WO2016107146A1 - 一种用于薄晶圆加工的临时键合胶及其制备方法 - Google Patents

一种用于薄晶圆加工的临时键合胶及其制备方法 Download PDF

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WO2016107146A1
WO2016107146A1 PCT/CN2015/084687 CN2015084687W WO2016107146A1 WO 2016107146 A1 WO2016107146 A1 WO 2016107146A1 CN 2015084687 W CN2015084687 W CN 2015084687W WO 2016107146 A1 WO2016107146 A1 WO 2016107146A1
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temporary bonding
bonding adhesive
parts
temporary
solvent
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French (fr)
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孙蓉
帅行天
邓立波
张国平
郭慧子
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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Priority to JP2016565384A priority patent/JP6148414B1/ja
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    • 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
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/16—Homopolymers or copolymers of alkyl-substituted styrenes
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • C09J133/12—Homopolymers or copolymers of methyl methacrylate
    • 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
    • C09J125/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Adhesives based on derivatives of such polymers
    • C09J125/02—Homopolymers or copolymers of hydrocarbons
    • C09J125/16—Homopolymers or copolymers of alkyl-substituted styrenes

Definitions

  • the invention relates to the technical field of adhesives, in particular to a temporary bonding adhesive for thin wafer processing and a preparation method thereof.
  • Cipheral Patent No. CN104130727A discloses a pressure-sensitive temporary bonding adhesive comprising 30-70 parts of a solvent, 30-50 parts of a base resin, and 5-30 parts of microcapsule particles, wherein the base resin is a cyclic olefin polymer particle, a solvent.
  • microcapsule particle structure being composed of an inner core of a polymer compound and an outer layer of a continuous or outer phase of a natural or synthetic polymer compound, and further comprising a tackifier and a low molecular weight ring.
  • Cisokida olefin copolymer One or a mixture of an olefin copolymer, a plasticizer, and an antioxidant.
  • Chinese patent CN102203917A discloses a composition for temporary wafer bonding, which composition is composed of a free tackifier, a low molecular weight cyclic olefin copolymer, a plasticizer, an antioxidant, wherein the tackifier is selected from the group consisting of Polymyrene resin, R-poly mushroom resin, styrene modified mushroom resin, polymerized rosin resin, rosin resin, alicyclic hydrocarbon resin, C 5 aliphatic hydrocarbon resin, hydrogenated hydrocarbon resin, low molecular weight cyclic olefin copolymer It has a weight average molecular weight of less than about 50,000 Daltons.
  • the temporary bonding adhesive still has a technical defect of low thermal stability and poor corrosion resistance.
  • an aspect of the present invention provides a temporary bonding adhesive having high thermal stability and high corrosion resistance.
  • a temporary bonding adhesive for thin wafer processing characterized in that the total mass of the temporary bonding adhesive is 100 parts, including 55 to 70 parts of a solvent, and 30 to 45 parts dissolved or dispersed in a solvent.
  • a base resin which is a high polymer or a blended polymer having a thermal decomposition temperature of 320 ° C or higher.
  • the thermal decomposition temperature of the base resin is above 320 ° C to ensure that the bonding layer formed by the temporary bonding adhesive has good thermal stability.
  • the base resin has a weight average molecular weight of from 5 ⁇ 10 3 to 5 ⁇ 10 5 and a melt index of 24 or more.
  • high polymer examples include polyalkyl acrylates, polyphenylenes, and polyesters.
  • the high polymer is a polyalkyl acrylate which contains repeating units in the molecular structure. a homopolymer or interpolymer, wherein R 1 is a C 1-2 aliphatic hydrocarbon or an aromatic hydrocarbon, and R 2 is a C 1-3 aliphatic hydrocarbon or an aromatic hydrocarbon.
  • R 1 is a C 1-2 aliphatic hydrocarbon or an aromatic hydrocarbon
  • R 2 is a C 1-3 aliphatic hydrocarbon or an aromatic hydrocarbon.
  • polymethyl methacrylate polymethyl methacrylate.
  • the T g is 65 ° C; the number of carbon atoms in R 1 is 4, and the number of carbon atoms in R 2 is 1 (ie PBMA), the T g is 20 ° C, and its thermal decomposition temperature in air is higher. Low (220 ° C only).
  • the number of carbon atoms of R 2 is preferably from 1 to 3, and may be an aromatic hydrocarbon. It is worth noting that the number of carbon atoms in R 2 may not be less than 1, and the methyl acrylate obtained when the number of carbon atoms of R 2 is zero Tg is too low (only 6 ° C).
  • Polyphenylene which contains repeating units in the molecular structure a homopolymer or interpolymer, wherein R 1 and R 2 are preferably C 1-3 aliphatic hydrocarbons or aromatic hydrocarbons. If both R 1 and R 2 are aliphatic hydrocarbon groups, the olefin polymer formed on the one hand has a low T g due to the absence of a side chain group in its molecular structure, and on the other hand it is easily crystallized (for example, PE, PP, PMP have High crystallinity), which may affect the performance of the base resin as an adhesive material; if the aliphatic hydrocarbon chain is too long, it will increase the flexibility of the polymer and lower its T g , which will affect the use temperature of the bonding adhesive. .
  • Polyester which contains repeating units in the molecular structure a homopolymer or interpolymer, wherein R is cyclohexane, phenyl or hexyloxy,
  • polyester a physical blend of three polyesters of A, B and C can be used.
  • the mass content ranges of A, B, and C are 10 to 60%, 10 to 80%, and 0 to 50%, respectively, and the molecular weight ranges of A, B, and C are 8,000 to 30,000, 5,000 to 50,000, and 5,000 to 100,000, respectively.
  • the blended polymer may be one or more polyalkyl acrylates, and may be one or more polyphenylenes or one or more polyesters. Also can be one A mixture of a polyalkyl acrylate and a polyphenylene, or a mixture of a polyalkyl acrylate and a polyester, and the like.
  • a polyacrylate having a molecular weight of 5,000 to 30,000,000 and a poly- ⁇ -methylstyrene having a molecular weight of 3,000 to 20,000 may be used, and the mass ratio of the two is 2:1 to 20:1.
  • the boiling point of the solvent is preferably above 80 ° C and the polarity is similar to the corresponding polymer.
  • the solvent may be, for example, one or at least two of propylene glycol monomethyl ether acetate, dimethylacetamide, propylene glycol monomethyl ether, ethyl lactate, decene, mesitylene, cyclododecene, and cyclopentanone. .
  • the total mass of the temporary bonding adhesive is 100 parts, and further includes 0.05 to 0.07 parts of a leveling agent and 0 to 0.15 parts of an antioxidant.
  • the leveling agent is preferably an acrylate-based leveling agent modified with fluorine.
  • the antioxidant is preferably composed of a multi-hindered phenolic antioxidant as a main antioxidant and a phosphite antioxidant as an auxiliary antioxidant, and the combination of the two helps to improve the heat of the bonding adhesive. stability.
  • a preferred formulation comprises 20-30 parts of PMMA, 10-15 parts of poly- ⁇ -methylstyrene, 55-70 parts of solvent and 0.05-0.07 parts of FC-4430 leveling. More preferably, the raw material comprises 24 parts of PMMA, 12 parts of poly- ⁇ -methylstyrene, 64.95 parts of DMAc and 0.05 parts of a type IV-4430 leveling agent.
  • a method for preparing a temporary bonding adhesive is provided, and a temporary bonding adhesive having high thermal stability and high corrosion resistance can be obtained by the preparation method.
  • a preparation method of the above temporary bonding glue wherein 30 to 45 parts of the base resin, 55 to 70 parts of the solvent and 0.05 to 0.07 parts of the leveling agent are stirred and mixed under heating conditions, and then cooled and degassed. , get temporary bonding glue.
  • the heating method is a water bath at 60 to 70 ° C; the stirring method is mechanical stirring at a speed of 100 to 1000 rpm; and the degassing treatment is vacuum degassing by a vacuum deaerator.
  • a method for bonding a thin wafer by using the above temporary bonding glue specifically: after the temporary bonding glue is spin-coated on the surface of the carrier wafer, and the solvent is dried, the device wafer is covered on the surface Then, the temporary bonding glue is heated to melt and cool to form a bonding layer.
  • the manner of heating the temporary bonding glue may be a baking method.
  • the other surface of the wafer that is not coated with the bonding adhesive can be directly transferred by baking.
  • the solvent in the bonding adhesive first volatilizes, and then with the continuation of the heating, the base resin slowly melts at about 200 ° C, and is cooled and solidified to form a bonding layer, thus carrying the wafer and the device wafer.
  • the surface is keyed.
  • the DMAc is used to clean the remaining adhesive layer on the periphery of the device wafer, and similarly, DMAc can be used as a cleaning agent to dissolve the bonding layer during the debonding of the device wafer.
  • the temporary bonding adhesive of the present invention comprises 55 to 70 parts of a solvent and 30 to 45 parts of a base resin dissolved or dispersed in a solvent, the base resin is a thermal decomposition temperature, based on 100 parts by mass of the total mass of the temporary bonding glue.
  • the layer is easy to clean and the preparation cost is economical.
  • FIG. 1 is a graph showing a thermogravimetric change of a dry film of a coating of a temporary bonding adhesive according to Embodiment 1 of the present invention
  • Example 2 is a graph showing the thermogravimetric change of the dry film of the coating of the temporary bonding adhesive of Example 2 of the present invention
  • Figure 3 is a graph showing the viscosity and temperature of a solvent-free temporary bonding adhesive of Example 2 of the present invention.
  • Figure 4 is a graph showing the thickness distribution of the temporary bonding adhesive coating dry film of Example 2 of the present invention.
  • Figure 5 is an ultrasonic scanning micrograph of a temporary bonding glue bonded wafer of Example 2 of the present invention.
  • the raw materials specifically include: 4 g of homemade polyester, 5 mg of 4430 leveling agent, and 5.995 g of solvent PGMEA; and stirred at room temperature for 1 hour.
  • the raw material specifically comprises: 2.0 g of polymethyl methacrylate, 1.0 g of poly- ⁇ -methylstyrene, 5 mg of FC-4430 type leveling agent, and 5.5 g of DMAc; example 1.
  • the raw material specifically includes: 3.0 g of polymethyl methacrylate, poly 1.5 g of ⁇ -methyl styrene, 7 mg of FC-4430 type leveling agent, and 7.0 g of DMAc; otherwise, the same applies to the examples. 1.
  • Example 1 The test results of the corrosion resistance of Example 1 and Example 2 are as follows in Table 1 and Table 2 below (in view of the specific test methods are well known to those skilled in the art, the method will not be described in detail herein):
  • thermogravimetric change curves of Examples 1 and 2, respectively can be seen from the figure, the phenomenon of decomposed weight loss occurs in the dry film from 300 ° C, and the weight loss rate at 450 ° C is 80%. That is, most of the decomposition occurs, and thus it can be seen that the temporary bonding adhesive of the present invention has good thermal stability.
  • FIG. 3 it is a viscosity graph of the temporary bonding adhesive of Example 1. As can be seen from the figure, the overall change in viscosity with temperature is mild, thus indicating that the temporary bonding adhesive of the present invention has better viscosity stability.
  • FIG. 4 it is a thickness distribution diagram of the dry film of the temporary bonding adhesive coating of Example 2 of the present invention. It can be seen from the figure that the thickness of the temporary bonding adhesive coating is relatively uniform, thereby indicating that the average thickness of the bonding layer is 22.7 ⁇ m and the standard deviation is 0.5, indicating that the thickness of the bonding layer is appropriate and the bonding layer is flat. The better coating effect, the process requirements of the coating are not critical.
  • an ultrasonic scanning micrograph after bonding a wafer using the temporary bonding glue of Example 2 of the present invention As can be seen from the figure, it can be seen that the bonding layer between the two bonded silicon wafers has no voids (no white spots) and is evenly distributed.
  • the present invention illustrates the detailed process equipment and process flow of the present invention by the above embodiments, but the present invention is not limited to the above detailed process equipment and process flow, that is, does not mean that the present invention must rely on the above detailed process equipment and The process can only be implemented. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitution of the various materials of the products of the present invention, addition of auxiliary components, selection of specific means, and the like, are all within the scope of the present invention.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Container, Conveyance, Adherence, Positioning, Of Wafer (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

本发明公开了一种用于薄晶圆加工的临时键合胶及其制备方法。该临时键合胶以临时键合胶的总质量为100份数计，包含55～70份的溶剂以及溶解或分散于溶剂中的30～45份基础树脂，所述基础树脂为热分解温度为320℃以上、熔融指数为24以上的高聚物或者共混高聚物，由此临时键合胶具有热稳定性高、抗腐蚀性强的优点，同时其键合/解键合效率高，残余粘接层易清洗，制备成本较为经济。

Description

一种用于薄晶圆加工的临时键合胶及其制备方法 技术领域
本发明涉及胶粘剂的技术领域，尤其涉及一种用于薄晶圆加工的临时键合胶及其制备方法。
背景技术
近年来，计算机、通讯、汽车电子和其它消费类产品对微电子封装提出了更高的要求，即更小、更薄、多功能与低成本。为满足这些产品的小型化需求，半导体工业需要将器件晶圆减薄至100μm以下。超薄晶圆具有柔性和易碎性、容易翘曲和起伏等特点，因此通常先将器件晶圆用临时键合材料键合到较厚的载体上，经过背部减薄、形成重布线层和内部互连制作后，再输入外界能量(光、电、热及外力)使粘结层失效，之后将器件晶圆从载体上分离开来，此过程即为晶圆的临时键合工艺。其中，用于固定薄晶圆的临时键合胶是临时键合工艺成功的关键。
中国专利CN104130727A公开了一种压敏临时键合胶，其原料包含溶剂30～70份，基础树脂30～50份，微胶囊粒子5～30份，其中基础树脂为环烯烃类聚合物颗粒，溶剂为环十二烯、双环己烯、柠檬烯、均二甲苯、环戊酮、甲基环己烷、甲基乙基酮、双戊烯、环辛烷、丁基环己烷、环庚烷和环己烷中的一种或几种的混合物，微胶囊粒子结构为由高分子化合物的内核和天然的或合成的高分子化合物连续壁或外相的外层包裹组成，还包括增粘剂、低分子量环烯烃共聚物、增塑剂、抗氧剂中的一种或几种混合物。中国专利CN102203917A公开了一种用于临时晶片粘合的组合物，该组合物由自由增粘剂、低分子量环 烯烃共聚物、增塑剂、抗氧剂所组成，其中增粘剂是选自由多菇烯树脂、R一多菇烯树脂、苯乙烯改性菇烯树脂、聚合松香树脂、松香酷树脂、脂环族烃树脂、C5脂肪烃树脂、氢化烃树脂，低分子量环烯烃共聚物为重均分子量小于约50000道尔顿。上述现有技术中，临时键合胶仍然普遍存在热稳定性低、抗腐蚀性差的技术缺陷。
发明内容
有鉴于此，本发明一方面提供一种具有热稳定性高、抗腐蚀性强的临时键合胶。
一种用于薄晶圆加工的临时键合胶，其特征在于，以临时键合胶的总质量为100份数计，包含55～70份的溶剂以及溶解或分散于溶剂中30～45份基础树脂，所述基础树脂为热分解温度为320℃以上的高聚物或者共混高聚物。
上述临时键合胶中，基础树脂的热分解温度在320℃以上保证了临时键合胶形成的粘接层具有较好的热稳定性。基础树脂的重均分子量为5×103～5×105之间，且熔融指数为24以上。
高聚物的具体实例有聚烃基丙烯酸酯类、聚苯基乙烯类和聚酯类。
高聚物为聚烃基丙烯酸酯类，其为分子结构中包含重复单元
Figure PCTCN2015084687-appb-000001
的均聚体或共聚体，其中R1为C1～2脂肪烃或芳香烃，R2为C1～3脂肪烃或芳香烃。例如，聚甲基丙烯酸甲酯。R1中碳原子数为1，R2中碳原子数为1(即PMMA)时，玻璃化转变温度Tg为105℃；R1中碳原子数为2，R2中碳原子数为1(即PEMA)时，Tg为65℃；R1中碳原子数为4，R2中碳原子数为1(即PBMA)时，Tg为20℃，其在空气中的热分解温度较低(仅为220℃)。随着R1碳原 子数增多，聚合物柔性增强，Tg越来越低，粘流温度(Tf)也会下降，Tf太小，则影响临时键合胶的使用温度。R2的碳原子个数优选为1～3，可以为芳香烃，值得说明的是，R2中碳原子数不能小于1，当R2的碳原子个数为零时所得到的丙烯酸甲酯Tg过低(仅为6℃)。
聚苯基乙烯类，其为分子结构中包含重复单元
Figure PCTCN2015084687-appb-000002
的均聚体或共聚体，其中R1、R2优选为C1～3脂肪烃或芳香烃。若R1和R2同为脂肪烃基，所形成烯烃聚合物一方面由于其分子结构中不含侧链基而导致Tg较低，另一方面其容易结晶(例如PE、PP、PMP都具有很高的结晶度)，这可能会影响到其作为胶粘剂材料的基础树脂的使用性能；若脂肪烃基链太长会增加聚合物柔顺性，使其Tg降低，则影响键合胶的使用温度。
聚酯类，其为分子结构中包含重复单元
Figure PCTCN2015084687-appb-000003
的均聚体或共聚体，其中R为环己烷基、苯基或己氧基，
即
Figure PCTCN2015084687-appb-000004
这里，聚酯类可以选用A、B和C三种聚酯的物理共混物。A、B、C的质量含量范围分别是10～60％、10～80％、0～50％，A、B、C的分子量范围分别是8000～30000、5000～50000、5000～100000。
值得说明的是，例如，共混高聚物可以为一种或多种聚烃基丙烯酸酯类，可以为一种或多种聚苯基乙烯类，也可为一种或多种聚酯类，此外还可以为一 种聚烃基丙烯酸酯类和一种聚苯基乙烯类的混合，或者一种聚烃基丙烯酸酯类和一种聚酯类的混合等等。作为一种实施方式，例如可采用分子量为5000～30000000的聚丙烯酸酯和分子量为3000～20000的聚α-甲基苯乙烯，两者的质量比为2∶1～20∶1。
溶剂的沸点优选为高于80℃，极性与相应聚合物相近。溶剂例如可以为丙二醇单甲醚乙酸酯、二甲基乙酰胺、丙二醇单甲醚、乳酸乙酯、苎烯、均三甲苯、环十二烯和环戊酮中的一种或至少两种。
进一步地，基于临时键合胶的总质量为100份数，还包括0.05～0.07份流平剂和0～0.15份抗氧剂。
这里，流平剂优选为采用氟改性的丙烯酸酯类流平剂。抗氧剂中优选为由以多元受阻酚型抗氧剂为主抗氧化剂和以亚磷酸酯类抗氧剂为辅助抗氧剂所组成，两者的复配有助于提高键合胶的热稳定性。
于上述临时键合胶中，一个较佳的配方为，包含20～30份PMMA、10～15份聚α-甲基苯乙烯、55～70份溶剂和0.05～0.07份FC-4430型流平剂；更好地，其原料包含24份PMMA、12份聚α-甲基苯乙烯、64.95份DMAc和0.05份FC-4430型流平剂。
本发明又一方面提供一种临时键合胶的制备方法，由该制备方法可得到具有热稳定性高、抗腐蚀性强的临时键合胶。
一种如上述临时键合胶的制备方法，按照质量份将30～45份基础树脂、55～70份溶剂和0.05～0.07份流平剂在加热条件下进行搅拌混合，而后冷却和脱气处理，得到临时键合胶。
上述制备方法中，加热的方式为在60～70℃下水浴；搅拌的方式为100～1000rpm转速下机械搅拌；脱气处理的方式为采用真空脱气机进行真空脱气。
本发明再一方面提供一种对薄晶圆进行键合的方法，该方法使用由上述具有良好热稳定性、抗腐蚀性强的临时键合胶。
一种使用上述临时键合胶对薄晶圆进行键合的方法，具体为：待将临时键合胶旋涂于承载晶圆表面，并将溶剂烘干后，将器件晶圆覆盖于该表面，而后加热临时键合胶使之熔化、冷却形成粘接层。
上述键合的方法中，加热临时键合胶的方式可为烘烤的方式。可直接通过烘烤承载晶圆未涂有键合胶的另外一表面。在键合胶受热的过程中，键合胶中的溶剂先挥发，而后伴随着加热的继续，基础树脂在200℃左右慢慢熔化，冷却固化形成粘接层，这样承载晶圆与器件晶圆的表面发生键合作用。固化形成粘接层之后还包括采用DMAc清洗器件晶圆外周残余的粘接层，由此类似地，在器件晶圆的解键合的过程中，也可采用DMAc作为清洗剂来溶解粘接层。
本发明的临时键合胶以临时键合胶的总质量为100份数计，包含55～70份的溶剂以及溶解或分散于溶剂中30～45份基础树脂，所述基础树脂为热分解温度在320℃以上、熔融指数24以上的高聚物或者共混高聚物，由此临时键合胶具有热稳定性高、抗腐蚀性强的优点，同时其键合/解键合效率高，残余粘接层易清洗，制备成本较为经济。
附图说明
图1是本发明实施例1临时键合胶的涂层干膜热重变化曲线图；
图2是本发明实施例2临时键合胶的涂层干膜热重变化曲线图；
图3是本发明实施例2经去溶剂的临时键合胶的粘度和温度的函数曲线图；
图4是本发明实施例2的临时键合胶涂层干膜的厚度分布图；
图5是本发明实施例2临时键合胶键合晶圆后的超声扫描显微照片。
具体实施方式
下面结合附图及实施例来进一步说明本发明的技术方案。
实施例1
将2.4g聚甲基丙烯酸甲酯、1.2g聚α-甲基苯乙烯、5mg FC-4430型流平剂、6.395g DMAc加入到带搅拌装置和配置有水浴加热系统的热溶解容器中。水浴温度控制在60～70℃，并启动搅拌机，调节转速为100～1000rpm，当上述原料充分搅拌均匀后取出，自然冷却冷却后置于真空脱气机中真空脱气，最后密封保存。
实施例2
本例中，其原料具体包含：4g自制聚酯、5mg 4430流平剂、5.995g溶剂PGMEA；室温下搅拌1小时。
除了上述条件外，其他均同于实施例1。
实施例3
本例中，原料具体包含：2.0g聚甲基丙烯酸甲酯、1.0g聚α-甲基苯乙烯、5mg FC-4430型流平剂、5.5g DMAc；除此之外，其他均同于实施例1。
实施例4
本例中，原料具体包含：3.0g聚甲基丙烯酸甲酯、聚1.5gα-甲基苯乙烯、7mg FC-4430型流平剂、7.0g DMAc；除此之外，其他均同于实施例1。
对实施例1和实施例2的抗腐蚀性的测试结果分别如下表1和下表2(鉴于具体测试方法已为本领域技术人员所熟知，在此对方法不再详述)：
表1
Figure PCTCN2015084687-appb-000005
Figure PCTCN2015084687-appb-000006
表2
Figure PCTCN2015084687-appb-000007
如图1、2所示，分别为实施例1、2的热重变化曲线图，从该图中可以看出自300℃，干膜才出现分解失重的现象，于450℃失重率为80％，即大部分发生分解，由此可见，本发明的临时键合胶具有较好的热稳定性。
如图3所示，为实施例1临时键合胶的粘度曲线图。从该图中可以看出，粘度随着温度的总体变化较为温和，由此说明了本发明的临时键合胶具有较好的粘度稳定性。
如图4所示，为本发明实施例2的临时键合胶涂层干膜的厚度分布图。从该图中可以看出，临时键合胶涂层的厚度较为均匀，由此说明粘接层平均厚度为22.7μm，标准偏差为0.5，说明粘接层厚度合适，粘接层很平整，具有较好的涂装效果，对涂装的工艺要求不苛刻。
如图5所示，为使用本发明实施例2临时键合胶键合晶圆后的超声扫描显微照片。从该图中可以看出，可以看出表明两片被粘接的硅晶圆之间的粘结层无空隙(没有白点)，分布均匀。
尽管本发明中所涉及的各工艺参数的数值范围在上述实施例中不可能全部体现，但本领域的技术人员完全可以想象到只要落入上述该数值范围内的任何数值均可实施本发明，当然也包括若干项数值范围内具体值的任意组合。此处，出于篇幅的考虑，省略了给出某一项或多项数值范围内具体值的实施例，在此不应当视为对本发明的技术方案要求保护的配方及工艺范围缺乏充足实施例支持的理解。
申请人声明，本发明通过上述实施例来说明本发明的详细工艺设备和工艺流程，但本发明并不局限于上述详细工艺设备和工艺流程，即不意味着本发明必须依赖上述详细工艺设备和工艺流程才能实施。所属技术领域的技术人员应该明了，对本发明的任何改进，对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等，均落在本发明的保护范围和公开范围之内。

Claims (10)

  1. 一种用于薄晶圆加工的临时键合胶，其特征在于，以临时键合胶的总质量为100份数计，包含55～70份的溶剂以及溶解或分散于溶剂中的30～45份基础树脂，所述基础树脂为热分解温度为320℃以上的高聚物或者共混高聚物。
  2. 根据权利要求1所述的临时键合胶，其特征在于，所述高聚物为聚烃基丙烯酸酯类，其为分子结构中包含重复单元
    Figure PCTCN2015084687-appb-100001
    的均聚体或共聚体，其中R1为C1～2脂肪烃或芳香烃，R2为C1～3脂肪烃或芳香烃；
    或者为聚苯基乙烯类，其为分子结构中包含重复单元
    Figure PCTCN2015084687-appb-100002
    的均聚体或共聚体，其中R1、R2为C1～3脂肪烃或芳香烃；
    又或者为聚酯类，其为分子结构中包含重复单元
    Figure PCTCN2015084687-appb-100003
    的均聚体或共聚体，其中R为环己烷基、苯基或己氧基。
  3. 根据权利要求2所述的临时键合胶，其特征在于，所述共混高聚物为所述聚烃基丙烯酸酯类、聚苯基乙烯类和聚酯类中的至少两种。
  4. 根据权利要求2所述的临时键合胶，其特征在于，所述基础树脂的重均分子量为5×103～5×105；
    优选地，所述基础树脂的熔融指数为24以上。
  5. 根据权利要求1所述的临时键合胶，其特征在于，所述溶剂为丙二醇单甲醚乙酸酯、二甲基乙酰胺、丙二醇单甲醚、乳酸乙酯、苎烯、均三甲苯、环十二烯和环戊酮中的一种或至少两种。
  6. 根据权利要求1所述的临时键合胶，其特征在于，基于临时键合胶的总 质量为100份数，还包括0.05～0.07份流平剂和0～0.15份抗氧剂；
    优选地，所述流平剂为氟改性的丙烯酸酯类流平剂；
    优选地，所述抗氧剂为多元受阻酚型抗氧剂抗氧化剂和亚磷酸酯类抗氧剂的混合物。
  7. 一种如权利要求1～6中任意一项所述临时键合胶的制备方法，其特征在于，以临时键合胶的总质量为100份数计，将30～45份基础树脂、55～70份溶剂和0.05～0.07份流平剂和0～0.15份抗氧剂在加热条件下进行搅拌混合，而后冷却和脱气处理，得到临时键合胶。
  8. 根据权利要求7所述的制备方法，其特征在于，所述加热的方式为在60～70℃下水浴；
    优选地，所述搅拌的方式为100～1000rpm转速下机械搅拌；
    优选地，所述脱气处理的方式为采用真空脱气机进行真空脱气。
  9. 一种使用权利要求1～6中任意一项所述临时键合胶对薄晶圆进行键合的方法，其特征在于，提供包括通过所述临时键合胶粘接的第一基片和第二基片的层叠件；以及加热所述临时键合胶使之固化形成粘接层。
  10. 根据权利要求9所述的方法，其特征在于，所述加热临时键合胶使之固化形成粘接层之后还包括采用DMAc清洗器件晶圆外周残余的粘接层的步骤。
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