Adhesive composition, laminate, and method for manufacturing processed semiconductor substrate
Patent Information
- Application Number
- CN202580024340.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Priority Date
- 2024-03-27
- Filing Date
- 2025-03-26
- Publication Date
- 2026-10-30
AI Technical Summary
但是,在半导体晶片的背面研磨时,因研磨应力而脱离或偏移,这是不优选的
根据本发明,能提供在使用了红外线激光的剥离中不花费处理时间、对基体的损伤少且清洗性良好的粘接剂组合物、使用了该粘接剂组合物的层叠体、以及使用了所述层叠体的经加工的半导体基板或电子器件层的制造方法。
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Figure CN123022772A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to adhesive compositions, laminates, and methods for manufacturing processed semiconductor substrates. Background Technology
[0002] In contrast to semiconductor wafers traditionally integrated in a two-dimensional planar direction, semiconductor integration technology aims for further integration by stacking the planar material in a three-dimensional direction. This three-dimensional stacking is a technique that integrates multiple layers while simultaneously connecting them via through-silicon vias (TSVs). During multi-layer integration, the back side (opposite to the circuit surface) of each wafer to be integrated is thinned through grinding, and the thinned semiconductor wafers are then stacked.
[0003] Before thinning, the semiconductor wafer (hereinafter referred to as the wafer) is bonded to a support for polishing using a polishing apparatus. This bonding must be easily detachable after polishing; therefore, it is called a temporary bond. This temporary bond must be easily detachable from the support. When applying significant force for detachment, the thinned semiconductor wafer may sometimes be cut or deformed; easy detachment is necessary to prevent this. However, during polishing of the back side of the semiconductor wafer, detachment or displacement due to polishing stress is undesirable. Therefore, the desired performance of a temporary bond is: resistance to the stress during polishing and easy detachment after polishing.
[0004] As temporary adhesives for such temporary bonding, adhesives containing polydimethylsiloxane (Patent Document 1) and temporary adhesives containing epoxy-modified polysiloxane (Patent Document 2) have been proposed. In these technologies, the separation of the support from the semiconductor wafer is performed by inserting the sharp part of a device with a pointed tip, called a debonder, into the layer of the temporary adhesive.
[0005] On the other hand, a method for separating the support from the semiconductor wafer using infrared light was proposed.
[0006] For example, an infrared peeling adhesive composition has been proposed, which is an infrared peeling adhesive composition that can be peeled by irradiation with infrared light, containing a component (A) that is cured by a hydrogenation silanization reaction, and a component (B) selected from at least one of the following groups: a component containing an epoxy-modified polyorganosiloxane, a component containing a methyl-containing polyorganosiloxane, and a component containing a phenyl-containing polyorganosiloxane (Patent Document 3).
[0007] Furthermore, a method for peeling a laminate is proposed, comprising: a first step, wherein when a laminate is formed by bonding a first substrate made of a semiconductor forming substrate and a second substrate made of a support substrate that transmits infrared laser light through a first adhesive layer disposed on the first substrate side and a second adhesive layer disposed on the second substrate side, the first adhesive layer is configured as an adhesive layer obtained by curing an adhesive (A) containing components that are cured by a hydrogenation silanization reaction, and the second adhesive layer is configured as an adhesive layer that transmits infrared laser light, obtained by using an adhesive (B) that is a polymeric adhesive having an aromatic ring in at least one of the main chain and side chain; and a second step, wherein the infrared laser light is irradiated from the second substrate side of the laminate, and peeling is performed between the first adhesive layer and the second adhesive layer (Patent Document 4).
[0008] In infrared peeling, the adhesive is degraded by irradiating it with infrared light, making it easier to peel off.
[0009] Existing technical documents Patent documents Patent Document 1: International Publication No. 2017 / 221772 Patent Document 2: International Publication No. 2018 / 216732 Patent Document 3: International Publication No. 2020 / 100966 Patent Document 4: International Publication No. 2020 / 100965 Summary of the Invention
[0010] The problem that the invention aims to solve The peeling process using a device with a pointed tip, as described in Patent Documents 1 and 2, requires a certain degree of insertion force, which can sometimes lead to problems such as processing time and damage to the semiconductor wafer or support substrate.
[0011] In the technologies described in Patent Documents 3 and 4, sufficient infrared laser irradiation is required for easy peeling. However, in this case, problems may arise due to processing time and decreased cleanability caused by adhesive deterioration.
[0012] The object of the present invention is to provide an adhesive composition that does not require processing time in the peeling process using infrared laser, causes little damage to the substrate and has good cleaning properties, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or electronic device layer using the laminate.
[0013] Solution for solving the problem The inventors conducted in-depth research to solve the aforementioned technical problem and found that the technical problem could be solved, thus completing the present invention with the following main objectives.
[0014] That is, the present invention includes the following.
[0015] [1] An adhesive composition for forming an adhesive layer, the adhesive layer being used for: processing the first substrate having a first substrate, a second substrate and the adhesive layer, irradiating the adhesive layer with an infrared laser from the second substrate side, and then separating the first substrate from the second substrate, the first substrate being a semiconductor substrate or an electronic device layer, the second substrate being a support substrate for transmitting infrared laser, the adhesive layer being disposed between the first substrate and the second substrate, the adhesive composition containing a release agent component, an infrared absorber and an adhesive component having siloxane bonds.
[0016] [2] The adhesive composition according to [1], wherein the adhesive component is a component that is cured by a hydrosilylation reaction.
[0017] [3] According to the adhesive composition of [2], wherein the component cured by the hydrogen silanization reaction contains: a component having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms (A-1); and a component having a Si-H group (A-2).
[0018] [4] According to the adhesive composition of [3], wherein the component (A-1) contains: a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.
[0019] [5] The adhesive composition according to [3] or [4], wherein the component (A-2) contains: a polyorganosiloxane having a Si-H group.
[0020] [6] An adhesive composition according to any one of [1] to [5], wherein the release agent is a polyorganosiloxane.
[0021] [7] An adhesive composition according to any one of [1] to [6], wherein the insertion force required to insert the sharp portion of the device having the sharp portion between the first substrate and the second substrate after irradiating the adhesive layer with the infrared laser and to separate the first substrate from the second substrate is smaller than the insertion force required to insert the sharp portion between the first substrate and the second substrate and to separate the first substrate from the second substrate after irradiating the adhesive layer with the infrared laser.
[0022] [8] A laminate comprising: a first substrate, which is a semiconductor substrate or an electronic device layer; a second substrate, which is a support substrate for transmitting infrared laser light; and an adhesive layer disposed between the first substrate and the second substrate, the adhesive layer being an adhesive layer formed from an adhesive composition as described in any one of [1] to [7].
[0023] [9] A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: a processing step of processing a first substrate of a laminate as described in [8]; and a separation step of irradiating the adhesive layer with an infrared laser from the second substrate side, and then separating the processed first substrate from the second substrate.
[0024]
[10] According to the manufacturing method of the processed semiconductor substrate or electronic device layer described in [9], by irradiating the adhesive layer with the infrared laser, the insertion force required to insert the sharp part of the device having the sharp part between the first substrate and the second substrate and to separate the first substrate and the second substrate is reduced compared with the case where the adhesive layer is not irradiated with the infrared laser.
[0025] Invention Effects According to the present invention, an adhesive composition that does not require processing time in the peeling process using infrared laser, causes minimal damage to the substrate and has good cleaning properties, a laminate using the adhesive composition, and a method for manufacturing a processed semiconductor substrate or electronic device layer using the laminate are provided. Attached Figure Description
[0026] Figure 1 This is a schematic cross-sectional view of an example of a laminate in the first embodiment.
[0027] Figure 2A This is a schematic cross-sectional view (one of the views) used to illustrate a method for manufacturing a laminated body representing an example of a first embodiment.
[0028] Figure 2B This is a schematic cross-sectional view (second one) used to illustrate a method for manufacturing a laminated body representing an example of the first embodiment.
[0029] Figure 3 This is a schematic cross-sectional view of an example of a laminate in the second embodiment.
[0030] Figure 4A This is a schematic cross-sectional view (one of the views) used to illustrate a method for manufacturing a laminate, representing an example of a second embodiment.
[0031] Figure 4BThis is a schematic cross-sectional view (second one) used to illustrate a method for manufacturing a laminated body representing an example of a second embodiment.
[0032] Figure 4C This is a schematic cross-sectional view (third one) used to illustrate a method for manufacturing a laminated body representing an example of the second embodiment.
[0033] Figure 5A This is a schematic cross-sectional view (one of the views) used to illustrate the processing method of a laminated body representing an example of a first embodiment.
[0034] Figure 5B This is a schematic cross-sectional view (second one) used to illustrate the processing method of a laminated body representing an example of the first embodiment.
[0035] Figure 5C This is a schematic cross-sectional view (third one) used to illustrate the processing method of a laminated body representing an example of the first embodiment.
[0036] Figure 5D This is a schematic cross-sectional view (fourth one) used to illustrate the processing method of a laminated body representing an example of the first embodiment.
[0037] Figure 5E This is a schematic cross-sectional view (fifth) used to illustrate the processing method of a laminated body representing an example of the first embodiment.
[0038] Figure 6A This is a schematic cross-sectional view (one of the views) used to illustrate the processing method of a laminated body representing an example of the second embodiment.
[0039] Figure 6B This is a schematic cross-sectional view (second one) used to illustrate the processing method of a laminated body representing an example of the second embodiment.
[0040] Figure 6C This is a schematic cross-sectional view (third one) used to illustrate the processing method of a laminated body representing an example of the second embodiment.
[0041] Figure 6D This is a schematic cross-sectional view (fourth one) used to illustrate the processing method of a laminated body representing an example of the second embodiment.
[0042] Figure 6E This is a schematic cross-sectional view (fifth) used to illustrate the processing method of a laminated body representing an example of the second embodiment.
[0043] Figure 6FThis is a schematic cross-sectional view (sixth) used to illustrate the processing method of a laminated body representing an example of the second embodiment.
[0044] Figure 6G This is a schematic cross-sectional view (seventh) used to illustrate the processing method of a laminated body representing an example of the second embodiment. Detailed Implementation
[0045] (Adhesive composition) The adhesive composition of the present invention contains a release agent, an infrared absorber, and an adhesive component having siloxane bonds.
[0046] The adhesive composition is an adhesive composition for forming an adhesive layer, said adhesive layer being used to: process a first substrate in a laminate, irradiate the adhesive layer with an infrared laser from the second substrate side, and then separate the first substrate from the second substrate.
[0047] The laminate has a first substrate, a second substrate, and an adhesive layer. The first substrate is a semiconductor substrate or an electronic device layer, the second substrate is a support substrate for transmitting infrared laser light, and the adhesive layer is disposed between the first substrate and the second substrate.
[0048] In the present invention, in the formation of the adhesive layer in a laminate having a first substrate, a second substrate, and an adhesive layer disposed between the first substrate and the second substrate, an adhesive composition (an adhesive composition containing a release agent component) that can be peeled off by a tool having a sharp part is used.
[0049] By using such an adhesive composition for the separation of a first substrate and a second substrate using infrared laser, the first substrate and the second substrate can be separated with a small amount of infrared laser irradiation. This eliminates processing time. Furthermore, it eliminates the need for peeling with sharp-pointed instruments, or reduces insertion force even when using instruments with sharp points, thus minimizing damage to the substrate adjacent to the adhesive layer. Moreover, while the adhesive layer deteriorates due to the absorption of infrared laser by the adhesive component with siloxane bonds, making the first substrate and the second substrate easier to separate, excessive deterioration of the adhesive layer caused by infrared laser is avoided by the presence of an infrared absorber in the adhesive composition. Because of minimal deterioration of the adhesive layer, it exhibits good cleanability.
[0050] It should be noted that the adhesive compositions described in Patent Documents 3 and 4, for example, contain components including epoxy-modified polyorganosiloxane, but are not necessarily adhesive compositions that can be peeled off using devices with sharp points, and therefore differ from the adhesive compositions of the present invention.
[0051] In this invention, it is preferable that the insertion force (Fb) required to insert the sharp part of the device having the sharp part between the first substrate and the second substrate and to separate the first substrate and the second substrate after irradiating the adhesive layer with an infrared laser is smaller than the insertion force (Fa) required to insert the sharp part between the first substrate and the second substrate and to separate the first substrate and the second substrate after irradiating the adhesive layer with an infrared laser.
[0052] Insertion force is expressed as an absolute value.
[0053] As the insertion force (Fa), examples can be listed as 0.1N to 100N.
[0054] The ratio of insertion force (Fa) to insertion force (Fb) (Fb / Fa) is not particularly limited, but is preferably less than 1.0, more preferably 0.9 or less, and even more preferably 0.6 or less.
[0055] There are no special restrictions on the lower limit of the ratio (Fb / Fa). The ratio (Fb / Fa) can be greater than 0.01, greater than 0.05, or greater than 0.1.
[0056] The insertion force is measured, for example, in the following manner.
[0057] After temporarily bonding a semiconductor substrate or electronic device layer to a support substrate using an adhesive layer to obtain a laminate, a peeling device is used to peel it off. During peeling, a replacement blade (manufactured by ESCO; blade thickness 0.2 mm) is mounted on the front end of a Newton's meter. The replacement blade is inserted parallel to the substrate into the adhesive layer formed by bonding the semiconductor substrate or electronic device layer to the support substrate, forming the starting point for peeling. At this point, a force gauge is used to measure the maximum force required to insert the blade, which is taken as the insertion force.
[0058] Insertion force can be measured using, for example, a force gauge or a texture analyzer. The force gauge value representing the insertion force is an absolute value.
[0059] <Adhesive Composition> There are no particular limitations on the adhesive component, but it is preferred to be a component that is cured, and more preferably a component that is cured by a hydrosilylation reaction.
[0060] There are no particular limitations on the components that are cured by the hydrosilylation reaction, but it is preferred to contain: a component having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms (hereinafter sometimes referred to as "component (A-1)"), a component having a Si-H group (hereinafter sometimes referred to as "component (A-2)"), and a platinum group metal catalyst (A-3).
[0061] <<Ingredients (A-1) and Ingredients (A-2)>> The adhesive composition preferably contains component (A-1).
[0062] The adhesive composition preferably contains component (A-2).
[0063] Hereinafter, the combination of component (A-1), component (A-2) and platinum group metal catalyst (A-3) will sometimes be referred to as "component (A) for curing" or "component (A)".
[0064] From the viewpoint of properly obtaining the effects of the present invention, component (A-1) preferably contains: a polyorganosiloxane (a1) having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.
[0065] From the viewpoint of properly obtaining the effects of the present invention, component (A-2) preferably contains: a polyorganosiloxane having Si-H groups (a2).
[0066] In this process, alkenyl groups with 2 to 40 carbon atoms are optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, and heteroaryl groups.
[0067] In another preferred embodiment, the adhesive composition cured by a hydrosilylation reaction comprises a polysiloxane (A1) and a platinum group metal catalyst (A-3), wherein the polysiloxane (A1) comprises siloxane units (Q units) selected from SiO2, R... 1 R 2 R 3 SiO 1 / 2 The siloxane unit (M unit) and R shown are shown. 4 R 5 SiO 2 / 2 The siloxane unit (D unit) and R shown are shown. 6 SiO 3 / 2 The polysiloxane (A1) comprises one or more units from the group consisting of the shown siloxane units (T units), and the polysiloxane (A1) includes polyorganosiloxane (a1') and polyorganosiloxane (a2'), wherein the polyorganosiloxane (a1') comprises siloxane units (Q' units) selected from SiO2, R 1 'R 2 'R 3 'SiO 1 / 2 The siloxane unit (M' unit) and R shown are shown. 4 'R 5 'SiO 2 / 2 The siloxane unit (D' unit) and R shown are shown. 6 'SiO 3 / 2The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of siloxane units (T' units) shown, and includes at least one unit selected from the group consisting of M' units, D' units, and T' units. 1 "R 2 "R 3 "SiO" 1 / 2 The siloxane unit (M” unit) and R shown are shown. 4 "R 5 "SiO" 2 / 2 The siloxane unit (D” unit) and R shown are shown. 6 "SiO" 3 / 2 The siloxane unit (T” unit) shown is one or more units from the group consisting of the siloxane unit (T” unit), and includes at least one unit selected from the group consisting of the M” unit, the D” unit and the T” unit.
[0068] It should be noted that (a1') is an example of (a1), and (a2') is an example of (a2).
[0069] R 1 ~R 6 The groups or atoms bonded to silicon atoms are each independently represented by an optionally substituted alkyl group, an optionally substituted alkenyl group, or a hydrogen atom. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.
[0070] R 1 '~R 6 'A group bonded to a silicon atom, each independently representing an optionally substituted alkyl or optionally substituted alkenyl group, R 1 '~R 6 At least one of the groups is an alkenyl group that is optionally substituted. Examples of substituents include halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.
[0071] R 1 "~R 6 "R represents a group or atom bonded to a silicon atom, each independently representing an optionally substituted alkyl or hydrogen atom." 1 "~R 6 At least one of the elements is a hydrogen atom. Examples of substituents include: halogen atoms, nitro groups, cyano groups, amino groups, hydroxyl groups, carboxyl groups, aryl groups, heteroaryl groups, etc.
[0072] The alkyl group can be any type of straight-chain, branched, or cyclic, with straight-chain or branched alkyl groups being preferred. The number of carbon atoms is not particularly limited, but is usually 1 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
[0073] Specific examples of linear or branched alkyl groups that may be optionally substituted include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1- Dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, etc., but not limited to these, generally have 1 to 14 carbon atoms, preferably 1 to 10, more preferably 1 to 6. Among them, methyl is particularly preferred.
[0074] Specific examples of optionally substituted cyclic alkyl groups include: cyclopropyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, cyclopentyl, 1-methyl-cyclobutyl, 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3-dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl - Cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl and other cycloalkyl groups; dicyclobutyl, dicyclopentyl, dicyclohexyl, dicycloheptyl, dicyclooctyl, dicyclononyl, dicyclodecyl and other dicycloalkyl groups, but not limited to these, and the number of carbon atoms is usually 3 to 14, preferably 4 to 10, and more preferably 5 to 6.
[0075] The alkenyl group can be any type of linear or branched chain, and its number of carbon atoms is not particularly limited, usually 2 to 40, preferably 30 or less, more preferably 20 or less, and even more preferably 10 or less.
[0076] Specific examples of linear or branched alkenyl groups that may be optionally substituted include vinyl, allyl, butenyl, pentenyl, etc., but are not limited to these, and the number of carbon atoms is usually 2 to 14, preferably 2 to 10, and more preferably 1 to 6. Among these, vinyl and 2-propenyl are particularly preferred.
[0077] Specific examples of cyclic alkenyl groups that may be optionally substituted include cyclopentenyl, cyclohexenyl, etc., but are not limited to these. The number of carbon atoms is usually 4 to 14, preferably 5 to 10, and more preferably 5 to 6.
[0078] As described above, the polysiloxane (A1) comprises polyorganosiloxane (a1') and polyorganosiloxane (a2'). The alkenyl group contained in the polyorganosiloxane (a1') and the hydrogen atoms (Si-H groups) contained in the polyorganosiloxane (a2') form a cross-linked structure and are cured through a hydrosilylation reaction using a platinum group metal catalyst (A-3). The result is the formation of a cured film.
[0079] The polyorganosiloxane (a1') comprises one or more units selected from the group consisting of Q' units, M' units, D' units, and T' units, and includes at least one unit selected from the group consisting of M' units, D' units, and T' units. Two or more polyorganosiloxanes satisfying these conditions may also be used in combination as the polyorganosiloxane (a1').
[0080] Examples of preferred combinations of two or more selected from the group consisting of Q' unit, M' unit, D' unit and T' unit include: (Q' unit and M' unit), (D' unit and M' unit), (T' unit and M' unit), (Q' unit, T' unit and M' unit), but are not limited to these.
[0081] Furthermore, when the polyorganosiloxanes contained in two or more polyorganosiloxanes (a1') are included, combinations of (Q' units and M' units) and (D' units and M' units), combinations of (T' units and M' units) and (D' units and M' units), and combinations of (Q' units, T' units and M' units) and (T' units and M' units) are preferred, but not limited to these.
[0082] The polyorganosiloxane (a2') comprises one or more units selected from the group consisting of Q" units, M" units, D" units, and T" units, and comprises at least one unit selected from the group consisting of M" units, D" units, and T" units. As a polyorganosiloxane (a2'), two or more polyorganosiloxanes satisfying such conditions may also be used in combination.
[0083] Examples of preferred combinations of two or more selected from the group consisting of Q", M", D" and T" units include (M" unit and D" unit), (Q" unit and M" unit), and (Q" unit, T" unit and M" unit), but are not limited to these.
[0084] Polyorganosiloxanes (a1') are composed of siloxane units formed by the bonding of silicon atoms with alkyl and / or alkenyl groups, R 1 '~R 6 The proportion of alkenyl groups in all the substituents shown is preferably 0.1 to 50.0 mol%, more preferably 0.5 to 30.0 mol%, with the remainder being R 1 '~R 6 'It can be set as an alkyl group.'
[0085] Polyorganosiloxanes (a2') are composed of siloxane units formed by the bonding of silicon atoms with alkyl and / or hydrogen atoms, R 1 "~R 6 The proportion of all substituents and hydrogen atoms in the substituted atoms shown is preferably 0.1 to 50.0 mol%, more preferably 10.0 to 40.0 mol%, with the remainder being R. 1 "~R 6 "It can be set as an alkyl group."
[0086] In the case where the adhesive composition comprises (a1) and (a2), in a preferred embodiment of the invention, the molar ratio of the alkenyl group contained in the polyorganosiloxane (a1) to the hydrogen atoms constituting the Si-H bond contained in the polyorganosiloxane (a2) is in the range of 1.0:0.5 to 1.0:0.66.
[0087] The weight-average molecular weight of polysiloxanes such as polyorganosiloxane (a1) and polyorganosiloxane (a2) is not particularly limited, and is usually 500 to 1,000,000. From the viewpoint of achieving the effect of the present invention with good reproducibility, it is preferably 5,000 to 50,000.
[0088] It should be noted that, in this invention, the weight-average molecular weight, number-average molecular weight, and dispersity of the polyorganosiloxane can be determined, for example, using a GPC apparatus (TOSOH Corporation EcoSEC, HLC-8320GPC) and a GPC column (TOSOH Corporation TSKgel SuperMultipore HZ-N, TSKgel SuperMultipore HZ-H), with the column temperature set to 40°C, tetrahydrofuran used as the eluent (dissolution solvent), the flow rate set to 0.35 mL / min, and polystyrene (Showa Denko Corporation, Shodex) used as the standard sample.
[0089] The viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are not particularly limited, and are typically 10 to 1,000,000 mPa·s, respectively. From the viewpoint of achieving the effects of the present invention with good reproducibility, 50 to 10,000 mPa·s is preferred. It should be noted that the viscosities of polyorganosiloxane (a1) and polyorganosiloxane (a2) are values measured using an E-type rotational viscometer at 25°C.
[0090] Polyorganosiloxane (a1) and polyorganosiloxane (a2) react with each other via a hydrosilylation reaction. Therefore, their curing mechanism is different from that of, for example, via silanol groups. Thus, any siloxane does not need to contain silanol groups, such as alkoxy groups, which are formed by hydrolysis to form silanol groups.
[0091] <<Platinum Group Metal Catalysts (A-3)>> Platinum group metal catalysts are metal catalysts based on the platinum group.
[0092] Such platinum-based metal catalysts are used to promote the hydrosilylation reaction of alkenes and Si-H groups.
[0093] As a specific example of a platinum-based metal catalyst, a substance known as a platinum-based compound (platinum or a compound containing platinum) can be used.
[0094] Specific examples include: platinum micro powder, platinum black, chloroplatinic acid, alcohol-modified chloroplatinic acid, complexes of chloroplatinic acid with dienes, platinum-olefin complexes, platinum-carbonyl complexes (such as bis(acetoacetic acid)platinum and bis(acetylacetone)platinum), chloroplatinic acid-alkenylsiloxane complexes (such as chloroplatinic acid-divinyltetramethyldisiloxane complex and chloroplatinic acid-tetravinyltetramethylcyclotetrasiloxane complex), platinum-alkenylsiloxane complexes (such as platinum-divinyltetramethyldisiloxane complex and platinum-tetravinyltetramethylcyclotetrasiloxane complex), and complexes of chloroplatinic acid with alkynyl alcohols. Among these, platinum-alkenylsiloxane complexes are particularly preferred due to their high promoting effect on the hydrogenation silylation reaction.
[0095] These hydrogen silanization reactions can use a single catalyst or a combination of two or more catalysts.
[0096] The alkenylsiloxane used in platinum-alkenylsiloxane complexes is not particularly limited, and examples include: 1,3-divinyl-1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetravinylcyclotetrasiloxane, alkenylsiloxane oligomers formed by substituting a portion of the methyl group of these alkenylsiloxanes with ethyl, phenyl, or the like, and alkenylsiloxane oligomers formed by substituting the vinyl group of these alkenylsiloxanes with allyl, hexenyl, or the like. In particular, 1,3-divinyl-1,1,3,3-tetramethyldisiloxane is preferred because of the good stability of the resulting platinum-alkenylsiloxane complexes.
[0097] The content of the platinum group metal catalyst (A-3) in the adhesive composition is not particularly limited, for example, it is in the range of 0.1 to 50.0 ppm relative to the total mass of components (A-1) and (A-2).
[0098] <<Polymer Inhibitors>> To inhibit the hydrosilylation reaction, the adhesive component may also contain polymerization inhibitors.
[0099] There are no particular limitations on polymerization inhibitors as long as they can inhibit the hydrosilylation reaction. Specific examples include 1-ethynyl-1-cyclohexanol, 1,1-diphenyl-2-propynyl-1-ol, and other alkynols.
[0100] There is no particular limitation on the amount of polymerization inhibitor. For example, from the viewpoint of obtaining its effect, it is usually above 1000.0 ppm relative to the total amount of polyorganosiloxane (a1) and polyorganosiloxane (a2), and usually below 10000.0 ppm from the viewpoint of preventing excessive inhibition of the hydrosilanization reaction.
[0101] The content of the adhesive component in the adhesive composition is not particularly limited. From the viewpoint of properly obtaining the effects of the present invention, it is preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 70% by mass or more, relative to the non-volatile components of the adhesive composition. As for the upper limit, there is no particular limitation, for example, it can be 95% by mass or less, 90% by mass or less, or 85% by mass or less.
[0102] The non-volatile components of an adhesive composition refer to components other than solvents in the adhesive composition.
[0103] <Stripping Agent Ingredients> There are no particular limitations on the components of the stripping agent, but from the viewpoint of obtaining the effects of the present invention more appropriately, polyorganosiloxanes are preferred.
[0104] Polysiloxanes used as release agents typically do not react with adhesive components.
[0105] For example, the polyorganosiloxane used as a stripping agent is a component that does not undergo hydrogenation silanization.
[0106] Polyorganosiloxanes typically contain siloxane units (D units), but can also contain Q units, M units, and T units. Examples include: cases consisting only of D units; combinations of D and Q units; combinations of D and M units; combinations of D and T units; combinations of D, Q, and M units; combinations of D, M, and T units; and so on.
[0107] As a polyorganosiloxane, there is no particular limitation. Examples include: polydimethylsiloxane, epoxy-containing polyorganosiloxane, phenyl-containing polyorganosiloxane, methanol-modified polyorganosiloxane, etc.
[0108] <<Polydimethylsiloxane>> The "polydimethylsiloxane" in this invention is different from epoxy-containing polydimethylsiloxane, phenyl-containing polydimethylsiloxane, methanol-modified polyorganosiloxane, etc. It is an unmodified polyorganosiloxane, which has methyl as an organic group bonded to silicon atoms.
[0109] As a specific example of polydimethylsiloxane, polydimethylsiloxanes represented by formula (M1) can be listed, but are not limited to this. (n4 represents the number of repeating units, which is a positive integer.) While the weight-average molecular weight of polydimethylsiloxane is not particularly limited, it is typically 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, its dispersibility is not particularly limited, but it is typically 1.0 to 10.0. From the viewpoint of achieving proper exfoliation with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersibility can be determined using the methods described above for polyorganosiloxanes.
[0110] The viscosity of polydimethylsiloxane is not particularly limited, and is typically 1,000 to 2,000,000 mm. 2 / s. It should be noted that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, denoted as centistokes (cSt) = mm. 2 / s. Alternatively, viscosity (mPa·s) can be divided by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be calculated from the kinematic viscosity (mm). 2 / s) = viscosity (mPa·s) / density (g / cm³) 3 The formula is used to calculate it.
[0111] <<Epoxy-containing Polyorganosiloxanes>> As epoxy-containing polyorganosiloxanes, examples include those containing R 11 R 12 SiO 2 / 2 The siloxane unit shown (D) 10 (Unit) Epoxy-containing polyorganosiloxanes.
[0112] R 11 The group that bonds to silicon atoms represents an alkyl group, R. 12 The group that bonds to silicon atoms represents an epoxy group or an organic group containing an epoxy group. Specific examples of alkyl groups can be listed above.
[0113] The epoxy group in an organic group containing an epoxy group can be an independent epoxy group without condensing with other rings, or it can be an epoxy group that forms a fused ring with other rings, like 1,2-epoxycyclohexyl.
[0114] Specific examples of organic groups containing epoxy groups include 3-epoxypropoxypropyl and 2-(3,4-epoxycyclohexyl)ethyl, but are not limited to these.
[0115] In this invention, a preferred example of an epoxy-containing polyorganosiloxane is an epoxy-containing polydimethylsiloxane, but it is not limited thereto.
[0116] Epoxy-containing polyorganosiloxanes contain the aforementioned siloxane units (D 10 (unit), but except for containing D 10 In addition to the unit, it may also include Q units, M units and / or T units.
[0117] In a preferred embodiment of the present invention, specific examples of epoxy-containing polyorganosiloxanes include: those consisting only of D 10 Polyorganosiloxanes composed of units; containing D 10 Polyorganosiloxanes containing D and Q units; 10 Polyorganosiloxanes containing D and M units; 10Polyorganosiloxanes containing D and T units; 10 Polyorganosiloxanes containing D, Q, and M units; 10 Polyorganosiloxanes containing D, M, and T units; 10 Polyorganosiloxanes with units such as Q-unit, M-unit, and T-unit.
[0118] Epoxy-containing polyorganosiloxanes can have epoxy groups on their side chains, on one end, or on both ends.
[0119] The epoxy-containing polyorganosiloxane is preferably a polydimethylsiloxane with an epoxy value of 0.1 to 5. Furthermore, its weight-average molecular weight is not particularly limited, but is typically 1,500 to 500,000, and preferably 100,000 or less from the viewpoint of suppressing precipitation in the composition.
[0120] Specific examples of epoxy-containing polyorganosiloxanes include those shown in formulas (E1) to (E3), but are not limited to these. (m1 and n1 represent the number of each repeating unit, which are positive integers.) (m2 and n2 represent the number of repeating units, which are positive integers, and R is an alkylene group with 1 to 10 carbon atoms that are optionally interrupted by at least one of oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bonds, carbon-carbon triple bonds, -N=N-).) (m3, n3, and o3 represent the number of repeating units, which are positive integers. R is an alkylene group with 1 to 10 carbon atoms that is optionally interrupted by at least one of oxygen atoms and unsaturated bonds (e.g., carbon-carbon double bonds, carbon-carbon triple bonds, -N=N-).) In the above general formula, when m1, m2, m3 and o3 are 2 or more, these repeating units can be arranged adjacently to form blocks, or they can be arranged randomly.
[0121] It should be noted that the polyorganosiloxane shown in formula (E3) is an epoxy-containing polyorganosiloxane because it contains both epoxy groups and phenyl groups, and it is also a phenyl-containing polyorganosiloxane. It should also be noted that epoxy-containing polyorganosiloxanes may or may not contain phenyl groups.
[0122] While the weight-average molecular weight of the epoxy-containing polyorganosiloxane is not particularly limited, it is typically 100,000 to 2,000,000. From the viewpoint of achieving the effects of the present invention with good reproducibility, it is preferably 200,000 to 1,200,000, and more preferably 300,000 to 900,000. Furthermore, its dispersity is not particularly limited, but it is typically 1.0 to 10.0. From the viewpoint of achieving appropriate peeling with good reproducibility, it is preferably 1.5 to 5.0, and more preferably 2.0 to 3.0. It should be noted that the weight-average molecular weight and dispersity can be determined using the methods described above for polyorganosiloxanes.
[0123] The viscosity of epoxy-containing polyorganosiloxanes is not particularly limited, and is typically 1,000 to 2,000,000 mm. 2 / s. It should be noted that the viscosity of epoxy-containing polyorganosiloxanes is expressed as kinematic viscosity, denoted as centistokes (cSt) = mm. 2 / s. This can be calculated by dividing viscosity (mPa·s) by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be calculated from the kinematic viscosity (mm). 2 / s) = viscosity (mPa·s) / density (g / cm³) 3 The formula is used to calculate it.
[0124] <<Phenyl-containing polyorganosiloxanes>> As phenyl-containing polyorganosiloxanes, examples include those containing R 31 R 32 SiO 2 / 2 The siloxane unit shown (D) 30 Polyorganosiloxane (unit).
[0125] R 31 The group that bonds to silicon atoms represents a phenyl or alkyl group, R. 32 The group that bonds to silicon atoms is represented by phenyl. Specific examples of alkyl groups can be listed above, with methyl being preferred.
[0126] Phenyl-containing polyorganosiloxanes contain the aforementioned siloxane units (D 30 (unit), but except for containing D 30 In addition to the unit, it may also include Q units, M units and / or T units.
[0127] In preferred embodiments, specific examples of phenyl-containing polyorganosiloxanes include: those consisting only of D 30 Polyorganosiloxanes composed of units; containing D 30 Polyorganosiloxanes containing D and Q units; 30Polyorganosiloxanes containing D and M units; 30 Polyorganosiloxanes containing D and T units; 30 Polyorganosiloxanes containing D, Q, and M units; 30 Polyorganosiloxanes containing D, M, and T units; 30 Polyorganosiloxanes with units of Q, M, and T.
[0128] Specific examples of phenyl-containing polyorganosiloxanes include those represented by formula (P1) or (P2), but are not limited to these. (m5 and n5 represent the number of each repeating unit, which are positive integers.) (m6 and n6 represent the number of each repeating unit, which are positive integers.) In the above general formula, when m5 and m6 are 2 or more, these repeating units can be arranged adjacently to form a block, or they can be arranged randomly.
[0129] <<Methanol-Modified Polyorganosiloxane>> There are no particular restrictions as it is a methanol-modified polyorganosiloxane.
[0130] Methanol-modified polyorganosiloxanes are polyorganosiloxanes with hydroxyl groups that are directly bonded to carbon atoms. Therefore, the methanol (carbinol) in "methanol-modified polyorganosiloxanes" is not limited to methanol in the narrow sense, but also includes methanol derivatives.
[0131] Methanol-modified polyorganosiloxanes, for example, methanol-modified polydimethylsiloxane.
[0132] The number of hydroxyl groups that are directly bonded to carbon atoms in methanol-modified polyorganosiloxanes is not particularly limited; it can be one or more.
[0133] Methanol-modified polyorganosiloxanes can have hydroxyl groups directly bonded to carbon atoms in their side chains, or hydroxyl groups directly bonded to carbon atoms in one end, or hydroxyl groups directly bonded to carbon atoms in both ends.
[0134] Methanol-modified polyorganosiloxanes preferably have hydroxyl groups directly bonded to carbon atoms in their side chains. In this case, even a small amount of methanol-modified polyorganosiloxane can impart good peelability to the adhesive layer formed from the adhesive composition.
[0135] Methanol-modified polyorganosiloxanes, for example, have groups represented by the following formula (Cg) as groups that are directly bonded to silicon atoms. (In formula (Cg), R 1 This indicates a group with one or more carbon atoms. * indicates a bond bonded to a silicon atom. In formula (Cg), the hydroxyl group is directly bonded to a carbon atom. The number of hydroxyl groups directly bonded to carbon atoms in the group represented by formula (Cg) can be one or more. For example, two, three, four, etc., can be listed.
[0136] As R 1 The number of carbon atoms is not particularly limited; for example, it can be 1 to 30, 1 to 20, or 1 to 10.
[0137] As the group represented by formula (Cg), for example, the groups represented by formulas (Cg-1) to (Cg-4) can be listed below. (In formula (Cg-1), R 11 It indicates an alkylene group having 1 to 6 carbon atoms that is optionally substituted with an alkoxy group having 1 to 3 carbon atoms.
[0138] In formula (Cg-2), R 12 R represents an alkylene group having 1 to 6 carbon atoms. 13 It refers to an alkylene group having 1 to 6 carbon atoms that is optionally substituted with an alkoxy or hydroxyl group having 1 to 3 carbon atoms.
[0139] In formula (Cg-3), R 14 R represents an alkylene group having 1 to 6 carbon atoms. 15 This indicates an alkylene group with 1 to 3 carbon atoms. m represents an integer from 1 to 10.
[0140] In formula (Cg-4), R 16 ~R 18 Each can be used independently to represent an alkylene group having 1 to 6 carbon atoms.
[0141] In formulas (Cg-1) to (Cg-4), * represents a bond bonded to a silicon atom. R 11 ~R 18 The alkylene groups can be linear, branched, or cyclic.
[0142] As a group represented by formula (Cg), the following groups can be listed as examples. (In the formula, m1 represents an integer from 2 to 10. * represents a bond bonded to a silicon atom.) Methanol-modified polyorganosiloxanes are represented, for example, by the following formula (CPS-1) or formula (CPS-2). (In formula (CPS-1), R) 51 Each can be represented independently as a hydrocarbon group. X 1 The group represented by the above formula (Cg) is indicated. n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1.
[0143] In formula (CPS-2), R 52 Each can be represented independently as a hydrocarbon group. X 2 X represents the group shown in the above formula (Cg). 3 This represents a hydrocarbon group or a group represented by the above formula (Cg). n3 represents an integer greater than or equal to 0. As R 51 R 52 and X 3 The hydrocarbon group in the form of the alkyl group can be exemplified by alkyl groups having 1 to 8 carbon atoms. Methyl groups are preferred as alkyl groups having 1 to 8 carbon atoms. That is, methanol-modified polyorganosiloxanes are preferably polydimethylsiloxanes represented by the formula (CPS-1a) or (CPS-2a). (In formula (CPS-1a), X) 1 The group represented by the above formula (Cg) is indicated. n1 represents an integer greater than or equal to 0. n2 represents an integer greater than or equal to 1.
[0144] In formula (CPS-2a), X 2 X represents the group shown in the above formula (Cg). 3 This represents a methyl group or a group represented by the above formula (Cg). n3 represents an integer greater than or equal to 0. It should be noted that the methanol-modified polyorganosiloxane shown in formula (CPS-1) and the methanol-modified polydimethylsiloxane shown in formula (CPS-1a) have hydroxyl groups in their side chains that are directly bonded to carbon atoms.
[0145] The methanol-modified polyorganosiloxane shown in formula (CPS-2) and the methanol-modified polydimethylsiloxane shown in formula (CPS-2a) have hydroxyl groups that are directly bonded to carbon atoms at one or both ends.
[0146] It should be noted that in the methanol-modified polyorganosiloxane shown in formula (CPS-1), when n2 is 2 or more, -Si(R 51 (X) 1The siloxane units shown in )-O- can be arranged adjacently to form blocks, or they can be arranged randomly.
[0147] Furthermore, in the methanol-modified polydimethylsiloxane shown in formula (CPS-1a), when n2 is 2 or more, -Si(CH3)(X 1 The siloxane units shown in )-O- can be arranged adjacently to form blocks, or they can be arranged randomly.
[0148] While the weight-average molecular weight of the methanol-modified polyorganosiloxane is not particularly limited, it is typically 500 to 1,000,000, and preferably 5,000 to 50,000 from the viewpoint of achieving the effects of the present invention with good reproducibility. Furthermore, its dispersibility is not particularly limited, but typically 1.0 to 10.0, and preferably 1.5 to 5.0, more preferably 2.0 to 3.0, from the viewpoint of achieving appropriate exfoliation with good reproducibility.
[0149] The viscosity of methanol-modified polyorganosiloxanes is not particularly limited, and is typically 100–200,000 mm. 2 / s. It should be noted that the viscosity of polydimethylsiloxane is expressed as kinematic viscosity, denoted as centistokes (cSt) = mm. 2 / s. Alternatively, viscosity (mPa·s) can be divided by density (g / cm³). 3 The value can be determined from the viscosity and density measured at 25°C using a type E rotational viscometer, and can be calculated from the kinematic viscosity (mm). 2 / s) = viscosity (mPa·s) / density (g / cm³) 3 The formula is used to calculate it.
[0150] Polyorganosiloxanes used as stripping agents can be used alone or in combination of two or more. Here, "two or more polyorganosiloxanes" refers to, for example, a combination of polydimethylsiloxane and an epoxy-containing polyorganosiloxane, or a combination of polydimethylsiloxane and a phenyl-containing polyorganosiloxane, etc., and does not refer to a combination of two epoxy-containing polyorganosiloxanes with different molecular weights, viscosities, or types of epoxy groups.
[0151] The polyorganosiloxane used as a stripping agent component (B) can be a commercially available product or a synthetic product.
[0152] Commercially available polysiloxanes include, for example, the WACKERSILICONE FLUID AK series (AK 50, AK 350, AK 1000, AK 10000, AK 1000000) and GENIOPLAST manufactured by Wacker Chemie. GUM; Dimethyl silicone oils (KF-96L, KF-96A, KF-96, KF-96H, KF-69, KF-965, KF-968) and cyclic dimethyl silicone oils (KF-995) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy-containing polysiloxanes (trade names CMS-227, ECMS-327, EMS-622) manufactured by Gelest Co., Ltd.; epoxy-containing polysiloxanes (KF-101, KF-1001, KF-1005, X-22-343) manufactured by Shin-Etsu Chemical Co., Ltd.; epoxy-containing polysiloxanes (DOWSIL) manufactured by Dow Toray Co., Ltd. BY16-839, DOWSIL8413, DOWSIL8411; phenyl-containing polyorganosiloxanes (PMM-1043, PMM-1025, PDM-0421, PDM-0821) manufactured by Gelest Corporation; phenyl-containing polyorganosiloxanes (KF50-3000CS) manufactured by Shin-Etsu Chemical Co., Ltd.; phenyl-containing polyorganosiloxanes (TSF431, TSF433) manufactured by MOMENTIVE Corporation, etc., but not limited to these.
[0153] In addition, commercially available methanol-modified polyorganosiloxanes include, for example: KF6000, KF6001, KF6002, KF6003, X-22-4039, and X-22-4015 manufactured by Shin-Etsu Silicones Co., Ltd.; DMS-C15, DMS-C16, DMS-C21, DMS-C23, DBE-C25, DBE-C22, DMS-CA21, DMS-CS26, CMS-221, CMS-222, CMS-832, CMS-626, MCR-C12, MCR-C18, MCR-C22, MCS-C11, MCS-C13, MCR-C61, MCR-C62, and MCR-C63 manufactured by Dow Toray Co., Ltd.; and DOWSIL BY 16-201 and DOWSIL BY 16-201 manufactured by Dow Toray Co., Ltd. SF 8427 Fluid, DOWSIL SF 8428 Fluid, etc.
[0154] The content of the release agent component in the adhesive composition is not particularly limited. From the viewpoint of properly obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.10% by mass or more, relative to the non-volatile components of the adhesive composition. As for the upper limit, there is no particular limitation, but for example, it is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less.
[0155] <Infrared absorber> As an infrared absorber, there are no particular limitations as long as it absorbs infrared radiation; it can be an inorganic material or an organic material.
[0156] It should be noted that in this invention, the "infrared absorber" is a component that is different from the adhesive and release agent components.
[0157] Infrared absorbers, for example, possess the function of transferring electrons and / or energy to other components through infrared excitation. Furthermore, they have the function of converting absorbed infrared radiation into heat. Infrared absorbers preferably exhibit maximum absorption in the wavelength region of 750–1400 nm. Examples of infrared absorbers include dyes or pigments, with dyes being preferred.
[0158] As dyes, commercially available dyes and well-known dyes listed in publications such as "Dye Handbook" (edited by the Organic Synthetic Chemistry Association, published in 1955) can be used. Specifically, examples include: azo dyes, metal complex salt azo dyes, pyrazolone azo dyes, naphthoquinone dyes, anthraquinone dyes, phthalocyanine dyes, carbomonium dyes, quinone imine dyes, methylene dyes, anthocyanine dyes, squaric acid cyanine pigments, pyranonium salts, and metal thiolate complexes.
[0159] Among the dyes, anthocyanin, squaric acid cyanin, and pyranonium salts are preferred, anthocyanin is more preferred, and pseudoindole anthocyanin is particularly preferred.
[0160] Specific examples of anthocyanins include: compounds described in paragraphs 0017 to 0019 of Japanese Patent Application Publication No. 2001-133969; compounds described in paragraphs 0016 to 0021 of Japanese Patent Application Publication No. 2002-023360; compounds described in paragraphs 0012 to 0037 of Japanese Patent Application Publication No. 2002-040638; preferably compounds described in paragraphs 0034 to 0041 of Japanese Patent Application Publication No. 2002-278057; compounds described in paragraphs 0080 to 0086 of Japanese Patent Application Publication No. 2008-195018; and particularly preferably compounds described in paragraphs 0035 to 0043 of Japanese Patent Application Publication No. 2007-90850.
[0161] Alternatively, compounds described in paragraphs 0008 to 0009 of Japanese Patent Application Publication No. 5-5005 and paragraphs 0022 to 0025 of Japanese Patent Application Publication No. 2001-222101 may be preferred.
[0162] As a pigment, compounds described in paragraphs 0072 to 0076 of Japanese Patent Application Publication No. 2008-195018 are preferred.
[0163] In addition to dyes or pigments, compounds that absorb infrared radiation can also be used.
[0164] As such compounds, compounds containing ester bonds or siloxane bonds as their chemical structure are preferred. Examples include acrylic resins, ester resins such as tannic acid, and organosilicon resins.
[0165] Infrared absorbers can be used alone or in combination with two or more.
[0166] The content of the infrared absorber in the adhesive composition is not particularly limited. From the viewpoint of properly obtaining the effects of the present invention, it is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.10% by mass or more, and particularly preferably 1% by mass or more, relative to the non-volatile components of the adhesive composition. As for the upper limit, there is no particular limitation, but for example, it is preferably 50% by mass or less, more preferably 40% by mass or less, even more preferably 30% by mass or less, and particularly preferably 20% by mass or less.
[0167] <Solvent> For purposes such as viscosity adjustment, adhesive compositions may contain solvents, such as aliphatic hydrocarbons, aromatic hydrocarbons, ketones, etc., but are not limited to these.
[0168] More specifically, examples include: hexane, heptane, octane, nonane, isononane, decane, undecane, dodecane, isododecane, menthol, limonene, toluene, xylene, mesitylene, cumene, MIBK (methyl isobutyl ketone), butyl acetate, diisobutyl ketone, 2-octanone, 2-nonanone, 5-nonanone, cyclohexanone, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc., but are not limited to these. Such solvents can be used alone or in combination of two or more.
[0169] When the adhesive composition contains a solvent, its content is appropriately set taking into account the desired viscosity of the composition, the coating method used, the thickness of the film produced, etc., and is in the range of about 10 to 90% by mass relative to the whole composition.
[0170] The viscosity of the adhesive composition used in this invention is not particularly limited, but is typically 500 to 20000 mPa·s at 25°C, preferably 1000 to 10000 mPa·s.
[0171] An example of the adhesive composition used in this invention can be manufactured by mixing component (A), release agent component (B), infrared absorber, and solvent.
[0172] It should be noted that when preparing adhesive compositions, appropriate heating can be applied within a range that will not cause the components to decompose or deteriorate.
[0173] In this invention, for the purpose of removing foreign matter, the solvent, solution, etc. used may be filtered using a filter or the like during the manufacturing of the adhesive composition or after all the components have been mixed.
[0174] (Layered structure) The laminate of the present invention has a first matrix, a second matrix, and an adhesive layer.
[0175] The first substrate is a semiconductor substrate or an electronic device layer.
[0176] The second substrate is a support substrate that allows infrared laser light to be transmitted.
[0177] An adhesive layer is disposed between the first substrate and the second substrate.
[0178] The adhesive layer is bonded to the first substrate and the second substrate.
[0179] The laminate of the present invention is used for temporary bonding during the processing of semiconductor substrates or electronic device layers, and can be appropriately used for processes such as thinning of semiconductor substrates or electronic device layers.
[0180] During the thinning and other processing of the semiconductor substrate, the semiconductor substrate is supported by a support substrate. On the other hand, after the semiconductor substrate is processed, the support substrate is separated from the semiconductor substrate.
[0181] Furthermore, during the thinning and other processing of the electronic device layer, the electronic device layer is supported by a support substrate. On the other hand, after the processing of the electronic device layer, the support substrate is subsequently separated from the electronic device layer.
[0182] After the semiconductor substrate or electronic device layer is separated from the support substrate, the residue remaining in the adhesive layer of the semiconductor substrate, electronic device layer or support substrate can be removed, for example, by a cleaning agent composition used for cleaning the semiconductor substrate, etc.
[0183] The cases are divided into those with a semiconductor substrate and those with an electronic device layer, which will be explained in detail below.
[0184] The first embodiment described below describes the case where the laminate has a semiconductor substrate, and the second embodiment described below describes the case where the laminate has an electronic device layer.
[0185] <First Implementation> A laminate containing a semiconductor substrate is used for the processing of the semiconductor substrate. During the processing of the semiconductor substrate, the semiconductor substrate is bonded to a support substrate. After the processing of the semiconductor substrate, the semiconductor substrate is separated from the support substrate.
[0186] <<Semiconductor Substrates>> As the main material constituting the semiconductor substrate, there are no particular limitations as long as it can be used for this purpose. Examples include: silicon, silicon carbide, compound semiconductors, and glass substrates with organic resins.
[0187] The shape of the semiconductor substrate is not particularly limited; for example, it can be disc-shaped. It should be noted that a disc-shaped semiconductor substrate does not need to have a completely circular surface. For example, the outer periphery of the semiconductor substrate can have a straight section called an orientation flat, or it can have a notch.
[0188] The thickness of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate, and there is no particular limitation. For example, it can be 500 to 1000 μm.
[0189] The diameter of the disc-shaped semiconductor substrate can be appropriately determined according to the intended use of the semiconductor substrate, and there is no particular limitation. For example, it can be 100 to 1000 mm.
[0190] Semiconductor substrates can also have bumps. Bumps refer to protruding terminals. For example, bumps can be electrodes.
[0191] In a laminate, where the semiconductor substrate has bumps, the semiconductor substrate has bumps on the support substrate side.
[0192] In semiconductor substrates, bumps are typically formed on the surface where circuitry is formed. The circuitry can be single-layered or multi-layered. There are no particular restrictions on the shape of the circuitry.
[0193] In a semiconductor substrate, the side opposite to the side with bumps (the back side) is the side to be processed.
[0194] There are no particular limitations on the material, size, shape, structure, or density of bumps on a semiconductor substrate.
[0195] Examples of bumps include: spherical bumps, printed bumps, stud bumps, plated bumps, etc.
[0196] Typically, the height, radius, and spacing of the bumps are determined appropriately based on the conditions that the bump height is approximately 1–200 μm, the bump radius is approximately 1–200 μm, and the bump spacing is approximately 1–500 μm.
[0197] Materials used for bumps include, for example, low-melting-point solder, high-melting-point solder, tin, indium, gold, silver, and copper. Bumps can be composed of a single component or multiple components. More specifically, examples include SnAg bumps, SnBi bumps, Sn bumps, AuSn bumps, and other alloy plating layers with Sn as the main component.
[0198] In addition, the bump can also have a stacked structure, which includes a metal layer composed of at least one of these components.
[0199] An example of a semiconductor substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 770 μm.
[0200] <<Support substrate>> As a support substrate, there are no particular limitations as long as it is a component that can support the semiconductor substrate during the processing of the semiconductor substrate and allows infrared laser to be transmitted. For example, silicon support substrates can be listed.
[0201] The shape of the support substrate is not particularly limited; for example, a disc shape can be cited. It should be noted that the disc-shaped support substrate does not need to have a completely circular surface. For example, the outer periphery of the support substrate may have a straight section called an orientation plane, or it may have a cutout called a groove.
[0202] The thickness of the disk-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, and there is no particular limitation. For example, it can be 500 to 1000 μm.
[0203] The diameter of the disc-shaped support substrate can be appropriately determined according to the size of the semiconductor substrate, etc., and there is no particular limitation. For example, it can be 100 to 1000 mm.
[0204] An example of a support substrate is a silicon wafer with a diameter of 300 mm and a thickness of about 700 μm.
[0205] <<Adhesive Layer>> An adhesive layer is disposed between the support substrate and the semiconductor substrate.
[0206] The adhesive layer may be bonded to a semiconductor substrate, for example. The adhesive layer may also be bonded to a support substrate, for example.
[0207] The adhesive layer is an adhesive layer formed from an adhesive composition.
[0208] The thickness of the adhesive layer in the laminate of the present invention is not particularly limited, and is generally 5 to 500 μm. From the viewpoint of maintaining film strength, it is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of avoiding non-uniformity caused by thick film, it is preferably 200 μm or less, more preferably 150 μm or less, even more preferably 120 μm or less, and even more preferably 100 μm or less.
[0209] The method for forming an adhesive layer from an adhesive composition is described in detail in the explanatory section of "A Method for Manufacturing an Example of a Laminate in the First Embodiment" described below.
[0210] Hereinafter, an example of the structure of the laminate of the first embodiment will be described using the accompanying drawings.
[0211] Figure 1 A schematic cross-sectional view showing an example of a laminated body according to the first embodiment.
[0212] Figure 1 The laminate sequentially comprises: a semiconductor substrate 1, an adhesive layer 2, and a support substrate 4. That is, the adhesive layer 2 is disposed between the semiconductor substrate 1 and the support substrate 4. The adhesive layer 2 is in contact with both the semiconductor substrate 1 and the support substrate 4.
[0213] <<Manufacturing Method of an Example of a Laminated Body in the First Embodiment>> In the laminated body of the first embodiment Figure 1 Taking the laminated body shown as an example, the manufacturing method of the laminated body will be explained below.
[0214] An example of the laminate of the present invention can be manufactured by a method including the following first step to second step.
[0215] The first step is to apply an adhesive composition onto a semiconductor substrate to form an adhesive coating layer.
[0216] The second step is to heat the adhesive coating layer to form the adhesive layer.
[0217] There are no particular limitations on the coating method of the adhesive composition; spin coating is usually used. It should be noted that the following method can be used: a coating film can be separately formed by spin coating or similar methods to form a sheet-like coating film, and then the sheet-like coating film can be pasted as an adhesive coating layer.
[0218] The heating temperature of the coated adhesive composition varies depending on the type and amount of adhesive components contained in the adhesive composition, whether it contains solvent, the boiling point of the solvent used, the desired thickness of the adhesive layer, etc., so it cannot be specified in general terms. It is usually 80 to 150°C, and the heating time is usually 30 seconds to 5 minutes.
[0219] When the adhesive composition contains a solvent, the coated adhesive composition is typically heated.
[0220] The thickness of the adhesive coating layer obtained by heating the coating composition, if necessary, is typically around 5 to 500 μm, appropriately determined in a manner that ultimately results in the aforementioned range of adhesive layer thickness.
[0221] In this invention, a load in the thickness direction of the semiconductor substrate and the support substrate can be applied while performing heat treatment or depressurization treatment, or both, followed by post-heat treatment, thereby obtaining the laminate of this invention. It should be noted that the choice between heat treatment, depressurization treatment, and which of the two treatment conditions is appropriate, taking into account various factors such as the type of adhesive composition, film thickness, and required adhesive strength.
[0222] From the viewpoint of removing solvent from the composition, the heat treatment is generally appropriately determined within the range of 20 to 160°C. In particular, from the viewpoint of suppressing or avoiding over-curing and unnecessary deterioration of the adhesive component (A), it is preferably 150°C or lower, more preferably 130°C or lower, and the heating time is appropriately determined according to the heating temperature and the type of adhesive. From the viewpoint of reliably achieving proper adhesion, it is generally 30 seconds or more, preferably 1 minute or more, and from the viewpoint of suppressing deterioration of the adhesive layer and other components, it is generally 10 minutes or less, preferably 5 minutes or less.
[0223] Decompression treatment simply involves exposing the adhesive coating layers that are in contact with each other to a pressure of 10–10000 Pa. The decompression treatment time is usually 1–30 minutes.
[0224] The load in the thickness direction of the semiconductor substrate and the support substrate is not particularly limited as long as it does not adversely affect the semiconductor substrate and the support substrate and the layers between them, and can make them firmly and tightly bonded. It is usually in the range of 10 to 50,000 N.
[0225] From the viewpoint of achieving sufficient curing speed, the post-heating temperature is preferably 120°C or higher, and from the viewpoint of preventing deterioration of the substrate and each layer, the post-heating temperature is preferably 260°C or lower.
[0226] From the viewpoint of achieving proper bonding between the substrate and the layers constituting the laminate, the post-heating time is usually 1 minute or more, preferably 5 minutes or more. From the viewpoint of suppressing or avoiding adverse effects on each layer caused by excessive heating, the post-heating time is usually 180 minutes or less, preferably 120 minutes or less.
[0227] Heating can be performed using a heating plate, oven, or similar equipment. When using a heating plate for post-heating, either the semiconductor substrate or the support substrate of the laminate can be heated with the substrate facing downwards. From the viewpoint of achieving proper peeling with good reproducibility, it is preferable to heat the substrate with the semiconductor substrate facing downwards.
[0228] It should be noted that one of the purposes of the post-heat treatment is to achieve an adhesive layer that functions as a more suitable self-supporting film, particularly to achieve proper curing based on the hydrosilylation reaction.
[0229] Figure 2A Figure 2C is a diagram illustrating one method for manufacturing a laminated body.
[0230] First, a laminate with an adhesive coating layer 2a is prepared on a semiconductor substrate 1. Figure 2A This laminate can be obtained, for example, by applying an adhesive composition onto a semiconductor substrate 1 and heating it.
[0231] Next, Figure 2A The laminate and support substrate 4 shown are bonded together with the adhesive coating layer 2a in contact with the support substrate 4. Then, after applying a load in the thickness direction of the semiconductor substrate 1 and the support substrate 4 under reduced pressure, a heating device (not shown; heating plate) is placed on the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive coating layer 2a. The adhesive coating layer 2a is heated by the heating device and cured, transforming into adhesive layer 2 ( Figure 2B ).
[0232] pass Figures 2A-2B The process shown can yield Figure 1 The layered structure shown.
[0233] <Second Implementation> A laminate with an electronic device layer is used for the fabrication of the electronic device layer. During the fabrication of the electronic device layer, the electronic device layer is bonded to a support substrate. After the fabrication of the electronic device layer, the electronic device layer is separated from the support substrate.
[0234] <<Electronic Devices Layer>> The electronic device layer refers to a layer containing electronic devices. In this invention, it refers to a layer in which multiple semiconductor chip substrates are embedded in the encapsulation resin, that is, a layer comprising multiple semiconductor chip substrates and encapsulation resin disposed between the semiconductor chip substrates.
[0235] Here, "electronic device" refers to a component that constitutes at least a part of an electronic component. There are no particular limitations on the term "electronic device," and it can be any electronic device with various mechanical structures and circuits formed on the surface of a semiconductor substrate. Preferably, the electronic device is a composite of a component made of metal or semiconductor and a resin that encapsulates or insulates that component. The electronic device can be an electronic device formed by encapsulating or insulating the redistribution layer and / or semiconductor elements or other components described later with encapsulation or insulating materials, and has a single-layer or multi-layer structure.
[0236] <<Support substrate>> As a support substrate, an example of a support substrate that is the same as the support substrate described in the "Support Substrate" section of the above-described "First Embodiment" can be shown.
[0237] <<Adhesive Layer>> The adhesive layer is formed using the adhesive composition described above.
[0238] The adhesive layer is described in detail in the "Adhesive Layer" section of the above-mentioned "First Embodiment".
[0239] The following description uses the accompanying drawings to illustrate an example of the structure of the laminate in the second embodiment.
[0240] Figure 3 The laminate sequentially comprises: a support substrate 24, an adhesive layer 22, and an electronic device layer 26.
[0241] The electronic device layer 26 has: a plurality of semiconductor chip substrates 21 and an encapsulation resin 25 disposed between the semiconductor chip substrates 21 as an encapsulation material.
[0242] An adhesive layer 22 is disposed between the electronic device layer 26 and the support substrate 24. The adhesive layer 22 is in contact with both the electronic device layer 26 and the support substrate 24.
[0243] <<Manufacturing Method of an Example of a Laminated Body in the Second Embodiment>> In the laminated body of the second embodiment Figure 3 Taking the laminated body shown as an example, the manufacturing method of the laminated body will be explained below.
[0244] The laminate of the present invention can be manufactured, for example, by a method including the following first to fourth steps.
[0245] First step: Applying the adhesive composition to the surface of the support substrate to form an adhesive coating layer (if necessary, further heating may be performed to form the adhesive layer). The second step involves placing the semiconductor chip substrate on an adhesive coating layer or adhesive layer, and simultaneously performing at least one of heat treatment and depressurization treatment to bond the semiconductor chip substrate to the adhesive coating layer or adhesive layer. The third step: This step involves post-heating the adhesive coating layer to cure it, thus forming the adhesive layer. The fourth step: encapsulating the semiconductor chip substrate fixed on the adhesive layer with encapsulating resin. If the second step is described in more detail, the steps of the following embodiment (i) can be listed, for example.
[0246] (i) The semiconductor chip substrate is placed on the adhesive coating layer or adhesive layer, and while performing at least one of the heat treatment and the decompression treatment, a load in the thickness direction of the semiconductor chip substrate and the support substrate is applied to make them fit together, thereby attaching the semiconductor chip substrate to the adhesive coating layer or adhesive layer.
[0247] It should be noted that the third step can be performed after the second step of bonding the semiconductor chip substrate to the adhesive coating layer, or it can be performed together with the second step. For example, the semiconductor chip substrate can be placed on the adhesive coating layer, and while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate, the adhesive coating layer can be heated to cure it. This allows for the simultaneous bonding of the semiconductor chip substrate and the adhesive coating layer, as well as the curing of the adhesive coating layer into an adhesive layer, thereby bonding the adhesive layer to the semiconductor chip substrate.
[0248] In addition, the third process can be performed before the second process, or the semiconductor chip substrate can be placed on the adhesive layer, and the adhesive layer can be bonded to the semiconductor chip substrate while applying a load in the thickness direction of the semiconductor chip substrate and the support substrate.
[0249] The coating method, the heating temperature of the coated adhesive composition, the heating method, etc., are as described in the above-described "Manufacturing Method of an Example of a Laminate in the First Embodiment" of the above-described "First Embodiment".
[0250] The manufacturing method of the laminate according to the second embodiment will be further described in detail below with reference to the accompanying drawings. This manufacturing method is used to manufacture... Figure 3 The layered structure shown.
[0251] like Figure 4AAs shown, an adhesive coating layer 22' formed of an adhesive composition is formed on the support substrate 24. At this time, the adhesive coating layer 22' can also be formed by heating the adhesive coating layer 22'.
[0252] Next, as Figure 4B As shown, a semiconductor chip substrate 21 is placed on an adhesive layer 22 or an adhesive coating layer 22'. While performing at least one of a heat treatment and a depressurization treatment, a load in the thickness direction of the semiconductor chip substrate 21 and the support substrate 24 is applied to bring them into close contact, thus attaching the semiconductor chip substrate 21 to the adhesive layer 22 or the adhesive coating layer 22'. When the semiconductor chip substrate 21 is attached to the adhesive coating layer 22', the adhesive layer 22 is formed by performing a post-heat treatment on the adhesive coating layer 22' to cure it, thereby fixing the semiconductor chip substrate 21 to the adhesive layer 22.
[0253] Next, as Figure 4C As shown, the semiconductor chip substrate 21, which is fixed to the adhesive layer 22, is encapsulated using encapsulating resin 25. Figure 4C In this process, multiple semiconductor chip substrates 21, which are temporarily bonded to a support substrate 24 by means of an adhesive layer 22, are encapsulated using an encapsulating resin 25. An electronic device layer 26 is formed on the adhesive layer 22, having semiconductor chip substrates 21 and encapsulating resin 25 disposed between the semiconductor chip substrates 21. Thus, the electronic device layer 26 becomes a substrate layer in which multiple semiconductor chip substrates are embedded in the encapsulating resin.
[0254] <<<Packaging Process>>> The semiconductor chip substrate 21 is encapsulated using encapsulation materials.
[0255] As a packaging material for encapsulating a semiconductor chip substrate 21, a component capable of insulating or encapsulating a component made of metal or semiconductor is used.
[0256] In this invention, a resin composition (encapsulating resin) is used as the encapsulation material. There are no particular limitations on the type of encapsulating resin, as long as it can encapsulate and / or insulate a metal or semiconductor; for example, epoxy resins or silicone resins are preferred.
[0257] In addition to resin components, encapsulation materials may also contain other components such as fillers. Examples of fillers include spherical silica particles.
[0258] In the encapsulation process, encapsulating resin, heated to, for example, 130–170°C to maintain a high viscosity, is supplied onto the adhesive layer 22 to cover the semiconductor chip substrate 21, and then compressed and molded, thereby forming a layer of encapsulating resin 25 on the adhesive layer 22. At this time, the temperature conditions are, for example, 130–170°C. Furthermore, the pressure applied to the semiconductor chip substrate 21 is, for example, 50–500 N / cm. 2 .
[0259] (Method for manufacturing processed semiconductor substrates or electronic device layers) If the laminate of the present invention is used, a method for manufacturing a processed semiconductor substrate or a method for manufacturing a processed electronic device layer can be provided.
[0260] The "method for manufacturing a processed semiconductor substrate" uses the laminate described in the "First Embodiment" section above. Furthermore, the "method for manufacturing a processed electronic device layer" uses the laminate described in the "Second Embodiment" section above.
[0261] The method for manufacturing a processed semiconductor substrate will be described in the following <Third Embodiment>, and the method for manufacturing a processed electronic device layer will be described in the following <Fourth Embodiment>.
[0262] The manufacturing method of the processed semiconductor substrate or electronic device layer includes the following steps.
[0263] • Processing steps for processing the first substrate of the laminate of the present invention • A separation process in which the adhesive layer is irradiated with an infrared laser from the second substrate side, followed by the separation of the processed first substrate from the second substrate. Examples of infrared lasers include those with wavelengths from 1 μm to 20 μm. The preferred wavelength for infrared lasers is 9.2 to 10.8 μm.
[0264] Examples of infrared laser light sources include semiconductor lasers, He-Ne lasers, Ar lasers, carbon dioxide lasers, YAG lasers, and fiber lasers.
[0265] The output power of the infrared laser is preferably 10W to 100W, and more preferably 30W to 90W.
[0266] Irradiation of the adhesive layer with infrared laser does not necessarily require irradiation of the entire adhesive layer. Even if irradiated and unirradiated areas are mixed, as long as the adhesive strength of a portion of the adhesive layer is sufficiently reduced, the second substrate can be peeled off from the laminate by applying a slight external force to lift it. The ratio and positional relationship between the irradiated and unirradiated areas vary depending on the adhesive composition forming the adhesive layer, the thickness of the adhesive layer, the intensity of the irradiated infrared laser, etc., but those skilled in the art can set appropriate conditions without excessive experimentation. For example, the unirradiated area can be positioned adjacent to the irradiated area with a width equal to the line width of the infrared line.
[0267] In addition, the infrared laser irradiation of the adhesive layer can also be performed only on the ends of the adhesive layer sandwiched between the first substrate and the second substrate.
[0268] After the adhesive layer is irradiated with an infrared laser, a device with a sharp point can be inserted between the first substrate and the second substrate to facilitate the separation of the first substrate and the second substrate.
[0269] Regarding the separation of the first substrate and the second substrate, after reducing the adhesive force of the adhesive layer by irradiating the adhesive layer with an infrared laser, methods such as holding the first substrate and the second substrate with holding devices and moving one or both of these holding devices in the direction of separation of the first substrate and the second substrate can be listed as follows:
[0270] As a retaining device, an adsorption plate can be cited as an example.
[0271] In the separation process, it is preferable to irradiate the adhesive layer with an infrared laser. Compared to the case where the adhesive layer is not irradiated with an infrared laser, the insertion force required to insert the pointed part of the device with the pointed portion between the first substrate and the second substrate and to separate the first substrate and the second substrate is reduced. In other words, it is preferable that the insertion force (Fb) required to insert the pointed part between the first substrate and the second substrate and to separate the first substrate and the second substrate after irradiating the adhesive layer with an infrared laser is smaller than the insertion force (Fa) required to insert the pointed part between the first substrate and the second substrate and to separate the first substrate and the second substrate after irradiating the adhesive layer with an infrared laser.
[0272] Insertion force is expressed as an absolute value.
[0273] As the insertion force (Fa), examples can be listed as 0.1N to 100N.
[0274] The ratio of insertion force (Fa) to insertion force (Fb) (Fb / Fa) is not particularly limited, but it is preferably less than 1.0, more preferably 0.9 or less, and even more preferably 0.6 or less.
[0275] There are no special restrictions on the lower limit of the ratio (Fb / Fa). The ratio (Fb / Fa) can be greater than 0.01, greater than 0.05, or greater than 0.1.
[0276] The insertion force is measured, for example, in the manner described above.
[0277] <Third Implementation Method> The method for manufacturing the processed semiconductor substrate of the present invention includes steps 5A and 6A as described below. The method for manufacturing the processed semiconductor substrate may further include step 7A as described below.
[0278] Here, step 5A is the process of processing the semiconductor substrate in the laminate described in the <First Embodiment> section above.
[0279] In addition, step 6A is a process that separates the semiconductor substrate processed in step 5A from the support substrate.
[0280] In addition, step 7A is a process of cleaning the processed semiconductor substrate after step 6A.
[0281] The processing performed on the semiconductor substrate in step 5A refers, for example, processing on the opposite side of the circuit surface of the wafer, such as wafer thinning achieved by grinding the back side of the wafer. Then, for example, through-silicon via (TSV) electrodes are formed, and the thinned wafer is peeled from the support substrate to form a wafer stack, which is then three-dimensionally packaged. Furthermore, for example, back-side electrodes are formed before and after this process. During the wafer thinning and TSV processes, the wafer is bonded to the support substrate and subjected to heat of approximately 250–350°C. The stack of the present invention typically includes an adhesive layer and possesses heat resistance to this load.
[0282] It should be noted that the processing is not limited to the above-mentioned processing, and also includes, for example, the semiconductor component mounting process implemented in the case of temporarily bonding the substrate to the support substrate for mounting the semiconductor component.
[0283] In step 6A, the method for separating (peeling) the semiconductor substrate from the support substrate is the separation step described above.
[0284] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least either of the separated semiconductor substrate and the support substrate, or by immersing the separated semiconductor substrate or the support substrate in the cleaning agent composition.
[0285] In addition, the surface of processed semiconductor substrates can also be cleaned using tools such as tape removers.
[0286] As an example of cleaning the substrate, step 7A can be performed after step 6A to clean the processed semiconductor substrate.
[0287] The following substances are examples of cleaning agent compositions used for cleaning.
[0288] Cleaning agent compositions typically contain solvents.
[0289] Examples of solvents include: lactones, ketones, polyols, compounds with ester bonds, derivatives of polyols, cyclic ethers, esters, and aromatic organic solvents.
[0290] Examples of lactones include γ-butyrolactone.
[0291] Examples of ketones include acetone, methyl ethyl ketone, cyclohexanone, methyl n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone.
[0292] Examples of polyols include ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol.
[0293] Examples of compounds containing ester bonds include ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, and dipropylene glycol monoacetate.
[0294] Examples of polyol derivatives include monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, and other monoalkyl ethers or monophenyl ethers of the aforementioned polyols or compounds having ester bonds. Among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred.
[0295] Examples of cyclic ethers include dioxane.
[0296] Examples of esters include: methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.
[0297] Examples of aromatic organic solvents include: anisole, benzyl ethyl ether, methyl anisole, diphenyl ether, dibenzyl ether, phenethyl ether, phenylbutyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, etc.
[0298] They can be used individually or in combination of two or more.
[0299] Among them, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), cyclohexanone, and ethyl lactate (EL) are preferred.
[0300] Furthermore, a mixed solvent prepared by mixing PGMEA with a polar solvent is preferred. The mixing ratio (mass ratio) can be appropriately determined by taking into account the compatibility of PGMEA with the polar solvent, etc. Preferably, it is set in the range of 1:9 to 9:1, and more preferably in the range of 2:8 to 8:2.
[0301] For example, when using EL as a polar solvent, the mass ratio of PGMEA to EL is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, when using PGME as a polar solvent, the mass ratio of PGMEA to PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Moreover, when using PGME and cyclohexanone as polar solvents, the mass ratio of PGMEA to (PGME + cyclohexanone) is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3.
[0302] The cleaning agent composition may or may not contain salt. From the perspective of increasing versatility when processing semiconductor substrates using laminates and reducing costs, it is preferable to not contain salt.
[0303] As an example of a cleaning agent composition containing salt, a cleaning agent composition containing quaternary ammonium salt and solvent can be cited.
[0304] Quaternary ammonium salts are composed of quaternary ammonium cations and anions, and there are no particular limitations as long as they are used for this purpose.
[0305] Typical examples of such quaternary ammonium cations include tetra(hydrocarbon)ammonium cations. On the other hand, examples of their paired anions include hydroxide ions (OH-). - ); Fluoride ions (F) - ), chloride ions (Cl) - ), bromide ions (Br) - ), iodide ions (I - Halogen ions such as tetrafluoroborate ions (BF4) - ); hexafluorophosphate ions (PF6) - (etc.), but not limited to these.
[0306] The quaternary ammonium salt is preferably a halogenated quaternary ammonium salt, and more preferably a fluorine-containing quaternary ammonium salt.
[0307] In quaternary ammonium salts, halogen atoms can be contained in cations or anions, preferably in anions.
[0308] In a preferred embodiment, the fluorine-containing quaternary ammonium salt is tetra(hydrocarbon)ammonium fluoride.
[0309] Specific examples of hydrocarbon groups in tetra(hydrocarbon)ammonium fluoride include: alkyl groups with 1 to 20 carbon atoms, alkenyl groups with 2 to 20 carbon atoms, alkynyl groups with 2 to 20 carbon atoms, and aryl groups with 6 to 20 carbon atoms.
[0310] In a more preferred embodiment, the tetra(hydrocarbon) fluoride comprises tetraalkyl ammonium fluoride.
[0311] Specific examples of tetraalkylammonium fluoride include tetramethylammonium fluoride, tetraethylammonium fluoride, tetrapropylammonium fluoride, and tetrabutylammonium fluoride (also known as tetrabutylammonium fluoride), but are not limited to these. Among them, tetrabutylammonium fluoride is preferred.
[0312] Quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can also be used in hydrate form. In addition, quaternary ammonium salts such as tetra(hydrocarbon)ammonium fluoride can be used alone or in combination of two or more.
[0313] There are no particular limitations on the amount of quaternary ammonium salt, as long as it is dissolved in the solvent contained in the cleaning agent composition, typically 0.1 to 30% by mass relative to the cleaning agent composition.
[0314] When the cleaning agent composition contains salt, there are no particular limitations on the solvent used, as long as it is used for this purpose and dissolves salts such as quaternary ammonium salts. From the viewpoint of obtaining a cleaning agent composition with excellent cleaning properties with good reproducibility, and from the viewpoint of obtaining a cleaning agent composition with excellent uniformity by good dissolution of salts such as quaternary ammonium salts, the cleaning agent composition preferably contains one or more amide solvents.
[0315] As a preferred example of an amide solvent, an amide derivative represented by formula (Z) can be cited. In the formula, R 0 The symbol represents ethyl, propyl, or isopropyl, with ethyl or isopropyl being preferred, and ethyl being more preferred. R A and R B Each alkyl group independently represents an alkyl group having 1 to 4 carbon atoms. Alkyl groups having 1 to 4 carbon atoms can be any type of linear, branched, or cyclic form, specifically including: methyl, ethyl, propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, etc. Among these, R... A and R B Preferably, it is methyl or ethyl, more preferably both are methyl or ethyl, and even more preferably both are methyl.
[0316] Examples of amide derivatives represented by formula (Z) include: N,N-dimethylpropionamide, N,N-diethylpropionamide, N-ethyl-N-methylpropionamide, N,N-dimethylbutyramide, N,N-diethylbutyramide, N-ethyl-N-methylbutyramide, N,N-dimethylisobutyramide, N,N-diethylisobutyramide, and N-ethyl-N-methylisobutyramide. Among these, N,N-dimethylpropionamide and N,N-dimethylisobutyramide are particularly preferred, and N,N-dimethylpropionamide is more preferred.
[0317] The amide derivatives shown in formula (Z) can be synthesized by substitution reaction of the corresponding carboxylic acid ester with an amine, or by using commercially available products.
[0318] Another example of a preferred amide solvent is a lactam compound represented by formula (Y). In formula (Y), R 101 R represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 102 This refers to alkylene groups having 1 to 6 carbon atoms. Specific examples of alkyl groups having 1 to 6 carbon atoms include methyl, ethyl, n-propyl, n-butyl, etc. Specific examples of alkylene groups having 1 to 6 carbon atoms include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, etc., but are not limited to these.
[0319] Specific examples of the lactam compounds represented by formula (Y) include: α-lactam compounds, β-lactam compounds, γ-lactam compounds, δ-lactam compounds, etc., which can be used alone or in combination of two or more.
[0320] In a preferred embodiment, the lactam compound represented by formula (Y) comprises 1-alkyl-2-pyrrolidone (N-alkyl-γ-butyrolactam), in a more preferred embodiment it comprises N-methylpyrrolidone (NMP) or N-ethylpyrrolidone (NEP), and in a further preferred embodiment it comprises N-methylpyrrolidone (NMP).
[0321] It should be noted that the cleaning agent composition used in this invention may also contain water as a solvent, but from the viewpoint of avoiding substrate corrosion, etc., it is generally intentionally used only as an organic solvent. It should be noted that this does not exclude the possibility of the cleaning agent composition containing hydrated water of salt or trace amounts of water contained in the organic solvent. The water content of the cleaning agent composition used in this invention is generally 5% by mass or less.
[0322] Regarding the constituent elements and method elements related to the above-described steps of the method for manufacturing the processed semiconductor substrate of the present invention, various modifications may be made as long as they do not depart from the spirit of the present invention.
[0323] The manufacturing method of the processed semiconductor substrate of the present invention may also include steps other than those described above.
[0324] use Figures 5A-5E An example of the third embodiment will be described. This example is an example of manufacturing a thinned semiconductor substrate.
[0325] First, prepare the stacked body ( Figure 5A This laminate is with Figure 1 and Figure 2B The stack shown is the same as the stack shown.
[0326] Next, a polishing apparatus (not shown) is used to polish the side of the semiconductor substrate 1 opposite to the side in contact with the adhesive layer 2, thereby thinning the semiconductor substrate 1. Figure 5B It should be noted that through-electrodes can also be formed on the thinned semiconductor substrate 1.
[0327] Next, infrared laser L is irradiated onto the adhesive layer 2 from the side of the support substrate 4. Figure 5C Infrared laser irradiation can be applied to the entire surface of adhesive layer 2 or to a portion thereof.
[0328] Next, using a peeling device (not shown), the thinned semiconductor substrate 1 is separated from the support substrate 4. Figure 5D ).
[0329] Thus, a thinned semiconductor substrate 1 is obtained. Figure 5E ).
[0330] Sometimes, residue of the adhesive layer 2 remains on the thinned semiconductor substrate 1. Therefore, it is preferable to clean the thinned semiconductor substrate 1 with a cleaning agent composition to remove the residue of the adhesive layer 2 from the semiconductor substrate 1.
[0331] <Fourth Implementation> The method for manufacturing the processed electronic device layer of the present invention includes steps 5B and 6B as described below. The method for manufacturing the processed electronic device layer may further include step 7B as described below.
[0332] Here, step 5B is the process of processing the electronic device layer in the laminate described in the <Second Embodiment> section above.
[0333] In addition, step 6B is a process that separates the electronic device layer processed in step 5B from the support substrate.
[0334] In addition, step 7B is a process that cleans the processed electronic device layer after step 6B.
[0335] The following uses Figures 6A to 6G Specific examples of the fourth implementation method will be described.
[0336] The processing performed on the electronic device layer in process 5B can include, for example, grinding and wiring layer formation.
[0337] <<Grinding Process>> The grinding process is a process of grinding the resin portion of the encapsulation resin 25 layer in the electronic device layer 26 with a portion of the semiconductor chip substrate 21 exposed.
[0338] Grinding of the encapsulating resin portion, for example, Figure 6B As shown, by Figure 6A The encapsulating resin 25 of the laminate shown is ground to approximately the same thickness as the semiconductor chip substrate 21. It should be noted that... Figure 6A The stacked body shown is with Figure 3 and Figure 4C The stack shown is the same as the stack shown.
[0339] <<Wireline Layer Formation Process>> The wiring layer formation process is a process of forming a wiring layer on the exposed semiconductor chip substrate 21 after the above-mentioned grinding process.
[0340] exist Figure 6C In this process, a wiring layer 28 is formed on an electronic device layer 26 that includes a semiconductor chip substrate 21 and an encapsulating resin 25.
[0341] The wiring layer 28, also known as the RDL (Redistribution Layer), is a thin film of wiring that forms the wiring connected to the substrate. It can have a single-layer or multi-layer structure. The wiring layer can utilize a conductor (such as metals like aluminum, copper, titanium, nickel, gold, and silver, as well as alloys like silver-tin alloys) on a dielectric (silicon oxide (SiO2)). x A layer formed by wiring between photosensitive resins such as photosensitive epoxy resin, etc., but not limited to this.
[0342] The following methods can be listed as examples of methods for forming the wiring layer 28.
[0343] First, silicon oxide (SiO2) is formed on the layer of encapsulating resin 25. xThe dielectric layer consists of a photosensitive resin and other dielectric layers. A dielectric layer made of silicon oxide can be formed, for example, by sputtering or vacuum evaporation. A dielectric layer made of photosensitive resin can be formed, for example, by applying the photosensitive resin onto the encapsulating resin 25 layer using methods such as spin coating, dip coating, roller blade coating, spraying, or slot coating.
[0344] Next, wiring is formed on the dielectric layer using a conductive material such as a metal. As a method for forming the wiring, known semiconductor processes such as photolithography (resist photolithography) and etching can be used. Examples of such photolithography processes include photolithography using a positive resist material and photolithography using a negative resist material.
[0345] In the manufacturing method of the laminate according to the fourth embodiment, bumps may be further formed or components may be mounted on the wiring layer 28. Component mounting on the wiring layer 28 may be performed, for example, using a pick-and-place machine.
[0346] The laminate in the fourth embodiment can be a laminate manufactured in a process based on the following technique: a fan-out technique in which terminals provided on a semiconductor chip substrate are mounted on a wiring layer that extends beyond the chip area.
[0347] In step 6B, the method for separating (peeling) the electronic device layer from the support substrate is the separation step described above.
[0348] Figures 6D to 6F This is a schematic cross-sectional view used to illustrate the separation method of laminated bodies. Figure 6G This is a schematic cross-sectional view used to illustrate the cleaning method after the separation of laminates. It can be viewed through... Figures 6D to 6G An embodiment of a method for manufacturing a semiconductor package (electronic component) will be described.
[0349] like Figures 6D to 6F As shown, the process of separating the laminate is the process of separating the electronic device layer 26 from the support substrate 24. Specifically, infrared laser L ( ) is irradiated onto the adhesive layer 22 from the support substrate 24 side. Figure 6D Infrared laser irradiation can be applied to the entire surface of adhesive layer 22 or to a portion of it. Next, a peeling device (not shown) is used to separate the thinned electronic device layer 26 from the support substrate 24. Figure 6E ).
[0350] The substrate can be cleaned by spraying a cleaning agent composition onto the surface of at least one of the separated electronic device layer and the support substrate, or by immersing the separated electronic device layer or the support substrate in the cleaning agent composition.
[0351] In addition, it can also be used to clean the surface of processed electronic device layers, etc., by removing adhesive tape.
[0352] For example, in Figure 6F In the process, after the separation step, an adhesive layer 22 is attached to the electronic device layer 26. The adhesive layer 22 can be removed by decomposing it using a cleaning agent composition such as an acid or alkali. By removing the adhesive layer, a suitable product can be obtained... Figure 6G The processed electronic device layer (electronic component) is shown.
[0353] Regarding the constituent elements and method elements related to the above-described steps of the method for manufacturing the processed electronic device layer of the present invention, various modifications can be made as long as they do not depart from the spirit of the present invention.
[0354] The manufacturing method of the processed electronic device layer of the present invention may also include processes other than those described above.
[0355] Example The present invention will be described in more detail below with reference to specific embodiments, but the present invention is not limited to the embodiments described below. It should be noted that the apparatus used is as described below.
[0356] [Apparatus] (1) Mixer A: ARE-500 self-rotating and revolution-rotating mixer manufactured by THINKY Corporation (2) Mixer B: AS ONE (Co., Ltd.) Mixing Rotor VMR-5R (3) Viscosity determination: TVE-22H rotational viscometer manufactured by Toki Sangyo Co., Ltd. (4) Spin coating device: APOGEE Co., Ltd. coating machine (5) Vacuum heating bonding device: Ayumi Industry Co., Ltd. VE09-07 (6) Force gauge: RZE-10 manufactured by Aikoh Engineering Co., Ltd. (7) Infrared laser stripping device: Aflair, AFS-MCTII-FX The structure and properties of the polysiloxanes (formulas (V) and (W)) used are shown below. (In equation (V), n represents the number of repeating units and is a positive integer.) It should be noted that a polysiloxane with the structure shown in equation (V) and the properties shown in Table 1 below is used. (In formula (W), n and m represent the number of repeating units, each being a positive integer independently.) Furthermore, vinyl groups with 2.7 mol / kg have a number-average molecular weight (Mn) of 9000 obtained by GPC.
[0357] [1] Preparation of adhesive composition [Preparation Example 1] Add 1.0 g of 1,1-diphenyl-2-propyn-1-ol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.0 g of 1-ethynyl-1-cyclohexanol (manufactured by Wacker Chemie) to a 50 mL screw tube, and stir with a mixer A for 5 minutes to obtain mixture (I).
[0358] 210.71 g of a menthol solution (concentration 81.2 wt%) containing vinyl MQ resin (manufactured by Wacker Chemie) and 0.05 g of platinum catalyst (valence 0, platinum content 1 wt%) diluted with polysiloxane of the above formula (W) were added to a 650 mL stirring container for a rotary mixer. The mixture was stirred for 5 minutes with mixer A to obtain mixture (II).
[0359] Add 0.17g of the obtained mixture (I) and 60.22g of the obtained mixture (II) to a 200mL mixing container for a rotary mixer, and mix with mixer A for 5 minutes to obtain mixture (III).
[0360] Add 16.84 g or less of mixture A, 13.01 g or less of mixture B, 0.80 g of epoxy-modified organosilicon (X-22-343, manufactured by Shin-Etsu Silicon Co., Ltd.), and 2.17 g of p-menthane to the obtained mixture (III), and stir with mixer A for 5 minutes to obtain mixture (IV).
[0361] Mixture A: A mixture prepared by mixing vinyl-containing MQ resin (manufactured by Wacker Chemie), a vinyl-containing linear polydimethylsiloxane with a viscosity of 200 mPa·s as shown in Formula (V) above (V1 in Table 1), and a SiH-containing linear polydimethylsiloxane (manufactured by Wacker Chemie) with a viscosity of 100 mPa·s in a mass ratio of 54.1:36.4:9.5. Mixture B: A mixture of GENIOPLAST GUM (manufactured by Wacker Chemie), a linear polydimethylsiloxane containing SiH groups with a viscosity of 100 mPa·s (manufactured by Wacker Chemie), and p-menthane in a mass ratio of 30.31:63.50:6.19. Finally, the resulting mixture (IV) was filtered using a 300-mesh nylon filter to obtain the adhesive composition.
[0362] [Preparation Example 2] 2.0 g of tannic acid AL (manufactured by Fuji Chemical Industry Co., Ltd.: equivalent to an infrared absorber) and 8.0 g of propylene glycol monomethyl ether were added to a 50 mL screw-cap tube and stirred with stirrer A for 5 minutes to obtain mixture (V). 0.5 g of the obtained mixture (V) and 9.5 g of the mixture (IV) obtained in Preparation Example 1 were added to a 100 mL capped glass container and stirred with stirrer A for 5 minutes. The obtained mixture was filtered through a 300-mesh nylon filter to obtain an adhesive composition (VI) containing an infrared absorber.
[0363] [2] Fabrication of laminated bodies [Example 1] The adhesive composition (VI) obtained in Preparation Example 2 was spin-coated onto a 4 cm square silicon substrate at 950 rpm for 30 seconds, and then heated at 90°C for 1.5 minutes (preheating treatment) to form an adhesive coating layer. Subsequently, in a vacuum heating bonding apparatus, the silicon substrate with the adhesive coating layer was bonded to a 4 cm square silicon substrate by clamping the adhesive coating layer. The substrate with the adhesive coating layer was heated face down on a heating plate at 130°C for 5 minutes, and then further heated at 200°C for 5 minutes (postheating treatment) to produce a laminate. It should be noted that the bonding was performed using a vacuum heating bonding apparatus with a temperature of 70°C and a pressure reduction of 1000 Pa, applying a load of 150 kg for 3 minutes.
[0364] [Comparative Example 1] Using the adhesive composition obtained in Preparation Example 1, the laminate was prepared by the same method as in Example 1.
[0365] [3] Laser irradiation [Example 2] For the laminate fabricated in Example 1, an infrared laser lifter was used to irradiate the silicon wafer on the carrier side with a 9.3 μm wavelength laser from a vertical direction across the entire surface of a 4 cm square substrate. It should be noted that the laser irradiation conditions are as follows.
[0366] • Scan speed: 1000nm / sec Laser power: 60W • Frequency: 20Hz [Comparative Example 2] The laminate prepared in Comparative Example 1 was used, except that laser irradiation was performed in the same manner as in Example 2.
[0367] [4] Evaluation of insertion force [Example 3] The device side of the laminate irradiated by laser in Example 2 is fixed to the worktable with double-sided tape. Next, a force gauge blade with a razor blade at the front end is inserted into the adhesive layer of the fixed laminate, and the maximum absolute value of the force gauge at this time is taken as the insertion force.
[0368] [Comparative Example 3] The laser-irradiated laminate used in Comparative Example 2 was used, and the insertion force was evaluated using the same test method as in Example 3.
[0369] The evaluation results of Example 3 and Comparative Example 3 are shown in Table 2. Based on the results of Example 3 and Comparative Example 3, it is evident that when a laminate containing an adhesive layer with an infrared absorber is irradiated with an infrared laser, a device with a sharp portion can be inserted between substrates with low insertion force in a laminate in which the adhesive layer is formed from a mixture containing an infrared absorber. This confirms that when using the composition and process of the present invention, there is minimal damage to the substrate during the separation of the laminate, enabling peeling.
[0370] Explanation of reference numerals in the attached figures 1: Semiconductor substrate; 2: Adhesive layer; 2a: Adhesive coating layer; 4: Support substrate; 21: Semiconductor chip substrate; 22: Adhesive layer; 22': Adhesive coating layer; 24: Support substrate; 25: Encapsulation resin; 26: Electronic device layer; 28: Wiring layer; L: Infrared laser.
Claims
1. An adhesive composition for forming an adhesive layer, the adhesive layer being used for: processing the first substrate having a first substrate, a second substrate, and the adhesive layer; irradiating the adhesive layer with infrared laser light from the second substrate side; and then separating the first substrate from the second substrate, wherein the first substrate is a semiconductor substrate or an electronic device layer, the second substrate is a support substrate for transmitting infrared laser light, and the adhesive layer is disposed between the first substrate and the second substrate. The adhesive composition contains a release agent, an infrared absorber, and an adhesive component having siloxane bonds.
2. The adhesive composition according to claim 1, wherein, The adhesive component is a component that is cured through a hydrogenation silanization reaction.
3. The adhesive composition according to claim 2, wherein, The component cured by the hydrogenation silanization reaction contains: Composition A-1 having an alkenyl group with 2 to 40 carbon atoms bonded to silicon atoms; and Component A-2 has Si-H groups.
4. The adhesive composition according to claim 3, wherein, The component A-1 contains: a polyorganosiloxane a1 having an alkenyl group having 2 to 40 carbon atoms bonded to silicon atoms.
5. The adhesive composition according to claim 3, wherein, The component A-2 contains: a polyorganosiloxane having Si-H groups.
6. The adhesive composition according to claim 1, wherein, The stripping agent is composed of polyorganosiloxane.
7. The adhesive composition according to claim 1, wherein, The insertion force required to insert the pointed portion of an instrument with a pointed portion between the first substrate and the second substrate and to separate the first substrate and the second substrate after irradiating the adhesive layer with the infrared laser is smaller than the insertion force required to insert the pointed portion between the first substrate and the second substrate and to separate the first substrate and the second substrate after irradiating the adhesive layer with the infrared laser.
8. A laminated body having: The first substrate is a semiconductor substrate or an electronic device layer; The second substrate is a support substrate for transmitting infrared laser light; and An adhesive layer is disposed between the first substrate and the second substrate. The adhesive layer is an adhesive layer formed from the adhesive composition as described in any one of claims 1 to 7.
9. A method for manufacturing a processed semiconductor substrate or electronic device layer, comprising: The processing step involves processing the first substrate of the laminate as described in claim 8; as well as In the separation process, the adhesive layer is irradiated with infrared laser from the second substrate side, and then the processed first substrate is separated from the second substrate.
10. The method for manufacturing the processed semiconductor substrate or electronic device layer according to claim 9, wherein, By irradiating the adhesive layer with infrared laser, compared to the case where the adhesive layer is not irradiated with infrared laser, the insertion force required to insert the sharp part of the device with the sharp part between the first substrate and the second substrate and to separate the first substrate and the second substrate is reduced.
Citation Information
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