WO2024066254A1 - 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用 - Google Patents

低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用 Download PDF

Info

Publication number
WO2024066254A1
WO2024066254A1 PCT/CN2023/084225 CN2023084225W WO2024066254A1 WO 2024066254 A1 WO2024066254 A1 WO 2024066254A1 CN 2023084225 W CN2023084225 W CN 2023084225W WO 2024066254 A1 WO2024066254 A1 WO 2024066254A1
Authority
WO
WIPO (PCT)
Prior art keywords
mass
parts
phenolic
curing agent
thin film
Prior art date
Application number
PCT/CN2023/084225
Other languages
English (en)
French (fr)
Inventor
伍得
李婷
廖述杭
苏峻兴
Original Assignee
武汉市三选科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 武汉市三选科技有限公司 filed Critical 武汉市三选科技有限公司
Publication of WO2024066254A1 publication Critical patent/WO2024066254A1/zh

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
    • H01L33/52—Encapsulations
    • H01L33/56—Materials, e.g. epoxy or silicone resin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the present invention belongs to the field of chip packaging, and in particular relates to a thin film die bonding adhesive for low modulus vertical stacking packaging, and a preparation method and application thereof.
  • Thin film adhesive is used to fix the chip on the substrate.
  • the method of use is: first stick the thin film adhesive on the substrate, then cover the chip on it, after wire bonding, stick the thin film adhesive again, and then cover the chip on it, and realize multi-chip packaging by stacking layers.
  • the current trend is: the thickness of wafers is decreasing day by day, while the number of stacked chips is increasing. Therefore, higher requirements are put forward for thin film adhesive: lower modulus, better flexibility, and stronger adhesion.
  • the object of the present invention is to provide a thin film die bonding adhesive for low modulus vertical stacking packaging, a preparation method and application thereof, wherein the thin film die bonding adhesive has a lower modulus, a stronger film tensile strength and a stronger silicon adhesion.
  • the thin film die-bonding adhesive for low modulus three-dimensional vertical stacking packaging provided by the present invention comprises the following raw materials:
  • the raw materials of the above-mentioned thin film adhesive include:
  • the raw materials of the above-mentioned thin film die-bonding adhesive include:
  • the raw materials of the above-mentioned thin film adhesive include:
  • the phenolic solid curing agent is selected from XYLOK aralkylphenolic resin.
  • the phenolic liquid curing agent is selected from liquid phenolic resin.
  • the silicone rubber alloy is obtained by blending silicone rubber alloy masterbatch with thermoplastic polyurethane elastomer rubber and granulating by twin-screw extruder, wherein the amount of silicone rubber alloy masterbatch is 5% of the thermoplastic polyurethane elastomer rubber.
  • the accelerator is selected from imidazole accelerators.
  • the preparation method of the above-mentioned low modulus three-dimensional vertical stacking packaging thin film crystal adhesive comprises: taking raw materials according to a ratio and mixing them, grinding the mixed raw materials into a colloid by a bead mill, vacuum degassing to obtain a crystal adhesive liquid, and using a coating machine to coat the crystal adhesive liquid to obtain a thin film crystal adhesive.
  • the invention provides an application of the low modulus three-dimensional vertical stacking packaging thin film die bonding adhesive in multi-chip stacking packaging.
  • the present invention has the following advantages and beneficial effects:
  • the thin film adhesive for bonding silicon wafers has low storage modulus, high glass transition temperature, high film tensile strength, low thermal expansion coefficient, low moisture absorption rate and high silicon wafer adhesion.
  • the storage modulus of the thin film adhesive can be as low as 1.1 MPa
  • the film tensile strength can be as high as 5.8 MPa
  • the moisture absorption rate can be as low as below 0.21%
  • the silicon wafer adhesion can be as high as 15.5 MPa.
  • the thin film die bonding adhesive of the present invention meets the requirements of multi-chip stacking packaging for thin film die bonding adhesive and is suitable for multi-chip stacking packaging.
  • An embodiment of the present invention provides a thin film die bonding adhesive for low modulus three-dimensional vertical stacking packaging, the raw materials of which include: 2-5 parts by mass of silicon dioxide, 15-25 parts by mass of acrylic epoxy resin, 5-15 parts by mass of flexible liquid epoxy resin, 4-6 parts by mass of phenolic solid curing agent, 5-9 parts by mass of phenolic liquid curing agent, 0-2 parts by mass of polymer silane coupling agent, 0-2 parts by mass of silicone rubber alloy, and 0.27-0.32 parts by mass of accelerator.
  • the raw materials of the above-mentioned thin film adhesive include: 2-4.5 parts by mass of silicon dioxide, 20-25 parts by mass of acrylic epoxy resin, 5-6 parts by mass of flexible liquid epoxy resin, 5-6 parts by mass of phenolic solid curing agent, 5-9 parts by mass of phenolic liquid curing agent, 0-2 parts by mass of polymer silane coupling agent, 0-2 parts by mass of silicone rubber alloy, and 0.31-0.32 parts by mass of accelerator.
  • the raw materials of the above-mentioned thin film adhesive include: 2-3 parts by mass of silicon dioxide, 20-25 parts by mass of acrylic epoxy resin, 5-6 parts by mass of flexible liquid epoxy resin, 5-6 parts by mass of phenolic solid curing agent, 5-9 parts by mass of phenolic liquid curing agent, 2 parts by mass of polymer silane coupling agent, 0-2 parts by mass of silicone rubber alloy, and 0.31-0.32 parts by mass of accelerator.
  • the raw materials of the above-mentioned thin film adhesive include: 2 parts by mass of silicon dioxide, 20-25 parts by mass of acrylic epoxy resin, 5-6 parts by mass of flexible liquid epoxy resin, 5-6 parts by mass of phenolic solid curing agent, 5-9 parts by mass of phenolic liquid curing agent, 2 parts by mass of polymer silane coupling agent, 2 parts by mass of silicone rubber alloy, and 0.31-0.32 parts by mass of accelerator.
  • Silica is a commonly used inorganic filler for crystal adhesives, mainly used to reduce the internal stress and thermal expansion coefficient of the colloidal material; spherical silica powder is preferred in this application.
  • Acrylic epoxy resin is used as a resin matrix to obtain a low modulus colloidal material; acrylic epoxy resin can be selected from G-2050M, G-0250SP, etc.
  • Flexible liquid epoxy resin is mainly used to reduce the storage modulus and enhance flexibility. Flexible liquid epoxy resin can use the EXA-4850 series products on the market, such as EXA-4850-150, EXA-4850-1000.
  • the preferred flexible liquid epoxy resin has an epoxy equivalent of 350g-450g/eq, a molecular weight of 700-900, and a viscosity of 15000-100000mPa•s at 25°C.
  • Accelerators and curing agents are conventional components of colloidal materials. Curing agents are used to cross-link with epoxy resins at a certain temperature and under the action of accelerators, so that the colloidal material changes from a fluid state to a solid state.
  • the curing agent is preferably a combination of a phenolic solid curing agent and a phenolic liquid curing agent.
  • the phenolic solid curing agent can be selected from XYLOK aralkylphenolic resin, which has a special structure of XYLOK, such as SH-4064 on the market; the phenolic liquid curing agent can be selected from liquid phenolic resins, such as MEH-8000 on the market.
  • the accelerator is used as a catalyst for the cross-linking reaction, mainly used to regulate the curing time, has no effect on the performance of the colloidal material, and a conventional accelerator can be selected and added in a conventional amount.
  • the accelerator selects an imidazole accelerator, such as 4,5-di(hydroxymethyl)-2-phenyl-1H-imidazole.
  • the polymer silane coupling agent is a polymer silane polymer, in which the alkyl part can be fused with the resin, and the silanol group is inorganic-friendly, so that a molecular bridge can be formed between the inorganic and organic interfaces, further improving the adhesion of the colloidal material to the silicon wafer.
  • the silicone rubber alloy can serve as a support in the colloidal material to release the internal stress of the material system. In this application, the silicone rubber alloy is obtained by blending the A-S/TPU silicone rubber alloy masterbatch with the thermoplastic polyurethane elastomer rubber TPU through twin-screw granulation, and the amount of the A-S/TPU silicone rubber alloy masterbatch is 5% of the TPU.
  • a method for preparing a thin film crystal adhesive for low modulus three-dimensional vertical stacking packaging includes: taking raw materials according to a ratio and mixing them, grinding the mixed raw materials into a colloid with a bead mill, vacuum degassing to obtain a crystal adhesive liquid, and using a coater to coat the crystal adhesive liquid to obtain a crystal adhesive film.
  • Silica commercially available spherical silica with a particle size of 0.6 ⁇ m at D50;
  • Acrylic epoxy resin G-2050M and G-0250SP from Japan NOF CORPORATION, G-2050M: weight average molecular weight: 200000, epoxy equivalent: 340 g/eq; G-0250SP: weight average molecular weight: 20000, epoxy equivalent: 310 g/eq;
  • Flexible liquid epoxy resin EXA-4850-150, epoxy equivalent: 450g/eq, molecular weight: 900, viscosity: 25°C, 15000mPa•s;
  • Bisphenol F type epoxy resin Nippon Steel 8170, epoxy equivalent: 155-165 g/eq, viscosity: 25°C, 1000cps;
  • Bisphenol A-alkylene oxide adduct diglycidyl ether SE-4125P, epoxy equivalent: 240 g/eq;
  • XYLOK aralkylphenol resin SH-4064, hydroxyl equivalent 168-172 g/eq;
  • MEH-8000 hydroxyl equivalent 141 g/eq, purchased from MEWA Chemical;
  • Silicone rubber alloy A-S/TPU masterbatch is blended with TPU and granulated by twin screw extruder. The mass fraction of A-S/TPU masterbatch is 5% of TPU.
  • Polymer silane coupling agent ADDITAL HMS from Metachemie.
  • Accelerator 4,5-bis(hydroxymethyl)-2-phenyl-1H-imidazole.
  • the die-bonding adhesive film was cured at 170°C for 1 hour to make a sample of size 55mm*10mm*2mm, and the storage modulus of the sample was measured in the measurement mode (double cantilever beam mode, vibration frequency: 1Hz, amplitude: 10 ⁇ m, heating rate: 3°C/min).
  • thermomechanical analysis TMA thermomechanical analysis TMA in compression mode.
  • the parameters of the thermomechanical analysis method in this embodiment are set as follows: preload force: 0.05N, first scan: heating rate 10°C/min, from room temperature to 250°C; second scan: heating rate 10°C/min, from room temperature to 250°C; the thermal expansion coefficient and glass transition temperature are calculated by taking the curve data of the second heating section.
  • a 10mm*50mm film material i.e., a sample strip
  • the thin film adhesive of Examples 1-9 of the present invention has better overall comprehensive performance: low storage modulus, high glass transition temperature, high film tensile strength, low thermal expansion coefficient, low moisture absorption rate, and high silicon wafer adhesion.
  • the inventor analyzed that this is the effect of the combined action of flexible liquid epoxy resin and phenolic curing agent.
  • a polymer silane coupling agent is added, the adhesion of the silicon wafer can be further significantly improved.
  • a silicone rubber alloy is added, the synergistic effect of the silicone rubber alloy and the polymer silane coupling agent can further significantly improve the tensile strength of the film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明公开了低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用，该薄膜黏晶胶，其原料包括：二氧化硅2-5质量份，丙烯酸环氧树脂15-25质量份，柔韧性液态环氧树脂5-15质量份，酚醛类固态固化剂4-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.27-0.32质量份。本发明薄膜黏晶胶兼具低储能模量，高玻璃化转变温度，高膜拉伸强度，低热膨胀系数，低吸湿率，高硅片粘着力，满足多芯片堆叠封装对薄膜黏晶胶的要求，适用于多芯片堆叠封装。

Description

低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用 技术领域
本发明属于芯片封装领域，具体涉及低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用。
 背景技术
薄膜黏晶胶用来将芯片固定在基板上。其使用方法为：先将薄膜黏晶胶贴在基板上，再将芯片覆盖于上，打线之后，再贴上薄膜黏晶胶，再将芯片覆盖于上，通过层层堆叠实现多芯片封装。随着半导体芯片的发展，目前趋势为：晶圆厚度与日俱减，而堆叠芯片数量则不断增加。所以对薄膜黏晶胶提出了更高的要求：模量更低，柔韧性更优，粘着力更强。
 发明内容
本发明的目的是提供低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用，该薄膜黏晶胶具有更低的模量，更强的膜拉伸强度以及更强的硅粘着力。
本发明提供的低模量三维垂直堆叠封装用薄膜黏晶胶，其原料包括：
二氧化硅2-5质量份，丙烯酸环氧树脂15-25质量份，柔韧性液态环氧树脂5-15质量份，酚醛类固态固化剂4-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.27-0.32质量份。
作为优选方案， 上述薄膜黏晶胶，其原料包括：
二氧化硅 2-4.5质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.31-0.32质量份。
作为进一步的优选方案， 上述薄膜黏晶胶，其原料包括：
二氧化硅2-3质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂2质量份，硅橡胶合金0-2质量份，促进剂0.31-0.32质量份。
作为最优选方案，上述薄膜黏晶胶，其原料包括：
二氧化硅2质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂2质量份，硅橡胶合金2质量份，促进剂0.31-0.32质量份。
在一些具体实施方式中，酚醛类固态固化剂选自XYLOK芳烷基酚醛树脂。
在一些具体实施方式中，酚醛类液体固化剂选自液态酚醛树脂。
在一些具体实施方式中，硅橡胶合金是将硅橡胶合金母粒与热塑性聚氨酯弹性体橡胶共混经双螺杆造粒得到，其中，硅橡胶合金母粒的用量为热塑性聚氨酯弹性体橡胶的5%。
在一些具体实施方式中，促进剂选自咪唑类促进剂。
本发明提供的上述低模量三维垂直堆叠封装用薄膜黏晶胶的制备方法，包括：按配比取原料并混合，用珠磨机将混合后的原料研磨至胶状物，经真空脱泡得黏晶胶胶液，采用涂布机对黏晶胶胶液进行涂布，得薄膜黏晶胶。
本发明提供的上述低模量三维垂直堆叠封装用薄膜黏晶胶在多芯片叠层封装中的应用。
和现有技术相比，本发明具有如下优点和有益效果：
（1）本发明薄膜黏晶胶兼具低储能模量，高玻璃化转变温度，高膜拉伸强度，低热膨胀系数，低吸湿率，高硅片粘着力。
（2）在优选方案中，薄膜黏晶胶的储能模量可低至1.1MPa，膜拉伸强度可高达5.8MPa，吸湿率可低至0.21%以下，硅片粘着力可高达15.5MPa。
（3）本发明薄膜黏晶胶满足多芯片堆叠封装对薄膜黏晶胶的要求，适用于多芯片堆叠封装。
 具体实施方式
为了使本发明的目的、技术方案及有益效果更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。
本发明实施例提供一种低模量三维垂直堆叠封装用薄膜黏晶胶，其原料包括： 二氧化硅2-5质量份，丙烯酸环氧树脂15-25质量份，柔韧性液态环氧树脂5-15质量份，酚醛类固态固化剂4-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.27-0.32质量份。
作为优选方案，上述薄膜黏晶胶的原料包括：二氧化硅 2-4.5质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.31-0.32质量份。
作为进一步优选方案，上述薄膜黏晶胶的原料包括：二氧化硅2-3质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂2质量份，硅橡胶合金0-2质量份，促进剂0.31-0.32质量份。
作为最优选方案，上述薄膜黏晶胶的原料包括：二氧化硅2质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂2质量份，硅橡胶合金2质量份，促进剂0.31-0.32质量份。
二氧化硅是黏晶胶常用的无机填充料，主要用来降低胶体材料的内应力和热膨胀系数；本申请中优选球形二氧化硅微粉。丙烯酸环氧树脂作为树脂基材，可获得低模量的胶体材料；丙烯酸环氧树脂可选自G-2050M、G-0250SP等。柔韧性液态环氧树脂主要用来降低储能模量，增强柔韧性，柔韧性液态环氧树脂可采用市面上的EXA-4850系列产品，例如EXA-4850-150，EXA-4850-1000。优选的柔韧性液态环氧树脂，其环氧当量：350g -450g/eq，分子量：700-900，粘度：25℃，15000-100000mPa•s。
促进剂和固化剂为胶体材料的常规组分。固化剂用来在一定温度和促进剂的作用下与环氧树脂发生交联反应，使胶体材料由流动状态变为固态。本申请中固化剂优选酚醛类固态固化剂和酚醛类液体固化剂的组合，酚醛类固态固化剂可选自XYLOK芳烷基酚醛树脂，其具有XYLOK特殊结构，例如市面上的SH-4064；酚醛类液体固化剂可选自液态酚醛树脂，例如市面上的MEH-8000。促进剂用作交联反应的催化剂，主要用来调控固化时间，对胶体材料性能无影响，选择常规促进剂按常规用量添加即可。在具体实施方式中，促进剂选择咪唑类促进剂，例如4,5-二（羟甲基）-2-苯基-1H-咪唑。
高分子硅烷偶联剂为高分子硅烷聚合物，其中烷基部分可与树脂融合，硅羟基亲无机，从而可在无机与有机界面间形成分子架桥，进一步提高胶体材料对硅片的附着力。硅橡胶合金可充当胶体材料中的支撑体，用来释放材料体系内应力。本申请中硅橡胶合金将A-S/TPU硅橡胶合金母粒与热塑性聚氨酯弹性体橡胶TPU共混经双螺杆造粒得到，A-S/TPU硅橡胶合金母粒的用量为TPU的5%。
本发明实施例中提供的一种低模量三维垂直堆叠封装用薄膜黏晶胶的制备方法，包括：按配比取原料并混合，用珠磨机将混合后的原料研磨至胶状物，经真空脱泡得黏晶胶胶液，采用涂布机对黏晶胶胶液进行涂布即得黏晶胶薄膜。
实施例和对比例中所用原材料具体如下：
二氧化硅：市购D50粒径0.6μm的球形二氧化硅；
丙烯酸环氧树脂：日本NOF CORPORATION公司的G-2050M和G-0250SP，G-2050M：重均分子量：200000，环氧当量：340 g/eq；G-0250SP：重均分子量：20000，环氧当量：310 g/eq；
柔韧性液态环氧树脂：EXA-4850-150，环氧当量：450g/eq，分子量：900，粘度：25℃，15000mPa•s；
双酚F型环氧树脂：日本新日铁8170，环氧当量：155-165 g/eq，粘度：25℃，1000cps；
双酚A-烷撑氧化物加成物二缩水甘油醚：SE-4125P，环氧当量：240 g/eq；
XYLOK芳烷基酚树脂：SH-4064，羟基当量168-172 g/eq；
MEH-8000：羟基当量141 g/eq，购于MEWA Chemical；
硅橡胶合金：A-S/TPU母粒与TPU共混经双螺杆造粒得到，A-S/TPU母粒的质量份为TPU的5%；
高分子硅烷偶联剂：Metachemie厂家的ADDITAL HMS。
促进剂：4,5-二（羟甲基）-2-苯基-1H-咪唑。
对比例和实施例的配方及性能参数分别见表1-2，对比例和实施例各项性能参数检测方法如下：
一、储能模量：
参考标准《ASTM E2254-2018 动态机械分析器的储能模量测定试验方法》，将黏晶胶薄膜在170℃固化1h，制作成大小55mm*10mm*2mm的样品，在测量模式（双悬臂梁模式，振动频率：1Hz，振幅：10μm，升温速率：3℃/min）下测量样品的储能模量。
二、热膨胀系数CTE1/CTE2和玻璃化转变温度：
参考标准《ASTM E831-2019 固体材料线性热膨胀热机械分析的标准试验方法》， 将黏晶胶薄膜在170℃固化1h ，制作成大小5mm*5mm*2mm的样品。采用热机械分析法 TMA在压缩模式下测试样品的热膨胀系数和玻璃化转变温度。本实施例中热机械分析法的参数设置为：预加载力：0.05N，第一次扫描：以升温速率 10℃/min，从室温升至250℃；第二次扫描：以升温速率10℃/min，从室温升至250℃；取第二次升温段曲线数据计算热膨胀系数和玻璃化转变温度。
三、膜拉伸强度：
从黏晶胶薄膜裁取尺寸10mm*50mm的膜材即样条，撕去轻离膜，样条两端用胶带粘好，采用万能材料试验机的夹具分别夹住两端的胶带，撕去重离膜，测试膜的拉伸强度。
四、吸湿率：
裁取尺寸50mm*50mm的膜材，转贴在硅片上，于170℃固化1h后称重。再将硅片垂直地完全浸入盛有25±1℃蒸馏水的玻璃容器中，表面不应附有气泡，与容器壁不接触。浸水24h后，用镊子将其取出，迅速用滤纸吸干膜表面水分，立即称重。根据前后两次重量计算吸湿率。
五、硅片粘着力：
将两片25um厚度的3mm*3mm的膜片转贴在硅片上，于170℃固化1h后，用万能拉力机测试剪切粘结强度。
表1 对比例的原料配方及性能参数测试值
表2 实施例的原料配方及性能参数测试值
结合表1-2可以看出，相对对比例，本发明实施例1-9的薄膜黏晶胶，整体具有更优的综合性能：低储能模量，高玻璃化转变温度，高膜拉伸强度，低热膨胀系数，低吸湿率，高硅片粘着力。发明人分析是柔韧性液态环氧树脂、酚醛类固化剂共同作用的效果。当添加高分子硅烷偶联剂后，可进一步显著改善硅片粘着力。当添加硅橡胶合金后，硅橡胶合金和高分子硅烷偶联剂协同作用，又可进一步显著改善膜拉伸强度。
上述实施例仅是为了清楚地说明所做的实施例，而并非对实施方式的限制。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其他不同形式的变化或者变动，这里无需也无法对所有的实施方式予以穷举，因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。

Claims (10)

  1. 低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是，其原料包括：
    二氧化硅2-5质量份，丙烯酸环氧树脂15-25质量份，柔韧性液态环氧树脂5-15质量份，酚醛类固态固化剂4-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.27-0.32质量份。
  2. 如权利要求1中所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是，其原料包括：
    二氧化硅 2-4.5质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂0-2质量份，硅橡胶合金0-2质量份，促进剂0.31-0.32质量份。
  3. 如权利要求1中所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是，其原料包括：
    二氧化硅2-3质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂2质量份，硅橡胶合金0-2质量份，促进剂0.31-0.32质量份。
  4. 如权利要求1中所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是，其原料包括：
    二氧化硅2质量份，丙烯酸环氧树脂20-25质量份，柔韧性液态环氧树脂5-6质量份，酚醛类固态固化剂5-6质量份，酚醛类液体固化剂5-9质量份，高分子硅烷偶联剂2质量份，硅橡胶合金2质量份，促进剂0.31-0.32质量份。
  5. 如权利要求1-4中任一项所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是：
    所述酚醛类固态固化剂选自XYLOK芳烷基酚醛树脂。
  6. 如权利要求1-4中任一项所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是：
    所述酚醛类液体固化剂选自液态酚醛树脂。
  7. 如权利要求1-4中任一项所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是：
    所述硅橡胶合金是将硅橡胶合金母粒与热塑性聚氨酯弹性体橡胶共混经双螺杆造粒得到，其中，硅橡胶合金母粒的用量为热塑性聚氨酯弹性体橡胶的5%。
  8. 如权利要求1-4中任一项所述的低模量三维垂直堆叠封装用薄膜黏晶胶，其特征是：
    所述促进剂选自咪唑类促进剂。
  9. 权利要求1-4中任一项所述的低模量三维垂直堆叠封装用薄膜黏晶胶的制备方法，其特征是：
    按配比取原料并混合，用珠磨机将混合后的原料研磨至胶状物，经真空脱泡得黏晶胶胶液，采用涂布机对黏晶胶胶液进行涂布，得薄膜黏晶胶。
  10. 权利要求1-4中任一项所述的低模量三维垂直堆叠封装用薄膜黏晶胶在多芯片叠层封装中的应用。
PCT/CN2023/084225 2022-09-27 2023-03-28 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用 WO2024066254A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211179189.6A CN115260963B (zh) 2022-09-27 2022-09-27 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用
CN202211179189.6 2022-09-27

Publications (1)

Publication Number Publication Date
WO2024066254A1 true WO2024066254A1 (zh) 2024-04-04

Family

ID=83757791

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/084225 WO2024066254A1 (zh) 2022-09-27 2023-03-28 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用

Country Status (2)

Country Link
CN (1) CN115260963B (zh)
WO (1) WO2024066254A1 (zh)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115260963B (zh) * 2022-09-27 2022-12-27 武汉市三选科技有限公司 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用

Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080226884A1 (en) * 2007-03-13 2008-09-18 Toray Saehan Inc. Adhesive film for stacking semiconductor chips
KR20080113670A (ko) * 2007-06-25 2008-12-31 주식회사 엘지화학 접착수지 조성물, 접착필름, 다이싱 다이 본딩 필름 및반도체 장치
CN102108276A (zh) * 2009-12-28 2011-06-29 第一毛织株式会社 用于半导体器件的粘合剂组合物和使用此组合物的粘性膜
US20110159294A1 (en) * 2009-12-30 2011-06-30 Gyu Seok Song Attach film composition for semiconductor assembly and attach film using the same
CN102226032A (zh) * 2011-04-11 2011-10-26 复旦大学 一种低模量环氧树脂体系及其制备方法
CN102265388A (zh) * 2008-12-24 2011-11-30 日东电工株式会社 热固型芯片接合薄膜
CN102925089A (zh) * 2012-11-21 2013-02-13 苏州赛伍应用技术有限公司 一种可挠性导热树脂及其制成的半固化片和金属基覆铜板
CN107384282A (zh) * 2017-08-02 2017-11-24 浙江大学 一种柔性电子基板用胶粘剂及其制备方法和应用
CN107523014A (zh) * 2016-06-16 2017-12-29 信越化学工业株式会社 环氧树脂组合物
CN108841353A (zh) * 2018-07-03 2018-11-20 烟台德邦科技有限公司 一种大尺寸芯片封装用底部填充胶的制备方法
JP2019151713A (ja) * 2018-03-01 2019-09-12 ナミックス株式会社 フィルム状半導体封止材
CN111440579A (zh) * 2019-12-24 2020-07-24 武汉市三选科技有限公司 一种高柔性环氧树脂胶粘剂、其制备方法以及应用
CN111825947A (zh) * 2019-04-22 2020-10-27 广东生益科技股份有限公司 一种用于金属基板的树脂组合物、包含其的树脂胶液以及金属基覆铜箔层压板
CN113150730A (zh) * 2021-05-13 2021-07-23 湖北三选科技有限公司 一种晶圆切割用保护胶
WO2022151517A1 (zh) * 2021-01-15 2022-07-21 武汉市三选科技有限公司 晶圆级封装密封用电路积层膜、其制备方法及应用
CN115260963A (zh) * 2022-09-27 2022-11-01 武汉市三选科技有限公司 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2946353B2 (ja) * 1990-11-21 1999-09-06 日本レック株式会社 エポキシ樹脂組成物
JP2003313526A (ja) * 2002-04-19 2003-11-06 Hitachi Kasei Polymer Co Ltd フレキシブルプリント配線板積層用接着剤組成物および接着フィルム
JP5879675B2 (ja) * 2010-06-17 2016-03-08 日立化成株式会社 半導体用接着フィルム、半導体搭載用配線基板、半導体装置、および接着剤組成物
JP6001273B2 (ja) * 2012-02-13 2016-10-05 信越化学工業株式会社 半導体ウエハ用保護フィルム及び半導体チップの製造方法
CN102925092B (zh) * 2012-11-14 2014-01-29 杭州师范大学 一种环氧树脂纳米复合粘结膜及其制备方法
CN103045051B (zh) * 2013-01-18 2015-09-09 天津凯华绝缘材料股份有限公司 一种低温韧性钢筋防腐粉末涂料及其制备方法
JP6190653B2 (ja) * 2013-07-26 2017-08-30 京セラ株式会社 導電性樹脂組成物および半導体装置
CN112409971B (zh) * 2020-11-20 2022-03-22 湖北三选科技有限公司 一种半导体芯片五边保护用液态模封胶及制备方法

Patent Citations (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080226884A1 (en) * 2007-03-13 2008-09-18 Toray Saehan Inc. Adhesive film for stacking semiconductor chips
KR20080113670A (ko) * 2007-06-25 2008-12-31 주식회사 엘지화학 접착수지 조성물, 접착필름, 다이싱 다이 본딩 필름 및반도체 장치
CN102265388A (zh) * 2008-12-24 2011-11-30 日东电工株式会社 热固型芯片接合薄膜
CN102108276A (zh) * 2009-12-28 2011-06-29 第一毛织株式会社 用于半导体器件的粘合剂组合物和使用此组合物的粘性膜
US20110159294A1 (en) * 2009-12-30 2011-06-30 Gyu Seok Song Attach film composition for semiconductor assembly and attach film using the same
CN102226032A (zh) * 2011-04-11 2011-10-26 复旦大学 一种低模量环氧树脂体系及其制备方法
CN102925089A (zh) * 2012-11-21 2013-02-13 苏州赛伍应用技术有限公司 一种可挠性导热树脂及其制成的半固化片和金属基覆铜板
CN107523014A (zh) * 2016-06-16 2017-12-29 信越化学工业株式会社 环氧树脂组合物
CN107384282A (zh) * 2017-08-02 2017-11-24 浙江大学 一种柔性电子基板用胶粘剂及其制备方法和应用
JP2019151713A (ja) * 2018-03-01 2019-09-12 ナミックス株式会社 フィルム状半導体封止材
CN108841353A (zh) * 2018-07-03 2018-11-20 烟台德邦科技有限公司 一种大尺寸芯片封装用底部填充胶的制备方法
CN111825947A (zh) * 2019-04-22 2020-10-27 广东生益科技股份有限公司 一种用于金属基板的树脂组合物、包含其的树脂胶液以及金属基覆铜箔层压板
CN111440579A (zh) * 2019-12-24 2020-07-24 武汉市三选科技有限公司 一种高柔性环氧树脂胶粘剂、其制备方法以及应用
WO2022151517A1 (zh) * 2021-01-15 2022-07-21 武汉市三选科技有限公司 晶圆级封装密封用电路积层膜、其制备方法及应用
CN113150730A (zh) * 2021-05-13 2021-07-23 湖北三选科技有限公司 一种晶圆切割用保护胶
CN115260963A (zh) * 2022-09-27 2022-11-01 武汉市三选科技有限公司 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, DAGANG: "A Brief Discussion on the Research on Toughening Modification of Epoxy Resin", ZHONG-XIAO QIYE GUANLI YU KEJI - MANAGEMENT & TECHNOLOGY OF SME, HEBEI SHENG ZHONGXIAO QIYE FUWU ZHONGXIN, CN, no. 05, 5 May 2009 (2009-05-05), CN , pages 287, XP009553469, ISSN: 1673-1069 *

Also Published As

Publication number Publication date
CN115260963A (zh) 2022-11-01
CN115260963B (zh) 2022-12-27

Similar Documents

Publication Publication Date Title
CN105453253B (zh) 中空型电子器件密封用树脂片及中空型电子器件封装件的制造方法
KR100900863B1 (ko) 에폭시 수지 조성물과 상기 조성물을 포함하는 다이본드제
JP2008127577A (ja) マルチチップパッケージ封止用エポキシ樹脂組成物、及びこれを用いたマルチチップパッケージ
WO2024066254A1 (zh) 低模量垂直堆叠封装用薄膜黏晶胶、其制备方法及应用
WO2016145650A1 (en) Epoxy molding compound with high adhesion for nickel surface, method for preparing the same and uses thereof
JPH11255864A (ja) 液状エポキシ樹脂組成物および樹脂封止型半導体装置
JP5527816B2 (ja) ダイボンド剤組成物及び半導体装置。
JPWO2020157805A1 (ja) 接着剤組成物、フィルム状接着剤、接着シート、及び半導体装置の製造方法
CN117186820B (zh) 一种可调控的底部填充胶、其制备方法及芯片封装结构
CN112457808A (zh) 氮化镓功率器件用低翘曲高接着力液态模封胶及制备方法
TW201829609A (zh) 樹脂組合物、樹脂片及半導體裝置、以及半導體裝置之製造方法
JP4975514B2 (ja) ダイボンド剤及びこれを用いてなる半導体装置
JP4044349B2 (ja) 薄型フィルム状接着剤
JP7099453B2 (ja) 封止用フィルム、封止構造体及び封止構造体の製造方法
CN114591598B (zh) 一种晶圆级封装用液体塑封料及其制备方法
JP2007142117A (ja) ダイボンディングペーストおよびそれを用いた半導体装置
TW201924924A (zh) 黏合劑組成物以及利用其的黏合膜
JP2010144086A (ja) ダイボンディングペースト、およびこれを用いた半導体装置
JP2000336244A (ja) 液状封止樹脂組成物及びそれを用いた半導体装置
JP7014195B2 (ja) 封止材、該封止材により封止されている半導体装置及び該封止材を有する半導体パッケージの製造方法
JP2021119239A (ja) アンダーフィル材、半導体パッケージ及び半導体パッケージの製造方法
JPH093167A (ja) 樹脂組成物及びこれを用いた樹脂封止型半導体装置
WO2017220137A1 (en) Curable liquid epoxy resin compositions useful as underfill material for semiconductor devices
TW202021997A (zh) 用於半導體電路連接的黏著劑組成物及含彼的黏著膜
KR20210047652A (ko) 반도체 몰딩용 에폭시 수지 조성물, 반도체 몰딩용 필름 및 이를 이용한 반도체 패키지

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23869513

Country of ref document: EP

Kind code of ref document: A1