CN115322691A - Wafer bonding adhesive, preparation method and use method thereof - Google Patents

Wafer bonding adhesive, preparation method and use method thereof Download PDF

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Publication number
CN115322691A
CN115322691A CN202210969107.1A CN202210969107A CN115322691A CN 115322691 A CN115322691 A CN 115322691A CN 202210969107 A CN202210969107 A CN 202210969107A CN 115322691 A CN115322691 A CN 115322691A
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China
Prior art keywords
wafer
wafer bonding
glue
bonding
parts
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CN202210969107.1A
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Chinese (zh)
Inventor
高满
罗海强
虞锦洪
陈韬
苏光临
李茂华
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Guangxi Poyuan New Material Co ltd
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Guangxi Poyuan New Material Co ltd
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Priority to CN202210969107.1A priority Critical patent/CN115322691A/en
Publication of CN115322691A publication Critical patent/CN115322691A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/67Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/683Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L21/6835Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2221/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof covered by H01L21/00
    • H01L2221/67Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere
    • H01L2221/683Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping
    • H01L2221/68304Apparatus for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components; Apparatus not specifically provided for elsewhere for supporting or gripping using temporarily an auxiliary support
    • H01L2221/68381Details of chemical or physical process used for separating the auxiliary support from a device or wafer
    • H01L2221/68386Separation by peeling

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to the field of semiconductors, in particular to a wafer bonding adhesive, a preparation method and a use method thereof. The wafer bonding adhesive is prepared from, by weight, 40-60 parts of difunctional acrylate monomer, 35-65 parts of polyurethane resin, 0.1-2 parts of accelerator and 0.1-2 parts of stabilizer. For prior art attenuate technology bonding glue adopts photocuring or thermosetting mode, has the problem that the difficulty was got rid of to excessive glue, uses bonding glue in this application, adopts the room temperature curing mode, washs the marginal uncured bonding glue, not only the energy is saved on the curing mode, and later stage excessive glue problem also obtains solving effectively.

Description

Wafer bonding adhesive, preparation method and use method thereof
Technical Field
The invention relates to the field of semiconductors, in particular to a wafer bonding adhesive, a preparation method and a use method thereof.
Background
As the production of ultra-small, ultra-thin and high-performance 3D integrated products is a trend, the wafer thinning and holding technology is pushed out in order to ensure the integrity of the wafer, the wafer holding technology mainly depends on bonding glue to fix the wafer on a glass slide so as to finish the back thinning process, and the bonding glue on the wafer is peeled off after the glass slide and the wafer are separated.
Chinese patent CN111755377A discloses a thin wafer debonding method, comprising the following steps: silicon etching removal-debonding the silicon wafer from the slide. The method comprises preparing a mask layer (photoresist) on the wafer side, and removing the photoresist on the edge of the silicon wafer through exposure and development processes; and directly etching the outer ring of the silicon wafer by a dry etching process. The problem of 'glue extrusion' of the temporary bonding glue for the thin wafer is solved, and the risk of fragments is avoided. However, this method is not only costly but also complicated in process. Patent CN107342241A proposes a bonding releasing device and method, which prevent the adhesive layer in the bonding sheet from being completely melted by the upper and lower suction cups, the heater and the constant temperature structure, and avoid the problems of thickness reduction, overflow and abrasion of the adhesive layer to the silicon wafer caused by the complete melting of the adhesive layer. The method needs to directly change equipment to deal with the overflow problem, and compared with the existing application end production line, the method needs to replace the production line from a new production line, and the cost is high.
It can be seen that, after bonding is released, a wafer with a high yield is obtained by aiming at the problem of glue extrusion, and the existing process for removing glue overflow is not only complex in process, but also increases energy consumption or labor cost, so that a better solution for glue overflow in wafer bonding needs to be provided: in combination with practical application problems, a more optimal curing form needs to be provided, and not only the overflowed glue can be removed more easily, but also the labor and energy consumption need to be better.
Disclosure of Invention
Aiming at some problems in the prior art, the first aspect of the invention provides a wafer bonding adhesive, which comprises, by weight, 40-60 parts of difunctional acrylate monomer, 35-65 parts of polyurethane resin, 0.1-2 parts of accelerator, 0.1-2 parts of stabilizer and 0.5-5 parts of initiator.
In one embodiment, the wafer bonding adhesive is prepared from 47 parts by weight of difunctional acrylate monomer, 51 parts by weight of polyurethane resin, 0.6 part by weight of accelerator, 0.4 part by weight of stabilizer and 2 parts by weight of initiator.
In one embodiment, the difunctional acrylate monomer is selected from one or more of diethylene glycol diacrylate, hexanediol diacrylate, 1, 3-butanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, and preferably diethylene glycol diacrylate.
Use diethylene glycol diacrylate as difunctional acrylate monomer in this application, provide flexibility for the glue film in the technological process of attenuate, prevent that the too big messenger's wafer of stress breaks in the attenuate process.
In one embodiment, the polyurethane is available under the trade designation PS0903-1.
The polyurethane resin used in the application can provide certain cohesive force and viscosity, and can be better spin-coated to a required thickness.
In one embodiment, the accelerator is selected from one or more of N, N-dimethyl-p-toluidine, tetramethylthiourea, N-dihydroxyethyl-p-toluidine, N-diethyl-p-toluidine, preferably N, N-dimethyl-p-toluidine.
The reaction time is accelerated by a promoter, the time cost is reduced, the bonding adhesive can be kept stable under the condition of oxygen, and the proper stripping force and bonding adhesive cohesion can ensure that the wafer does not fall off during thinning and can not be damaged due to overlarge mechanical property in the process of removing the bonding adhesive. The applicant unexpectedly finds that the specific polyurethane resin and the specific difunctional acrylate monomer enable the bonding glue in the application to have good fluidity of large and small molecules during spin coating without adding a leveling agent, the spin coating thickness is uniform, and the curing reaction is uniform in the vacuum phase attaching process.
The stabilizer is not particularly limited in this application and may be routinely selected by one skilled in the art, and in a preferred embodiment is a hindered phenol type stabilizer, more preferably 1, 4-hydroquinone.
The initiator is not particularly limited in the present application and can be selected conventionally by those skilled in the art, and in a preferred embodiment, the initiator is selected from one or more of organic peroxide initiator, inorganic peroxide initiator, azo type initiator, more preferably organic peroxide initiator, and even more preferably organic peroxide initiator is selected from one or more of cumene hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, and diisopropyl peroxydicarbonate, more preferably cumene hydroperoxide. After the wafer coated with the bonding glue is attached to the glass slide, the monomer and the resin are crosslinked under the action of no oxygen, so that temporary bonding is provided for the subsequent process.
The second aspect of the present invention provides a method for preparing a wafer bonding paste, comprising the steps of:
(1) Mixing and stirring difunctional acrylate monomer, accelerator and stabilizer;
(2) Heating to 30-50 ℃, adding polyurethane resin, and stirring;
(3) Cooling, and adding an initiator;
(4) Fully mixing and then vacuumizing to obtain the product.
In one embodiment, the method for preparing the wafer bonding paste comprises the following steps:
(1) Mixing a difunctional acrylate monomer, an accelerant and a stabilizer, and stirring for 30min;
(2) Heating to 40 ℃, adding polyurethane resin, and stirring for 45min;
(3) Cooling to room temperature, and adding an initiator;
(4) Mixing completely, and vacuumizing for 30 min.
Room temperature in this application means 25 ℃.
The bonding glue is obtained by using diethylene glycol diacrylate, matching with polyurethane resin, N-dimethyl-p-toluidine, 1, 4-hydroquinone and cumyl peroxide, in the subsequent use process, the bonding glue is coated on a wafer in a spinning mode and then is attached to a glass slide with a laser release layer in vacuum, due to the oxygen-free effect, free radicals of the bonding glue between the glass slide and the wafer are initiated, functional groups are crosslinked, the bonding glue exposed outside the wafer and overflowing does not polymerize due to the oxygen inhibition effect, one-step edge cleaning is added in the subsequent process, and edge overflow glue is removed. After the thinning process is finished, the glass slide and the wafer bonded with the bonding glue are separated, the bonding glue on the wafer is separated through the adhesive tape, the adhesive film is completely torn off, and no residue is left on the wafer. The existing process adopts a thermal curing or light curing mode, and in the bonding process, due to the action of the gravity of the glass slide, a part of bonding glue can be pressed out of the edge to form the glue overflow condition (edge covering phenomenon), so that the glass slide and the wafer can not be well separated in the glass sheet removing process, and when the glue layer of the wafer is removed, the glue layer and the wafer can not be well separated, and the risks of wafer breakage and the like can be caused. Therefore, the removal of the flash by manual scraping is required, which not only affects efficiency but also causes a risk of chipping. Compared with the prior art, the bonding adhesive has the advantages that different curing mechanisms are adopted, the overflowing part exists in a liquid form, the overflowing part is mechanically removed through the subsequent process, the phenomenon that the wafer is damaged in the process of removing the adhesive film can be completely eliminated, the yield is improved, automatic operation can be realized, and the labor cost is reduced. After the edge glue overflow is removed, the wafer is ground into a target thickness in a water medium through a grinding wheel, then the glass slide is removed through processes of ion injection and the like, laser key release is carried out, and then the bonding glue is stripped through an adhesive tape to obtain a clean wafer.
The third aspect of the present invention provides a method for using a wafer bonding adhesive, comprising: the wafer bonding glue is coated on the wafer in a spinning mode, the wafer bonding glue is matched with a glass sheet with a laser release layer in a vacuum cavity, the wafer and the glass slide are bonded through the bonding glue under the oxygen-free effect, the active free radicals cause double bond reaction due to the oxygen-free effect of the bonding part, the edge glue pressed out by the glass slide is in contact with oxygen and is not solidified, the back face thinning process is started through washing of the automatic cleaning process, after the required process is completed, laser bonding is carried out, the glass slide is removed, and the bonding glue is completely removed from the wafer through a peeling adhesive tape.
Compared with the prior art, the invention has the following beneficial effects:
for prior art attenuate technology bonding glue adopts photocuring or thermosetting mode, has the problem that the difficulty was got rid of to excessive glue, uses bonding glue in this application, adopts the room temperature curing mode, washs the marginal uncured bonding glue, not only the energy is saved on the curing mode, and later stage excessive glue problem also obtains solving effectively.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
Example 1
A wafer bonding adhesive is prepared from 47 g of diethylene glycol diacrylate, 0.6 g of N, N-dimethyl-p-toluidine, 0.4 g of 1, 4-hydroquinone, 51 g of polyurethane resin and 2 g of cumene hydroperoxide. Wherein the polyurethane resin is made from Guangxi Pop new materials, inc. with the brand number PS0903-1.
The preparation method comprises the following steps:
(1) Starting the stirring kettle, adding diethylene glycol diacrylate, N-dimethyl-p-toluidine and 1, 4-hydroquinone, stirring for 30min, fully dissolving the solid, and uniformly mixing.
(2) Heating the stirring kettle to 40 ℃, adding the polyurethane resin, and stirring for 45min.
(3) The temperature was reduced to room temperature and cumene hydroperoxide was added.
(4) Mixing, vacuumizing for 30min, and canning.
The use method of the wafer bonding adhesive comprises the following steps:
the method comprises the steps of spin-coating bonding glue on a wafer, uniformly spin-coating, matching with a glass sheet with a laser release layer in a vacuum cavity, solidifying the wafer and the glass slide, washing through an automatic cleaning process, starting to enter a back thinning process, after the required process is completed, laser de-bonding, removing the glass slide, and completely removing the bonding glue from the wafer by using a stripping adhesive tape.
Example 2
A wafer bonding adhesive is prepared from 52 g of diethylene glycol diacrylate, 0.6 g of N, N-dimethyl-p-toluidine, 0.4 g of 1, 4-hydroquinone, 46 g of polyurethane resin and 2 g of cumene hydroperoxide.
The preparation method and the using method of the wafer bonding adhesive are the same as those of the embodiment 1.
Comparative example 1
A wafer bonding adhesive is prepared from 47 g of diethylene glycol diacrylate, 0.4 g of 1, 4-hydroquinone, 41 g of polyurethane resin and 2.6 g of cumene hydroperoxide.
The preparation method of the wafer bonding adhesive comprises the following steps:
(1) Starting the stirring kettle, adding diethylene glycol diacrylate and 1, 4-hydroquinone, stirring for 30min, fully dissolving the solid, and uniformly mixing.
(2) Heating the stirring kettle to 40 ℃, adding the polyurethane resin, and stirring for 45min.
(3) The temperature was reduced to room temperature and cumene hydroperoxide was added.
(4) Mixing, vacuumizing for 30min, and canning.
Performance evaluation
1. Peeling force: and (3) testing environment: the temperature is 23 +/-2 ℃; and (3) coating bonding glue on a 25mm silicon plate by using a wire rod with the relative humidity of 50 +/-5%, then covering the bonding glue by using a 50-micron frosted PET film, standing for 20min, starting an electronic tensile testing machine, and selecting a 180-degree stripping force test with the stripping speed of 300mm/min.
2. Curing time: the wire rod coats the bonding glue on a 25mm silicon plate, the silicon plate is covered by frosted PET with the thickness of 50 mu m, the silicon plate is placed for different time, the mechanical property is kept stable for a certain time, and the time is the curing time.
3. Elongation at break: pouring the bonding glue into a sample tank coated with a release agent, vacuumizing to remove bubbles, covering the upper surface of the sample tank with a ground glass cover plate, placing the sample tank in a 30-DEG C oven for 1 hour, dismantling a mold, polishing flaws, and keeping the temperature at 23 +/-2 ℃; and (5) starting an electric tension tester to select elongation at break for testing, wherein the relative humidity is 50% +/-5%.
TABLE 1
Peel force (N) Curing time (min) Elongation at Break (%)
Example 1 0.15 20 28
Example 2 0.19 20 36
Comparative example 0.09 20 18
Through a large number of tests and client verification, the curing time is 20min and relatively meets the process requirements, when the stripping force is about 0.15N, the wafer can be ensured not to fall off during thinning, the wafer is protected from being damaged in the process of removing bonding glue, and the yield of bond breaking is improved by 0.8% compared with that of a comparative example. The bonding adhesive is cured at normal temperature, so that energy consumption can be saved, and compared with the conventional thermal curing and light curing mode of the semiconductor thinning process, the bonding adhesive is different from the conventional thermal curing and light curing mode of the semiconductor thinning process, the bonding adhesive can save 50 w.h energy consumption for thermally curing each wafer; compared with photocuring, the method can save 10 w.h; edge overflow glues because do not solidify, can be with mechanical automation washing edge, get rid of the bonding with the sticky tape and glue the in-process, improved the yield of wafer greatly, moreover for the manual work strikes off the edge comparatively, a machine saves a manual work.

Claims (10)

1. The wafer bonding adhesive is characterized in that the preparation raw materials comprise, by weight, 40-60 parts of difunctional acrylate monomer, 35-65 parts of polyurethane resin, 0.1-2 parts of accelerator, 0.1-2 parts of stabilizer and 0.5-5 parts of initiator.
2. The wafer bonding adhesive of claim 1, wherein the difunctional acrylate monomer is selected from one or more of diethylene glycol diacrylate, hexanediol diacrylate, 1, 3-butanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate.
3. The wafer bonding adhesive according to claim 2, wherein the accelerator is one or more selected from the group consisting of N, N-dimethyl-p-toluidine, tetramethylthiourea, N-dihydroxyethyl-p-toluidine, and N, N-diethyl-p-toluidine.
4. The wafer bonding paste according to any one of claims 1 to 3, wherein the stabilizer is a hindered phenol type stabilizer.
5. The wafer bonding tape according to claim 4, wherein the initiator is selected from one or more of organic peroxide initiator, inorganic peroxide initiator, and azo initiator.
6. The wafer bonding adhesive according to claim 5, wherein the organic peroxide initiator is selected from one or more of cumene hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate and diisopropyl peroxydicarbonate.
7. The wafer bonding adhesive according to any one of claims 1 to 3, wherein the polyurethane is PS0903-1.
8. A method for preparing a wafer bonding paste according to any one of claims 1 to 7, comprising the steps of:
(1) Mixing and stirring difunctional acrylate monomer, accelerator and stabilizer;
(2) Heating to 30-50 deg.C, adding polyurethane resin, and stirring;
(3) Cooling, and adding an initiator;
(4) Mixing completely, and vacuumizing.
9. The method for preparing the wafer bonding paste according to claim 8, comprising the steps of:
(1) Mixing difunctional acrylate monomer, accelerator and stabilizer, and stirring for 30min;
(2) Heating to 40 ℃, adding polyurethane resin, and stirring for 45min;
(3) Cooling to room temperature, and adding an initiator;
(4) Mixing completely, and vacuumizing for 30 min.
10. A method of using the wafer bonding paste according to any one of claims 1 to 7, comprising: the wafer bonding glue is coated on a wafer in a spinning mode, the wafer bonding glue is matched with a glass sheet with a laser release layer in a vacuum cavity, after the bonding glue between the wafer and the glass slide glass is subjected to oxygen-free initiation of cross-linking curing, edge glue is pressed out due to gravity of the glass slide glass and is not cured when being contacted with oxygen, the wafer is washed through an automatic cleaning process, the back face thinning process is started, after the back process of the wafer is completed, the glass slide glass is separated from the wafer stuck with the bonding glue, and the bonding glue on the wafer is peeled off through an adhesive tape.
CN202210969107.1A 2022-08-12 2022-08-12 Wafer bonding adhesive, preparation method and use method thereof Pending CN115322691A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199659A (en) * 2015-10-15 2015-12-30 烟台德邦科技有限公司 Curable adhesive for temporary bonding of wafer grinding
CN107502274A (en) * 2017-09-25 2017-12-22 广州双科新材料有限公司 One-component boiling glue and preparation method thereof
CN109722186A (en) * 2018-12-03 2019-05-07 云南光电辅料有限公司 A kind of alcohol-soluble is temporarily bonded glue and preparation method thereof
CN111205809A (en) * 2020-02-27 2020-05-29 南宁珀源能源材料有限公司 Rod adhesive for cutting solar silicon wafer and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105199659A (en) * 2015-10-15 2015-12-30 烟台德邦科技有限公司 Curable adhesive for temporary bonding of wafer grinding
CN107502274A (en) * 2017-09-25 2017-12-22 广州双科新材料有限公司 One-component boiling glue and preparation method thereof
CN109722186A (en) * 2018-12-03 2019-05-07 云南光电辅料有限公司 A kind of alcohol-soluble is temporarily bonded glue and preparation method thereof
CN111205809A (en) * 2020-02-27 2020-05-29 南宁珀源能源材料有限公司 Rod adhesive for cutting solar silicon wafer and preparation method thereof

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