內填充材料用途。另一方面，於半導體裝置中，理想的是即便不密封半導體元件，亦可充分保護半導體元件。又，專利文獻1~5中所記載之環氧樹脂組合物一般並未為了保護半導體元件而塗佈於該半導體元件之表面上使用。
In addition,
又，近年，就裝置之薄度或設計性之觀點而言，要求減少IC驅動 器。若減少IC驅動器，則施加於半導體元件之負擔增加，進而易帶來相當多之熱。先前之硬化物由於散熱性較低，故而要求散熱性較高之硬化物。進而，先前之硬化物容易因變形應力而產生剝離。 In addition, in recent years, from the viewpoint of device thinness or designability, it is required to reduce IC driver Device. If the IC driver is reduced, the burden imposed on the semiconductor element will increase, which in turn will easily generate considerable heat. Since the previous hardened material has low heat dissipation, a hardened material with higher heat dissipation is required. Furthermore, the previous hardened product is likely to peel off due to deformation stress.
本發明之目的在於提供一種半導體元件保護用材料，其於半導體裝置中，用於為了保護半導體元件而塗佈於該半導體元件之表面上，於上述半導體元件之表面上形成硬化物。 The object of the present invention is to provide a semiconductor device protection material, which is used in a semiconductor device to be coated on the surface of the semiconductor device in order to protect the semiconductor device, and to form a cured product on the surface of the semiconductor device.
進而，本發明之目的在於提供一種半導體元件保護用材料，其於上述用途中，塗佈性優異，可獲得散熱性及柔軟性優異之硬化物，可良好地保護半導體元件。又，本發明之目的亦在於提供一種使用上述半導體元件保護用材料之半導體裝置。 Furthermore, an object of the present invention is to provide a material for protecting semiconductor elements, which has excellent coating properties, obtains a cured product excellent in heat dissipation and flexibility, and can protect semiconductor elements well. In addition, the object of the present invention is to provide a semiconductor device using the above-mentioned semiconductor element protection material.
於本發明之較廣之態樣中，提供一種半導體元件保護用材料，其係用於為了保護半導體元件而塗佈於上述半導體元件之表面上，於上述半導體元件之表面上形成硬化物者，其不同於配置於半導體元件與其他連接對象構件之間，形成以不使上述半導體元件與上述其他連接對象構件剝離之方式將該等接著及固定之硬化物者，且包含：可撓性環氧化合物、與可撓性環氧化合物不同之環氧化合物、23℃下為液狀之硬化劑、硬化促進劑、及熱導率為10W/m．K以上且為球狀之無機填料。 In a broader aspect of the present invention, there is provided a semiconductor device protection material, which is used for protecting the semiconductor device and is coated on the surface of the semiconductor device to form a hardened substance on the surface of the semiconductor device, It is different from the one that is arranged between the semiconductor element and the other connection object member, and forms a hardened object that adheres and fixes the semiconductor element and the other connection object member so as not to peel off the semiconductor element and the other connection object member, and includes: flexible epoxy Compound, epoxy compound that is different from flexible epoxy compound, hardener that is liquid at 23°C, hardening accelerator, and thermal conductivity of 10W/m. K or more and spherical inorganic filler.
於本發明之半導體元件保護用材料之某一特定態樣中，上述硬化劑係烯丙基苯酚酚醛清漆化合物。 In a specific aspect of the semiconductor device protection material of the present invention, the curing agent is an allyl phenol novolak compound.
於本發明之半導體元件保護用材料之某一特定態樣中，上述可撓性環氧化合物係具有伸烷基二醇基之重複數為9以上之結構單元之聚伸烷基二醇二縮水甘油醚。 In a specific aspect of the semiconductor device protection material of the present invention, the above-mentioned flexible epoxy compound is a polyalkylene glycol dihydrate having a structural unit with an alkylene glycol group having a repeating number of 9 or more Glyceryl ether.
於本發明之半導體元件保護用材料之某一特定態樣中，相對於上述 可撓性環氧化合物100重量份，與上述可撓性環氧化合物不同之環氧化合物之含量為10重量份以上且100重量份以下。 In a specific aspect of the semiconductor device protection material of the present invention, relative to the above For 100 parts by weight of the flexible epoxy compound, the content of the epoxy compound different from the above-mentioned flexible epoxy compound is 10 parts by weight or more and 100 parts by weight or less.
於本發明之半導體元件保護用材料之某一特定態樣中，上述無機填料係氧化鋁、氮化鋁或碳化矽。 In a specific aspect of the semiconductor device protection material of the present invention, the above-mentioned inorganic filler is alumina, aluminum nitride or silicon carbide.
於本發明之半導體元件保護用材料之某一特定態樣中，上述半導體元件保護用材料包含100℃下之重量減少為10重量%以下之矽烷偶合劑、100℃下之重量減少為10重量%以下之鈦酸酯偶合劑或100℃下之重量減少為10重量%以下之鋁酸酯偶合劑。 In a specific aspect of the semiconductor device protection material of the present invention, the semiconductor device protection material includes a silane coupling agent with a weight loss of 10% by weight or less at 100°C and a weight loss of 10% by weight at 100°C The following titanate coupling agents or aluminate coupling agents whose weight loss at 100°C is less than 10% by weight.
本發明之半導體元件保護用材料較佳用於為了保護半導體元件而於上述半導體元件之表面上形成硬化物，且於上述硬化物之與上述半導體元件側相反之表面上配置保護膜而獲得半導體裝置。 The semiconductor element protection material of the present invention is preferably used to form a cured product on the surface of the semiconductor element to protect the semiconductor element, and arrange a protective film on the surface of the cured product opposite to the semiconductor element side to obtain a semiconductor device .
根據本發明之較廣之態樣，提供一種半導體裝置，其具備半導體元件、及配置於上述半導體元件之第1表面上之硬化物，上述硬化物係藉由使上述半導體元件保護用材料硬化而形成。 According to a broader aspect of the present invention, there is provided a semiconductor device including a semiconductor element and a cured product disposed on a first surface of the semiconductor element, the cured product being formed by curing the semiconductor element protection material form.
於本發明之半導體裝置之某一特定態樣中，上述半導體元件於與上述第1表面側相反之第2表面側具有第1電極，上述半導體元件之第1電極與表面具有第2電極之連接對象構件之上述第2電極電性連接。 In a specific aspect of the semiconductor device of the present invention, the semiconductor element has a first electrode on a second surface side opposite to the first surface side, and the first electrode of the semiconductor element and the surface have a second electrode connected The above-mentioned second electrode of the target member is electrically connected.
於本發明之半導體裝置之某一特定態樣中，於上述硬化物之與上述半導體元件側相反之表面上配置有保護膜。 In a specific aspect of the semiconductor device of the present invention, a protective film is arranged on the surface of the cured product opposite to the semiconductor element side.
本發明之半導體元件保護用材料由於包含可撓性環氧化合物、與可撓性環氧化合物不同之環氧化合物、23℃下為液狀之硬化劑、硬化促進劑、及熱導率為10W/m．K以上且為球狀之無機填料，故而塗佈性優異。進而，本發明之半導體元件保護用材料之硬化物之散熱性及柔軟性優異。 因此，為了保護半導體元件，而於上述半導體元件之表面上塗佈本發明之半導體元件保護用材料並使之硬化，藉此，可良好地保護上述半導體元件。 The semiconductor device protection material of the present invention contains a flexible epoxy compound, an epoxy compound different from the flexible epoxy compound, a curing agent that is liquid at 23°C, a curing accelerator, and a thermal conductivity of 10W /m. K or more and spherical inorganic filler, so it has excellent coating properties. Furthermore, the hardened material of the semiconductor element protection material of the present invention is excellent in heat dissipation and flexibility. Therefore, in order to protect the semiconductor element, the semiconductor element protection material of the present invention is coated on the surface of the semiconductor element and hardened, whereby the semiconductor element can be protected well.
1:半導體裝置 1: Semiconductor device
1X:半導體裝置 1X: Semiconductor device
2:半導體元件 2: Semiconductor components
2a:第1表面
2a:
2b:第2表面
2b:
2A:第1電極 2A: 1st electrode
3:硬化物 3: Hardened object
3X:硬化物 3X: Hardened object
4:連接對象構件 4: Connection object component
4a:表面 4a: surface
4A:第2電極 4A: 2nd electrode
5:其他硬化物 5: Other hardened objects
6:導電性粒子 6: Conductive particles
7:保護膜 7: Protective film
圖1係表示使用本發明之第1實施形態之半導體元件保護用材料之半導體裝置之局部切開前視剖視圖。 FIG. 1 is a partially cut-away front sectional view of a semiconductor device using the semiconductor device protection material of the first embodiment of the present invention.
圖2係表示使用本發明之第2實施形態之半導體元件保護用材料之半導體裝置之局部切開前視剖視圖。 2 is a partially cut-away front sectional view of a semiconductor device using the semiconductor device protection material of the second embodiment of the present invention.
以下，就本發明進行詳細說明。 Hereinafter, the present invention will be described in detail.
本發明之半導體元件保護用材料係用於為了保護半導體元件而塗佈於上述半導體元件之表面上，於上述半導體元件之表面上形成硬化物。本發明之半導體元件保護用材料不同於配置於半導體元件與其他連接對象構件之間，形成以不使上述半導體元件與上述其他連接對象構件剝離之方式將該等接著及固定之硬化物者(材料)。 The semiconductor element protection material of the present invention is used to coat the surface of the semiconductor element in order to protect the semiconductor element to form a cured product on the surface of the semiconductor element. The semiconductor element protection material of the present invention is different from being arranged between the semiconductor element and other connection object members, and forms a cured product (materials) that adheres and fixes the semiconductor element and the other connection object member so as not to peel off ).
本發明之半導體元件保護用材料包含：(A)可撓性環氧化合物、(B)與可撓性環氧化合物不同之環氧化合物、(C)23℃下為液狀之硬化劑、(D)硬化促進劑、及(E)熱導率為10W/m．K以上且為球狀之無機填料。本發明之半導體元件保護用材料為了塗佈於半導體元件之表面上，於23℃下為液狀，於23℃下不為固體。再者，液狀亦包含黏稠之漿料。 The semiconductor device protection material of the present invention includes: (A) a flexible epoxy compound, (B) an epoxy compound different from a flexible epoxy compound, (C) a curing agent that is liquid at 23°C, ( D) Hardening accelerator and (E) thermal conductivity of 10W/m. K or more and spherical inorganic filler. The semiconductor element protection material of the present invention is liquid at 23°C and not solid at 23°C in order to be coated on the surface of the semiconductor element. Furthermore, the liquid state also includes viscous slurry.
本發明之半導體元件保護用材料由於具備上述構成，故而塗佈性優異，可抑制塗佈時之意料之外之流動。上述半導體元件保護用材料可良好地塗佈於半導體元件之表面上。例如，可於半導體元件之欲提高散熱性之部位之表面上選擇性地、精度良好地塗佈上述半導體元件保護用材料。 Since the semiconductor element protection material of the present invention has the above-mentioned structure, it has excellent coating properties and can suppress unexpected flow during coating. The above-mentioned semiconductor element protection material can be well coated on the surface of the semiconductor element. For example, the semiconductor element protection material can be selectively and accurately coated on the surface of the portion of the semiconductor element where heat dissipation is desired.
進而，由於本發明之半導體元件保護用材料具備上述構成，故而硬化物之散熱性優異。因此，藉由於半導體元件之表面上配置硬化物，可自半導體元件之表面經由硬化物充分散發熱。因此，可有效地抑制半導體裝置之熱劣化。 Furthermore, since the semiconductor element protection material of the present invention has the above-mentioned structure, the cured product has excellent heat dissipation properties. Therefore, by disposing the hardened material on the surface of the semiconductor element, heat can be sufficiently dissipated from the surface of the semiconductor element through the hardened material. Therefore, the thermal degradation of the semiconductor device can be effectively suppressed.
進而，本發明之半導體元件保護用材料之硬化物之柔軟性亦優異。因此，難以因半導體元件之變形應力等而產生半導體元件之損傷，進而可難以自半導體元件之表面剝離硬化物。 Furthermore, the cured product of the semiconductor element protection material of the present invention is also excellent in flexibility. Therefore, it is difficult to cause damage to the semiconductor element due to deformation stress of the semiconductor element, etc., and it is also difficult to peel the hardened product from the surface of the semiconductor element.
因此，為了保護半導體元件，而將本發明之半導體元件保護用材料塗佈於上述半導體元件之表面上並使之硬化，藉此，可良好地保護上述半導體元件。 Therefore, in order to protect the semiconductor element, the semiconductor element protection material of the present invention is coated on the surface of the semiconductor element and hardened, whereby the semiconductor element can be protected well.
又，上述半導體元件保護用材料之硬化物之耐熱性亦優異，難以產生龜裂。進而，上述半導體元件保護用材料之硬化物之尺寸穩定性亦優異。 In addition, the cured product of the semiconductor element protection material is also excellent in heat resistance and hardly cracks. Furthermore, the dimensional stability of the cured product of the above-mentioned semiconductor element protection material is also excellent.
又，就提高半導體元件保護用材料對半導體元件之表面之潤濕性，進一步提高硬化物之柔軟性，進而進一步提高硬化物之耐濕性之觀點而言，上述半導體元件保護用材料較佳為包含(F)偶合劑。 In addition, from the viewpoint of improving the wettability of the semiconductor element protection material to the surface of the semiconductor element, further improving the flexibility of the cured product, and further improving the moisture resistance of the cured product, the above-mentioned semiconductor element protection material is preferably Contains (F) coupling agent.
以下，說明可用於上述半導體元件保護用材料之各成分之詳細情況。 Hereinafter, the details of each component that can be used in the above-mentioned semiconductor element protection material will be described.
((A)可撓性環氧化合物) ((A) Flexible epoxy compound)
藉由使用(A)可撓性環氧化合物，可提高硬化物之柔軟性。可僅使用1種(A)可撓性環氧化合物，亦可將2種以上併用。 By using (A) a flexible epoxy compound, the flexibility of the hardened product can be improved. Only one type of (A) flexible epoxy compound may be used, or two or more types may be used in combination.
作為(A)可撓性環氧化合物，可列舉：聚伸烷基二醇二縮水甘油醚、聚丁二烯二縮水甘油醚、硫醚改性環氧樹脂、及聚環氧烷改性雙酚A型環氧樹脂等。就進一步提高硬化物之柔軟性之觀點而言，較佳為聚伸烷基二 醇二縮水甘油醚。 (A) Flexible epoxy compounds include: polyalkylene glycol diglycidyl ether, polybutadiene diglycidyl ether, thioether modified epoxy resin, and polyalkylene oxide modified double Phenolic A type epoxy resin, etc. From the viewpoint of further improving the flexibility of the hardened material, polyalkylene oxide is preferred Alcohol diglycidyl ether.
就進一步提高硬化物之柔軟性之觀點而言，上述聚伸烷基二醇二縮水甘油醚較佳為具有伸烷基二醇基之重複數為9以上之結構單元。伸烷基之重複數之上限並無特別限定。伸烷基之重複數可為30以下。上述伸烷基之碳數較佳為2以上，較佳為5以下。 From the viewpoint of further improving the flexibility of the cured product, the polyalkylene glycol diglycidyl ether is preferably a structural unit having an alkylene glycol group with a repeating number of 9 or more. The upper limit of the number of repeating alkylene groups is not particularly limited. The number of repeating alkylene groups may be 30 or less. The carbon number of the above-mentioned alkylene group is preferably 2 or more, preferably 5 or less.
作為上述聚伸烷基二醇二縮水甘油醚，可列舉：聚乙二醇二縮水甘油醚、聚丙二醇二縮水甘油醚及聚四亞甲基二醇二縮水甘油醚等。 As said polyalkylene glycol diglycidyl ether, polyethyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, etc. are mentioned.
上述半導體元件保護用材料100重量%中，(A)可撓性環氧化合物之含量較佳為3重量%以上，更佳為5重量%以上，且較佳為10重量%以下，更佳為8重量%以下。若(A)可撓性環氧化合物之含量為上述下限以上，則硬化物之柔軟性進一步提高。若(A)可撓性環氧化合物之含量為上述上限以下，則半導體元件保護用材料之塗佈性進一步提高。 In 100% by weight of the above-mentioned semiconductor element protection material, the content of (A) the flexible epoxy compound is preferably 3% by weight or more, more preferably 5% by weight or more, and preferably 10% by weight or less, more preferably 8% by weight or less. If the content of the (A) flexible epoxy compound is more than the above lower limit, the flexibility of the cured product will be further improved. If the content of the (A) flexible epoxy compound is less than or equal to the above upper limit, the coatability of the semiconductor element protection material is further improved.
((B)與可撓性環氧化合物不同之環氧化合物) ((B) Epoxy compound different from flexible epoxy compound)
(B)與可撓性環氧化合物不同之環氧化合物不具有可撓性。藉由同時使用(A)可撓性環氧化合物及(B)環氧化合物，半導體元件保護用材料之硬化物之耐濕性提高，可降低對保護膜之貼附性。可僅使用1種(B)環氧化合物，亦可將2種以上併用。 (B) The epoxy compound which is different from the flexible epoxy compound does not have flexibility. By using (A) a flexible epoxy compound and (B) an epoxy compound at the same time, the moisture resistance of the cured product of the semiconductor element protection material is improved, and the adhesion to the protective film can be reduced. Only 1 type of (B) epoxy compound may be used, and 2 or more types may be used together.
作為(B)環氧化合物，可列舉：具有雙酚骨架之環氧化合物、具有二環戊二烯骨架之環氧化合物、具有萘骨架之環氧化合物、具有金剛烷骨架之環氧化合物、具有茀骨架之環氧化合物、具有聯苯骨架之環氧化合物、具有雙(縮水甘油氧基苯基)甲烷骨架之環氧化合物、具有二苯并吡喃骨架之環氧化合物、具有蒽骨架之環氧化合物、及具有芘骨架之環氧化合物等。亦可使用該等之氫化物或改性物。較佳為(B)環氧化合物不為聚伸烷基二醇二縮水甘油醚。 (B) Epoxy compounds include epoxy compounds having a bisphenol skeleton, epoxy compounds having a dicyclopentadiene skeleton, epoxy compounds having a naphthalene skeleton, epoxy compounds having an adamantane skeleton, Epoxy compounds with pyran skeleton, epoxy compounds with biphenyl skeleton, epoxy compounds with bis(glycidoxyphenyl) methane skeleton, epoxy compounds with dibenzopyran skeleton, ring with anthracene skeleton Oxygen compounds, epoxy compounds with pyrene skeleton, etc. These hydrides or modified products can also be used. It is preferable that (B) epoxy compound is not polyalkylene glycol diglycidyl ether.
就本發明之效果進一步優異而言，(B)環氧化合物較佳為具有雙酚骨架之環氧化合物(雙酚型環氧化合物)。 In terms of further excellent effects of the present invention, the epoxy compound (B) is preferably an epoxy compound having a bisphenol skeleton (bisphenol-type epoxy compound).
作為上述具有雙酚骨架之環氧化合物，例如可列舉：具有雙酚A型、雙酚F型或雙酚S型之雙酚骨架之環氧單體等。 Examples of the epoxy compound having a bisphenol skeleton include epoxy monomers having a bisphenol skeleton of bisphenol A type, bisphenol F type, or bisphenol S type.
作為上述具有二環戊二烯骨架之環氧化合物，可列舉：二氧化二環戊二烯及具有二環戊二烯骨架之苯酚酚醛清漆環氧單體等。 Examples of the epoxy compound having a dicyclopentadiene skeleton include dicyclopentadiene dioxide and a phenol novolak epoxy monomer having a dicyclopentadiene skeleton.
作為上述具有萘骨架之環氧化合物，可列舉：1-縮水甘油基萘、2-縮水甘油基萘、1,2-二縮水甘油基萘、1,5-二縮水甘油基萘、1,6-二縮水甘油基萘、1,7-二縮水甘油基萘、2,7-二縮水甘油基萘、三縮水甘油基萘、及1,2,5,6-四縮水甘油基萘等。 Examples of the epoxy compound having a naphthalene skeleton include: 1-glycidyl naphthalene, 2-glycidyl naphthalene, 1,2-diglycidyl naphthalene, 1,5-diglycidyl naphthalene, 1,6 -Diglycidyl naphthalene, 1,7-diglycidyl naphthalene, 2,7-diglycidyl naphthalene, triglycidyl naphthalene, and 1,2,5,6-tetraglycidyl naphthalene, etc.
作為上述具有金剛烷骨架之環氧化合物，可列舉：1,3-雙(4-縮水甘油氧基苯基)金剛烷、及2,2-雙(4-縮水甘油氧基苯基)金剛烷等。 Examples of the epoxy compound having an adamantane skeleton include 1,3-bis(4-glycidyloxyphenyl)adamantane and 2,2-bis(4-glycidyloxyphenyl)adamantane Wait.
作為上述具有茀骨架之環氧化合物，可列舉：9,9-雙(4-縮水甘油氧基苯基)茀、9,9-雙(4-縮水甘油氧基-3-甲基苯基)茀、9,9-雙(4-縮水甘油氧基-3-氯苯基)茀、9,9-雙(4-縮水甘油氧基-3-溴苯基)茀、9,9-雙(4-縮水甘油氧基-3-氟苯基)茀、9,9-雙(4-縮水甘油氧基-3-甲氧基苯基)茀、9,9-雙(4-縮水甘油氧基-3,5-二甲基苯基)茀、9,9-雙(4-縮水甘油氧基-3,5-二氯苯基)茀、及9,9-雙(4-縮水甘油氧基-3,5-二溴苯基)茀等。 As the above-mentioned epoxy compound having a glycidyl skeleton, 9,9-bis(4-glycidyloxyphenyl) pyrene, 9,9-bis(4-glycidyloxy-3-methylphenyl)茀, 9,9-bis(4-glycidyloxy-3-chlorophenyl) 茀, 9,9-bis(4-glycidoxy-3-bromophenyl) 茀, 9,9-bis( 4-glycidyloxy-3-fluorophenyl)pyridium, 9,9-bis(4-glycidoxy-3-methoxyphenyl)pyridium, 9,9-bis(4-glycidyloxy) -3,5-Dimethylphenyl)pyridium, 9,9-bis(4-glycidyloxy-3,5-dichlorophenyl)pyridium, and 9,9-bis(4-glycidyloxy) -3,5-Dibromophenyl) 茀 and so on.
作為上述具有聯苯骨架之環氧化合物，可列舉：4,4'-二縮水甘油基聯苯、及4,4'-二縮水甘油基-3,3',5,5'-四甲基聯苯等。 Examples of the epoxy compound having a biphenyl skeleton include: 4,4'-diglycidyl biphenyl and 4,4'-diglycidyl-3,3',5,5'-tetramethyl Biphenyl etc.
作為上述具有雙(縮水甘油氧基苯基)甲烷骨架之環氧化合物，可列舉：1,1'-雙(2,7-縮水甘油氧基萘基)甲烷、1,8'-雙(2,7-縮水甘油氧基萘基)甲烷、1,1'-雙(3,7-縮水甘油氧基萘基)甲烷、1,8'-雙(3,7-縮水甘油氧基萘基)甲烷、1,1'-雙(3,5-縮水甘油氧基萘基)甲烷、1,8'-雙(3,5-縮水甘油氧基 萘基)甲烷、1,2'-雙(2,7-縮水甘油氧基萘基)甲烷、1,2'-雙(3,7-縮水甘油氧基萘基)甲烷、及1,2'-雙(3,5-縮水甘油氧基萘基)甲烷等。 Examples of the epoxy compound having a bis(glycidoxyphenyl)methane skeleton include: 1,1'-bis(2,7-glycidoxynaphthyl)methane, 1,8'-bis(2 ,7-glycidoxynaphthyl)methane, 1,1'-bis(3,7-glycidoxynaphthyl)methane, 1,8'-bis(3,7-glycidoxynaphthyl) Methane, 1,1'-bis(3,5-glycidoxynaphthyl)methane, 1,8'-bis(3,5-glycidoxynaphthyl) Naphthyl)methane, 1,2'-bis(2,7-glycidoxynaphthyl)methane, 1,2'-bis(3,7-glycidoxynaphthyl)methane, and 1,2' -Bis(3,5-glycidoxynaphthyl)methane and the like.
作為上述具有二苯并吡喃骨架之環氧化合物，可列舉：1,3,4,5,6,8-六甲基-2,7-雙-環氧乙烷基甲氧基-9-苯基-9H-二苯并吡喃等。 Examples of the epoxy compound having a dibenzopyran skeleton include: 1,3,4,5,6,8-hexamethyl-2,7-bis-oxiranylmethoxy-9- Phenyl-9H-dibenzopyran and so on.
上述半導體元件保護用材料100重量%中，(A)可撓性環氧化合物與(B)環氧化合物之合計之含量較佳為5重量%以上，更佳為8重量%以上，且較佳為15重量%以下，更佳為12重量%以下。若(A)可撓性環氧化合物與(B)環氧化合物之合計之含量為上述下限以上及上述上限以下，則半導體元件保護用材料之塗佈性、硬化物之柔軟性、耐濕性、硬化物對半導體元件之接著性進一步變良好，可進一步抑制對保護膜之貼附。 In 100% by weight of the semiconductor element protection material, the total content of (A) flexible epoxy compound and (B) epoxy compound is preferably 5% by weight or more, more preferably 8% by weight or more, and more preferably It is 15% by weight or less, more preferably 12% by weight or less. If the total content of (A) flexible epoxy compound and (B) epoxy compound is above the above lower limit and below the above upper limit, the coating property of the semiconductor element protection material, the flexibility of the cured product, and the moisture resistance , The adhesion of the cured product to the semiconductor element is further improved, and the adhesion to the protective film can be further suppressed.
相對於(A)可撓性環氧化合物100重量份，(B)環氧化合物之含量較佳為10重量份以上，更佳為20重量份以上，且較佳為100重量份以下，更佳為90重量份以下。若(B)環氧化合物之含量為上述下限以上，則半導體元件保護用材料之塗佈性進一步提高，硬化物對半導體元件之接著性進一步提高。若(B)環氧化合物之含量為上述上限以下，則硬化物之柔軟性進一步提高。 Relative to 100 parts by weight of (A) flexible epoxy compound, the content of (B) epoxy compound is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and preferably 100 parts by weight or less, more preferably It is 90 parts by weight or less. If the content of the epoxy compound (B) is more than the above lower limit, the coating property of the semiconductor element protection material is further improved, and the adhesiveness of the cured product to the semiconductor element is further improved. If the content of the epoxy compound (B) is not more than the above upper limit, the flexibility of the cured product will be further improved.
((C)23℃下為液狀之硬化劑) ((C) Liquid hardener at 23℃)
(C)硬化劑於23℃下為液狀。因此，半導體元件保護用材料之塗佈性提高。又，半導體元件保護用材料對半導體元件之表面之潤濕性提高。可僅使用1種(C)硬化劑，亦可將2種以上併用。 (C) The hardener is liquid at 23°C. Therefore, the coatability of the semiconductor element protection material improves. In addition, the wettability of the semiconductor element protection material to the surface of the semiconductor element is improved. Only one type of (C) hardener may be used, or two or more types may be used in combination.
作為(C)硬化劑，可列舉：胺化合物(胺硬化劑)、咪唑化合物(咪唑硬化劑)、酚化合物(酚硬化劑)及酸酐(酸酐硬化劑)等。但於使用該等硬化劑之情形時，選擇23℃下為液狀之硬化劑。(C)硬化劑亦可不為咪唑化合物。 (C) Hardeners include amine compounds (amine hardeners), imidazole compounds (imidazole hardeners), phenol compounds (phenol hardeners), acid anhydrides (acid anhydride hardeners), and the like. However, when using these hardeners, choose a hardener that is liquid at 23°C. (C) The hardener may not be an imidazole compound.
就進一步抑制硬化物中之空隙之產生，進一步提高硬化物之耐熱性之觀點而言，(C)硬化劑較佳為酚化合物。 From the viewpoint of further suppressing the generation of voids in the cured product and further improving the heat resistance of the cured product, the (C) curing agent is preferably a phenol compound.
就進一步提高半導體元件保護用材料之塗佈性，進一步抑制硬化物中之空隙之產生，進一步提高硬化物之耐熱性之觀點而言，(C)硬化劑較佳為具有烯丙基，上述酚化合物較佳為具有烯丙基。 From the viewpoint of further improving the coating properties of the semiconductor element protection material, further suppressing the generation of voids in the cured product, and further improving the heat resistance of the cured product, the curing agent (C) preferably has an allyl group, and the above-mentioned phenol The compound preferably has an allyl group.
作為上述酚化合物，可列舉：苯酚酚醛清漆、鄰甲酚酚醛清漆、對甲酚酚醛清漆、第三丁基苯酚酚醛清漆、二環戊二烯甲酚、聚對乙烯基苯酚、雙酚A型酚醛清漆、苯二甲基改性酚醛清漆、十氫萘改性酚醛清漆、聚(二鄰羥基苯基)甲烷、聚(二間羥基苯基)甲烷、及聚(二對羥基苯基)甲烷等。 Examples of the phenol compound include: phenol novolac, ortho-cresol novolac, p-cresol novolak, tertiary butylphenol novolak, dicyclopentadiene cresol, poly(p-vinylphenol), and bisphenol A type Novolac, xylylene modified novolac, decalin modified novolac, poly(di-o-hydroxyphenyl)methane, poly(di-m-hydroxyphenyl)methane, and poly(di-p-hydroxyphenyl)methane Wait.
相對於(A)可撓性環氧化合物與(B)環氧化合物之合計100重量份，(C)硬化劑之含量較佳為10重量份以上，更佳為20重量份以上，進而較佳為30重量份以上，且較佳為100重量份以下，更佳為90重量份以下，進而較佳為80重量份以下。若(C)硬化劑之含量為上述下限以上，則可使半導體元件保護用材料良好地硬化。若(C)硬化劑之含量為上述上限以下，則硬化物內之無助於硬化之(C)硬化劑之殘餘量變少。 The content of (C) hardener is preferably 10 parts by weight or more, more preferably 20 parts by weight or more, and more preferably, relative to 100 parts by weight of the total of (A) flexible epoxy compound and (B) epoxy compound It is 30 parts by weight or more, preferably 100 parts by weight or less, more preferably 90 parts by weight or less, and still more preferably 80 parts by weight or less. If the content of the (C) curing agent is more than the above lower limit, the semiconductor element protection material can be cured well. If the content of (C) hardener is below the above upper limit, the residual amount of (C) hardener in the hardened product that does not contribute to hardening will decrease.
((D)硬化促進劑) ((D) Hardening accelerator)
藉由使用(D)硬化促進劑，可加快硬化速度，有效率地使半導體元件保護用材料硬化。可僅使用1種(D)硬化促進劑，亦可將2種以上併用。 By using the (D) hardening accelerator, the hardening speed can be accelerated, and the semiconductor device protection material can be hardened efficiently. Only one type of (D) hardening accelerator may be used, or two or more types may be used in combination.
作為(D)硬化促進劑，可列舉：咪唑化合物、磷化合物、胺化合物、及有機金屬化合物等。其中，就本發明之效果進一步優異而言，較佳為咪唑化合物。 (D) Hardening accelerators include imidazole compounds, phosphorus compounds, amine compounds, and organometallic compounds. Among them, imidazole compounds are preferred in terms of further excellent effects of the present invention.
作為上述咪唑化合物，可列舉：2-十一烷基咪唑、2-十七烷基咪唑、2-甲咪唑、2-乙基-4-甲咪唑、2-苯咪唑、2-苯基-4-甲咪唑、1-苄基-2-甲
咪唑、1-苄基-2-苯咪唑、1,2-二甲咪唑、1-氰乙基-2-甲咪唑、1-氰乙基-2-乙基-4-甲咪唑、1-氰乙基-2-十一烷基咪唑、1-氰乙基-2-苯咪唑、偏苯三酸1-氰乙基-2-十一烷基咪唑鎓、偏苯三酸1-氰乙基-2-苯基咪唑鎓、2,4-二胺基-6-[2'-甲基咪唑基-(1')]-乙基對稱三
作為上述磷化合物，可列舉：三苯基膦等。 As said phosphorus compound, triphenylphosphine etc. are mentioned.
作為上述胺化合物，可列舉：2,4,6-三(二甲胺基甲基)苯酚、二乙胺、三乙胺、二伸乙基四胺、三伸乙基四胺及4,4-二甲胺基吡啶等。 Examples of the above-mentioned amine compounds include 2,4,6-tris(dimethylaminomethyl)phenol, diethylamine, triethylamine, diethylenetetramine, triethylenetetramine, and 4,4 -Dimethylaminopyridine and the like.
作為上述有機金屬化合物，可列舉：環烷酸鋅、環烷酸鈷、辛酸錫、辛酸鈷、雙乙醯丙酮鈷(II)及三乙醯丙酮鈷(III)等。 As said organometallic compound, zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, cobalt diacetone (II), cobalt triacetone (III), etc. are mentioned.
相對於(A)可撓性環氧化合物與(B)環氧化合物之合計100重量份，(D)硬化促進劑之含量較佳為0.1重量份以上，更佳為0.5重量份以上，且較佳為10重量份以下，更佳為8重量份以下。若(D)硬化促進劑之含量為上述下限以上，則可使半導體元件保護用材料良好地硬化。若(D)硬化促進 劑之含量為上述上限以下，則硬化物內之無助於硬化之(D)硬化促進劑之殘餘量變少。 The content of (D) hardening accelerator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more with respect to 100 parts by weight of the total of (A) flexible epoxy compound and (B) epoxy compound It is preferably 10 parts by weight or less, and more preferably 8 parts by weight or less. If the content of the (D) hardening accelerator is more than the above lower limit, the material for protecting semiconductor elements can be hardened well. If (D) hardening is promoted If the content of the agent is below the above upper limit, the residual amount of (D) hardening accelerator that does not contribute to hardening in the hardened product will decrease.
((E)熱導率為10W/m．K以上且為球狀之無機填料) ((E) Inorganic filler with a thermal conductivity of 10W/m.K or more and spherical)
藉由使用(E)熱導率為10W/m．K以上且為球狀之無機填料，可將半導體元件保護用材料之塗佈性維持得較高，且將硬化物之柔軟性維持得較高，並且提高硬化物之散熱性。若(E)無機填料之熱導率為10W/m．K以上且為球狀，則並無特別限定。可僅使用1種(E)無機填料，亦可將2種以上併用。 By using (E) the thermal conductivity is 10W/m. Inorganic fillers above K and spherical in shape can maintain high coatability of semiconductor device protection materials, maintain high flexibility of the cured product, and improve the heat dissipation of the cured product. If (E) the thermal conductivity of the inorganic filler is 10W/m. K or more and spherical shape is not particularly limited. Only one type of (E) inorganic filler may be used, or two or more types may be used in combination.
就進一步提高硬化物之散熱性之觀點而言，(E)無機填料之熱導率較佳為10W/m．K以上，更佳為15W/m．K以上，進而較佳為20W/m．K以上。(E)無機填料之熱導率之上限並無特別限定。熱導率為300W/m．K左右之無機填料已廣為人知，又，容易得到熱導率為200W/m．K左右之無機填料。 From the viewpoint of further improving the heat dissipation of the hardened material, (E) the thermal conductivity of the inorganic filler is preferably 10W/m. Above K, more preferably 15W/m. K or more, more preferably 20W/m. Above K. (E) The upper limit of the thermal conductivity of the inorganic filler is not particularly limited. The thermal conductivity is 300W/m. Inorganic fillers around K have been widely known, and it is easy to get a thermal conductivity of 200W/m. Inorganic fillers around K.
就有效地提高硬化物之散熱性之觀點而言，(E)無機填料較佳為氧化鋁、氮化鋁或碳化矽。於使用該等較佳之無機填料之情形時，可僅使用1種該等無機填料，亦可將2種以上併用。作為(E)無機填料，亦可適當使用除上述以外之無機填料。 From the viewpoint of effectively improving the heat dissipation of the hardened material, (E) the inorganic filler is preferably alumina, aluminum nitride or silicon carbide. When these preferable inorganic fillers are used, only one of these inorganic fillers may be used, or two or more of them may be used in combination. As the (E) inorganic filler, inorganic fillers other than the above can also be used appropriately.
(E)無機填料為球狀。所謂球狀係指縱橫比(長徑/短徑)為1以上且2以下。 (E) The inorganic filler is spherical. The term "spherical shape" means that the aspect ratio (longer diameter/shorter diameter) is 1 or more and 2 or less.
(E)無機填料之平均粒徑較佳為0.1μm以上，且較佳為150μm以下。若(E)無機填料之平均粒徑為上述下限以上，則可以高密度容易地填充(E)無機填料。若(E)無機填料之平均粒徑為上述上限以下，則半導體元件保護用材料之塗佈性進一步提高。 (E) The average particle diameter of the inorganic filler is preferably 0.1 μm or more, and preferably 150 μm or less. If the average particle size of the (E) inorganic filler is greater than or equal to the above lower limit, the (E) inorganic filler can be easily filled with high density. (E) If the average particle size of the inorganic filler is less than or equal to the above upper limit, the coating property of the semiconductor element protection material is further improved.
所謂上述「平均粒徑」係根據藉由雷射繞射式粒度分佈測定裝置所 測定之以體積平均計之粒度分佈測定結果求出之平均粒徑。 The so-called "average particle size" is based on the laser diffraction particle size distribution measuring device The average particle size obtained from the measurement result of the particle size distribution measured by volume average.
上述半導體元件保護用材料100重量%中，(E)無機填料之含量較佳為60重量%以上，更佳為70重量%以上，進而較佳為80重量%以上，特佳為82重量%以上，且較佳為92重量%以下，更佳為90重量%以下。若(E)無機填料之含量為上述下限以上，則硬化物之散熱性進一步提高。若(E)無機填料之含量為上述上限以下，則半導體元件保護用材料之塗佈性進一步提高。 In 100% by weight of the above-mentioned semiconductor element protection material, the content of (E) inorganic filler is preferably 60% by weight or more, more preferably 70% by weight or more, still more preferably 80% by weight or more, and particularly preferably 82% by weight or more , And preferably 92% by weight or less, more preferably 90% by weight or less. If the content of the (E) inorganic filler is more than the above lower limit, the heat dissipation of the hardened product is further improved. If the content of the (E) inorganic filler is less than or equal to the above upper limit, the coating property of the semiconductor element protection material is further improved.
((F)偶合劑) ((F) coupling agent)
上述半導體元件保護用材料較佳為包含(F)偶合劑。藉由使用(F)偶合劑，半導體元件保護用材料之硬化物之耐濕性進一步提高。可僅使用1種(F)偶合劑，亦可將2種以上併用。 The material for protecting the semiconductor element preferably contains (F) a coupling agent. By using the (F) coupling agent, the moisture resistance of the cured material of the semiconductor device protection material is further improved. Only one type of (F) coupling agent may be used, or two or more types may be used in combination.
上述半導體元件保護用材料100重量%中，(F)偶合劑之含量較佳為0.1重量%以上，更佳為0.3重量%以上，且較佳為2重量%以下，更佳為1重量%以下。若(F)偶合劑之含量為上述下限以上，則半導體元件保護用材料之硬化物之耐濕性進一步提高。若(F)偶合劑之含量為上述上限以下，則半導體元件保護用材料之塗佈性進一步提高。 In 100% by weight of the above-mentioned semiconductor element protection material, the content of (F) coupling agent is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, and preferably 2% by weight or less, and more preferably 1% by weight or less . If the content of the (F) coupling agent is more than the above lower limit, the moisture resistance of the cured product of the semiconductor element protection material is further improved. If the content of the coupling agent (F) is not more than the above upper limit, the coating properties of the semiconductor element protection material will be further improved.
上述(F)偶合劑較佳為包含100℃下之重量減少為10重量%以下之矽烷偶合劑、100℃下之重量減少為10重量%以下之鈦酸酯偶合劑或100℃下之重量減少為10重量%以下之鋁酸酯偶合劑。於使用該等較佳之矽烷偶合劑之情形時，可僅使用1種該等矽烷偶合劑，亦可將2種以上併用。 The above-mentioned (F) coupling agent preferably contains a silane coupling agent with a weight loss of 10% by weight or less at 100°C, a titanate coupling agent with a weight loss of 10% by weight or less at 100°C, or a weight loss at 100°C The aluminate coupling agent is less than 10% by weight. In the case of using these preferred silane coupling agents, only one type of these silane coupling agents may be used, or two or more types may be used in combination.
若100℃下之重量減少為10重量%以下，則可抑制硬化中(F)偶合劑之揮發，對半導體元件之潤濕性進一步提高，硬化物之散熱性進一步提高。 If the weight reduction at 100°C is 10% by weight or less, the volatilization of the (F) coupling agent during curing can be suppressed, the wettability of the semiconductor element is further improved, and the heat dissipation of the cured product is further improved.
再者，100℃下之重量減少可藉由使用紅外線水分計(Kett Electric Laboratory公司製造之「FD-720」)，以50℃/分鐘之升溫速度升溫至100 ℃，測定10分鐘後之重量減少而求出。 Furthermore, the weight reduction at 100°C can be achieved by using an infrared moisture meter ("FD-720" manufactured by Kett Electric Laboratory) at a temperature increase rate of 50°C/min to 100 It is determined by measuring the weight loss after 10 minutes at °C.
(其他成分) (Other ingredients)
上述半導體元件保護用材料視需要可包含：巴西棕櫚蠟等天然蠟、聚乙烯蠟等合成蠟、硬脂酸或硬脂酸鋅等高級脂肪酸及其金屬鹽類或石蠟等脫模劑；碳黑、鐵丹等著色劑；溴化環氧樹脂、三氧化二銻、氫氧化鋁、氫氧化鎂、硼酸鋅、鉬酸鋅、膦腈等阻燃劑；氧化鉍水合物等無機離子交換體；聚矽氧油、聚矽氧橡膠等低應力化成分；抗氧化劑等各種添加劑。 The above-mentioned semiconductor element protection materials may include natural waxes such as carnauba wax, synthetic waxes such as polyethylene wax, higher fatty acids such as stearic acid or zinc stearate, and metal salts thereof, or mold release agents such as paraffin wax as needed; Coloring agents such as, iron red; flame retardants such as brominated epoxy resin, antimony trioxide, aluminum hydroxide, magnesium hydroxide, zinc borate, zinc molybdate, phosphazene; inorganic ion exchangers such as bismuth oxide hydrate; Low-stress ingredients such as silicone oil and silicone rubber; various additives such as antioxidants.
上述半導體元件保護用材料較佳為包含聚乙烯蠟等合成蠟。上述半導體元件保護用材料100重量%中，聚乙烯蠟等合成蠟之含量較佳為0.1重量%以上，更佳為0.2重量%以上，且較佳為2重量%以下，更佳為1重量%以下。 The material for protecting the semiconductor element preferably contains synthetic wax such as polyethylene wax. In 100% by weight of the semiconductor element protection material, the content of synthetic wax such as polyethylene wax is preferably 0.1% by weight or more, more preferably 0.2% by weight or more, and preferably 2% by weight or less, more preferably 1% by weight the following.
(半導體元件保護用材料之其他詳情及半導體裝置) (Other details of semiconductor device protection materials and semiconductor devices)
上述半導體元件保護用材料係為了保護半導體元件而塗佈於上述半導體元件之表面上使用。上述半導體元件保護用材料不同於配置於半導體元件與其他連接對象構件之間，形成以不使上述半導體元件與上述其他連接對象構件剝離之方式將該等接著及固定之硬化物者。上述半導體元件保護用材料較佳為覆蓋半導體元件之表面之被覆材料。上述半導體元件保護用材料較佳為不塗佈於半導體元件之側面上。上述半導體元件保護用材料較佳為與用以密封上述半導體元件之材料不同，較佳為並非用以密封上述半導體元件之密封劑。上述半導體元件保護用材料較佳為並非底部填充劑材料。較佳為上述半導體元件於第2表面側具有第1電極，上述半導體元件保護用材料係塗佈於上述半導體元件之與上述第2表面側相反之第1表面上使用。上述半導體元件保護用材料於半導體裝置中，可較佳地用於為了保 護半導體元件而於上述半導體元件之表面上形成硬化物。上述半導體元件保護用材料可較佳地用於為了保護半導體元件而於上述半導體元件之表面上形成硬化物，且可較佳地用於在上述硬化物之與上述半導體元件側相反之表面上配置保護膜而獲得半導體裝置。 The material for protecting the semiconductor element is applied to the surface of the semiconductor element for use in order to protect the semiconductor element. Unlike the semiconductor element protection material, which is arranged between the semiconductor element and the other connection object member, it forms a cured product that adheres and fixes the semiconductor element and the other connection object member so as not to peel off the semiconductor element and the other connection object member. The material for protecting the semiconductor element is preferably a coating material covering the surface of the semiconductor element. The material for protecting the semiconductor element is preferably not coated on the side surface of the semiconductor element. The material for protecting the semiconductor element is preferably different from the material for sealing the semiconductor element, and is preferably not a sealant for sealing the semiconductor element. The material for protecting the semiconductor element is preferably not an underfill material. Preferably, the semiconductor element has a first electrode on the second surface side, and the material for protecting the semiconductor element is applied to the first surface of the semiconductor element opposite to the second surface side for use. The above-mentioned semiconductor element protection materials are preferably used in semiconductor devices for protection The semiconductor element is protected to form a hardened substance on the surface of the semiconductor element. The above-mentioned semiconductor element protection material can be preferably used to form a cured product on the surface of the semiconductor element in order to protect the semiconductor element, and can be preferably used to arrange the cured product on the opposite surface of the semiconductor element side Protect the film to obtain a semiconductor device.
作為塗佈上述半導體元件保護用材料之方法，可列舉：利用分注器之塗佈方法、利用網版印刷之塗佈方法、及利用噴墨裝置之塗佈方法等。上述半導體元件保護用材料較佳為藉由利用分注器、網版印刷、真空網版印刷或噴墨裝置之塗佈方法塗佈使用。就容易塗佈，且於硬化物中更加難以產生空隙之觀點而言，上述半導體元件保護用材料較佳為藉由分注器塗佈使用。 As a method of applying the above-mentioned semiconductor element protection material, a coating method using a dispenser, a coating method using screen printing, a coating method using an inkjet device, and the like can be cited. The material for protecting the semiconductor element is preferably applied by a coating method using a dispenser, screen printing, vacuum screen printing, or an inkjet device. From the viewpoint of ease of coating and more difficult to generate voids in the cured product, the above-mentioned semiconductor element protection material is preferably used by dispenser coating.
本發明之半導體裝置具備半導體元件、及配置於上述半導體元件之第1表面上之硬化物。於本發明之半導體裝置中，上述硬化物係藉由使上述半導體元件保護用材料硬化而形成。 The semiconductor device of the present invention includes a semiconductor element and a cured product arranged on the first surface of the semiconductor element. In the semiconductor device of the present invention, the cured product is formed by curing the material for protecting the semiconductor element.
較佳為上述半導體元件保護用材料係用於為了保護半導體元件而於上述半導體元件之表面上形成硬化物，且於上述硬化物之與上述半導體元件側相反之表面上配置保護膜而獲得半導體裝置，或用於獲得為了保護半導體元件而於上述半導體元件之表面上形成硬化物，且上述硬化物之與上述半導體元件側相反之表面外露之半導體裝置。上述保護膜可於電子零件等之使用前使用，亦可於電子零件等之使用時剝離。 Preferably, the semiconductor element protection material is used to form a cured product on the surface of the semiconductor element to protect the semiconductor element, and a protective film is arranged on the surface of the cured product opposite to the semiconductor element side to obtain a semiconductor device , Or used to obtain a semiconductor device in which a cured product is formed on the surface of the semiconductor element in order to protect the semiconductor element, and the surface of the cured product opposite to the semiconductor element side is exposed. The above-mentioned protective film can be used before the use of electronic parts, etc., and can also be peeled off when the electronic parts are used.
圖1係表示使用本發明之第1實施形態之半導體元件保護用材料之半導體裝置之局部切開前視剖視圖。 FIG. 1 is a partially cut-away front sectional view of a semiconductor device using the semiconductor device protection material of the first embodiment of the present invention.
圖1所示之半導體裝置1具備半導體元件2及配置於半導體元件2之第1表面2a上之硬化物3。硬化物3係藉由使上述半導體元件保護用材料硬化而形成。硬化物3配置於半導體元件2之第1表面2a上之部分區域。
The
半導體元件2於與第1表面2a側相反之第2表面2b側具有第1電極2A。半導體裝置1進而具備連接對象構件4。連接對象構件4於表面4a具有第2電極4A。半導體元件2與連接對象構件4係經由其他硬化物5(連接部)接著及固定。半導體元件2之第1電極2A與連接對象構件4之第2電極4A相對向，利用導電性粒子6電性連接。亦可藉由使第1電極2A與第2電極4A相接觸而電性連接。硬化物3配置於半導體元件2之與配置有第1電極2A側相反之側之第1表面2a上。
The
於硬化物3之與半導體元件2側相反之表面上配置有保護膜7。藉此，不僅可藉由硬化物3提高散熱性及半導體元件之保護性，亦可藉由保護膜7進一步提高半導體元件之保護性。由於硬化物3係具有上述組成而獲得，故而可抑制硬化物3對保護膜7之貼附。
A
作為上述連接對象構件，可列舉：玻璃基板、環氧玻璃基板、可撓性印刷基板、及聚醯亞胺基板等。 As said connection object member, a glass substrate, an epoxy glass substrate, a flexible printed circuit board, a polyimide substrate, etc. are mentioned.
於半導體元件之表面上，半導體元件保護用材料之硬化物之厚度較佳為400μm以上，更佳為500μm以上，且較佳為2000μm以下，更佳為1900μm以下。半導體元件保護用材料之硬化物之厚度可薄於半導體元件之厚度。 On the surface of the semiconductor device, the thickness of the cured product of the semiconductor device protection material is preferably 400 μm or more, more preferably 500 μm or more, and preferably 2000 μm or less, and more preferably 1900 μm or less. The thickness of the hardened material of the semiconductor device protection material can be thinner than the thickness of the semiconductor device.
圖2係表示使用本發明之第2實施形態之半導體元件保護用材料之半導體裝置之局部切開前視剖視圖。 2 is a partially cut-away front sectional view of a semiconductor device using the semiconductor device protection material of the second embodiment of the present invention.
圖2所示之半導體裝置1X具備半導體元件2及配置於半導體元件2之第1表面2a上之硬化物3X。硬化物3X係藉由使上述半導體元件保護用材料硬化而形成。硬化物3X配置於半導體元件2之第1表面2a上之整個區域。於硬化物3X之與半導體元件2側相反之表面上未配置保護膜。硬化物3X之與半導體元件2側相反之表面外露。
The
於上述半導體裝置中，較佳為於上述硬化物之與上述半導體元件側相反之表面上配置有保護膜，或，上述硬化物之與上述半導體元件側相反之表面外露。 In the above semiconductor device, it is preferable that a protective film is disposed on the surface of the cured product opposite to the semiconductor element side, or the surface of the cured product opposite to the semiconductor element side is exposed.
再者，圖1、2所示之結構僅為半導體裝置之一例，可對半導體元件保護用材料之硬化物之配置結構等進行適當變化。 Furthermore, the structure shown in FIGS. 1 and 2 is only an example of a semiconductor device, and the arrangement structure of the hardened material of the semiconductor element protection material can be appropriately changed.
半導體元件保護用材料之硬化物之熱導率並無特別限定，較佳為1.8W/m．K以上。 The thermal conductivity of the hardened material of the semiconductor device protection material is not particularly limited, and it is preferably 1.8W/m. Above K.
以下，藉由列舉本發明之具體之實施例及比較例，對本發進行闡明。再者，本發明並不限定於以下實施例。 Hereinafter, the present invention will be clarified by citing specific examples and comparative examples of the present invention. In addition, the present invention is not limited to the following examples.
使用以下材料。 Use the following materials.
(A)可撓性環氧化合物 (A) Flexible epoxy compound
EX-821(n=4)(長瀨化成公司製造，聚乙二醇二縮水甘油醚，環氧當量：185) EX-821 (n=4) (manufactured by Nagase Chemical Co., polyethylene glycol diglycidyl ether, epoxy equivalent: 185)
EX-830(n=9)(長瀨化成公司製造，聚乙二醇二縮水甘油醚，環氧當量：268) EX-830 (n=9) (manufactured by Nagase Chemical Co., polyethylene glycol diglycidyl ether, epoxy equivalent: 268)
EX-931(n=11)(長瀨化成公司製造，聚丙二醇二縮水甘油醚，環氧當量：471) EX-931(n=11) (manufactured by Nagase Kasei Co., polypropylene glycol diglycidyl ether, epoxy equivalent: 471)
EX-861(n=22)(長瀨化成公司製造，聚乙二醇二縮水甘油醚，環氧當量：551) EX-861 (n=22) (manufactured by Nagase Kasei Co., polyethylene glycol diglycidyl ether, epoxy equivalent: 551)
PB3600(大賽璐公司製造，聚丁二烯改性環氧樹脂) PB3600 (manufactured by Daicel, polybutadiene modified epoxy resin)
(B)與可撓性環氧化合物不同之環氧化合物 (B) Epoxy compounds different from flexible epoxy compounds
jER828(三菱化學公司製造，雙酚A型環氧樹脂，環氧當量：188) jER828 (manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, epoxy equivalent: 188)
jER834(三菱化學公司製造，雙酚A型環氧樹脂，軟化點：30℃，環氧當量：255) jER834 (manufactured by Mitsubishi Chemical Corporation, bisphenol A epoxy resin, softening point: 30°C, epoxy equivalent: 255)
(C)23℃下為液狀之硬化劑 (C) Liquid hardener at 23℃
FUJICURE 7000(富士化成公司製造，23℃下為液狀，胺化合物) FUJICURE 7000 (manufactured by Fuji Chemical Co., liquid at 23°C, amine compound)
MEH-8005(明和化成公司製造，23℃下為液狀，烯丙基苯酚酚醛清漆化合物) MEH-8005 (manufactured by Meiwa Chemical Co., Ltd., liquid at 23°C, allyl phenol novolac compound)
(C')其他硬化劑 (C') other hardeners
TD-2131(DIC公司製造，23℃下為固體狀，苯酚酚醛清漆化合物) TD-2131 (manufactured by DIC, solid at 23°C, phenol novolac compound)
(D)硬化促進劑 (D) Hardening accelerator
SA-102(San-Apro公司製造，DBU(diazabicycloundecene，二氮雜雙環十一烯)辛酸鹽) SA-102 (manufactured by San-Apro, DBU (diazabicycloundecene, diazabicycloundecene) caprylate)
(E)熱導率為10W/m．K以上且為球狀之無機填料 (E) The thermal conductivity is 10W/m. Inorganic filler above K and spherical
FAN-f05(古河電子公司製造，氮化鋁，熱導率：100W/m．K，球狀，平均粒徑：6μm) FAN-f05 (manufactured by Furukawa Electronics, aluminum nitride, thermal conductivity: 100W/m·K, spherical, average particle size: 6μm)
FAN-f50(古河電子公司製造，氮化鋁，熱導率：100W/m．K，球狀，平均粒徑：30μm) FAN-f50 (manufactured by Furukawa Electronics, aluminum nitride, thermal conductivity: 100W/m·K, spherical, average particle size: 30μm)
CB-P05(昭和電工公司製造，氧化鋁，熱導率：20W/m．K，球狀，平均粒徑：4μm) CB-P05 (manufactured by Showa Denko Corporation, alumina, thermal conductivity: 20W/m.K, spherical, average particle size: 4μm)
CB-P40(昭和電工公司製造，氧化鋁，熱導率：20W/m．K，球狀，平均粒徑：44μm) CB-P40 (manufactured by Showa Denko Corporation, alumina, thermal conductivity: 20W/m.K, spherical, average particle size: 44μm)
SSC-A15(信濃電氣精煉公司製造，氮化矽，熱導率：100W/m．K，球狀，平均粒徑：19μm) SSC-A15 (manufactured by Shinano Electric Refining Co., Ltd., silicon nitride, thermal conductivity: 100W/m.K, spherical, average particle size: 19μm)
SSC-A30(信濃電氣精煉公司製造，氮化矽，熱導率：100W/m．K，球狀，平均粒徑：34μm) SSC-A30 (manufactured by Shinano Electric Refining Co., Ltd., silicon nitride, thermal conductivity: 100W/m.K, spherical, average particle size: 34μm)
(E')其他無機填料 (E') Other inorganic fillers
HS-306(Micron公司製造，氧化矽，熱導率：2W/m．K，球狀，平 均粒徑：2.5μm) HS-306 (manufactured by Micron, silicon oxide, thermal conductivity: 2W/m.K, spherical, flat Average particle size: 2.5μm)
HS-304(Micron公司製造，氧化矽，熱導率：2W/m．K，球狀，平均粒徑：25μm) HS-304 (manufactured by Micron, silicon oxide, thermal conductivity: 2W/m.K, spherical, average particle size: 25μm)
(F)偶合劑 (F) Coupling agent
KBM-403(信越化學工業公司製造，3-甘油氧基丙基三甲氧基矽烷，100℃下之重量減少：超過10重量%) KBM-403 (manufactured by Shin-Etsu Chemical Co., 3-glyceroxypropyltrimethoxysilane, weight reduction at 100°C: more than 10% by weight)
A-LINK599(momentive公司製造，3-辛醯基硫代-1-丙基三乙氧基矽烷，100℃下之重量減少：10重量%以下) A-LINK599 (manufactured by Momentive, 3-octylthio-1-propyltriethoxysilane, weight loss at 100°C: 10% by weight or less)
TOG(IPA CUT)(日本曹達公司製造，異丙氧基辛二醇鈦，100℃下之重量減少：10重量%以下) TOG (IPA CUT) (manufactured by Soda Japan, titanium isopropoxy octanodiol, weight reduction at 100°C: 10% by weight or less)
AL-M(Ajinomoto Fine-Techno公司製造，乙醯烷氧基二異丙醇鋁，100℃下之重量減少：10重量%以下) AL-M (manufactured by Ajinomoto Fine-Techno, acetylated aluminum diisopropoxide, weight reduction at 100°C: 10% by weight or less)
(其他成分) (Other ingredients)
Hi-Wax 200PF(三井化學公司製造，聚乙烯蠟) Hi-Wax 200PF (made by Mitsui Chemicals, polyethylene wax)
(實施例1) (Example 1)
將EX-821(n=4)6.5重量份、jER828 2.5重量份、FUJICURE 7000 5重量份、SA-102 0.5重量份、CB-P05 42.5重量份、CB-P40 42.5重量份、及Hi-Wax 200PF 0.5重量份混合，進行消泡，而獲得半導體元件保護用材料。 Ex-821 (n=4) 6.5 parts by weight, jER828 2.5 parts by weight, FUJICURE 7000 5 parts by weight, SA-102 0.5 parts by weight, CB-P05 42.5 parts by weight, CB-P40 42.5 parts by weight, and Hi-Wax 200PF 0.5 parts by weight are mixed and defoamed to obtain a material for protecting semiconductor elements.
(實施例2~15及比較例1~4) (Examples 2 to 15 and Comparative Examples 1 to 4)
除如下述表1、2所示變更調配成分之種類及調配量以外，以與實施例1相同之方式獲得半導體元件保護用材料。 The semiconductor element protection material was obtained in the same manner as in Example 1, except that the type and the amount of the compounding components were changed as shown in Tables 1 and 2 below.
(評價) (Evaluation)
(1)25℃下之黏度之測定 (1) Measurement of viscosity at 25℃
使用B型黏度計(東機產業公司製造之「TVB-10型」)，測定半導體元件保護用材料於25℃下且10rpm下之黏度(mPa．s)。 Use a type B viscometer ("TVB-10" manufactured by Toki Sangyo Co., Ltd.) to measure the viscosity (mPa·s) of the semiconductor device protection material at 25°C and 10 rpm.
(2)熱導率 (2) Thermal conductivity
將所獲得之半導體元件保護用材料以150℃加熱2小時使其硬化，獲得100mm×100mm×厚度50μm之硬化物。將該硬化物作為評價樣品。 The obtained semiconductor element protection material was heated at 150° C. for 2 hours to be cured to obtain a cured product of 100 mm×100 mm×thickness 50 μm. This cured product was used as an evaluation sample.
使用京都電子工業公司製造之熱導率計「迅速熱導率計QTM-500」，測定所獲得之評價樣品之熱導率。 The thermal conductivity meter "Quick Thermal Conductivity Meter QTM-500" manufactured by Kyoto Electronics Industry Co., Ltd. was used to measure the thermal conductivity of the obtained evaluation sample.
(3)塗佈性 (3) Coatability
將所獲得之半導體元件保護用材料以成為直徑5mm、高度2mm之方式直接自分注器裝置(Musashi Engineering公司製造之「SHOTMASTER-300」)噴出至聚醯亞胺膜後，將半導體元件保護用材料以150℃加熱2小時使其硬化。根據硬化後之半導體元件保護用材料之形狀，以下述標準判定塗佈性。 The obtained semiconductor element protection material was sprayed directly from a dispenser device ("SHOTMASTER-300" manufactured by Musashi Engineering) onto the polyimide film in a diameter of 5 mm and a height of 2 mm, and the semiconductor element protection material Heat at 150°C for 2 hours to harden. According to the shape of the semiconductor device protection material after curing, the applicability is determined according to the following criteria.
[塗佈性之判定標準] [Criteria for applicability]
○：直徑為5.3mm以上，高度未達1.8mm(有流動性) ○: The diameter is 5.3mm or more, and the height is less than 1.8mm (with fluidity)
△：直徑超過5mm且未達5.3mm，高度超過1.8mm且未達2mm(稍有流動性) △: The diameter exceeds 5mm and does not reach 5.3mm, and the height exceeds 1.8mm but does not reach 2mm (slightly fluid)
×：直徑為5mm，高度為2mm未變(無流動性) ×: The diameter is 5mm, the height is 2mm unchanged (no fluidity)
(4)耐濕性 (4) Humidity resistance
將所獲得之半導體元件保護用材料以150℃加熱2小時使其硬化，獲得100mm×100mm×厚度50μm之硬化物。將該硬化物作為評價樣品。 The obtained semiconductor element protection material was heated at 150° C. for 2 hours to be cured to obtain a cured product of 100 mm×100 mm×thickness 50 μm. This cured product was used as an evaluation sample.
利用DSM-8104(日置電機公司製造，數位超絕緣/微電流計)、平板試樣用電極SME-8310(日置電機公司製造)，對所獲得之評價樣品測定體積電阻率。 The volume resistivity of the obtained evaluation sample was measured using DSM-8104 (digital super-insulation/micro-amperometer, manufactured by Hioki Electric Co., Ltd.) and SME-8310 (manufactured by Hioki Electric Co., Ltd.).
繼而，利用高度加速壽命試驗裝置EHS-211(愛斯佩克公司製造)進行壓力鍋試驗。於121℃、濕度100%RH及2atm之條件下放置24小時，繼而於23℃及濕度50%RH之環境下放置24小時後，測定體積電阻率。計算壓力鍋試驗前後之體積電阻率之降低率，以下述標準判定耐濕性。 Then, the pressure cooker test was performed using the highly accelerated life test device EHS-211 (manufactured by Espec). Place it at 121°C, humidity 100%RH and 2atm for 24 hours, and then place it at 23°C and humidity 50%RH for 24 hours, then measure the volume resistivity. Calculate the reduction rate of volume resistivity before and after the pressure cooker test, and determine the moisture resistance according to the following standards.
[耐濕性之判定標準] [Determination Criteria for Moisture Resistance]
○：試驗前後之體積電阻率之降低率為10%以下 ○: The reduction rate of volume resistivity before and after the test is less than 10%
△：試驗前後之體積電阻率之降低率超過10%且為20%以下 △: The reduction rate of volume resistivity before and after the test is more than 10% and less than 20%
×：試驗前後之體積電阻率之降低率超過20% ×: The reduction rate of volume resistivity before and after the test exceeds 20%
(5)接著力(由晶片剪切強度進行評價) (5) Adhesion (evaluated by wafer shear strength)
於聚醯亞胺基板上，以接著面積成為3mm×3mm之方式塗佈半導體元件保護用材料，載置1.5mm見方之Si晶片，獲得試驗樣品。 On the polyimide substrate, a semiconductor element protection material was coated so that the bonding area became 3 mm×3 mm, and a 1.5 mm square Si wafer was placed to obtain a test sample.
將所獲得之試驗樣品以150℃加熱2小時，使半導體元件保護用材料硬化。繼而，使用晶片剪切強度測試機(Arctek公司製造之「DAGE 4000」)，以300μm/秒之速度評價25℃下之晶片剪切強度。 The obtained test sample was heated at 150°C for 2 hours to harden the semiconductor element protection material. Then, a wafer shear strength tester ("DAGE 4000" manufactured by Arctek) was used to evaluate the wafer shear strength at 25°C at a speed of 300 μm/sec.
[晶片剪切強度之判定標準] [Judgment standard of wafer shear strength]
○：晶片剪切強度為10N以上 ○: The wafer shear strength is 10N or more
△：晶片剪切強度為6N以上且未達10N △: The wafer shear strength is 6N or more and less than 10N
△△：晶片剪切強度為5N以上且未達6N △△: The wafer shear strength is above 5N and less than 6N
×：晶片剪切強度未達5N ×: The shear strength of the wafer is less than 5N
(6)觸黏性(保護膜貼附性) (6) Touch adhesion (protective film adhesion)
將所獲得之半導體元件保護用材料以150℃加熱2小時使其硬化，獲得100mm×100mm×厚度50μm之硬化物。將該硬化物作為評價樣品。 The obtained semiconductor element protection material was heated at 150° C. for 2 hours to be cured to obtain a cured product of 100 mm×100 mm×thickness 50 μm. This cured product was used as an evaluation sample.
將所獲得之評價樣品於23℃及濕度50%RH之環境下放置24小時。放置24小時後，立即使用觸黏性測試機TA-500(UBM公司製造)，對評價樣 品之表面之黏著性測定觸黏性。 Place the obtained evaluation sample in an environment of 23° C. and a humidity of 50% RH for 24 hours. After being left for 24 hours, immediately use the tack tester TA-500 (manufactured by UBM) to compare the evaluation samples The tackiness of the surface of the product is measured.
[觸黏性之判定標準] [Judgment Criteria for Tackiness]
○：應力未達50gf/cm2 ○: The stress is less than 50gf/cm 2
△：應力為50gf/cm2以上且未達100gf/cm2 △: The stress is 50gf/cm 2 or more and less than 100gf/cm 2
×：應力為100gf/cm2以上 ×: The stress is 100gf/cm 2 or more
(7)膜翹曲 (7) Film warpage
將所獲得之半導體元件保護用材料以成為縱20mm、橫100mm、高10mm之方式直接自分注器裝置(Musashi Engineering公司製造之「SHOTMASTER-300」)噴出至聚醯亞胺膜後，將半導體元件保護用材料以150℃加熱2小時使其硬化。硬化後利用目視確認聚醯亞胺膜之翹曲，以下述標準判定膜翹曲。 The obtained material for protecting the semiconductor element was sprayed directly from the dispenser device ("SHOTMASTER-300" manufactured by Musashi Engineering) onto the polyimide film in a form of 20 mm in length, 100 mm in width and 10 mm in height, and then the semiconductor element The protective material is heated at 150°C for 2 hours to harden it. After curing, the warpage of the polyimide film was visually confirmed, and the warpage of the film was judged by the following criteria.
[膜翹曲之判定標準] [Judgment criteria for film warpage]
○：無聚醯亞胺膜之翹曲 ○: No warpage of polyimide film
×：產生聚醯亞胺膜之翹曲 ×: Warpage of polyimide film
(8)耐熱性 (8) Heat resistance
將所獲得之半導體元件保護用材料以150℃加熱2小時使其硬化，獲得100mm×100mm×厚度50μm之硬化物。將該硬化物作為評價樣品。 The obtained semiconductor element protection material was heated at 150° C. for 2 hours to be cured to obtain a cured product of 100 mm×100 mm×thickness 50 μm. This cured product was used as an evaluation sample.
利用DSM-8104(日置電機公司製造，數位超絕緣/微電流計)、平板試樣用電極SME-8310(日置電機公司製造)進行所獲得之評價樣品之體積電阻率之測定。 The volume resistivity of the obtained evaluation sample was measured using DSM-8104 (manufactured by Hioki Electric Co., Ltd., digital super-insulation/micro ammeter) and electrode SME-8310 (manufactured by Hioki Electric Co., Ltd.) for flat samples.
繼而，於180℃下放置100小時，繼而於23℃及濕度50%RH之環境下放置24小時後，測定體積電阻率。計算耐熱試驗前後之體積電阻率之降低率，以下述標準判定耐熱性。 Then, it was placed at 180°C for 100 hours, and then placed in an environment of 23°C and a humidity of 50%RH for 24 hours, and then the volume resistivity was measured. Calculate the reduction rate of volume resistivity before and after the heat resistance test, and judge the heat resistance according to the following standards.
[耐熱性之判定標準] [Criteria for heat resistance]
○：試驗前後之體積電阻率之降低率為10%以下 ○: The reduction rate of volume resistivity before and after the test is less than 10%
△：試驗前後之體積電阻率之降低率超過10%且為20%以下 △: The reduction rate of volume resistivity before and after the test is more than 10% and less than 20%
×：試驗前後之體積電阻率之降低率超過20% ×: The reduction rate of volume resistivity before and after the test exceeds 20%
將組成及結果示於下述表1、2。 The composition and results are shown in Tables 1 and 2 below.
1‧‧‧半導體裝置 1‧‧‧Semiconductor device
2‧‧‧半導體元件 2‧‧‧Semiconductor components
2a‧‧‧第1表面 2a‧‧‧The first surface
2b‧‧‧第2表面 2b‧‧‧Second surface
2A‧‧‧第1電極 2A‧‧‧First electrode
3‧‧‧硬化物 3‧‧‧hardened object
4‧‧‧連接對象構件 4‧‧‧Connecting object components
4a‧‧‧表面 4a‧‧‧surface
4A‧‧‧第2電極 4A‧‧‧Second electrode
5‧‧‧其他硬化物 5‧‧‧Other hardened objects
6‧‧‧導電性粒子 6‧‧‧Conductive particles
7‧‧‧保護膜 7‧‧‧Protective film
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