WO2016165230A1 - 晶圆减薄的临时键合胶、其制备方法、键合及解键合方法 - Google Patents

晶圆减薄的临时键合胶、其制备方法、键合及解键合方法 Download PDF

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WO2016165230A1
WO2016165230A1 PCT/CN2015/084685 CN2015084685W WO2016165230A1 WO 2016165230 A1 WO2016165230 A1 WO 2016165230A1 CN 2015084685 W CN2015084685 W CN 2015084685W WO 2016165230 A1 WO2016165230 A1 WO 2016165230A1
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temporary bonding
solvent
bonding adhesive
bonding
base resin
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PCT/CN2015/084685
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English (en)
French (fr)
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孙蓉
方浩明
张国平
邓立波
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深圳先进技术研究院
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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
    • C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
    • C08G12/04—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08G12/06—Amines
    • C08G12/08—Amines aromatic
    • 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
    • C09J161/00—Adhesives based on condensation polymers of aldehydes or ketones; Adhesives based on derivatives of such polymers
    • C09J161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C09J161/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
    • C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive

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  • the invention relates to the technical field of adhesives, in particular to a temporary bonding adhesive for wafer thinning, a preparation method thereof, a bonding and debonding method.
  • Chinese Patent No. CN104204126A discloses an adhesive composition for a wafer processing film comprising an acrylic polymer and a photosensitive gas generating agent, and the adhesive layer formed by the composition can be debonded using ultraviolet light.
  • Chinese 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 adhesive layer formed by the temporary bonding adhesive has low debonding efficiency, and the debonding requires the use of expensive supporting equipment.
  • the adhesive layer has
  • an aspect of the present invention provides a temporary bonding adhesive having high debonding efficiency.
  • a wafer-thinned temporary bonding adhesive comprising a base resin for producing an adhesion, the base resin being a polymer which can be depolymerized into a linear oligomer and/or a low molecular compound under the action of a strong acid.
  • the base resin is an acid-degraded polymer, so that the adhesive layer formed by the bonding adhesive is subjected to a significant depolymerization reaction under the full immersion of the acid solution, that is, the structure of the bulk polymer is destroyed, and the resulting low molecular compound and/or Linear oligomers cause the bonding layer to fail to achieve the purpose of debonding.
  • low molecular compound with respect to “polymer” means a molecular weight of less than 1000.
  • Linear oligomer refers to a non-polymer having a molecular weight greater than 1000 comprising a plurality of monomeric molecular structures.
  • the strong acid is not limited, and for example, sulfuric acid, hydrochloric acid, nitric acid or the like is preferred, and an acid having a pH of less than 2 is preferred.
  • the thermal decomposition temperature of the base resin is above 270 ° C, which ensures that the bonding layer formed by the temporary bonding adhesive has good thermal stability.
  • the acid-degrading polymer of the present invention is not particularly limited, and specific examples thereof include a system of an acetal or a ketal diepoxide (refer to the literature "Buchwalter* and Laura L. Kosbar, Cleavable epoxy resins: Design for disassembly of a Thermoset, Journal of Polymer Science Part A: Polymer Chemistry Volume 34, Issue 2, pages 249-260, 30 January 1996”); or in the addition of bisphenol A and cresol-containing phenolic resin, epoxy ethyl glycidyl ester and A system consisting of cyclohexanedimethanol vinyl glycidyl ester, which can be degraded in acid-containing THF after curing (refer to the literature "Hashimoto, T., Meiji, H., Urushisaki, M., Sakaguchi, T., Kawabe, K., Tsuchida, C.
  • the present invention is preferably a network polymer obtained by polycondensation of a diamine and a fatty aldehyde. Its molecular structure consists of repeating units whose main body is a six-membered carbon-nitrogen heterocycle, and its repeating unit Wherein R 1 is C 1 ⁇ 4 aliphatic hydrocarbon or an aromatic hydrocarbon group, R 2 is C 1 ⁇ 4 aliphatic hydrocarbon or an aromatic hydrocarbon group.
  • the above diamine compound refers to a compound having two amino groups in its molecule.
  • the temperature of the above polycondensation reaction is preferably 50 to 80 °C.
  • the molar ratio of the diamine compound to the fatty aldehyde is preferably from 1:2 to 1:3, and the polycondensation reaction is carried out by a well-known Mannich classical reaction based on a primary amine and an aldehyde.
  • the specific synthetic route is as follows:
  • a polymer synthesized by reacting formaldehyde with 4,4-diaminodiphenyl ether has a glass transition temperature (T g ) of 32 ° C, at which time R 1 is a diphenyl ether and R 2 is a hydrogen atom; acetaldehyde
  • the polymer synthesized by the reaction with 4,4-diaminodiphenyl ether has no obvious glass transition at 250 ° C, at which time R 1 is diphenyl ether, R 2 is methyl; propionaldehyde and 4,4-
  • the polymer synthesized by the diaminodiphenyl ether reaction has no obvious glass transition at 250 ° C, where R 1 is diphenyl ether and R 2 is ethyl; when the R 2 group is an aromatic hydrocarbon group, the primary amine
  • the reaction with the aldehyde can be carried out, but a stable six-membered ring network structure cannot be formed, so that no obvious solid glue is obtained
  • the R 2 group is an aromatic hydrocarbon group or an isopropyl group, since the steric hindrance of the aromatic hydrocarbon and the isopropyl group is large, the stability of ring formation is poor, and thus the crosslinked network structure is not obtained. Therefore, preferably, the R 2 group is a C 1-3 linear aliphatic hydrocarbon group.
  • the bonding gel also contains a solvent.
  • the solvent can be used as a solvent for the polycondensation reaction of the above diamine and a fatty aldehyde, and the base resin obtained by the reaction is dispersed in a solvent.
  • the solvent has a boiling point above 80 ° C and a polarity similar to that of the corresponding polymer.
  • the solvent may be, for example, propylene glycol monomethyl ether acetate, dimethyl One or at least two of acetamide, propylene glycol monomethyl ether, ethyl lactate, and pyrrolidone.
  • the amount of the solvent is not particularly limited, but is preferably not limited to 50 to 70% by mass based on the total mass of the solvent and the base resin.
  • the method further comprises, in an amount of 100 parts by weight based on the total mass of the solvent and the base resin, 8 to 10 parts of a tackifier, 0.05 to 0.07 parts of a leveling agent, and 0 to 1 part of an antioxidant.
  • the tackifier is used to increase the viscosity of the bonding adhesive, and is preferably a polymethyl methacrylate resin.
  • the polymethyl methacrylate has good compatibility with the base resin, and its molecular weight is preferably from 10 4 to 10 7 .
  • the leveling agent generally employs a fluorine-modified acrylate leveling agent.
  • the primary antioxidant is a multi-hindered phenolic antioxidant
  • the secondary antioxidant is a phosphite antioxidant, which helps to improve the thermal stability of the bonding adhesive.
  • a preferred formulation comprises 8 to 12 parts of 4,4-diaminodiphenyl ether, 10 to 15 parts of acetaldehyde, 55 to 70 parts of solvent, 0.05 to 0.07 based on the total mass of the base resin and the solvent. a portion of the FC-4430 leveling agent, 0.8 to 1.2 parts of the antioxidant 1076, and 8 to 10 parts of the polymethyl methacrylate tackifier; more preferably, the raw material comprises 10 parts of 4,4-diaminodiphenyl ether, 10.9 parts acetaldehyde, 68.05 parts DMAc and 0.05 parts FC-4430 leveling agent, 10 parts polymethyl methacrylate tackifier, 1 part 1076 antioxidant.
  • a method for preparing a temporary bonding adhesive which can obtain a temporary bonding adhesive having high thermal stability and high corrosion resistance.
  • a method for preparing a temporary bonding adhesive as described above providing a base resin; according to a base resin to solvent mass ratio of (30-50): (50-70) proportioning solvent; the solvent and the solvent and the base resin
  • the total mass is 100 parts, 8-10 parts of tackifier, 0.05-0.07 parts of leveling agent, 0-1 part of antioxidant are mixed to form a mixed solution; the mixture is cooled and degassed to obtain a temporary bond.
  • the specific method for providing the base resin is to mix and mix 30 to 50 parts of the total mass of the reaction monomers (that is, the sum of the masses of the diamine and the fatty aldehyde), 50 to 70 parts of the solvent under heating, and then to cool. And the filter is more viscous transparent liquid (there is some poor solubility system, so it needs to be filtered out) is the base resin.
  • the flat agent and 0 to 0.15 parts of the antioxidant are stirred and degassed to obtain a temporary bonding gel.
  • the heating method is a water bath at 50 to 80 ° C; the stirring method is mechanical stirring at a rotation speed of 100 to 1000 rpm; and the degassing treatment method is vacuum degassing by using a vacuum degasser.
  • Yet another aspect of the present invention provides a method of bonding thin wafers using a temporary bonding adhesive having better bonding efficiency as described above.
  • a method for bonding a thinned wafer using the temporary bonding adhesive described above specifically: providing a laminate including a first substrate and a second substrate bonded by the temporary bonding adhesive; and a heating station The temporary bonding glue is cured 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 paste can be directly passed through the baking device wafer.
  • the solvent in the bonding adhesive first volatilizes, and then with the continuation of the heating, the polymer is completely cured to a bonding layer at a curing temperature of about 120 to 180 ° C, thus carrying the wafer and the device. Bonding occurs on the surface of the wafer.
  • a method of debonding a thin wafer bonded by the above method comprising the step of dissolving the adhesive layer with a strong acid.
  • the strong acid is preferably at least one selected from the group consisting of sulfuric acid solution, hydrochloric acid, and nitric acid.
  • the molar concentration of the strong acid is 0.5 to 6 M.
  • M is an abbreviation of "mol/L”.
  • the temporary bonding adhesive for wafer thinning in the present invention comprises a base resin for generating adhesion, and the base resin is a polymer which can be depolymerized into a low molecular compound and/or a linear oligomer under the action of a strong acid, so that When the adhesive layer formed by the bonding adhesive is fully impregnated with an acid liquid, a significant depolymerization reaction occurs, that is, the structure of the bulk polymer is destroyed, and the resulting low molecular compound or linear oligomer causes the adhesive layer to fail, thereby improving the debonding. effectiveness. Further, the decomposition temperature of the high polymer is 270 ° C or more, so that the thermal stability of the adhesive layer is high. In addition, the bonding adhesive of the present invention is also strong in corrosion resistance, and the preparation cost is economical.
  • Example 1 is an infrared spectrum diagram of a temporary bonding adhesive of Example 1 of the present invention before and after curing;
  • Example 2 is a diagram showing the acid degradation and acid degradation rate of the temporary bonding adhesive of Example 2 of the present invention
  • Figure 3 is a graph showing the thermogravimetric change of the dry film of the temporary bonding adhesive coating of Example 2 of the present invention.
  • Example 4 is a DSC graph of a dry film of a temporary bonding adhesive bond coating of Example 2 of the present invention.
  • FIG. 5 is a bonding and debonding process after the temporary bonding glue of the present invention bonds the wafer.
  • the raw materials specifically include: 3 g of paraformaldehyde, 4 g of 4,4-diamine diphenyl ether, and 28 g of solvent NMP, which are added to a hot-dissolving vessel equipped with a stirring device and a water bath heating system.
  • the temperature of the water bath was controlled at 60 to 70 ° C and the mixer was started.
  • the rotation speed was adjusted to 100 to 1000 rpm and stirred for 15 minutes.
  • filtration was carried out to obtain a viscous filtrate.
  • Add 17 mg of 4430 leveling agent to the filtrate and mix well. It is vacuum degassed in a vacuum degasser and finally sealed and stored.
  • the raw material specifically comprises: 4.4 g of acetaldehyde (99% solution), 3.96 g of 4,4-diamine diphenyl Alkane, 28 g of NMP, 20 mg of FC-4430 type leveling agent, 4 g of polymethyl methacrylate; otherwise, the same applies to Example 1.
  • the raw material specifically comprises: 4.4 g of acetaldehyde (99% solution), 2.16 g of p-phenylenediamine, 28 g of NMP, 18 mg of FC-4430 type leveling agent, and 4 g of polymethyl methacrylate; The others are the same as in the first embodiment.
  • Figure 1 is an infrared spectrum of Example 1 before and after curing. As can be seen from the figure, a large amount of hydroxyl groups (wavenumber of 3300 cm -1 position) existed before curing, and the hydroxyl peak disappeared after curing, thereby demonstrating that the reaction occurred and a crosslinked network was formed.
  • 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 and the DSC thermogram of the embodiment 2 are respectively shown.
  • the dry film of the temporary bonding adhesive has a decomposition weight loss from 280 ° C. Phenomenon, the weight loss rate at 500 ° C is 80%, that is, most of the decomposition.
  • Fig. 2 it can be seen that in the range of 250 ° C, the sample has a glass transition at 50 ° C, but there is no transition zone in the processing temperature range.
  • the temporary bonding adhesive of the present invention has better thermal stability.

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Abstract

本发明公开了晶圆减薄的临时键合胶、其制备方法、键合及解键合方法。该临时键合胶包含用于产生粘合作用的基础树脂，基础树脂为在强酸作用下可解聚成低分子化合物和/或线性低聚物，由此使得键合胶形成的粘合层采用酸液充分浸渍下发生明显的解聚合反应，即体型聚合物的结构被破坏，生成的低分子化合物或线性低聚物使得粘合层失效，达到提高解键合效率。另外，高聚物的分解温度在270℃以上，使得粘合层的热稳定性高。此外，所发明的键合胶抗腐蚀性优良，制备成本较为经济。

Description

晶圆减薄的临时键合胶、其制备方法、键合及解键合方法 技术领域
本发明涉及胶粘剂的技术领域，尤其涉及晶圆减薄的临时键合胶、其制备方法、键合及解键合方法。
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，半导体工业需要将薄晶圆减薄至100μm以下。超薄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，用于固定器件晶圆的临时键合胶是临时键合工艺成功的关键。
中国专利CN104204126A公开了一种用于晶圆加工薄膜的粘合剂组合物，该组合物包含丙烯酸类聚合物及光敏气体发生剂，该组合物形成的粘合层可使用紫外光进行解键合。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，采用临时键合胶形成的粘合层解键合效率较低，解键合需借助昂贵配套设备，此外，粘合层的热稳定性低、抗腐蚀性差。
发明内容
有鉴于此，本发明一方面提供一种具有解键效率高的临时键合胶。
一种晶圆减薄的临时键合胶，包含用于产生粘合作用的基础树脂，所述基础树脂为在强酸作用下可解聚成线性低聚体和/或低分子化合物的高聚物。
基础树脂为酸降解的高聚物，这样可使得键合胶形成的粘合层采用酸液充分浸渍下发生明显的解聚合反应，即体型聚合物的结构被破坏，生成的低分子化合物和或线性低聚体使得粘合层失效，达到解键合的目的。术语“低分子化合物”相对于“高分子”而言，指分子量小于1000。“线性低聚体”指非高聚物，其分子量大于1000的包括多个单体分子结构的聚合物。本发明中对强酸不做任何限定，例如硫酸、盐酸、硝酸等，优选为pH小于2的酸。
基础树脂的热分解温度在270℃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。
本发明具有酸降解高聚物无特殊限定，具体实例有：缩醛或缩酮二环氧化物的体系(具体可参照文献“Buchwalter*and Laura L.Kosbar，Cleavable epoxy  resins：Design for disassembly of a thermoset，Journal of Polymer Science Part A：Polymer Chemistry Volume 34，Issue 2，pages 249-260，30January 1996”)；或者在双酚A与含有甲酚的酚醛树脂中，加入环氧乙基缩水甘油酯和环己烷二甲醇乙烯基缩水甘油酯组成的体系，固化后可在含酸的THF中降解(具体可参照文献“Hashimoto，T.，Meiji，H.，Urushisaki，M.，Sakaguchi，T.，Kawabe，K.，Tsuchida，C.and Kondo，K.(2012)，Degradable and chemically recyclable epoxy resins containing acetal linkages：Synthesis，properties，and application for carbon fiber-reinforced plastics.J.Polym.Sci.A Polym.Chem.，50：3674-368”)。本发明优选为为二胺与脂肪醛缩聚反应而成的网状聚合物。其分子结构由主体为六元碳氮杂环的重复单元所构成，其重复单元
Figure PCTCN2015084685-appb-000001
其中R1为C1～4的脂肪烃基或芳香烃基，R2为C1～4的脂肪烃基或芳香烃基。
上述二胺化合物指分子中含有两个氨基的化合物。上述缩聚反应的温度优选为50～80℃。二胺化合物与脂肪醛的摩尔比优选为1∶2～1∶3，缩聚反应采用公知的基于伯胺与醛的Mannich经典反应。具体合成路线如下：
Figure PCTCN2015084685-appb-000002
例如，使用甲醛与4，4-二氨基二苯醚反应合成的聚合物，其玻璃化转变温度(Tg)为32℃，此时R1为二苯醚，R2为氢原子；乙醛与4，4-二氨基二苯醚反应合成的聚合物，在250℃下，无明显的玻璃化转变，此时时R1为二苯醚，R2为甲基；丙醛与4，4-二氨基二苯醚反应合成的聚合物，在250℃下，无明显的玻璃化转变，此时R1为二苯醚，R2为乙基；当R2基团为芳香烃基时，伯胺与醛的反应可以进行，但是不能形成稳定的六元环网状结构，因此热固化时得不到明显固体胶，粘合性能差。随着R2基团的碳原子数目增多，聚合物网状结构缠绕加剧，聚合物刚性增强，Tg升高。而在加工温度中不发生玻璃化转变证明该临时键合胶的热稳定性优异。而R2基团为芳香烃基或者异丙基时，由于芳香烃和异丙基的位阻较大，导致成环的稳定较差，因此得不到交联网络结构。因此优选地，R2基团为C1～3的直链脂肪烃基。
可以理解的是，键合胶还包含溶剂。溶剂可作为上述二胺与脂肪醛的缩聚反应的溶剂，由此反应得到的基础树脂是分散于溶剂中。溶剂的沸点要高于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、和吡咯烷酮中的一种或至少两种。溶剂用量不做特别限定，优选但不限定为占溶剂与基础树脂总质量的50～70％。
进一步地，还包含，以溶剂与基础树脂总质量为100份计，8～10份的增粘剂、0.05～0.07份流平剂、0～1份抗氧剂。
增粘剂用于提高键合胶的粘度，优选为聚甲基丙烯酸甲酯树脂，聚甲基丙烯酸甲酯与基础树脂相容性好，其分子量优选为为104～107。流平剂一般采用氟改性的丙烯酸酯类流平剂。抗氧剂中，主抗氧剂为多元受阻酚型抗氧剂，辅助抗氧剂为亚磷酸酯类抗氧剂，它们有助于提高键合胶的热稳定性。
一个较佳的配方为，以基础树脂和溶剂总质量为100份计，包含8～12份4，4-二氨基二苯醚、10～15份乙醛、55～70份溶剂，0.05～0.07份FC-4430型流平剂、0.8～1.2份抗氧化剂1076、8～10份聚甲基丙烯酸甲酯增粘剂；更好地，其原料包含10份4，4-二氨基二苯醚，10.9份乙醛、68.05份DMAc和0.05份FC-4430型流平剂，10份聚甲基丙烯酸甲酯增粘剂，1份1076抗氧化剂。
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，提供基础树脂；按照基础树脂与溶剂质量比为(30～50)∶(50～70)配比溶剂；将所述溶剂及，以溶剂与基础树脂总质量为100份计，8～10份的增粘剂、0.05～0.07份流平剂、0～1份抗氧剂混合以形成混合液；将混合液经冷却和脱气处理，得到临时键合胶。
提供基础树脂的具体方法为，按照质量份将30～50份反应单体总质量(即二胺和脂肪醛两者质量之和)、50～70份溶剂在加热条件下进行搅拌混合，而后冷却和过滤得较粘稠透明液体(存在一些溶解性较差的体系，故需要进行过滤出来)即为基础树脂。将得到的基础树脂与8～10份增稠剂，0.05～0.07份流 平剂和0～0.15份抗氧剂进行搅拌混合和脱气处理，得到临时键合胶。
上述制备方法中，加热的方式为在50～80℃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键合的方法，该方法使用由上述具有较好键合效率的临时键合胶。
一种使用上述临时键合胶对减薄晶圆进行键合的方法，具体为：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。
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。可直接通过烘烤器件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，该聚合物在固化温度为120～180℃左右彻底固化成粘接层，这样承载晶圆与器件晶圆的表面发生键合作用。
一种对上述方法键合的薄晶圆进行解键合的方法，包括采用强酸溶解粘接层的步骤。
强酸优选为选自硫酸溶液、盐酸、硝酸至少一种。强酸的摩尔浓度为采用0.5～6M。这里“M”即“mol/L”的简称。
本发明中晶圆减薄的临时键合胶，包含用于产生粘合作用的基础树脂，基础树脂为在强酸作用下可解聚成低分子化合物和/或线性低聚体的高聚物，这样将键合胶形成的粘合层采用酸液充分浸渍下即发生明显的解聚合反应，即体型聚合物的结构被破坏，生成的低分子化合物或线性低聚体使得粘合层失效，达到提高解键合效率。另外，高聚物的分解温度在270℃以上，使得粘合层的热稳定性高。此外，本发明的键合胶抗腐蚀性也较强，制备成本较为经济。
附图说明
图1是本发明实施例1临时键合胶的固化前后的红外光谱图；
图2是本发明实施例2临时键合胶的酸降解情况及酸降解速率图；
图3是本发明实施例2的临时键合胶涂层干膜热重变化曲线图；
图4是本发明实施例2临时键合胶键合胶涂层干膜DSC曲线图。
图5是本发明临时键合胶键合晶圆后的键合及解键合过程。
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4.4g乙醛(99％溶液)、4g 4，4-二胺二苯醚、28gDMAc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，搅拌15min后当上述原料充分搅拌均匀后取出，加入20mg的FC-4430型流平剂，4g聚甲基丙烯酸甲酯，搅拌均匀。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：3g多聚甲醛、4g 4，4-二胺二苯醚、28g溶剂NMP，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，搅拌15min。冷却后进行过滤得到粘稠的滤液。往滤液中加入17mg 4430流平剂，搅拌均匀。置于真空脱气机中真空脱气，最后密封保存。
实施例3
本例中，原料具体包含：将4.4g乙醛(99％溶液)、3.96g 4，4-二胺二苯甲 烷、28g NMP、20mg FC-4430型流平剂，4g聚甲基丙烯酸甲酯；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：将4.4g乙醛(99％溶液)、2.16g对苯二胺、28g NMP、18mg FC-4430型流平剂，4g聚甲基丙烯酸甲酯；除此之外，其他均同于实施例1。
图1为实例1的固化前与固化后的红外光谱图。从图中可以得知，固化前存在大量羟基(波数为3300cm-1位置)，固化后羟基峰消失，从而证明该反应发生并且形成交联网络。
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 PCTCN2015084685-appb-000003
表2
Figure PCTCN2015084685-appb-000004
如图3、4所示，分别为实施例2的热重变化及DSC热谱曲线图，从该图1中可以看出自280℃起，临时键合胶的涂层干膜才出现分解失重的现象，于500℃失重率为80％，即大部分分解。而在图2中，可以看出在250℃范围内，样品在50℃时候存在玻璃化转变，但在加工温度范围内，不存在转变区。由此可见，本发明的临时键合胶具有较好的热稳定性。
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. 一种晶圆减薄的临时键合胶，其特征在于，包含用于产生粘合作用的基础树脂，所述基础树脂为在强酸作用下可解聚成低分子化合物和/或线性低聚体的高聚物。
  2. 根据权利要求1所述的临时键合胶，其特征在于，所述强酸为pH低于2的酸。
  3. 根据权利要求1所述的临时键合胶，其特征在于，所述高聚物的分解温度在270℃以上。
  4. 根据权利要求1所述的临时键合胶，其特征在于，所述高聚物为二胺化合物与脂肪醛进行缩聚反应而成的网状聚合物，其分子结构由主体为六元碳氮杂环的重复单元所构成，其重复单元结构为：
    Figure PCTCN2015084685-appb-100001
    其中，R1为C1～4的脂肪烃基或芳香烃基，R2为C1～4的脂肪烃基或芳香烃基；
    优选地，所述缩聚反应的温度为50～80℃；
    优选地，所述二胺化合物与脂肪醛的摩尔比为1∶2～1∶3；
    优选地，所述高聚物的重均分子量为5×103～5×106。
  5. 根据权利要求1所述的临时键合胶，其特征在于，还包含溶剂，所述溶剂的沸点高于80℃；
    优选地，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、乳酸乙酯和吡咯烷酮中的一种或至少两种；
    优选地，所述溶剂用量为占溶剂与基础树脂总质量的50～70％。
  6. 根据权利要求5所述的临时键合胶，其特征在于，还包含：以溶剂与基础树脂总质量为100份计，8～10份的增粘剂、0.05～0.07份流平剂、0～1份抗氧剂；
    优选地，所述增粘剂为聚甲基丙烯酸甲酯；
    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所述临时键合胶的制备方法，其特征在于，包括：提供基础树脂；按照基础树脂与溶剂质量比为(30～50)∶(50～70)配比溶剂；将所述溶剂及，以溶剂与基础树脂总质量为100份计，8～10份的增粘剂、0.05～0.07份流平剂、0～1份抗氧剂混合以形成混合液；将混合液经冷却和脱气处理，得到临时键合胶。
  8. 一种使用权利要求1所述临时键合胶对减薄晶圆键合的方法，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。
  9. 根据权利要求9所述的方法，其特征在于，所述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的具体方式为，在400～1400rpm转速下将所述临时键合胶涂布于第一基片和第二基片上；
    优选地，所述固化温度为120～180℃。
  10. 一种对采用如权利要求8所述方法键合的减薄晶圆进行解键合的方法，其特征在于，包括采用强酸溶解粘接层的步骤。
    优选地，所述强酸为选自硫酸溶液、盐酸、硝酸中的至少一种；
    优选地，所述强酸的摩尔浓度为0.5～6M。
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