TW201546230A - Sheet-like resin composition, multilayer sheet and method for manufacturing semiconductor device - Google Patents

Sheet-like resin composition, multilayer sheet and method for manufacturing semiconductor device Download PDF

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TW201546230A
TW201546230A TW104114939A TW104114939A TW201546230A TW 201546230 A TW201546230 A TW 201546230A TW 104114939 A TW104114939 A TW 104114939A TW 104114939 A TW104114939 A TW 104114939A TW 201546230 A TW201546230 A TW 201546230A
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sheet
resin composition
resin
mpa
adherend
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TW104114939A
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Akihiro Fukui
Naohide Takamoto
Hiroyuki Hanazono
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Nitto Denko Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • H01L23/295—Organic, e.g. plastic containing a filler
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/14—Structure, shape, material or disposition of the bump connectors prior to the connecting process of a plurality of bump connectors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/16—Structure, shape, material or disposition of the bump connectors after the connecting process of an individual bump connector
    • H01L2224/161—Disposition
    • H01L2224/16151—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/16221—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/16225—Disposition the bump connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/15—Structure, shape, material or disposition of the bump connectors after the connecting process
    • H01L2224/17—Structure, shape, material or disposition of the bump connectors after the connecting process of a plurality of bump connectors
    • H01L2224/171—Disposition
    • H01L2224/1718—Disposition being disposed on at least two different sides of the body, e.g. dual array
    • H01L2224/17181—On opposite sides of the body
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/26—Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L2224/31—Structure, shape, material or disposition of the layer connectors after the connecting process
    • H01L2224/32—Structure, shape, material or disposition of the layer connectors after the connecting process of an individual layer connector
    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/32221—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/32225—Disposition the layer connector connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being non-metallic, e.g. insulating substrate with or without metallisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/731—Location prior to the connecting process
    • H01L2224/73101—Location prior to the connecting process on the same surface
    • H01L2224/73103—Bump and layer connectors
    • H01L2224/73104—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73—Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732—Location after the connecting process
    • H01L2224/73201—Location after the connecting process on the same surface
    • H01L2224/73203—Bump and layer connectors
    • H01L2224/73204—Bump and layer connectors the bump connector being embedded into the layer connector
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/83—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a layer connector
    • H01L2224/8319—Arrangement of the layer connectors prior to mounting
    • H01L2224/83191—Arrangement of the layer connectors prior to mounting wherein the layer connectors are disposed only on the semiconductor or solid-state body

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)
  • Wire Bonding (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)
  • Dicing (AREA)

Abstract

Provided is a method for manufacturing a semiconductor device, which is capable of manufacturing a highly reliable semiconductor device by suppressing the occurrence of voids which affect the reliability at the interface between a sheet-like resin composition and a body to be bonded. The present invention is a thermosetting sheet-like resin composition for filling the space between a body to be bonded and a semiconductor element that is electrically connected to the body to be bonded, and this sheet-like resin composition has a viscosity ([eta]150) at 150 DEG C satisfying 0.05 MPa.s ≤ [eta]150 ≤2.2 MPa.s and a viscosity ([eta]200) at 200 DEG C satisfying 1.0 MPa.s ≤ [eta]200 ≤ 100.0 MPa.s as determined over the temperature range of from 50 DEG C to 250 DEG C at a heating rate of 10 DEG C/min at a frequency of 1 Hz.

Description

片狀樹脂組合物、積層片及半導體裝置之製造方法 Sheet-like resin composition, laminated sheet, and method of manufacturing semiconductor device

本發明係關於一種片狀樹脂組合物、積層片及半導體裝置之製造方法。 The present invention relates to a sheet-like resin composition, a laminate sheet, and a method of producing a semiconductor device.

近年來，更進一步追求半導體裝置及其封裝體之薄型化、小型化。作為實現其之對策，而廣泛利用藉由覆晶接合將半導體晶片等半導體元件安裝於基板上(覆晶連接)而得之覆晶型半導體裝置。覆晶連接係藉由將半導體晶片之電路面設為與被黏著體之電極形成面對向之狀態(面朝下)，並將形成於半導體晶片之電路面之突起電極與被黏著體之電極接合而固定的安裝法。 In recent years, the semiconductor device and its package have been further reduced in thickness and size. As a countermeasure for achieving this, a flip-chip type semiconductor device obtained by mounting a semiconductor element such as a semiconductor wafer on a substrate by flip chip bonding (a flip chip connection) is widely used. The flip chip connection is formed by facing the circuit surface of the semiconductor wafer with the electrode of the adherend (face down), and forming the bump electrode formed on the circuit surface of the semiconductor wafer and the electrode of the adherend A fixed and fixed mounting method.

為了確保半導體元件表面之保護或半導體元件與基板之間之連接可靠性，覆晶連接後對半導體元件與基板之間之空間進行密封樹脂填充。作為此種密封樹脂，雖然廣泛地使用液狀密封樹脂，但液狀密封樹脂難以調節注入位置或注入量。因此，業界提出有使用片狀密封樹脂(底部填充片)填充半導體元件與基板之間之空間的技術(專利文獻1)。 In order to secure the surface of the semiconductor element or the connection reliability between the semiconductor element and the substrate, the space between the semiconductor element and the substrate is filled with a sealing resin after the flip chip connection. Although such a sealing resin is widely used as a liquid sealing resin, it is difficult to adjust the injection position or the injection amount of the liquid sealing resin. Therefore, the industry has proposed a technique of filling a space between a semiconductor element and a substrate using a sheet-like sealing resin (underfill sheet) (Patent Document 1).

一般而言，於使用片狀樹脂組合物作為底部填充片之製程中，採用一面利用貼附於半導體元件之片狀樹脂組合物填充基板等被黏著體與半導體元件之間之空間一面將半導體元件連接於被黏著體而安裝的順序。於上述製程中，易進行被黏著體與半導體元件之間之空間之填充。 In general, in the process of using the sheet-like resin composition as the underfill sheet, the semiconductor element is filled with a space between the adherend and the semiconductor element, such as a substrate, by a sheet-like resin composition attached to the semiconductor element. The order in which it is attached to the adherend. In the above process, the filling of the space between the adherend and the semiconductor element is facilitated.

[先前技術文獻] [Previous Technical Literature] [專利文獻] [Patent Literature]

[專利文獻1]日本專利第4438973號 [Patent Document 1] Japanese Patent No. 44387973

於上述製程中，貼合於半導體元件之片狀樹脂組合物與被黏著體經貼合，因此要求片狀樹脂組合物追隨於被黏著體表面之凹凸而密接。然而，伴隨著被黏著體上之電極等立體構造物之數量之增加或電路之狹小化，有片狀樹脂組合物對被黏著體之密接程度降低而於被黏著體與片狀樹脂組合物之間產生空隙(氣泡)的情況。若存在此種氣泡，則於以下之步驟中進行減壓處理或加熱處理之情形時，有氣泡膨脹而導致被黏著體與片狀樹脂組合物之間之密接性降低之情況，其結果為，將半導體元件安裝於被黏著體時半導體元件與被黏著體之連接可靠性降低。尤其，雖然當為規模相對較大之先前之半導體裝置時可忽略微小空隙之存在，但伴隨著半導體裝置之小型化、薄型化進展，而變得無法忽略微小空隙之影響。 In the above process, since the sheet-like resin composition bonded to the semiconductor element is bonded to the adherend, it is required that the sheet-like resin composition follows the unevenness of the surface of the adherend and is in close contact with each other. However, with the increase in the number of three-dimensional structures such as electrodes on the adherend or the narrowing of the circuit, the degree of adhesion of the sheet-like resin composition to the adherend is lowered to the adherend and the sheet-like resin composition. A case where a gap (bubble) is generated. When such a bubble is present, when the pressure reduction treatment or the heat treatment is performed in the following step, the bubble is swollen, and the adhesion between the adherend and the sheet-like resin composition is lowered. As a result, When the semiconductor element is mounted on the adherend, the reliability of connection between the semiconductor element and the adherend is lowered. In particular, although the existence of minute voids can be neglected in the case of a conventional semiconductor device having a relatively large scale, the influence of minute voids cannot be ignored as the size and thickness of the semiconductor device progress.

本發明之目的在於提供一種抑制對被黏著體與片狀樹脂組合物之界面之可靠性產生影響的空隙之產生，而可製造高可靠性之半導體裝置的半導體裝置之製造方法。 An object of the present invention is to provide a method of manufacturing a semiconductor device capable of producing a highly reliable semiconductor device by suppressing generation of voids which affect the reliability of the interface between the adherend and the sheet-like resin composition.

本案發明者等人努力進行研究，結果發現可藉由採用下述構成而達成上述目的，從而完成本發明。 The inventors of the present invention have diligently conducted research, and as a result, have found that the above object can be attained by the following constitution, and the present invention has been completed.

即，本發明係用以填充被黏著體與電性連接於該被黏著體之半導體元件之間之空間的熱硬化性片狀樹脂組合物，且於溫度範圍50℃~250℃、升溫速度10℃/min、頻率1Hz之測定條件下測定上述片狀樹脂組合物之黏度時， 溫度150℃下之黏度η150為0.05MPa‧s≦η150≦2.2MPa‧s，溫度200℃下之黏度η200為1.0MPa‧s≦η200≦100.0MPa‧s。 That is, the present invention is a thermosetting sheet-like resin composition for filling a space between an adherend and a semiconductor element electrically connected to the adherend, and has a temperature range of 50 ° C to 250 ° C and a temperature increase rate of 10 When the viscosity of the above-mentioned sheet-like resin composition is measured under the measurement conditions of ° C/min and a frequency of 1 Hz, the viscosity η 150 at a temperature of 150 ° C is 0.05 MPa ‧ ≦ 150 150 ≦ 2.2 MPa ‧ s, and the viscosity at a temperature of 200 ° C η 200 is 1.0 MPa ‧ ≦ 200 200 ≦ 100.0 MPa ‧ s.

該片狀樹脂組合物於在特定之測定條件下測定黏度時，溫度150℃下之黏度η150為0.05MPa‧s≦η150≦2.2MPa‧s。熱硬化性之該片狀樹脂組合物於150℃下處於自此前未硬化之狀態開始進行熱硬化之階段、或正在進行熱硬化之階段。與此同時，於存在空隙之情形時，即便其為極其微小之空隙，空隙之膨脹程度亦隨著升溫而變大。藉由於熱硬化之初期階段使黏度η150成為上述範圍，可成為如下狀態，即，黏度上升至能夠抑制空隙膨脹之程度，且黏度之上升被抑制至被黏著體-半導體元件間形成良好接合狀態之程度。有當黏度η150過低時難以抑制空隙之膨脹、而當過高時被黏著體與半導體元件之接合不充分之虞。 When the sheet-like resin composition was measured for viscosity under specific measurement conditions, the viscosity η 150 at a temperature of 150 ° C was 0.05 MPa ‧ ≦ 150 150 ≦ 2.2 MPa ‧ s. The sheet-like resin composition which is thermosetting is at a stage of heat hardening from a state which has not been previously cured at 150 ° C, or a stage in which heat hardening is being performed. At the same time, in the case where there is a void, even if it is an extremely small gap, the degree of expansion of the void becomes larger as the temperature rises. When the viscosity η 150 is in the above range due to the initial stage of thermal curing, the viscosity can be increased to such an extent that the void expansion can be suppressed, and the increase in viscosity is suppressed to form a good bonding state between the adherend and the semiconductor element. The extent of it. When the viscosity η 150 is too low, it is difficult to suppress the expansion of the void, and when it is too high, the bonding between the adherend and the semiconductor element is insufficient.

進而，該片狀樹脂組合物於溫度200℃下之黏度η200為1.0MPa‧s≦η200≦100.0MPa‧s。熱硬化性之該片狀樹脂組合物於200℃下處於熱硬化進行至相當程度而接近於視為熱硬化反應結束之階段(為方便起見，將該階段稱為「完全硬化」)之狀態。於存在空隙之情形時，雖然於200℃之高溫下膨脹之程度變得更大，但藉由於熱硬化之最終階段使黏度η200成為上述範圍，可抑制空隙之膨脹。有當黏度η200過低時空隙之膨脹之抑制不充分，而當過高時被黏著體與半導體元件之接合不充分之虞。 Further, the sheet-like resin composition had a viscosity η 200 at a temperature of 200 ° C of 1.0 MPa ‧ ≦ 200 200 ≦ 100.0 MPa ‧ s. The sheet-like resin composition having thermosetting properties is subjected to thermal hardening at 200 ° C to a considerable extent and is close to a state in which the end of the thermosetting reaction is considered (this stage is referred to as "complete hardening" for convenience). . In the case where a void is present, although the degree of expansion at a high temperature of 200 ° C becomes larger, the viscosity η 200 becomes the above range by the final stage of thermal hardening, and the expansion of the void can be suppressed. When the viscosity η 200 is too low, the suppression of the expansion of the void is insufficient, and when it is too high, the adhesion between the adherend and the semiconductor element is insufficient.

如此，本發明係基於如下新穎概念之技術思想：著眼於用以使將附有片狀樹脂組合物之半導體元件貼合於被黏著體後之片狀樹脂組合物熱硬化的加熱過程中之空隙之膨脹現象，藉由控制各溫度下之黏度而抑制空隙之膨脹，從而維持微小狀態。藉由該片狀樹脂組合物，可製造假設即便產生空隙之夾雜亦具有優異之連接可靠性的半導體裝置。 Thus, the present invention is based on the technical idea of the following novel concept: focusing on the void in the heating process for thermally hardening the sheet-like resin composition after attaching the semiconductor element to which the sheet-like resin composition is attached to the adherend The expansion phenomenon suppresses the expansion of the void by controlling the viscosity at each temperature, thereby maintaining a minute state. By the sheet-like resin composition, it is possible to manufacture a semiconductor device which is excellent in connection reliability even in the case where voids are formed.

於上述測定條件下測定上述片狀樹脂組合物之黏度時，進而較佳為溫度80℃下之黏度η80為0.001MPa‧s≦η80≦1.0MPa‧s。藉由將該片狀樹脂組合物之溫度80℃下之黏度η80設為上述範圍，而於被黏著體與該片狀樹脂組合物貼合時，該片狀樹脂組合物充分地追隨被黏著體上之凹凸，因此可防止空隙之夾雜。其結果為，可減少自起初起之要素間之空隙之絕對量，可製造連接可靠性更良好之半導體裝置。當黏度η80過低時，自被黏著體-半導體元件間之溢出量變大，當過高時，對被黏著體之凹凸之追隨性降低。 When the viscosity of the sheet-like resin composition is measured under the above-described measurement conditions, it is further preferred that the viscosity η 80 at a temperature of 80 ° C is 0.001 MPa ‧ s η 80 ≦ 1.0 MPa ‧ s. When the viscosity η 80 of the sheet-like resin composition at a temperature of 80 ° C is in the above range, when the adherend is bonded to the sheet-like resin composition, the sheet-like resin composition sufficiently follows the adhesion. The unevenness of the body prevents the inclusion of voids. As a result, the absolute amount of the gap between the elements from the beginning can be reduced, and a semiconductor device having better connection reliability can be manufactured. When the viscosity η 80 is too low, the amount of overflow from the adherend-semiconductor element becomes large, and when it is too high, the followability to the unevenness of the adherend is lowered.

較佳為，上述黏度η80為0.01MPa‧s≦η80≦0.1MPa‧s，上述黏度η150為0.1MPa‧s≦η150≦2.2MPa‧s，上述黏度η200為1.0MPa‧s≦η200≦50.0MPa‧s。藉由將各溫度下之黏度控制於上述範圍，能以更高之級別達成對被黏著體之凹凸之追隨、空隙膨脹之抑制及被黏著體與半導體元件之接合中之任一者。 Preferably, the viscosity η 80 is 0.01 MPa ‧ ≦ η 80 ≦ 0.1 MPa ‧ s, the viscosity η 150 is 0.1 MPa ‧ ≦ 150 150 ≦ 2.2 MPa ‧ s, and the viscosity η 200 is 1.0 MPa ‧ ≦ η 200 ≦ 50.0MPa‧s. By controlling the viscosity at each temperature to the above range, it is possible to achieve the tracking of the unevenness of the adherend, the suppression of the void expansion, and the bonding between the adherend and the semiconductor element at a higher level.

該片狀樹脂組合物較佳為含有環氧樹脂、硬化劑、熱塑性樹脂、無機填充劑及熱硬化促進觸媒。藉此，可高效率地進行該片狀樹脂組合物之黏度之控制。 The sheet-like resin composition preferably contains an epoxy resin, a curing agent, a thermoplastic resin, an inorganic filler, and a thermosetting-promoting catalyst. Thereby, the control of the viscosity of the sheet-like resin composition can be efficiently performed.

上述熱塑性樹脂較佳為重量平均分子量為5×105以上之丙烯酸系樹脂。藉此，可對該片狀樹脂組合物賦予適度之黏度，可更有效地抑制空隙之膨脹。 The thermoplastic resin is preferably an acrylic resin having a weight average molecular weight of 5 × 10 5 or more. Thereby, an appropriate viscosity can be imparted to the sheet-like resin composition, and the expansion of the void can be more effectively suppressed.

上述無機填充劑之平均粒徑較佳為10nm以上且500nm以下。藉此，易於控制該片狀樹脂組合物之黏度，進而可對該片狀樹脂組合物賦予適度之透明性。 The average particle diameter of the inorganic filler is preferably 10 nm or more and 500 nm or less. Thereby, the viscosity of the sheet-like resin composition can be easily controlled, and the sheet-like resin composition can be imparted with appropriate transparency.

上述熱硬化促進觸媒係於分子內含有氮原子之有機化合物，且較佳為該有機化合物之分子量為50~500。藉此，可控制該片狀樹脂組合物之升溫所伴隨之熱硬化反應之進行程度，其結果為，容易進行如於各溫度下具有所需黏度之設計。 The thermosetting-promoting catalyst is an organic compound containing a nitrogen atom in the molecule, and preferably the molecular weight of the organic compound is 50 to 500. Thereby, the degree of progress of the thermosetting reaction accompanying the temperature rise of the sheet-like resin composition can be controlled, and as a result, it is easy to carry out a design having a desired viscosity at each temperature.

又，本發明係關於一種積層片，其包括：黏著帶，其具有基材及設置於該基材上之黏著劑層；及該片狀樹脂組合物，其積層於上述黏著劑層上。 Further, the present invention relates to a laminated sheet comprising: an adhesive tape having a substrate and an adhesive layer provided on the substrate; and the sheet-like resin composition laminated on the adhesive layer.

根據該構成，可獲得黏著帶一體型片狀樹脂組合物，因此於可省略將貼合有片狀樹脂組合物之半導體元件與黏著帶貼合之步驟方面，可使生產性進一步提高。 According to this configuration, the adhesive sheet-integrated sheet-like resin composition can be obtained. Therefore, the step of bonding the semiconductor element to which the sheet-like resin composition is bonded to the adhesive tape can be omitted, and the productivity can be further improved.

上述黏著帶可為半導體晶圓之背面研削用帶或切晶帶中之任一者。 The adhesive tape may be any one of a back grinding tape or a dicing tape of a semiconductor wafer.

進而，本發明係關於一種半導體裝置之製造方法，其係包括被黏著體、與該被黏著體電性連接之半導體元件、及填充該被黏著體與該半導體元件之間之空間之片狀樹脂組合物的半導體裝置之製造方法，且該方法包括如下步驟：準備該片狀樹脂組合物貼合於上述半導體元件而成之附有片狀樹脂組合物之半導體元件；及連接步驟，其係將上述被黏著體與上述半導體元件之間之空間以上述片狀樹脂組合物予以填充而將上述半導體元件與上述被黏著體電性連接。 Furthermore, the present invention relates to a method of fabricating a semiconductor device, comprising: an adherend, a semiconductor element electrically connected to the adherend, and a sheet-like resin filling a space between the adherend and the semiconductor element; a method of producing a semiconductor device of a composition, comprising the steps of: preparing a semiconductor element having a sheet-like resin composition obtained by bonding the sheet-like resin composition to the semiconductor element; and a connecting step of The space between the adherend and the semiconductor element is filled with the sheet-like resin composition, and the semiconductor element is electrically connected to the adherend.

該製造方法中，使用各溫度下之黏度受到控制之片狀樹脂組合物，因此可達成被黏著體與半導體元件之良好接合狀態，並且抑制空隙之膨脹而製造高可靠性之半導體裝置。 In the production method, since the sheet-like resin composition whose viscosity is controlled at each temperature is used, it is possible to achieve a high-reliability semiconductor device by achieving a good bonding state between the adherend and the semiconductor element and suppressing the expansion of the void.

1‧‧‧背面研削用帶 1‧‧‧Back grinding belt

1a‧‧‧基材 1a‧‧‧Substrate

1b‧‧‧黏著劑層 1b‧‧‧Adhesive layer

2‧‧‧片狀樹脂組合物 2‧‧‧Flake resin composition

3‧‧‧半導體晶圓 3‧‧‧Semiconductor wafer

3a‧‧‧電路面 3a‧‧‧ circuit surface

3b‧‧‧背面 3b‧‧‧back

4‧‧‧連接構件 4‧‧‧Connecting components

5‧‧‧半導體晶片(半導體元件) 5‧‧‧Semiconductor wafer (semiconductor component)

10‧‧‧積層片 10‧‧‧Layered film

11‧‧‧切晶帶 11‧‧‧Cutting Tape

11a‧‧‧基材 11a‧‧‧Substrate

11b‧‧‧黏著劑層 11b‧‧‧Adhesive layer

16‧‧‧被黏著體 16‧‧‧Adhesive body

17‧‧‧導電材 17‧‧‧Electrical materials

20‧‧‧半導體裝置 20‧‧‧Semiconductor device

41‧‧‧切晶帶 41‧‧‧Cutting Tape

41a‧‧‧基材 41a‧‧‧Substrate

41b‧‧‧黏著劑層 41b‧‧‧Adhesive layer

42‧‧‧片狀樹脂組合物 42‧‧‧Flake resin composition

43‧‧‧半導體晶圓 43‧‧‧Semiconductor wafer

44‧‧‧連接構件 44‧‧‧Connecting members

45‧‧‧半導體晶片(半導體元件) 45‧‧‧Semiconductor wafer (semiconductor component)

60‧‧‧半導體裝置 60‧‧‧Semiconductor device

66‧‧‧被黏著體 66‧‧‧Adhesive body

圖1係表示本發明之一實施形態之積層片的剖面模式圖。 Fig. 1 is a schematic cross-sectional view showing a laminated sheet according to an embodiment of the present invention.

圖2A係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 2A is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to an embodiment of the present invention.

圖2B係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 2B is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to an embodiment of the present invention.

圖2C係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 2C is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to an embodiment of the present invention.

圖2D係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 2D is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to an embodiment of the present invention.

圖2E係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 2E is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to an embodiment of the present invention.

圖2F係表示本發明之一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 2F is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to an embodiment of the present invention.

圖3A係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 3A is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

圖3B係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 3B is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

圖3C係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 3C is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

圖3D係表示本發明之另一實施形態之半導體裝置之製造步驟之一步驟的剖面模式圖。 Fig. 3D is a schematic cross-sectional view showing a step of a manufacturing step of a semiconductor device according to another embodiment of the present invention.

以下，一面參照圖式一面對本發明之實施形態進行說明。其中，於圖之一部分或全部中，省略對說明無用之部分，又，存在為了易於說明而放大或縮小等而進行圖示之部分。表示上下等位置關係之用語若未特別言及，則僅僅為了易於說明而使用，無任何限定本發明之構成之意圖。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in some or all of the drawings, a portion that is not useful for explanation is omitted, and a portion that is enlarged or reduced for ease of explanation is shown. The term "upper and lower positional relationship" is used unless otherwise specified, and is used for ease of explanation only, without any intention of limiting the constitution of the present invention.

<第1實施形態> <First embodiment>

於本實施形態中，以使用背面研削用帶作為黏著帶、且片狀樹脂組合物與背面研削用帶成為一體之積層片及使用其之半導體裝置之製造方法為例進行說明。以下之說明除了關於黏著劑層之事項以外， 基本上亦可用於單獨為片狀樹脂組合物之情形。 In the present embodiment, a laminated sheet in which a back side grinding belt is used as an adhesive tape, a sheet-like resin composition and a back grinding belt, and a manufacturing method of a semiconductor device using the same will be described as an example. The following instructions are in addition to the matters concerning the adhesive layer. Basically, it can also be used in the case of a sheet-like resin composition alone.

(積層片) (layered film)

如圖1所示般，積層片10具備背面研削用帶1、及積層於背面研削用帶1上之片狀樹脂組合物2。再者，片狀樹脂組合物2只要如圖1所示般以對於與半導體晶圓3(參照圖2A)之貼合足夠之尺寸設置即可，亦可積層於背面研削用帶1之整個表面。 As shown in FIG. 1, the laminated sheet 10 is provided with the back grinding belt 1 and the sheet-like resin composition 2 laminated on the back grinding belt 1. Further, the sheet-like resin composition 2 may be provided in a size sufficient for bonding to the semiconductor wafer 3 (see FIG. 2A) as shown in FIG. 1, and may be laminated on the entire surface of the back grinding belt 1. .

(片狀樹脂組合物) (flaky resin composition)

本實施形態中之片狀樹脂組合物2可用作對表面安裝之半導體元件與被黏著體之間之空間進行填充的密封用膜。 The sheet-like resin composition 2 in the present embodiment can be used as a film for sealing which fills a space between a surface-mounted semiconductor element and an adherend.

片狀樹脂組合物2於溫度範圍50℃~250℃、升溫速度10℃/min、頻率1Hz之測定條件下測定黏度時，溫度150℃下之黏度η150為0.05MPa‧s≦η150≦2.2MPa‧s即可。進而，黏度η150較佳為0.1MPa‧s≦η150≦2.2MPa‧s。熱硬化性之該片狀樹脂組合物於150℃下處於自此前未硬化之狀態開始進行熱硬化之階段、或正在進行熱硬化之階段。與此同時，於存在空隙之情形時，即便其為極其微小之空隙，空隙之膨脹程度亦隨著升溫而變大。藉由於熱硬化之初期階段將黏度η150設為上述範圍，可成為如下狀態：黏度上升至能夠抑制空隙膨脹之程度，且將黏度之上升抑制至被黏著體-半導體元件間形成良好之接合狀態之程度。有當黏度η150過低時難以抑制空隙之膨脹，當過高時被黏著體與半導體元件之接合不充分之虞。 When the sheet-like resin composition 2 is measured under the measurement conditions of a temperature range of 50 ° C to 250 ° C, a temperature increase rate of 10 ° C / min, and a frequency of 1 Hz, the viscosity η 150 at a temperature of 150 ° C is 0.05 MPa ‧ s 150 150 ≦ 2.2 MPa‧s can be. Further, the viscosity η 150 is preferably 0.1 MPa ‧ s ≦ 150 ≦ 2.2 MPa ‧ s. The sheet-like resin composition which is thermosetting is at a stage of heat hardening from a state which has not been previously cured at 150 ° C, or a stage in which heat hardening is being performed. At the same time, in the case where there is a void, even if it is an extremely small gap, the degree of expansion of the void becomes larger as the temperature rises. By setting the viscosity η 150 to the above range in the initial stage of thermal curing, the viscosity can be increased to such an extent that the void expansion can be suppressed, and the increase in viscosity can be suppressed to a good bonding state between the adherend and the semiconductor element. The extent of it. When the viscosity η 150 is too low, it is difficult to suppress the expansion of the void, and when it is too high, the bonding between the adherend and the semiconductor element is insufficient.

進而，該片狀樹脂組合物於在上述測定條件下所測定之於溫度200℃下之黏度η200為1.0MPa‧s≦η200≦100.0MPa‧s。進而，黏度η200較佳為1.0MPa‧s≦η200≦50.0MPa‧s。熱硬化性之該片狀樹脂組合物於200℃下處於熱硬化進展至相當程度而接近於完全硬化之狀態。於存在空隙之情形時，於200℃之高溫下膨脹之程度變得更大，但藉由於熱硬化之最終階段將黏度η200設為上述範圍，可抑制空隙之 膨脹。有當黏度η200過低時空隙之膨脹之抑制不充分，當過高時被黏著體與半導體元件之接合不充分之虞。 Further, the sheet-like resin composition had a viscosity η 200 measured at a temperature of 200 ° C under the above-described measurement conditions of 1.0 MPa ‧ ≦ 200 200 ≦ 100.0 MPa ‧ s. Further, the viscosity η 200 is preferably 1.0 MPa ‧ s ≦ 200 ≦ 50.0 MPa ‧ s. The sheet-like resin composition having thermosetting properties is in a state in which the thermosetting progresses to a considerable extent at 200 ° C and is close to the state of complete hardening. In the case where a void is present, the degree of expansion at a high temperature of 200 ° C becomes larger, but by the viscosity η 200 in the final stage of the thermal hardening, the expansion of the void can be suppressed. When the viscosity η 200 is too low, the suppression of the expansion of the void is insufficient, and when it is too high, the bonding between the adherend and the semiconductor element is insufficient.

於在上述測定條件下測定片狀樹脂組合物2之黏度時，進而，溫度80℃下之黏度η80較佳為0.001MPa‧s≦η80≦1.0MPa‧s，更佳為0.005MPa‧s≦η80≦0.5MPa‧s。藉由將該片狀樹脂組合物之溫度80℃下之黏度η80設為上述範圍，而被黏著體與該片狀樹脂組合物貼合時，該片狀樹脂組合物充分地追隨於被黏著體上之凹凸，因此可防止空隙之夾雜。其結果為，可減少自起初起之要素間之空隙之絕對量，可製造連接可靠性更良好之半導體裝置。當黏度η80過低時，自被黏著體-半導體元件間之溢出量變大，當過高時對被黏著體之凹凸之追隨性降低。 When the viscosity of the sheet-like resin composition 2 is measured under the above-described measurement conditions, the viscosity η 80 at a temperature of 80 ° C is preferably 0.001 MPa ‧ s η 80 ≦ 1.0 MPa ‧ , more preferably 0.005 MPa ‧ s ≦η 80 ≦0.5MPa‧s. When the viscosity η 80 at a temperature of 80 ° C in the sheet-like resin composition is in the above range, when the adherend is bonded to the sheet-like resin composition, the sheet-like resin composition sufficiently follows the adhesion. The unevenness of the body prevents the inclusion of voids. As a result, the absolute amount of the gap between the elements from the beginning can be reduced, and a semiconductor device having better connection reliability can be manufactured. When the viscosity η 80 is too low, the amount of overflow from the adherend-semiconductor element becomes large, and when it is too high, the followability to the unevenness of the adherend is lowered.

作為片狀樹脂組合物之構成材料，可列舉併用熱塑性樹脂與熱硬化性樹脂者。又，亦可單獨使用熱塑性樹脂或熱硬化性樹脂。 As a constituent material of the sheet-like resin composition, a thermoplastic resin and a thermosetting resin are used in combination. Further, a thermoplastic resin or a thermosetting resin may be used alone.

作為上述熱塑性樹脂，可列舉：天然橡膠、丁基橡膠、異戊二烯橡膠、氯丁二烯橡膠、乙烯-乙酸乙烯酯共聚物、乙烯-丙烯酸共聚物、乙烯-丙烯酸酯共聚物、聚丁二烯樹脂、聚碳酸酯樹脂、熱塑性聚醯亞胺樹脂、6-尼龍或6,6-尼龍等聚醯胺樹脂、苯氧基樹脂、丙烯酸系樹脂、PET(polyethylene terephthalate，聚對苯二甲酸乙二酯)或PBT(polybutylene terephthalate，聚對苯二甲酸丁二酯)等飽和聚酯樹脂、聚醯胺醯亞胺樹脂、或氟樹脂等。該等熱塑性樹脂可單獨使用或併用2種以上而使用。該等熱塑性樹脂中，尤佳為離子性雜質較少、耐熱性較高、且可確保半導體元件之可靠性之丙烯酸系樹脂。 Examples of the thermoplastic resin include natural rubber, butyl rubber, isoprene rubber, chloroprene rubber, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylate copolymer, and polybutylene. Diene resin, polycarbonate resin, thermoplastic polyimide resin, polyamide resin such as 6-nylon or 6,6-nylon, phenoxy resin, acrylic resin, PET (polyethylene terephthalate, polyterephthalic acid) A saturated polyester resin such as ethylene glycol) or PBT (polybutylene terephthalate), a polyamidoximine resin, or a fluororesin. These thermoplastic resins may be used singly or in combination of two or more. Among these thermoplastic resins, an acrylic resin having less ionic impurities, high heat resistance, and reliability of a semiconductor element is particularly preferable.

上述丙烯酸系樹脂之重量平均分子量較佳為5×105以上，更佳為7×105以上。藉此，可對該片狀樹脂組合物賦予適度之黏度，可更有效率地抑制空隙之膨脹。再者，就抑制黏度之過度上升之觀點而言，上述重量平均分子量較佳為1×107以下。 The weight average molecular weight of the acrylic resin is preferably 5 × 10 5 or more, and more preferably 7 × 10 5 or more. Thereby, an appropriate viscosity can be imparted to the sheet-like resin composition, and the expansion of the void can be more effectively suppressed. Further, from the viewpoint of suppressing excessive increase in viscosity, the weight average molecular weight is preferably 1 × 10 7 or less.

作為上述丙烯酸系樹脂，並無特別限定，可列舉以具有碳數30以下、尤其碳數4~18之直鏈或支鏈之烷基的丙烯酸或甲基丙烯酸之酯之1種或2種以上作為成分之聚合物等。作為上述烷基，例如可列舉：甲基、乙基、丙基、異丙基、正丁基、第三丁基、異丁基、戊基、異戊基、己基、庚基、環己基、2-乙基己基、辛基、異辛基、壬基、異壬基、癸基、異癸基、十一烷基、月桂基、十三烷基、十四烷基、硬脂基、十八烷基、或十二烷基等。 The acrylic resin is not particularly limited, and one or more kinds of esters of acrylic acid or methacrylic acid having a linear or branched alkyl group having a carbon number of 30 or less, particularly a carbon number of 4 to 18, may be mentioned. A polymer or the like as a component. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, and a cyclohexyl group. 2-ethylhexyl, octyl, isooctyl, decyl, isodecyl, decyl, isodecyl, undecyl, lauryl, tridecyl, tetradecyl, stearyl, ten Octaalkyl, or dodecyl, and the like.

又，作為形成上述聚合物之其他單體，並無特別限定，例如可列舉：丙烯酸、甲基丙烯酸、丙烯酸羧基乙酯、丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸或丁烯酸等各種含有羧基之單體；順丁烯二酸酐或伊康酸酐等各種酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯或(甲基)丙烯酸(4-羥基甲基環己基)甲酯等各種含有羥基之單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯或(甲基)丙烯醯氧基萘磺酸等各種含有磺酸基之單體；或2-羥基乙基丙烯醯基磷酸酯等各種含有磷酸基之單體；如丙烯腈等之含有氰基之單體等。 Further, the other monomer forming the polymer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, carboxyethyl acrylate, carboxypentyl acrylate, itaconic acid, maleic acid, and antibutene. Various carboxyl group-containing monomers such as diacid or crotonic acid; various anhydride monomers such as maleic anhydride or itaconic anhydride; 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, (meth)acrylic acid Various hydroxyl group-containing monomers such as 12-hydroxylauryl ester or (4-hydroxymethylcyclohexyl)methyl (meth)acrylate; styrenesulfonic acid, allylsulfonic acid, 2-(methyl)acrylamide a sulfonic acid group-containing monomer such as -2-methylpropanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate or (meth)acryloxynaphthalenesulfonic acid; Or a monomer containing a phosphate group such as 2-hydroxyethylpropenyl phosphate; a monomer containing a cyano group such as acrylonitrile or the like.

作為上述熱硬化性樹脂，可列舉酚系樹脂、胺基樹脂、不飽和聚酯樹脂、環氧樹脂、聚胺基甲酸酯樹脂、聚矽氧樹脂、或熱硬化性聚醯亞胺樹脂等。該等樹脂可單獨使用或併用2種以上而使用。尤佳為含有較少之使半導體元件腐蝕之離子性雜質等之環氧樹脂。又，作為環氧樹脂之硬化劑，較佳為酚系樹脂。 Examples of the thermosetting resin include a phenol resin, an amine resin, an unsaturated polyester resin, an epoxy resin, a polyurethane resin, a polyoxyxylene resin, or a thermosetting polyimide resin. . These resins may be used singly or in combination of two or more. More preferably, it is an epoxy resin containing a small amount of ionic impurities which cause corrosion of a semiconductor element. Further, as the curing agent for the epoxy resin, a phenol resin is preferable.

上述環氧樹脂只要為一般用作接著劑組合物者則無特別限定，例如可使用雙酚A型、雙酚F型、雙酚S型、溴化雙酚A型、氫化雙酚A型、雙酚AF型、聯苯型、萘型、茀型、苯酚酚醛清漆型、鄰甲酚酚 醛清漆型、三羥基苯基甲烷型、四酚基乙烷型等二官能環氧樹脂或多官能環氧樹脂、或乙內醯脲型、三縮水甘油基異氰尿酸酯型或縮水甘油胺型等環氧樹脂。該等可單獨使用或併用2種以上而使用。該等環氧樹脂中，尤佳為酚醛清漆型環氧樹脂、聯苯型環氧樹脂、三羥基苯基甲烷型樹脂或四酚基乙烷型環氧樹脂。其原因在於，該等環氧樹脂與作為硬化劑之酚系樹脂之反應性充分，耐熱性等優異。 The epoxy resin is not particularly limited as long as it is generally used as an adhesive composition, and for example, bisphenol A type, bisphenol F type, bisphenol S type, brominated bisphenol A type, hydrogenated bisphenol A type, or the like can be used. Bisphenol AF type, biphenyl type, naphthalene type, anthraquinone type, phenol novolac type, o-cresol Difunctional epoxy resin or polyfunctional epoxy resin such as aldehyde varnish type, trihydroxyphenylmethane type or tetraphenol ethane type, or carbendazim type, triglycidyl isocyanurate type or glycidol Amine type epoxy resin. These may be used alone or in combination of two or more. Among these epoxy resins, a novolak type epoxy resin, a biphenyl type epoxy resin, a trishydroxyphenylmethane type resin or a tetraphenol ethane type epoxy resin is particularly preferable. This is because the epoxy resin and the phenol resin as a curing agent have sufficient reactivity and are excellent in heat resistance and the like.

進而，上述酚系樹脂係作為上述環氧樹脂之硬化劑而發揮作用者，例如可列舉苯酚酚醛清漆樹脂、苯酚芳烷基樹脂、甲酚酚醛清漆樹脂、第三丁基苯酚酚醛清漆樹脂、壬基苯酚酚醛清漆樹脂等酚醛清漆型酚系樹脂、可溶酚醛型酚系樹脂、聚對羥基苯乙烯等聚羥基苯乙烯等。該等可單獨使用或併用2種以上而使用。該等酚系樹脂中，尤佳為苯酚酚醛清漆樹脂、苯酚芳烷基樹脂。其原因在於：可使半導體裝置之連接可靠性提高。 Further, the phenol-based resin functions as a curing agent for the epoxy resin, and examples thereof include a phenol novolak resin, a phenol aralkyl resin, a cresol novolak resin, a third butyl phenol novolak resin, and a hydrazine. A novolak type phenol type resin such as a phenol novolak resin, a novolac type phenol type resin, or a polyhydroxystyrene such as polyparaxyl styrene. These may be used alone or in combination of two or more. Among these phenolic resins, a phenol novolac resin and a phenol aralkyl resin are particularly preferable. The reason for this is that the connection reliability of the semiconductor device can be improved.

上述環氧樹脂與酚系樹脂之調配比率例如較佳為以相對於上述環氧樹脂成分中之環氧基每1當量而酚系樹脂中之羥基成為0.5~2.0當量之方式調配。更佳為0.8~1.2當量。即，其原因在於，若兩者之調配比率偏離上述範圍，則無法進行充分之硬化反應，而環氧樹脂硬化物之特性容易劣化。 For example, the ratio of the epoxy resin to the phenol resin is preferably 0.5 to 2.0 equivalents per equivalent of the epoxy group in the epoxy resin component and the hydroxyl group in the phenol resin. More preferably, it is 0.8 to 1.2 equivalents. That is, the reason is that if the blending ratio of the two is out of the above range, a sufficient curing reaction cannot be performed, and the properties of the cured epoxy resin are likely to deteriorate.

再者，於本實施形態中，尤佳為使用環氧樹脂、酚系樹脂及丙烯酸系樹脂之片狀樹脂組合物。該等樹脂由於離子性雜質較少且耐熱性較高，故而可確保半導體元件之可靠性。此情形時之調配比係環氧樹脂與酚系樹脂之混合量相對於丙烯酸系樹脂成分100重量份為10~1000重量份。 Further, in the present embodiment, a sheet-like resin composition of an epoxy resin, a phenol resin, and an acrylic resin is particularly preferably used. These resins have low ionic impurities and high heat resistance, so that the reliability of the semiconductor element can be ensured. In this case, the blending ratio of the epoxy resin to the phenol resin is 10 to 1000 parts by weight based on 100 parts by weight of the acrylic resin component.

作為環氧樹脂與酚系樹脂之熱硬化促進觸媒，並無特別限制，可自公知之熱硬化促進觸媒中適當選擇而使用。熱硬化促進觸媒可單獨使用或組合2種以上而使用。作為熱硬化促進觸媒，例如可使用胺 系熱硬化促進觸媒、磷系熱硬化促進觸媒、咪唑系熱硬化促進觸媒、硼系熱硬化促進觸媒、磷-硼系熱硬化促進觸媒等。 The thermosetting-promoting catalyst of the epoxy resin and the phenol resin is not particularly limited, and can be appropriately selected from known thermal hardening catalysts. The thermosetting-suppressing catalyst may be used singly or in combination of two or more. As a thermosetting promoting catalyst, for example, an amine can be used. It is a thermosetting-promoting catalyst, a phosphorus-based thermosetting-promoting catalyst, an imidazole-based thermosetting-promoting catalyst, a boron-based thermosetting-promoting catalyst, and a phosphorus-boron-based thermosetting-promoting catalyst.

其中，熱硬化促進觸媒係於分子內含有氮原子之有機化合物，且較佳為該有機化合物之分子量為50~500。藉此，可控制該片狀樹脂組合物之升溫所伴隨之熱硬化反應之進行程度，其結果為，易於進行如於各溫度下具有所需黏度之設計。作為上述有機化合物之例，可較佳地使用咪唑系熱硬化促進觸媒。亦可較佳地利用市售品，例如可列舉商品名「2PHZ-PW」(四國化成股份有限公司製造)等。 Among them, the thermosetting-promoting catalyst is an organic compound containing a nitrogen atom in the molecule, and preferably the molecular weight of the organic compound is 50 to 500. Thereby, the degree of progress of the thermosetting reaction accompanying the temperature rise of the sheet-like resin composition can be controlled, and as a result, it is easy to carry out a design having a desired viscosity at each temperature. As an example of the above organic compound, an imidazole-based thermosetting-promoting catalyst can be preferably used. Commercially available products can be preferably used, and examples thereof include "2PHZ-PW" (manufactured by Shikoku Chemicals Co., Ltd.).

為了去除焊接凸塊表面之氧化膜而使半導體元件之安裝較為容易，亦可於片狀樹脂組合物2中添加助焊劑。作為助焊劑，並無特別限定，可使用先前公知之具有助焊劑作用之化合物，例如可列舉雙酚酸、己二酸、乙醯基水楊酸、苯甲酸、二苯羥乙酸、壬二酸、苄基苯甲酸、丙二酸、2,2-雙(羥基甲基)丙酸、水楊酸、鄰甲氧基苯甲酸(鄰大茴香酸)、間羥基苯甲酸、琥珀酸、2,6-二甲氧基甲基對甲酚、苯甲醯肼、碳醯肼、丙二醯肼、丁二醯肼、戊二醯肼、水楊醯肼、亞胺基二乙二醯肼、伊康二醯肼、檸檬三醯肼、硫代碳醯肼、二苯甲酮腙、4,4'-氧代雙苯磺醯肼及己二酸二醯肼等。助焊劑之添加量只要為發揮上述助焊劑作用之程度即可，通常相對於片狀樹脂組合物中所含之樹脂成分100重量份為0.1~20重量份左右。 In order to remove the oxide film on the surface of the solder bump and to facilitate mounting of the semiconductor element, a flux may be added to the sheet-like resin composition 2. The flux is not particularly limited, and a conventionally known compound having a flux action can be used, and examples thereof include bisphenolic acid, adipic acid, acetylsalicylic acid, benzoic acid, diphenylglycolic acid, and sebacic acid. , benzyl benzoic acid, malonic acid, 2,2-bis(hydroxymethyl)propionic acid, salicylic acid, o-methoxybenzoic acid (o-anisic acid), m-hydroxybenzoic acid, succinic acid, 2, 6-Dimethoxymethyl-p-cresol, benzamidine, carbon oxime, propylene dioxime, butyl hydrazine, pentane oxime, salicin, iminodiethylene dioxime, itan II Lanthanum, lemon triterpene, thiocarbon oxime, benzophenone oxime, 4,4'-oxobisbenzenesulfonate and diammonium adipate. The amount of the flux to be added may be about 0.1 to 20 parts by weight based on 100 parts by weight of the resin component contained in the sheet-like resin composition.

於本實施形態中，片狀樹脂組合物2亦可著色。於片狀樹脂組合物2中，作為藉由著色而呈現之顏色，並無特別限制，例如較佳為黑色、藍色、紅色、綠色等。著色時，可自顏料、染料等公知之著色劑中適當選擇而使用。 In the present embodiment, the sheet-like resin composition 2 can also be colored. In the sheet-like resin composition 2, the color to be exhibited by coloring is not particularly limited, and for example, black, blue, red, green, or the like is preferable. In the case of coloring, it can be suitably selected and used from a known coloring agent such as a pigment or a dye.

於預先使本實施形態之片狀樹脂組合物2以某種程度交聯之情形時，製作時，較良好為預先添加與聚合物之分子鏈末端之官能基等反應之多官能性化合物作為交聯劑。藉此，可使高溫下之接著特性提 高，謀求耐熱性之改善。 When the sheet-like resin composition 2 of the present embodiment is crosslinked to some extent in advance, it is preferable to add a polyfunctional compound which reacts with a functional group or the like at the end of the molecular chain of the polymer in advance. Joint agent. Thereby, the subsequent characteristics at high temperatures can be improved High, seeking improvement in heat resistance.

作為上述交聯劑，尤其更佳為甲苯二異氰酸酯、二苯基甲烷二異氰酸酯、對苯二異氰酸酯、1,5-萘二異氰酸酯、多元醇與二異氰酸酯之加成物等聚異氰酸酯化合物。作為交聯劑之添加量，相對於上述聚合物100重量份，通常較佳為設為0.05~7重量份。若交聯劑之量多於7重量份，則接著力降低，因此欠佳。另一方面，若少於0.05重量份，則凝聚力不足，因此欠佳。又，亦可視需要而與此種聚異氰酸酯化合物一併含有環氧樹脂等其他多官能性化合物。 As the crosslinking agent, a polyisocyanate compound such as toluene diisocyanate, diphenylmethane diisocyanate, p-phenylene diisocyanate, 1,5-naphthalene diisocyanate, or an adduct of a polyhydric alcohol and a diisocyanate is more preferable. The amount of the crosslinking agent to be added is usually preferably 0.05 to 7 parts by weight based on 100 parts by weight of the polymer. If the amount of the crosslinking agent is more than 7 parts by weight, the subsequent force is lowered, which is not preferable. On the other hand, if it is less than 0.05 part by weight, the cohesive strength is insufficient, which is not preferable. Further, other polyfunctional compounds such as an epoxy resin may be contained together with such a polyisocyanate compound as needed.

又，可於片狀樹脂組合物2中適當調配無機填充劑。無機填充劑之調配使得導電性之賦予或導熱性之提高、儲存彈性模數之調節等成為可能。 Further, an inorganic filler can be appropriately formulated in the sheet-like resin composition 2. The formulation of the inorganic filler makes it possible to impart conductivity or thermal conductivity, adjust the storage elastic modulus, and the like.

作為上述無機填充劑，例如可列舉二氧化矽、黏土、石膏、碳酸鈣、硫酸鋇、氧化鋁、氧化鈹、碳化矽、氮化矽等陶瓷類、鋁、銅、銀、金、鎳、鉻、鉛、錫、鋅、鈀、焊料等金屬、或合金類，此外可列舉包含碳等之各種無機粉末。該等可單獨使用或併用2種以上而使用。其中，較佳地使用二氧化矽，尤其是熔融二氧化矽。 Examples of the inorganic filler include ceramics such as cerium oxide, clay, gypsum, calcium carbonate, barium sulfate, aluminum oxide, cerium oxide, cerium carbide, and cerium nitride, and aluminum, copper, silver, gold, nickel, and chromium. Examples of the metal, or an alloy such as lead, tin, zinc, palladium or solder, and various inorganic powders including carbon. These may be used alone or in combination of two or more. Among them, cerium oxide, especially molten cerium oxide, is preferably used.

無機填充劑之平均粒徑並無特別限定，但較佳為10nm以上且500nm以下，更佳為20nm以上且400nm以下，進而較佳為50nm以上且300nm以下。藉由將無機填充劑之平均粒徑設為上述範圍，而易於控制片狀樹脂組合物之黏度，進而可對片狀樹脂組合物賦予適度之透明性。若上述無機填充劑之平均粒徑過小，則容易產生粒子之凝聚，有難以形成片狀樹脂組合物或難以控制黏度之情況。另一方面，若上述平均粒徑過大，則片狀樹脂組合物之透明性降低，或容易產生無機粒子混入片狀樹脂組合物與被黏著體之接合部，因此有半導體裝置之連接可靠性降低之虞。再者，於本發明中，亦可將平均粒徑互不相同之無機填充劑彼此組合而使用。又，平均粒徑係藉由光度式之粒度分 佈計(HORIBA製造，裝置名：LA-910)而求出之值。 The average particle diameter of the inorganic filler is not particularly limited, but is preferably 10 nm or more and 500 nm or less, more preferably 20 nm or more and 400 nm or less, and still more preferably 50 nm or more and 300 nm or less. By setting the average particle diameter of the inorganic filler to the above range, it is easy to control the viscosity of the sheet-like resin composition, and it is possible to impart appropriate transparency to the sheet-like resin composition. When the average particle diameter of the inorganic filler is too small, aggregation of particles tends to occur, and it may be difficult to form a sheet-like resin composition or it may be difficult to control the viscosity. On the other hand, when the average particle diameter is too large, the transparency of the sheet-like resin composition is lowered, or the inorganic particles are likely to be mixed into the joint portion between the sheet-like resin composition and the adherend, so that the connection reliability of the semiconductor device is lowered. After that. Further, in the present invention, inorganic fillers having different average particle diameters may be used in combination with each other. The average particle size is determined by the photometric size. The value obtained by the cloth meter (manufactured by HORIBA, device name: LA-910).

關於上述無機填充劑之調配量，於片狀樹脂組合物包含丙烯酸系樹脂之情形時，相對於丙烯酸系樹脂成分100重量份較佳為100~1500重量份，更佳為200~1000重量份。若無機填充劑之調配量未達10重量份，則有儲存彈性模數降低而封裝體之應力可靠性較大受損之情況。另一方面，若超過400重量份，則有導致全光線透過率降低，或片狀樹脂組合物2之流動性降低而未充分地填入至基板或半導體元件之凹凸從而導致空隙或龜裂之產生的情況。 In the case where the sheet-like resin composition contains an acrylic resin, the amount of the inorganic filler is preferably from 100 to 1,500 parts by weight, more preferably from 200 to 1,000 parts by weight, per 100 parts by weight of the acrylic resin component. When the amount of the inorganic filler is less than 10 parts by weight, the storage elastic modulus may be lowered and the stress reliability of the package may be largely impaired. On the other hand, when it exceeds 400 parts by weight, the total light transmittance is lowered, or the fluidity of the sheet-like resin composition 2 is lowered, and the unevenness of the substrate or the semiconductor element is not sufficiently filled to cause voids or cracks. The situation that arises.

片狀樹脂組合物較佳為含有如上所述之環氧樹脂、硬化劑、熱塑性樹脂、無機填充劑及熱硬化促進觸媒。藉此，可高效率地進行片狀樹脂組合物之黏度之控制。 The sheet-like resin composition preferably contains an epoxy resin, a curing agent, a thermoplastic resin, an inorganic filler, and a thermosetting-promoting catalyst as described above. Thereby, the control of the viscosity of the sheet-like resin composition can be performed efficiently.

再者，於片狀樹脂組合物2中，除上述無機填充劑以外，視需要可適當地調配其他添加劑。作為其他添加劑，例如可列舉難燃劑、矽烷偶合劑或離子捕捉劑等。作為上述難燃劑，例如可列舉三氧化二銻、五氧化二銻、溴化環氧樹脂等。該等可單獨使用或併用2種以上而使用。作為上述矽烷偶合劑，例如可列舉β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基甲基二乙氧基矽烷等。該等化合物可單獨使用或併用2種以上而使用。作為上述離子捕捉劑，例如可列舉水滑石類、氫氧化鉍等。該等可單獨使用或併用2種以上而使用。 In addition, in the sheet-like resin composition 2, other additives may be appropriately formulated in addition to the above-mentioned inorganic filler. Examples of other additives include a flame retardant, a decane coupling agent, and an ion scavenger. Examples of the flame retardant include antimony trioxide, antimony pentoxide, and brominated epoxy resin. These may be used alone or in combination of two or more. Examples of the above decane coupling agent include β-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, γ-glycidoxypropyltrimethoxydecane, and γ-glycidoxypropyl group. Diethoxy decane and the like. These compounds may be used singly or in combination of two or more. Examples of the ion trapping agent include hydrotalcites and barium hydroxide. These may be used alone or in combination of two or more.

進而，熱硬化前之上述片狀樹脂組合物2於溫度23℃、濕度70%之條件下之吸水率較佳為1重量%以下，更佳為0.5重量%以下。藉由片狀樹脂組合物2具有如上所述之吸水率，可抑制水分向片狀樹脂組合物2之吸收，而更有效率地抑制半導體元件5安裝時之空隙之產生。再者，上述吸水率之下限越小越好，較佳為實質上為0重量%，更佳為0重量%。 Further, the water absorption ratio of the sheet-like resin composition 2 before the heat curing at a temperature of 23 ° C and a humidity of 70% is preferably 1% by weight or less, more preferably 0.5% by weight or less. By having the water absorption ratio as described above, the sheet-like resin composition 2 can suppress the absorption of moisture into the sheet-like resin composition 2, and more effectively suppress the generation of voids when the semiconductor element 5 is mounted. Further, the lower limit of the water absorption rate is preferably as small as possible, and is preferably substantially 0% by weight, more preferably 0% by weight.

片狀樹脂組合物2之厚度(於複層之情形時為總厚度)並無特別限定，若考慮片狀樹脂組合物2之強度或半導體元件5與被黏著體16之間之空間之填充性，則亦可為10μm以上且100μm以下程度。再者，片狀樹脂組合物2之厚度考慮半導體元件5與被黏著體16之間之間隙或連接構件之高度而適當設定即可。 The thickness of the sheet-like resin composition 2 (the total thickness in the case of the multi-layer) is not particularly limited, and the strength of the sheet-like resin composition 2 or the filling property of the space between the semiconductor element 5 and the adherend 16 is considered. Further, it may be 10 μm or more and 100 μm or less. In addition, the thickness of the sheet-like resin composition 2 may be appropriately set in consideration of the gap between the semiconductor element 5 and the adherend 16 or the height of the connecting member.

積層片10之片狀樹脂組合物2較佳為由隔離件予以保護(未圖示)。隔離件具有於供於實際應用之前作為保護片狀樹脂組合物2之保護材之功能。隔離件係於積層片之片狀樹脂組合物2上貼附半導體晶圓3時被剝離。作為隔離件，亦可使用藉由聚對苯二甲酸乙二酯(PET)、聚乙烯、聚丙烯、或氟系剝離劑、丙烯酸長鏈烷基酯系剝離劑等剝離劑進行過表面塗佈之塑膠膜或紙等。 The sheet-like resin composition 2 of the laminated sheet 10 is preferably protected by a separator (not shown). The separator has a function as a protective material for protecting the sheet-like resin composition 2 before being used for practical use. When the separator is attached to the sheet-like resin composition 2 of the laminated sheet, the semiconductor wafer 3 is peeled off. As the separator, surface coating may be carried out by using a stripping agent such as polyethylene terephthalate (PET), polyethylene, polypropylene, or a fluorine-based release agent or a long-chain alkyl ester-based release agent. Plastic film or paper.

(背面研削用帶) (back grinding belt)

背面研削用帶1具備基材1a及積層於基材1a上之黏著劑層1b。再者，片狀樹脂組合物2係積層於黏著劑層1b上。 The back grinding belt 1 includes a base material 1a and an adhesive layer 1b laminated on the base material 1a. Further, the sheet-like resin composition 2 is laminated on the adhesive layer 1b.

(基材) (substrate)

上述基材1a成為積層片10之強度母體。例如可列舉：低密度聚乙烯、直鏈狀聚乙烯、中密度聚乙烯、高密度聚乙烯、超低密度聚乙烯、無規共聚聚丙烯、嵌段共聚聚丙烯、均聚丙烯、聚丁烯、聚甲基戊烯等聚烯烴；乙烯-乙酸乙烯酯共聚物、離子聚合物樹脂、乙烯-(甲基)丙烯酸共聚物、乙烯-(甲基)丙烯酸酯(無規、交替)共聚物、乙烯-丁烯共聚物、乙烯-己烯共聚物、聚胺基甲酸酯、聚對苯二甲酸乙二酯、聚萘二甲酸乙二酯等聚酯；聚碳酸酯、聚醯亞胺、聚醚醚酮、聚醯亞胺、聚醚醯亞胺、聚醯胺、全芳香族聚醯胺、聚苯硫醚、芳族聚醯胺(紙)、玻璃、玻璃布、氟樹脂、聚氯乙烯、聚偏二氯乙烯、纖維素系樹脂、聚矽氧樹脂、金屬(箔)、紙等。於黏著劑層1b為紫外線硬化型之情形時，基材1a較佳為對紫外線具有透過性者。 The base material 1a is a strength matrix of the laminated sheet 10. For example, low density polyethylene, linear polyethylene, medium density polyethylene, high density polyethylene, ultra low density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutene Polyolefin such as polymethylpentene; ethylene-vinyl acetate copolymer, ionic polymer resin, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylate (random, alternating) copolymer, Polyesters such as ethylene-butene copolymer, ethylene-hexene copolymer, polyurethane, polyethylene terephthalate, polyethylene naphthalate; polycarbonate, polyimine, Polyetheretherketone, polyimide, polyetherimine, polyamine, fully aromatic polyamine, polyphenylene sulfide, aromatic polyamine (paper), glass, glass cloth, fluororesin, poly Vinyl chloride, polyvinylidene chloride, cellulose resin, polyoxyxylene resin, metal (foil), paper, and the like. When the adhesive layer 1b is an ultraviolet curing type, the substrate 1a is preferably transparent to ultraviolet rays.

又，作為基材1a之材料，可列舉上述樹脂之交聯體等聚合物。上述塑膠膜可未經延伸而使用，亦可視需要使用實施過單軸或雙軸之延伸處理者。 Moreover, as a material of the base material 1a, a polymer such as a crosslinked body of the above resin may be mentioned. The above plastic film can be used without extension, and it is also possible to use a one-axis or two-axis extension processor as needed.

關於基材1a之表面，為了提高與鄰接之層之密接性、保持性等，可實施慣用之表面處理，例如鉻酸處理、臭氧暴露、火焰暴露、高壓電擊暴露、離子化放射線處理等化學或物理處理、利用底塗劑(例如下述黏著物質)之塗佈處理。 The surface of the substrate 1a may be subjected to conventional surface treatment such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, or the like in order to improve adhesion to the adjacent layer, retention, and the like. Physical treatment, coating treatment using a primer (for example, an adhesive described below).

上述基材1a可適當選擇同種或異種者而使用，視需要可使用摻合有數種者。又，為了對基材1a賦予抗靜電功能，可於上述基材1a上設置包含金屬、合金、其等之氧化物等之厚度為30~500Å左右之導電性物質之蒸鍍層。亦可藉由於基材中添加抗靜電劑而賦予抗靜電功能。基材1a可為單層或2種以上之複層。 The substrate 1a may be appropriately selected from the same species or a different species, and may be used in combination with several kinds as needed. Moreover, in order to provide an antistatic function to the base material 1a, a vapor deposition layer containing a conductive material having a thickness of about 30 to 500 Å, such as a metal, an alloy, or the like, may be provided on the base material 1a. Antistatic function can also be imparted by adding an antistatic agent to the substrate. The substrate 1a may be a single layer or a composite layer of two or more types.

基材1a之厚度可適當決定，一般而言為5μm以上且200μm以下程度，較佳為35μm以上且120μm以下。 The thickness of the substrate 1a can be appropriately determined, and is generally 5 μm or more and 200 μm or less, and preferably 35 μm or more and 120 μm or less.

再者，於基材1a中，亦可於無損本發明之效果等之範圍內含有各種添加劑(例如著色劑、填充劑、塑化劑、抗老化劑、抗氧化劑、界面活性劑、難燃劑等)。 Further, in the substrate 1a, various additives such as a color former, a filler, a plasticizer, an anti-aging agent, an antioxidant, a surfactant, and a flame retardant may be contained within a range not impairing the effects of the present invention and the like. Wait).

(黏著劑層) (adhesive layer)

用於形成黏著劑層1b之黏著劑只要為如下者則無特別限制，即，於背面研削時經由片狀樹脂組合物牢固地保持半導體晶圓，並且於背面研削後使附有片狀樹脂組合物之半導體晶圓向切晶帶移行時能夠可剝離地控制附有片狀樹脂組合物之半導體晶圓。例如可使用丙烯酸系黏著劑、橡膠系黏著劑等一般之感壓性接著劑。作為上述感壓性接著劑，就半導體晶圓或玻璃等避忌污染之電子零件之利用超純水或醇等有機溶劑之清潔洗淨性等方面而言，較佳為以丙烯酸系聚合物作為基礎聚合物之丙烯酸系黏著劑。 The adhesive for forming the adhesive layer 1b is not particularly limited as long as it is firmly held by the sheet-like resin composition at the time of back grinding, and is bonded with a sheet-like resin after grinding on the back side. When the semiconductor wafer is transferred to the dicing tape, the semiconductor wafer to which the sheet-like resin composition is attached can be peelably controlled. For example, a general pressure-sensitive adhesive such as an acrylic adhesive or a rubber-based adhesive can be used. The pressure-sensitive adhesive is preferably based on an acrylic polymer in terms of cleaning and cleaning properties of an organic solvent such as a semiconductor wafer or glass, which is resistant to contamination, such as ultrapure water or an organic solvent such as an alcohol. A polymer based acrylic adhesive.

作為上述丙烯酸系聚合物，可列舉使用丙烯酸酯作為主單體成分者。作為上述丙烯酸酯，例如可列舉使用(甲基)丙烯酸烷基酯(例如甲酯、乙酯、丙酯、異丙酯、丁酯、異丁酯、第二丁酯、第三丁酯、戊酯、異戊酯、己酯、庚酯、辛酯、2-乙基己酯、異辛酯、壬酯、癸酯、異癸酯、十一烷基酯、十二烷基酯、十三烷基酯、十四烷基酯、十六烷基酯、十八烷基酯、二十烷基酯等烷基之碳數1~30、尤其碳數4~18之直鏈狀或支鏈狀之烷基酯等)及(甲基)丙烯酸環烷基酯(例如環戊酯、環己酯等)之1種或2種以上作為單體成分的丙烯酸系聚合物等。再者，(甲基)丙烯酸酯係指丙烯酸酯及/或甲基丙烯酸酯，本發明之(甲基)均為相同之含義。 As the acrylic polymer, those using acrylate as a main monomer component can be mentioned. As the acrylate, for example, an alkyl (meth)acrylate (for example, methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, second butyl ester, third butyl ester, pentane) can be used. Ester, isoamyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, decyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester, thirteen Alkyl esters, tetradecyl esters, cetyl esters, octadecyl esters, eicosyl esters and the like have a carbon number of from 1 to 30, especially a linear or branched carbon number of from 4 to 18. One or two or more kinds of acrylic polymers having a monomer component such as a cycloalkyl ester (such as a cyclopentyl ester or a cyclohexyl ester). Further, (meth) acrylate means acrylate and/or methacrylate, and (meth) of the present invention has the same meaning.

以凝聚力、耐熱性等之改質作為目的，上述丙烯酸系聚合物亦可視需要含有與可與上述(甲基)丙烯酸烷基酯或環烷基酯進行共聚之其他單體成分對應之單元。作為此種單體成分，例如可列舉：丙烯酸、甲基丙烯酸、(甲基)丙烯酸羧基乙酯、(甲基)丙烯酸羧基戊酯、伊康酸、順丁烯二酸、反丁烯二酸、丁烯酸等含有羧基之單體；順丁烯二酸酐、伊康酸酐等酸酐單體；(甲基)丙烯酸2-羥基乙酯、(甲基)丙烯酸2-羥基丙酯、(甲基)丙烯酸4-羥基丁酯、(甲基)丙烯酸6-羥基己酯、(甲基)丙烯酸8-羥基辛酯、(甲基)丙烯酸10-羥基癸酯、(甲基)丙烯酸12-羥基月桂酯、(甲基)丙烯酸(4-羥基甲基環己基)甲酯等含有羥基之單體；苯乙烯磺酸、烯丙基磺酸、2-(甲基)丙烯醯胺-2-甲基丙磺酸、(甲基)丙烯醯胺丙磺酸、(甲基)丙烯酸磺丙酯、(甲基)丙烯醯氧基萘磺酸等含有磺酸基之單體；2-羥基乙基丙烯醯基磷酸酯等含有磷酸基之單體；丙烯醯胺、丙烯腈等。該等可共聚之單體成分可使用1種或2種以上。該等可共聚之單體之使用量較佳為所有單體成分之40重量%以下。 For the purpose of reforming such as cohesive force and heat resistance, the acrylic polymer may optionally contain a unit corresponding to another monomer component copolymerizable with the alkyl (meth)acrylate or the cycloalkyl ester. Examples of such a monomer component include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, and fumaric acid. a monomer having a carboxyl group such as crotonic acid; an acid anhydride monomer such as maleic anhydride or itaconic acid anhydride; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; ) 4-hydroxybutyl acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxy decyl (meth) acrylate, 12-hydroxy laurel (meth) acrylate a monomer having a hydroxyl group such as an ester or a (4-hydroxymethylcyclohexyl)methyl (meth)acrylate; a styrenesulfonic acid, an allylsulfonic acid, or a 2-(methyl)propenylamine-2-methyl group a sulfonic acid group-containing monomer such as propanesulfonic acid, (meth)acrylamide, propanesulfonic acid, sulfopropyl (meth)acrylate, (meth)acryloxynaphthalenesulfonic acid; 2-hydroxyethylpropene a monomer containing a phosphate group such as mercaptophosphate; acrylamide, acrylonitrile, or the like. One or two or more kinds of these copolymerizable monomer components can be used. The amount of the copolymerizable monomer used is preferably 40% by weight or less of all the monomer components.

進而，為了進行交聯，上述丙烯酸系聚合物視需要亦可含有多 官能性單體等作為共聚用單體成分。作為此種多官能性單體，例如可列舉己二醇二(甲基)丙烯酸酯、(聚)乙二醇二(甲基)丙烯酸酯、(聚)丙二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、季戊四醇二(甲基)丙烯酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、環氧(甲基)丙烯酸酯、聚酯(甲基)丙烯酸酯、(甲基)丙烯酸胺基甲酸酯等。該等多官能性單體亦可使用1種或2種以上。多官能性單體之使用量就黏著特性等方面而言較佳為所有單體成分之30重量%以下。 Further, in order to carry out crosslinking, the above acrylic polymer may contain more if necessary A functional monomer or the like is used as a comonomer component. Examples of such a polyfunctional monomer include hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, and new Pentandiol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate Ester, epoxy (meth) acrylate, polyester (meth) acrylate, (meth) acrylate urethane, and the like. These polyfunctional monomers may be used alone or in combination of two or more. The amount of the polyfunctional monomer to be used is preferably 30% by weight or less of all the monomer components in terms of adhesion characteristics and the like.

上述丙烯酸系聚合物係藉由使單一單體或2種以上之單體混合物聚合而獲得。聚合亦可藉由溶液聚合、乳化聚合、塊狀聚合、懸濁聚合等任一方式進行。就防止對清潔之被黏著體之污染等方面而言，較佳為低分子量物質之含量較小。就該方面而言，丙烯酸系聚合物之數量平均分子量較佳為30萬以上，進而較佳為40萬~300萬左右。 The acrylic polymer is obtained by polymerizing a single monomer or a mixture of two or more monomers. The polymerization can also be carried out by any one of solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, and the like. It is preferred that the content of the low molecular weight substance is small in terms of preventing contamination of the adherend to be cleaned and the like. In this respect, the number average molecular weight of the acrylic polymer is preferably 300,000 or more, and more preferably about 400,000 to 3,000,000.

又，為了提高作為基礎聚合物之丙烯酸系聚合物等之數量平均分子量，於上述黏著劑中，亦可適當地採用外部交聯劑。作為外部交聯方法之具體方法，可列舉添加聚異氰酸酯化合物、環氧化合物、氮丙啶化合物、三聚氰胺系交聯劑等所謂交聯劑而進行反應之方法。於使用外部交聯劑之情形時，關於其使用量，根據與應交聯之基礎聚合物之平衡，進而根據作為黏著劑之使用用途而適當決定。一般而言，相對於上述基礎聚合物100重量份，較佳為調配約5重量份以下，進而較佳為調配0.1~5重量份。進而，於黏著劑中，除上述成分以外，亦可視需要使用先前公知之各種黏著賦予劑、抗老化劑等添加劑。 Moreover, in order to increase the number average molecular weight of the acrylic polymer or the like as the base polymer, an external crosslinking agent may be suitably used in the above-mentioned adhesive. A specific method of the external crosslinking method is a method in which a reaction is carried out by adding a so-called crosslinking agent such as a polyisocyanate compound, an epoxy compound, an aziridine compound or a melamine crosslinking agent. In the case of using an external crosslinking agent, the amount of the crosslinking agent is appropriately determined depending on the balance with the base polymer to be crosslinked and the use as the adhesive. In general, it is preferably formulated in an amount of about 5 parts by weight or less, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the base polymer. Further, in the adhesive, in addition to the above components, additives such as various conventionally known adhesion-imparting agents and anti-aging agents may be used as needed.

黏著劑層1b可藉由放射線硬化型黏著劑而形成。放射線硬化型黏著劑可藉由照射紫外線等放射線而使交聯度增大而容易地降低其黏著力，可易於進行附有片狀樹脂組合物之半導體晶圓之剝離。作為放射線，可列舉X射線、紫外線、電子束、α射線、β射線、中子射線 等。 The adhesive layer 1b can be formed by a radiation hardening type adhesive. The radiation-curable adhesive can easily reduce the adhesion by irradiating radiation such as ultraviolet rays to increase the degree of crosslinking, and can easily peel off the semiconductor wafer with the sheet-like resin composition. Examples of the radiation include X-ray, ultraviolet light, electron beam, α-ray, β-ray, and neutron beam. Wait.

放射線硬化型黏著劑可無特別限制地使用具有碳-碳雙鍵等放射線硬化性官能基且顯示黏著性者。作為放射線硬化型黏著劑，例如可例示於上述丙烯酸系黏著劑、橡膠系黏著劑等一般之感壓性黏著劑中調配放射線硬化性之單體成分或低聚物成分而成之添加型放射線硬化性黏著劑。 The radiation-curable adhesive can be used without any particular limitation, and a radiation curable functional group such as a carbon-carbon double bond is used and adhesion is exhibited. The radiation-curable adhesive is exemplified by the addition of a radioactive monomer component or an oligomer component to a general pressure-sensitive adhesive such as an acrylic pressure-sensitive adhesive or a rubber-based pressure-sensitive adhesive. Adhesive.

作為所調配之放射線硬化性單體成分，例如可列舉胺基甲酸酯低聚物、(甲基)丙烯酸胺基甲酸酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、二季戊四醇單羥基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯等。又，放射線硬化性低聚物成分可列舉胺基甲酸酯系、聚醚系、聚酯系、聚碳酸酯系、聚丁二烯系等各種低聚物，其重量平均分子量適宜為100~30000左右之範圍。放射線硬化性單體成分或低聚物成分之調配量可根據上述黏著劑層之種類而適當地決定能夠降低黏著劑層之黏著力之量。一般而言，相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為5~500重量份，較佳為40~150重量份左右。 Examples of the radiation curable monomer component to be blended include a urethane oligomer, a (meth)acrylic acid urethane, a trimethylolpropane tri(meth)acrylate, and a tetrahydroxyl group. Methane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,4-butanediol di(meth)acrylate or the like. Further, examples of the radiation curable oligomer component include various oligomers such as a urethane type, a polyether type, a polyester type, a polycarbonate type, and a polybutadiene type, and the weight average molecular weight thereof is preferably 100~. The range of around 30,000. The amount of the radiation-curable monomer component or the oligomer component can be appropriately determined depending on the type of the pressure-sensitive adhesive layer, and the amount of adhesion of the pressure-sensitive adhesive layer can be reduced. In general, it is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

又，作為放射線硬化型黏著劑，除上述所說明之添加型放射線硬化性黏著劑以外，可列舉使用在聚合物側鏈或主鏈中或主鏈末端具有碳-碳雙鍵者作為基礎聚合物的內在型放射線硬化性黏著劑。內在型放射線硬化性黏著劑無需含有作為低分子成分之低聚物成分等，或不大量含有，因此無低聚物成分等經過一段時間於黏著劑中移動而可形成穩定之層構造之黏著劑層，因此較佳。 In addition, as the radiation-curable adhesive, in addition to the above-described additive-type radiation-curable adhesive, a base polymer having a carbon-carbon double bond in a polymer side chain or a main chain or a main chain terminal may be used. An intrinsic radiation curable adhesive. Since the intrinsic type radiation curable adhesive does not need to contain an oligomer component as a low molecular component or the like, or does not contain a large amount of the adhesive, it is possible to form an adhesive having a stable layer structure by moving the adhesive over a period of time, such as an oligomer component. Layer, therefore better.

上述具有碳-碳雙鍵之基礎聚合物可無特別限制地使用具有碳-碳雙鍵且具有黏著性者。作為此種基礎聚合物，較佳為以丙烯酸系聚合物作為基本骨架者。作為丙烯酸系聚合物之基本骨架，可列舉上述所 例示之丙烯酸系聚合物。 The above base polymer having a carbon-carbon double bond can be used without any particular limitation, and has a carbon-carbon double bond and has adhesiveness. As such a base polymer, an acrylic polymer is preferably used as a basic skeleton. As a basic skeleton of an acrylic polymer, the above-mentioned An exemplary acrylic polymer.

向上述丙烯酸系聚合物導入碳-碳雙鍵之方法並無特別限制，可採用各種方法，但碳-碳雙鍵導入至聚合物側鏈時容易進行分子設計。例如可列舉如下方法，即，預先使於丙烯酸系聚合物中具有官能基之單體共聚後，使具有可與該官能基反應之官能基及碳-碳雙鍵之化合物維持著碳-碳雙鍵之放射線硬化性而進行縮合或加成反應。 The method of introducing the carbon-carbon double bond to the above acrylic polymer is not particularly limited, and various methods can be employed. However, when a carbon-carbon double bond is introduced into the polymer side chain, molecular design is easily performed. For example, a method in which a monomer having a functional group in an acrylic polymer is copolymerized in advance, and a compound having a functional group reactive with the functional group and a carbon-carbon double bond is maintained as a carbon-carbon double The bond is hardenable and undergoes a condensation or addition reaction.

作為該等官能基之組合之例，可列舉羧基與環氧基、羧基與氮丙啶基、羥基與異氰酸酯基等。該等官能基之組合中，就追蹤反應之容易性而言，較佳為羥基與異氰酸酯基之組合。又，若為如藉由該等官能基之組合而生成上述具有碳-碳雙鍵之丙烯酸系聚合物之組合，則官能基可處於丙烯酸系聚合物與上述化合物之任一側，上述較佳之組合中，較佳為丙烯酸系聚合物具有羥基，且上述化合物具有異氰酸酯基之情形。於此情形時，作為具有碳-碳雙鍵之異氰酸酯化合物，例如可列舉甲基丙烯醯基異氰酸酯、異氰酸2-甲基丙烯醯氧基乙酯、間異丙烯基-α,α-二甲基苄基異氰酸酯等。又，作為丙烯酸系聚合物，可使用使上述例示之含有羥基之單體或2-羥基乙基乙烯醚、4-羥基丁基乙烯醚、二乙二醇單乙烯醚之醚系化合物等進行共聚而成者。 Examples of the combination of these functional groups include a carboxyl group, an epoxy group, a carboxyl group and an aziridine group, a hydroxyl group and an isocyanate group. In the combination of these functional groups, in view of easiness of the reaction, a combination of a hydroxyl group and an isocyanate group is preferred. Further, in the case where a combination of the above-mentioned acrylic polymer having a carbon-carbon double bond is produced by a combination of the functional groups, the functional group may be on either side of the acrylic polymer and the above compound, preferably the above. In the combination, it is preferred that the acrylic polymer has a hydroxyl group and the above compound has an isocyanate group. In this case, examples of the isocyanate compound having a carbon-carbon double bond include methacryl oxime isocyanate, 2-methylpropenyloxyethyl isocyanate, m-isopropenyl-α, α-di Methylbenzyl isocyanate and the like. Further, as the acrylic polymer, copolymerization of the above-exemplified hydroxyl group-containing monomer or 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether or diethylene glycol monovinyl ether ester compound can be used. Founder.

上述內在型放射線硬化性黏著劑可單獨使用上述具有碳-碳雙鍵之基礎聚合物(尤其丙烯酸系聚合物)，但亦能以不使特性惡化之程度調配上述放射線硬化性單體成分或低聚物成分。放射線硬化性之低聚物成分等通常相對於基礎聚合物100重量份為30重量份之範圍內，較佳為0~10重量份之範圍。 The above-mentioned intrinsic type radiation curable adhesive may be used alone as the base polymer (especially an acrylic polymer) having a carbon-carbon double bond, but it is also possible to prepare the above-mentioned radiation curable monomer component or low without deteriorating the properties. Polymer component. The radiation curable oligomer component or the like is usually in the range of 30 parts by weight, preferably 0 to 10 parts by weight, per 100 parts by weight of the base polymer.

於藉由紫外線等進行硬化之情形時，上述放射線硬化型黏著劑中較佳為含有光聚合起始劑。作為光聚合起始劑，例如可列舉：4-(2-羥基乙氧基)苯基(2-羥基-2-丙基)酮、α-羥基-α,α'-二甲基苯乙酮、2-甲基-2-羥基苯丙酮、1-羥基環己基苯基酮等α-酮醇系化合物；甲氧基苯 乙酮、2,2-二甲氧基-2-苯基苯乙酮、2,2-二乙氧基苯乙酮、2-甲基-1-[4-(甲硫基)-苯基]-2-啉基丙烷-1-酮等苯乙酮系化合物；安息香***、安息香異丙醚、大茴香偶姻甲醚等安息香醚系化合物；苯偶醯二甲基縮酮等縮酮系化合物；2-萘磺醯氯等芳香族磺醯氯系化合物；1-苯基-1,2-丙二酮-2-(O-乙氧基羰基)肟等光活性肟系化合物；二苯甲酮、苯甲醯苯甲酸、3,3'-二甲基-4-甲氧基二苯甲酮等二苯甲酮系化合物；噻噸酮、2-氯噻噸酮、2-甲基噻噸酮、2,4-二甲基噻噸酮、異丙基噻噸酮、2,4-二氯噻噸酮、2,4-二乙基噻噸酮、2,4-二異丙基噻噸酮等噻噸酮系化合物；樟腦醌；鹵代酮；醯基氧化膦；醯基膦酸酯等。光聚合起始劑之調配量相對於構成黏著劑之丙烯酸系聚合物等基礎聚合物100重量份，例如為0.05~20重量份左右。 In the case where it is cured by ultraviolet rays or the like, the radiation curable adhesive preferably contains a photopolymerization initiator. As the photopolymerization initiator, for example, 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)one, α-hydroxy-α,α'-dimethylacetophenone can be exemplified. , an α-keto alcohol compound such as 2-methyl-2-hydroxypropiophenone or 1-hydroxycyclohexyl phenyl ketone; methoxyacetophenone, 2,2-dimethoxy-2-phenylbenzene Ketone, 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)-phenyl]-2- An acetophenone-based compound such as phenylpropanoid-1-one; a benzoin ether compound such as benzoin ethyl ether, benzoin isopropyl ether, aniseed methoxyether; a ketal compound such as benzoin dimethyl ketal; An aromatic sulfonium chloride compound such as naphthosulfonium chloride; a photoactive lanthanide compound such as 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)anthracene; benzophenone, benzene a benzophenone compound such as formazanic acid or 3,3'-dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone And other thioxanthone compounds; camphorquinone; halogenated ketone; fluorenylphosphine oxide; decylphosphonate. The amount of the photopolymerization initiator to be added is, for example, about 0.05 to 20 parts by weight based on 100 parts by weight of the base polymer such as the acrylic polymer constituting the pressure-sensitive adhesive.

再者，照射放射線時，於發生由氧引起之硬化障礙之情形時，較理想為利用一些方法自放射線硬化型黏著劑層1b之表面阻隔氧(空氣)。例如可列舉：以隔離件被覆上述黏著劑層1b之表面之方法、或於氮氣環境中進行紫外線等放射線之照射之方法等。 Further, when radiation is irradiated, when a hardening disorder due to oxygen occurs, it is preferable to block oxygen (air) from the surface of the radiation-curable adhesive layer 1b by some methods. For example, a method of coating the surface of the above-mentioned pressure-sensitive adhesive layer 1b with a separator or a method of irradiating radiation such as ultraviolet rays in a nitrogen atmosphere may be mentioned.

再者，於黏著劑層1b中，亦可於無損本發明之效果等之範圍內含有各種添加劑(例如著色劑、增黏劑、增量劑、填充劑、黏著賦予劑、塑化劑、抗老化劑、抗氧化劑、界面活性劑、交聯劑等)。 Further, in the adhesive layer 1b, various additives (for example, coloring agents, tackifiers, extenders, fillers, adhesion-imparting agents, plasticizers, anti-drugs) may be contained in the range which does not impair the effects of the present invention and the like. Aging agent, antioxidant, surfactant, crosslinking agent, etc.).

黏著劑層1b之厚度並無特別限定，就同時實現防止半導體晶圓之研削面缺損、片狀樹脂組合物2之固定保持等觀點而言，較佳為1~50μm左右。較佳為5~40μm，進而較佳為10~30μm。 The thickness of the adhesive layer 1b is not particularly limited, and is preferably about 1 to 50 μm from the viewpoint of preventing the grinding surface of the semiconductor wafer from being damaged and fixing the sheet-like resin composition 2. It is preferably 5 to 40 μm, more preferably 10 to 30 μm.

(積層片之製造方法) (Manufacturing method of laminated sheet)

本實施形態之積層片10例如可藉由分別預先製作背面研削用帶1及片狀樹脂組合物2，最後將其等貼合而製成。具體而言，可依照如下順序而製作。 The laminated sheet 10 of the present embodiment can be produced by, for example, separately preparing the back grinding tape 1 and the sheet-shaped resin composition 2 in advance, and finally bonding them. Specifically, it can be produced in the following order.

首先，基材1a可藉由先前公知之製膜方法而製膜。作為該製膜方 法，例如可例示壓延製膜法、有機溶劑中之流延法、密閉系統中之吹脹擠出法、T型模頭擠出法、共擠出法、乾式層壓法等。 First, the substrate 1a can be formed into a film by a conventionally known film forming method. As the film making side The method may, for example, be a calendering film forming method, a casting method in an organic solvent, an inflation extrusion method in a closed system, a T-die extrusion method, a co-extrusion method, a dry lamination method, or the like.

其次，製備黏著劑層形成用之黏著劑組合物。黏著劑組合物中調配有如黏著劑層一項中所說明之樹脂或添加物等。將所製備之黏著劑組合物塗佈於基材1a上而形成塗佈膜後，使該塗佈膜於特定條件下乾燥(視需要使其加熱交聯)而形成黏著劑層1b。作為塗佈方法，並無特別限定，例如可列舉輥塗敷、網版塗敷、凹版塗敷等。又，作為乾燥條件，例如可於乾燥溫度80~150℃、乾燥時間0.5~5分鐘之範圍內進行。又，亦可於隔離件上塗佈黏著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成黏著劑層1b。其後，將黏著劑層1b與隔離件一併貼合至基材1a上。藉此，製作具備基材1a及黏著劑層1b之背面研削用帶1。 Next, an adhesive composition for forming an adhesive layer is prepared. The adhesive composition is formulated with a resin or an additive as described in the adhesive layer. After the prepared adhesive composition is applied onto the substrate 1a to form a coating film, the coated film is dried under specific conditions (heat-crosslinking if necessary) to form an adhesive layer 1b. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions can be carried out, for example, at a drying temperature of 80 to 150 ° C and a drying time of 0.5 to 5 minutes. Further, after the adhesive composition is applied onto the separator to form a coating film, the coating film is dried under the above drying conditions to form the adhesive layer 1b. Thereafter, the adhesive layer 1b and the separator are bonded together to the substrate 1a. Thereby, the back grinding belt 1 including the base material 1a and the adhesive layer 1b was produced.

片狀樹脂組合物2例如以如下方式製作。首先，製備作為片狀樹脂組合物2之形成材料之接著劑組合物。如片狀樹脂組合物一項中所說明般，該接著劑組合物中調配有熱塑性成分或環氧樹脂、各種添加劑等。 The sheet-like resin composition 2 is produced, for example, in the following manner. First, an adhesive composition as a material for forming the sheet-like resin composition 2 is prepared. As described in the section of the sheet-like resin composition, a thermoplastic component or an epoxy resin, various additives, and the like are blended in the adhesive composition.

其次，將所製備之接著劑組合物以成為特定厚度之方式塗佈於基材隔離件上而形成塗佈膜後，使該塗佈膜於特定條件下乾燥，形成片狀樹脂組合物。作為塗佈方法，並無特別限定，例如可列舉輥塗敷、網版塗敷、凹版塗敷等。又，作為乾燥條件，例如於乾燥溫度70~160℃、乾燥時間1~5分鐘之範圍內進行。又，亦可於隔離件上塗佈接著劑組合物而形成塗佈膜後，於上述乾燥條件下使塗佈膜乾燥而形成片狀樹脂組合物。其後，將片狀樹脂組合物與隔離件一併貼合至基材隔離件上。 Next, the prepared adhesive composition is applied onto a substrate separator to have a specific thickness to form a coating film, and then the coating film is dried under specific conditions to form a sheet-like resin composition. The coating method is not particularly limited, and examples thereof include roll coating, screen coating, and gravure coating. Further, the drying conditions are carried out, for example, at a drying temperature of 70 to 160 ° C and a drying time of 1 to 5 minutes. Further, after the adhesive composition is applied onto the separator to form a coating film, the coating film is dried under the above drying conditions to form a sheet-like resin composition. Thereafter, the sheet-like resin composition and the separator are attached together to the substrate separator.

繼而，自背面研削用帶1及片狀樹脂組合物2分別剝離隔離件，以片狀樹脂組合物與黏著劑層成為貼合面之方式將兩者貼合。貼合例 如可藉由壓接進行。此時，層壓溫度並無特別限定，例如較佳為30~100℃，更佳為40~80℃。又，線壓並無特別限定，例如較佳為0.98~196N/cm，更佳為9.8~98N/cm。其次，剝離片狀樹脂組合物上之基材隔離件，獲得本實施形態之積層片。 Then, the separator is peeled off from the back side grinding belt 1 and the sheet-like resin composition 2, and the sheet-like resin composition and the pressure-sensitive adhesive layer are bonded to each other. Fitting example This can be done by crimping. In this case, the laminating temperature is not particularly limited, and is, for example, preferably from 30 to 100 ° C, more preferably from 40 to 80 ° C. Further, the linear pressure is not particularly limited, and is, for example, preferably 0.98 to 196 N/cm, more preferably 9.8 to 98 N/cm. Next, the substrate separator on the sheet-like resin composition was peeled off to obtain a laminated sheet of the present embodiment.

<半導體裝置之製造方法> <Method of Manufacturing Semiconductor Device>

於本實施形態中，使用具備積層於背面研削用帶上之片狀樹脂組合物的積層片進行半導體晶圓之背面研削，其後進行切晶帶上之切晶、半導體元件之拾取，最後將半導體元件安裝於被黏著體。 In the present embodiment, the back surface of the semiconductor wafer is ground using a laminated sheet having a sheet-like resin composition laminated on the back grinding belt, and then the dicing on the dicing tape and the pick-up of the semiconductor element are performed, and finally, The semiconductor component is mounted on the adherend.

作為本實施形態之代表性步驟，包括如下步驟：貼合步驟，其係將半導體晶圓之形成有連接構件之電路面與上述積層片之片狀樹脂組合物貼合；研削步驟，其係對上述半導體晶圓之背面進行研削；固定步驟，其係將上述片狀樹脂組合物與半導體晶圓一併自背面研削用帶剝離，並將該半導體晶圓貼附於切晶帶；切晶步驟，其係對上述半導體晶圓進行切晶而形成附有上述片狀樹脂組合物之半導體元件；拾取步驟，其係將上述附有片狀樹脂組合物之半導體元件自上述切晶帶剝離；及連接步驟，其係將上述被黏著體與上述半導體元件之間之空間以上述片狀樹脂組合物予以填充並且經由上述連接構件而將上述半導體元件與上述被黏著體電性連接。 A representative step of the embodiment includes a bonding step of bonding a circuit surface on which a connection member of a semiconductor wafer is formed and a sheet-like resin composition of the laminate; the grinding step is performed Performing a grinding process on the back surface of the semiconductor wafer; and fixing the sheet-like resin composition and the semiconductor wafer together from the back grinding tape, and attaching the semiconductor wafer to the dicing tape; A semiconductor element in which the semiconductor wafer is diced to form the sheet-like resin composition, and a pick-up step of peeling off the semiconductor element with the sheet-like resin composition from the dicing tape; In the connecting step, the space between the adherend and the semiconductor element is filled with the sheet-like resin composition, and the semiconductor element and the adherend are electrically connected via the connecting member.

[貼合步驟] [Finishing step]

於貼合步驟中，將半導體晶圓3之形成有連接構件4之電路面3a與上述積層片10之片狀樹脂組合物2貼合(參照圖2A)。 In the bonding step, the circuit surface 3a of the semiconductor wafer 3 on which the connecting member 4 is formed is bonded to the sheet-like resin composition 2 of the laminated sheet 10 (see FIG. 2A).

(半導體晶圓) (semiconductor wafer)

於半導體晶圓3之電路面3a形成有複數個連接構件4(參照圖2A)。作為凸塊或導電材等連接構件之材質，並無特別限定，例如可列舉錫-鉛系金屬材、錫-銀系金屬材、錫-銀-銅系金屬材、錫-鋅系金屬材、錫-鋅-鉍系金屬材等焊料類(合金)、或金系金屬材、銅系金屬材等。 連接構件之高度亦視用途而定，一般而言為15~100μm左右。當然，半導體晶圓3中之各個連接構件之高度可相同，亦可不同。 A plurality of connecting members 4 are formed on the circuit surface 3a of the semiconductor wafer 3 (see FIG. 2A). The material of the connecting member such as a bump or a conductive material is not particularly limited, and examples thereof include a tin-lead metal material, a tin-silver metal material, a tin-silver-copper metal material, and a tin-zinc metal material. A solder (alloy) such as a tin-zinc-bismuth metal material, a gold-based metal material, or a copper-based metal material. The height of the connecting member is also dependent on the application, and is generally about 15 to 100 μm. Of course, the heights of the respective connecting members in the semiconductor wafer 3 may be the same or different.

於本實施形態之半導體裝置之製造方法中，作為片狀樹脂組合物之厚度，形成於半導體晶圓表面之連接構件之高度X(μm)與上述片狀樹脂組合物之厚度Y(μm)較佳為滿足下述關係。 In the method of manufacturing a semiconductor device of the present embodiment, the height X (μm) of the connecting member formed on the surface of the semiconductor wafer and the thickness Y (μm) of the sheet-like resin composition are compared as the thickness of the sheet-like resin composition. Jia is satisfied with the following relationship.

0.5≦Y/X≦2 0.5≦Y/X≦2

藉由使上述連接構件之高度X(μm)與上述硬化膜之厚度Y(μm)滿足上述關係，可充分地填充半導體元件與被黏著體之間之空間，並且可防止片狀樹脂組合物自該空間之過量溢出，可防止因片狀樹脂組合物所致之半導體元件之污染等。再者，於各連接構件之高度不同之情形時，將最高之連接構件之高度作為基準。 By satisfying the above relationship between the height X (μm) of the connecting member and the thickness Y (μm) of the cured film, the space between the semiconductor element and the adherend can be sufficiently filled, and the sheet-like resin composition can be prevented from being self-contained. Excessive overflow of the space prevents contamination of the semiconductor element due to the sheet-like resin composition and the like. Furthermore, in the case where the heights of the respective connecting members are different, the height of the highest connecting member is used as a reference.

(貼合) (fit)

首先，適當地剝離任意地設置於積層片10之片狀樹脂組合物2上之隔離件，如圖2A所示，使上述半導體晶圓3之形成有連接構件4之電路面3a與片狀樹脂組合物2對向，將上述片狀樹脂組合物2與上述半導體晶圓3貼合(安裝)。 First, the separator arbitrarily provided on the sheet-like resin composition 2 of the laminated sheet 10 is appropriately peeled off, and as shown in FIG. 2A, the circuit surface 3a of the semiconductor wafer 3 on which the connecting member 4 is formed and the sheet-like resin are formed. The composition 2 is aligned, and the sheet-like resin composition 2 is bonded (mounted) to the semiconductor wafer 3.

貼合之方法並無特別限定，較佳為藉由壓接之方法。壓接通常藉由壓接輥等公知之按壓器件負荷較佳為0.1~1MPa、更佳為0.3~0.7MPa之壓力一面按壓一面進行。此時，亦可一面加熱至40~100℃左右一面壓接。又，為了提高密接性，亦較佳為於減壓下(1~1000Pa)壓接。 The method of bonding is not particularly limited, and is preferably a method of crimping. The pressure bonding is usually performed by pressing a pressure of a known pressing device such as a pressure roller, preferably 0.1 to 1 MPa, more preferably 0.3 to 0.7 MPa. At this time, it is also possible to press it while heating to about 40 to 100 °C. Further, in order to improve the adhesion, it is also preferred to press under pressure (1 to 1000 Pa).

[研削步驟] [grinding step]

於研削步驟中，對上述半導體晶圓3之與電路面3a為相反側之面(即，背面)3b進行研削(參照圖2B)。作為用於半導體晶圓3之背面研削之薄型加工機，並無特別限定，例如可例示研削機(背面研磨機)、研磨墊等。又，亦可藉由蝕刻等化學方法進行背面研削。背面研削進行 至半導體晶圓成為所需之厚度(例如700~25μm)為止。 In the grinding step, the surface of the semiconductor wafer 3 opposite to the circuit surface 3a (that is, the back surface) 3b is ground (see FIG. 2B). The thin processing machine used for the back grinding of the semiconductor wafer 3 is not particularly limited, and examples thereof include a grinding machine (back grinding machine), a polishing pad, and the like. Further, back grinding can be performed by a chemical method such as etching. Back grinding Until the semiconductor wafer has a desired thickness (for example, 700 to 25 μm).

[固定步驟] [fixed step]

於研削步驟後，於貼合有片狀樹脂組合物2之狀態下將半導體晶圓3自背面研削用帶1剝離，並將半導體晶圓3與切晶帶11貼合(參照圖2C)。此時，以半導體晶圓3之背面3b與切晶帶11之黏著劑層11b對向之方式貼合。因此，貼合於半導體晶圓3之電路面3a之片狀樹脂組合物2成為露出之狀態。再者，切晶帶11具有於基材11a上積層有黏著劑層11b之構造。作為基材11a及黏著劑層11b，可使用上述背面研削用帶1之基材1a及黏著劑層1b之項中所示之成分及製法而較佳地製作。 After the grinding step, the semiconductor wafer 3 is peeled off from the back grinding tape 1 in a state in which the sheet-like resin composition 2 is bonded, and the semiconductor wafer 3 is bonded to the dicing tape 11 (see FIG. 2C). At this time, the back surface 3b of the semiconductor wafer 3 is bonded to the adhesive layer 11b of the dicing tape 11 so as to face each other. Therefore, the sheet-like resin composition 2 bonded to the circuit surface 3a of the semiconductor wafer 3 is exposed. Further, the dicing tape 11 has a structure in which an adhesive layer 11b is laminated on the substrate 11a. The base material 11a and the pressure-sensitive adhesive layer 11b can be preferably produced by using the components and the production methods shown in the items of the base material 1a and the pressure-sensitive adhesive layer 1b of the back grinding belt 1.

自背面研削用帶1剝離半導體晶圓3時，於黏著劑層1b具有放射線硬化性之情形時，對黏著劑層1b照射放射線使黏著劑層1b硬化，藉此可容易地進行剝離。放射線之照射量考慮所使用之放射線之種類或黏著劑層之硬化度等而適當設定即可。 When the semiconductor wafer 3 is peeled off from the back-grinding tape 1, when the adhesive layer 1b has radiation curability, the adhesive layer 1b is irradiated with radiation to cure the adhesive layer 1b, whereby peeling can be easily performed. The amount of radiation to be irradiated may be appropriately set in consideration of the type of radiation to be used, the degree of hardening of the adhesive layer, and the like.

本實施形態之積層片較佳為上述片狀樹脂組合物自上述背面研削用帶之剝離力為0.03~0.10N/20mm。藉由此種輕剝離力，可防止自背面研削用帶剝離時片狀樹脂組合物之斷裂或變形，並且可防止半導體晶圓之變形。 In the laminated sheet of the present embodiment, it is preferable that the sheet-like resin composition has a peeling force of 0.03 to 0.10 N/20 mm from the back grinding belt. By such a light peeling force, it is possible to prevent breakage or deformation of the sheet-like resin composition from peeling of the tape for back grinding, and to prevent deformation of the semiconductor wafer.

上述剝離力之測定係自積層片切出寬度20mm之樣片，將其貼附於載置於40℃之加熱板上之矽鏡面晶圓。放置約30分鐘，使用拉伸試驗機測定剝離力。測定條件設為剝離角度：90°、拉伸速度：300mm/min。再者，剝離力之測定係於溫度23℃、相對濕度50%之環境下進行。但是，於黏著劑層為紫外線硬化型之情形時，於與上述相同之條件下貼附於矽鏡面晶圓，放置約30分鐘後，以如下所述之方式設定紫外線之照射條件而自積層片側進行紫外線照射，進行此時之剝離力之測定。 The peeling force was measured by cutting a sample having a width of 20 mm from the laminated sheet and attaching it to a mirror-finished wafer placed on a hot plate at 40 °C. The peeling force was measured using a tensile tester for about 30 minutes. The measurement conditions were a peeling angle: 90° and a tensile speed: 300 mm/min. Further, the measurement of the peeling force was carried out in an environment of a temperature of 23 ° C and a relative humidity of 50%. However, when the adhesive layer is of an ultraviolet curing type, it is attached to the mirror wafer under the same conditions as described above, and after being left for about 30 minutes, the ultraviolet irradiation conditions are set as described below, and the laminated sheet side is set as described below. Ultraviolet irradiation was performed, and the peeling force at this time was measured.

<紫外線之照射條件> <Ultraviolet irradiation conditions>

紫外線(UV)照射裝置：高壓水銀燈 Ultraviolet (UV) irradiation device: high pressure mercury lamp

紫外線照射累積光量：500mJ/cm2 Accumulated light amount by ultraviolet irradiation: 500mJ/cm 2

輸出：75W Output: 75W

照射強度：150mW/cm2 Irradiation intensity: 150mW/cm 2

[切晶步驟] [Cutting step]

於切晶步驟中，基於藉由直接光或間接光、紅外線等所求出之切晶位置，如圖2D所示般對半導體晶圓3及片狀樹脂組合物2進行切晶，而形成附有經切晶之片狀樹脂組合物之半導體元件5。藉由經過切晶步驟，將半導體晶圓3切斷成特定尺寸而單片化(小片化)，製造半導體晶片(半導體元件)5。此處所得之半導體晶片5與被切斷為相同形狀之片狀樹脂組合物2成為一體。切晶係自半導體晶圓3之貼合有片狀樹脂組合物2之電路面3a依照常法進行。 In the dicing step, the semiconductor wafer 3 and the sheet-like resin composition 2 are diced, as shown in FIG. 2D, based on the dicing position determined by direct light, indirect light, infrared ray, or the like. A semiconductor element 5 having a diced sheet-like resin composition. The semiconductor wafer 3 is manufactured by dicing (slices) the semiconductor wafer 3 into a specific size by a dicing step, thereby manufacturing a semiconductor wafer (semiconductor element) 5. The semiconductor wafer 5 obtained here is integrated with the sheet-like resin composition 2 cut into the same shape. The dicing system is performed on the circuit surface 3a of the semiconductor wafer 3 to which the sheet-like resin composition 2 is bonded, in accordance with a conventional method.

於本步驟中，例如可採用藉由切晶刀片切入至切晶帶11為止的被稱為全切之切斷方式等。作為本步驟中所使用之切晶裝置，並無特別限定，可使用先前公知者。又，半導體晶圓係被切晶帶11以優異之密接性接著固定，因此可抑制晶片缺損或晶片鼓出，並且亦可抑制半導體晶圓之破損。再者，若片狀樹脂組合物由包含環氧樹脂之樹脂組合物形成，則即便藉由切晶被切斷，亦可抑制或防止於該切斷面產生片狀樹脂組合物的片狀樹脂組合物之糊劑溢出。其結果為，可抑制或防止切斷面彼此再附著(黏連)，可進一步良好地進行下述拾取。 In this step, for example, a cutting method called full cutting by cutting the dicing tape 11 by a dicing blade can be employed. The dicing apparatus used in this step is not particularly limited, and those known in the art can be used. Further, since the semiconductor wafer is fixed by the dicing tape 11 with excellent adhesion, it is possible to suppress wafer defects or wafer bulging, and it is also possible to suppress breakage of the semiconductor wafer. In addition, when the sheet-like resin composition is formed of a resin composition containing an epoxy resin, even if it is cut by dicing, it is possible to suppress or prevent the sheet-like resin which produces the sheet-like resin composition on the cut surface. The paste of the composition overflows. As a result, it is possible to suppress or prevent the cut surfaces from reattaching (adhesion) to each other, and the following pick-up can be performed more satisfactorily.

再者，於繼切晶步驟後進行切晶帶之擴展之情形時，該擴展可使用先前公知之擴展裝置進行。擴展裝置具有經由切晶環可將切晶帶向下方按壓之環狀外圈、及直徑小於外圈且支持切晶帶之內圈。藉由該擴展步驟，於下述拾取步驟中可防止相鄰之半導體晶片彼此接觸而破損。 Further, in the case where the dicing band is expanded after the dicing step, the expansion can be carried out using a previously known expansion device. The expansion device has an annular outer ring that can press the dicing tape downward through the dicing ring, and an inner ring that has a smaller diameter than the outer ring and supports the dicing band. By this expansion step, adjacent semiconductor wafers can be prevented from coming into contact with each other and broken in the pickup step described below.

[拾取步驟] [pickup step]

為了回收接著固定於切晶帶11之半導體晶片5，如圖2E所示，進行附有片狀樹脂組合物2之半導體晶片5之拾取，將半導體晶片5與片狀樹脂組合物2之積層體A自切晶帶11剝離。 In order to recover the semiconductor wafer 5 which is then fixed to the dicing tape 11, as shown in FIG. 2E, the semiconductor wafer 5 with the sheet-like resin composition 2 is picked up, and the laminate of the semiconductor wafer 5 and the sheet-like resin composition 2 is laminated. A is peeled off from the dicing tape 11.

作為拾取方法，並無特別限定，可採用先前公知之各種方法。例如可列舉藉由針將各個半導體晶片自切晶帶之基材側頂起，藉由拾取裝置拾取被頂起之半導體晶片的方法等。再者，所拾取之半導體晶片5與貼合於電路面3a之片狀樹脂組合物2成為一體而構成積層體A。 The picking method is not particularly limited, and various conventionally known methods can be employed. For example, a method in which each semiconductor wafer is lifted up from the substrate side of the dicing tape by a needle, and the semiconductor wafer to be lifted is picked up by a pick-up device. Further, the semiconductor wafer 5 picked up is integrated with the sheet-like resin composition 2 bonded to the circuit surface 3a to form a laminated body A.

於黏著劑層11b為紫外線硬化型之情形時，拾取係於對該黏著劑層11b照射紫外線後進行。藉此，黏著劑層11b對半導體晶片5之黏著力降低，易於剝離半導體晶片5。其結果為，可不損傷半導體晶片5而進行拾取。照射紫外線時之照射強度、照射時間等條件並無特別限定，只要視需要適當設定即可。又，作為用於紫外線照射之光源，例如可使用低壓水銀燈、低壓高輸出燈、中壓水銀燈、無電極水銀燈、氙氣閃光燈、準分子燈、紫外LED等。 In the case where the adhesive layer 11b is of an ultraviolet curing type, the pickup is performed by irradiating the adhesive layer 11b with ultraviolet rays. Thereby, the adhesion of the adhesive layer 11b to the semiconductor wafer 5 is lowered, and the semiconductor wafer 5 is easily peeled off. As a result, the semiconductor wafer 5 can be picked up without damaging it. The conditions such as the irradiation intensity and the irradiation time when the ultraviolet ray is irradiated are not particularly limited, and may be appropriately set as necessary. Further, as the light source for ultraviolet irradiation, for example, a low pressure mercury lamp, a low pressure high output lamp, a medium pressure mercury lamp, an electrodeless mercury lamp, a xenon flash lamp, an excimer lamp, an ultraviolet LED, or the like can be used.

[安裝步驟] [installation steps]

於安裝步驟中，藉由直接光或間接光、紅外線等預先求出半導體元件5之安裝位置，依照所求出之安裝位置，將被黏著體16與半導體元件5之間之空間以片狀樹脂組合物2予以填充，並且經由連接構件4將半導體元件5與被黏著體16電性連接(參照圖2F)。具體而言，使積層體A之半導體晶片5以半導體晶片5之電路面3a與被黏著體16對向之形態依照常法固定於被黏著體16。例如，使形成於半導體晶片5之凸塊(連接構件)4與被黏著於被黏著體16之連接墊的接合用導電材17(焊料等)接觸，一面按壓一面使導電材熔融，藉此可確保半導體晶片5與被黏著體16之電性連接，使半導體晶片5固定於被黏著體16。於半導體晶片5之電路面3a貼附有片狀樹脂組合物2，因此於半導體晶片5與被黏著體16電性連接之同時，半導體晶片5與被黏著體16之間之空間 被片狀樹脂組合物2填充。 In the mounting step, the mounting position of the semiconductor element 5 is obtained in advance by direct light, indirect light, infrared light or the like, and the space between the adherend 16 and the semiconductor element 5 is made into a sheet-like resin in accordance with the obtained mounting position. The composition 2 is filled, and the semiconductor element 5 is electrically connected to the adherend 16 via the connecting member 4 (refer to FIG. 2F). Specifically, the semiconductor wafer 5 of the laminated body A is fixed to the adherend 16 in a conventional manner in such a manner that the circuit surface 3a of the semiconductor wafer 5 faces the adherend 16 . For example, the bumps (connection members) 4 formed on the semiconductor wafer 5 are brought into contact with the bonding conductive material 17 (solder or the like) adhered to the connection pads of the adherend 16, and the conductive material is melted while being pressed. The semiconductor wafer 5 is electrically connected to the adherend 16 to fix the semiconductor wafer 5 to the adherend 16. The sheet-like resin composition 2 is attached to the circuit surface 3a of the semiconductor wafer 5, so that the space between the semiconductor wafer 5 and the adherend 16 is electrically connected to the semiconductor wafer 5 and the adherend 16 It is filled with the sheet-like resin composition 2.

一般而言，安裝步驟中之加熱條件為100~300℃，加壓條件為0.5~500N。又，亦可以多階段進行安裝步驟中之熱壓接處理。例如，可採用於150℃、100N下處理10秒鐘後於300℃、100~200N下處理10秒鐘之順序。藉由以多階段進行熱壓接處理，可高效率地去除連接構件與墊間之樹脂，獲得更良好之金屬間接合。 In general, the heating conditions in the mounting step are 100 to 300 ° C, and the pressing conditions are 0.5 to 500 N. Further, the thermocompression bonding process in the mounting step may be performed in multiple stages. For example, it can be processed at 150 ° C, 100 N for 10 seconds, and then at 300 ° C, 100 to 200 N for 10 seconds. By performing the thermocompression bonding treatment in multiple stages, the resin between the connecting member and the mat can be efficiently removed, and a better intermetallic joining can be obtained.

作為被黏著體16，可使用半導體晶圓、引線框架或電路基板(配線電路基板等)等各種基板、其他半導體元件。作為基板之材質，並無特別限定，可列舉陶瓷基板或塑膠基板。作為塑膠基板，例如可列舉環氧基板、雙順丁烯二醯亞胺三基板、聚醯亞胺基板、玻璃環氧基板等。安裝於1個被黏著體之半導體元件之數量亦無限定，可為1個或複數個之任一者。片狀樹脂組合物2亦可較佳地應用於在半導體晶圓安裝多個半導體晶片的晶片磊晶圓製程。 As the adherend 16 , various substrates such as a semiconductor wafer, a lead frame, or a circuit board (such as a printed circuit board) and other semiconductor elements can be used. The material of the substrate is not particularly limited, and examples thereof include a ceramic substrate and a plastic substrate. As the plastic substrate, for example, an epoxy substrate or a bis-xenylene diimide III can be cited. A substrate, a polyimide substrate, a glass epoxy substrate, or the like. The number of semiconductor elements mounted on one of the adherends is not limited, and may be one or plural. The sheet-like resin composition 2 can also be preferably applied to a wafer wafer wafer process in which a plurality of semiconductor wafers are mounted on a semiconductor wafer.

再者，於安裝步驟中，使連接構件及導電材之一者或兩者熔融，而使半導體晶片5之連接構件形成面3a之凸塊4與被黏著體16之表面之導電材17連接，作為該凸塊4及導電材17熔融時之溫度，通常為260℃左右(例如250℃~300℃)。本實施形態之積層片藉由利用環氧樹脂等形成片狀樹脂組合物2，可製成具有亦可耐受該安裝步驟中之高溫之耐熱性者。 Further, in the mounting step, one or both of the connecting member and the conductive material are melted, and the bump 4 of the connecting member forming surface 3a of the semiconductor wafer 5 is connected to the conductive material 17 on the surface of the adherend 16 . The temperature at which the bump 4 and the conductive material 17 are melted is usually about 260 ° C (for example, 250 ° C to 300 ° C). The laminated sheet of the present embodiment can be formed into a sheet-like resin composition 2 by an epoxy resin or the like, and can have a heat resistance which can withstand the high temperature in the mounting step.

[片狀樹脂組合物硬化步驟] [Sheet resin composition hardening step]

於進行半導體元件5與被黏著體16之電性連接後，藉由加熱使片狀樹脂組合物2硬化。藉此，可保護半導體元件5之表面，並且可確保半導體元件5與被黏著體16之間之連接可靠性。作為用以使片狀樹脂組合物硬化之加熱溫度，並無特別限定，為150~250℃左右即可。再者，於藉由安裝步驟中之加熱處理使片狀樹脂組合物硬化之情形時，本步驟可省略。 After the semiconductor element 5 is electrically connected to the adherend 16, the sheet-like resin composition 2 is cured by heating. Thereby, the surface of the semiconductor element 5 can be protected, and the connection reliability between the semiconductor element 5 and the adherend 16 can be ensured. The heating temperature for curing the sheet-like resin composition is not particularly limited, and may be about 150 to 250 °C. Further, in the case where the sheet-like resin composition is cured by the heat treatment in the mounting step, this step can be omitted.

[密封步驟] [sealing step]

其次，為了保護具備經安裝之半導體晶片5之半導體裝置20整體，亦可進行密封步驟。密封步驟係使用密封樹脂進行。作為此時之密封條件，並無特別限定，通常藉由於175℃下進行60秒鐘~90秒鐘之加熱而進行密封樹脂之熱硬化，但本發明並不限定於此，例如可於165℃~185℃下固化數分鐘。 Next, in order to protect the entire semiconductor device 20 having the mounted semiconductor wafer 5, a sealing step may be performed. The sealing step is carried out using a sealing resin. The sealing condition at this time is not particularly limited, and the sealing resin is usually thermally cured by heating at 175 ° C for 60 seconds to 90 seconds. However, the present invention is not limited thereto, and for example, it can be 165 ° C. Curing for several minutes at ~185 °C.

作為上述密封樹脂，只要為具有絕緣性之樹脂(絕緣樹脂)則無特別限制，可自公知之密封樹脂等密封材中適當選擇而使用，更佳為具有彈性之絕緣樹脂。作為密封樹脂，例如可列舉包含環氧樹脂之樹脂組合物等。作為環氧樹脂，可列舉上述所例示之環氧樹脂等。又，作為由包含環氧樹脂之樹脂組合物獲得之密封樹脂，作為樹脂成分，除環氧樹脂以外，亦可包含環氧樹脂以外之熱硬化性樹脂(酚系樹脂等)、或熱塑性樹脂等。再者，作為酚系樹脂，亦可用作環氧樹脂之硬化劑，作為此種酚系樹脂，可列舉上述所例示之酚系樹脂等。 The sealing resin is not particularly limited as long as it is an insulating resin (insulating resin), and can be appropriately selected from known sealing materials such as sealing resins, and more preferably an insulating resin having elasticity. The sealing resin may, for example, be a resin composition containing an epoxy resin. Examples of the epoxy resin include the epoxy resins exemplified above. In addition, as a resin component, a sealing resin obtained from a resin composition containing an epoxy resin may contain, in addition to an epoxy resin, a thermosetting resin (such as a phenol resin) other than an epoxy resin, or a thermoplastic resin. . In addition, the phenolic resin can also be used as a curing agent for an epoxy resin, and examples of such a phenolic resin include the above-exemplified phenolic resins.

[半導體裝置] [semiconductor device]

其次，一面參照圖式一面對使用該積層片獲得之半導體裝置進行說明(參照圖2F)。本實施形態之半導體裝置20中，半導體元件5與被黏著體16係經由形成於半導體元件5上之凸塊(連接構件)4及設置於被黏著體16上之導電材17而電性連接。又，於半導體元件5與被黏著體16之間，以填充該空間之方式配置有片狀樹脂組合物2。半導體裝置20係藉由採用特定之片狀樹脂組合物2之上述製造方法而獲得，因此於半導體元件5與被黏著體16之間達成良好之電性連接。因此，半導體元件5之表面保護、半導體元件5與被黏著體16之間之空間之填充、及半導體元件5與被黏著體16之間之電性連接分別成為充分之級別，作為半導體裝置20可發揮較高之可靠性。 Next, a description will be given of a semiconductor device obtained by using the laminated sheet with reference to the drawings (see FIG. 2F). In the semiconductor device 20 of the present embodiment, the semiconductor element 5 and the adherend 16 are electrically connected via a bump (connection member) 4 formed on the semiconductor element 5 and a conductive material 17 provided on the adherend 16. Moreover, the sheet-like resin composition 2 is disposed between the semiconductor element 5 and the adherend 16 so as to fill the space. Since the semiconductor device 20 is obtained by the above-described manufacturing method using the specific sheet-like resin composition 2, a good electrical connection is achieved between the semiconductor element 5 and the adherend 16. Therefore, the surface protection of the semiconductor element 5, the filling of the space between the semiconductor element 5 and the adherend 16 , and the electrical connection between the semiconductor element 5 and the adherend 16 are respectively sufficient levels, and the semiconductor device 20 can be used. Play a higher level of reliability.

<第2實施形態> <Second embodiment>

第1實施形態中使用單面形成有電路之半導體晶圓，與此相對，本實施形態中使用兩面形成有電路之半導體晶圓而製造半導體裝置。又，本實施形態中使用之半導體晶圓具有目標厚度，因此省略研削步驟。因此，作為第2實施形態中之積層片，使用具備切晶帶與積層於該切晶帶上之特定之片狀樹脂組合物的積層片。作為較第2實施形態中之連接步驟之前之代表性步驟，可列舉：準備步驟，其係準備上述積層片；貼合步驟，其係將於兩面形成有具有連接構件之電路面之半導體晶圓與上述積層片之片狀樹脂組合物貼合；切晶步驟，其係對上述半導體晶圓進行切晶而形成附有上述片狀樹脂組合物之半導體元件；拾取步驟，其係將附有上述片狀樹脂組合物之半導體元件自上述積層片剝離。其後，進行連接步驟以後之步驟而製造半導體裝置。 In the first embodiment, a semiconductor wafer in which a circuit is formed on one side is used. In the present embodiment, a semiconductor wafer in which a circuit is formed on both sides is used to manufacture a semiconductor device. Further, since the semiconductor wafer used in the present embodiment has a target thickness, the grinding step is omitted. Therefore, as the laminated sheet in the second embodiment, a laminated sheet having a dicing tape and a specific sheet-like resin composition laminated on the dicing tape is used. As a representative step before the connecting step in the second embodiment, a preparation step of preparing the laminated sheet; and a bonding step of forming a semiconductor wafer having a circuit surface having a connecting member on both sides is exemplified. Bonding to the sheet-like resin composition of the laminated sheet; a dicing step of dicing the semiconductor wafer to form a semiconductor element having the sheet-like resin composition; and a picking step, which is attached The semiconductor element of the sheet-like resin composition is peeled off from the above laminated sheet. Thereafter, a semiconductor device is manufactured by performing the steps subsequent to the connection step.

[準備步驟] [Preparation steps]

於準備步驟中，準備具備切晶帶41及積層於該切晶帶41上之特定之片狀樹脂組合物42的積層片(參照圖3A)。切晶帶41具備基材41a及積層於基材41a上之黏著劑層41b。再者，片狀樹脂組合物42積層於黏著劑層41b上。作為此種切晶帶41之基材41a及黏著劑層41b、以及片狀樹脂組合物42，可使用與第1實施形態相同者。 In the preparation step, a laminated sheet having a dicing tape 41 and a specific sheet-like resin composition 42 laminated on the dicing tape 41 is prepared (see FIG. 3A). The dicing tape 41 is provided with a base material 41a and an adhesive layer 41b laminated on the base material 41a. Further, the sheet-like resin composition 42 is laminated on the adhesive layer 41b. The base material 41a, the adhesive layer 41b, and the sheet-like resin composition 42 of the dicing tape 41 can be the same as those of the first embodiment.

[貼合步驟] [Finishing step]

於貼合步驟中，如圖3A所示，將兩面形成有具有連接構件44之電路面的半導體晶圓43與上述積層片之片狀樹脂組合物42貼合。再者，由於薄型化至特定厚度之半導體晶圓之強度較弱，故而有時為了強化而將半導體晶圓經由暫時固定材固定於支持玻璃等支持體(未圖示)。於此情形時，亦可包括如下步驟：於半導體晶圓與片狀樹脂組合物貼合後，將支持體與暫時固定材一併剝離。關於將半導體晶圓43之哪一電路面與片狀樹脂組合物42貼合，根據目標之半導體裝置之構造進行變更即可。 In the bonding step, as shown in FIG. 3A, the semiconductor wafer 43 having the circuit surface having the connection member 44 formed on both sides thereof is bonded to the sheet-like resin composition 42 of the laminated sheet. Further, since the strength of the semiconductor wafer which is thinned to a specific thickness is weak, the semiconductor wafer may be fixed to a support such as a support glass (not shown) via a temporary fixing material for reinforcement. In this case, the method may further include the step of peeling off the support and the temporary fixing material after bonding the semiconductor wafer and the sheet-like resin composition. Which of the circuit surfaces of the semiconductor wafer 43 is bonded to the sheet-like resin composition 42 may be changed according to the structure of the intended semiconductor device.

作為半導體晶圓43，於兩面形成具有連接構件44之電路面，且具有特定之厚度，除此方面以外，與第1實施形態之半導體晶圓相同。半導體晶圓43之兩面之連接構件44彼此可電性連接，亦可不連接。連接構件44彼此之電性連接可列舉藉由被稱為TSV(Through-Silicon Via，矽穿孔)形式之經由通孔之連接的連接等。作為貼合條件，可較佳地採用第1實施形態之貼合條件。 The semiconductor wafer 43 has the same circuit surface as the circuit surface having the connection member 44 on both surfaces, and is the same as the semiconductor wafer of the first embodiment. The connecting members 44 on both sides of the semiconductor wafer 43 may or may not be electrically connected to each other. The electrical connection of the connecting members 44 to each other may be exemplified by a connection via a through hole such as a TSV (Through-Silicon Via). As the bonding conditions, the bonding conditions of the first embodiment can be preferably used.

[切晶步驟] [Cutting step]

於切晶步驟中，對上述半導體晶圓43及片狀樹脂組合物42進行切晶，而形成附有上述片狀樹脂組合物之半導體元件45(參照圖3B)。作為切晶條件，可較佳地採用第1實施形態中之各條件。再者，切晶係對半導體晶圓43所露出之電路面進行，因此切晶位置之檢測較容易，但視需要亦可照射光而確認切晶位置後進行切晶。 In the dicing step, the semiconductor wafer 43 and the sheet-like resin composition 42 are diced to form a semiconductor element 45 to which the sheet-like resin composition is attached (see FIG. 3B). As the dicing conditions, the respective conditions in the first embodiment can be preferably employed. Further, since the dicing system is performed on the circuit surface on which the semiconductor wafer 43 is exposed, it is easy to detect the dicing position, but it is also possible to illuminate the light to confirm the dicing position and then perform dicing.

[拾取步驟] [pickup step]

於拾取步驟中，將附有上述片狀樹脂組合物42之半導體元件45自上述切晶帶41剝離(圖3C)。作為拾取條件，可較佳地採用第1實施形態中之各條件。 In the pickup step, the semiconductor element 45 to which the above-mentioned sheet-like resin composition 42 is attached is peeled off from the above-described dicing tape 41 (Fig. 3C). As the pickup conditions, the respective conditions in the first embodiment can be preferably employed.

於本實施形態之積層片中，上述片狀樹脂組合物自上述切晶帶之剝離力較佳為0.03~0.10N/20mm。藉此，可容易地進行附有片狀樹脂組合物之半導體元件之拾取。 In the laminated sheet of the present embodiment, the peeling force of the sheet-like resin composition from the dicing tape is preferably 0.03 to 0.10 N/20 mm. Thereby, picking up of the semiconductor element with the sheet-like resin composition can be easily performed.

[安裝步驟] [installation steps]

於安裝步驟中，將被黏著體66與半導體元件45之間之空間以片狀樹脂組合物42予以填充，並且經由連接構件44將半導體元件45與被黏著體66電性連接(參照圖3D)。安裝步驟中之條件可較佳地採用第1實施形態中之各條件。藉此，可製造本實施形態之半導體裝置60。 In the mounting step, the space between the adherend 66 and the semiconductor element 45 is filled with the sheet-like resin composition 42, and the semiconductor element 45 and the adherend 66 are electrically connected via the connecting member 44 (refer to FIG. 3D). . The conditions in the mounting step can be preferably those in the first embodiment. Thereby, the semiconductor device 60 of this embodiment can be manufactured.

以下，亦可與第1實施形態同樣地視需要進行片狀樹脂組合物硬化步驟及密封步驟。 In the same manner as in the first embodiment, the sheet-like resin composition curing step and the sealing step may be carried out as needed.

<第3實施形態> <Third embodiment>

於第1實施形態中，使用背面研削用帶作為積層片之構成構件，但於本實施形態中未設置該背面研削用帶之黏著劑層而單獨使用基材。因此，作為本實施形態之積層片，成為於基材上積層有片狀樹脂組合物之狀態。於本實施形態中，研削步驟可任意地進行，但拾取步驟前之紫外線照射因省略黏著劑層而不進行。藉由經過除了該等方面以外而其他與第1實施形態相同之步驟，可製造特定之半導體裝置。 In the first embodiment, the back grinding belt is used as the constituent member of the laminated sheet. However, in the present embodiment, the adhesive layer of the back grinding belt is not provided, and the base material is used alone. Therefore, the laminated sheet of the present embodiment is in a state in which a sheet-like resin composition is laminated on a substrate. In the present embodiment, the grinding step can be carried out arbitrarily, but the ultraviolet irradiation before the picking step is not performed because the adhesive layer is omitted. A specific semiconductor device can be manufactured by performing the same steps as those of the first embodiment except for these points.

<其他實施形態> <Other Embodiments>

於第1實施形態至第3實施形態中，於切晶步驟中採用使用切晶刀片之切晶，但亦可取而代之而採用所謂的隱形切晶，即，藉由雷射照射而於半導體晶圓內部形成改質部分，沿著該改質部分將半導體晶圓分割而單片化。 In the first embodiment to the third embodiment, the dicing using the dicing blade is employed in the dicing step, but instead, so-called stealth dicing, that is, laser irradiation may be employed in the semiconductor wafer. A modified portion is formed inside, and the semiconductor wafer is divided and singulated along the modified portion.

[實施例] [Examples]

以下，例示性且詳細地說明該發明之較佳實施例。其中，該實施例所記載之材料或調配量等只要無特別限定之記載，則本發明之宗旨並非將該發明之範圍僅限定於上述記載。又，記為份之情況係指重量份。 Hereinafter, preferred embodiments of the invention will be described by way of example and in detail. However, the materials, the blending amounts, and the like described in the examples are not intended to limit the scope of the invention to the above description unless otherwise specified. In addition, the case of a part is a weight part.

[實施例1~2及比較例1~3] [Examples 1 to 2 and Comparative Examples 1 to 3]

<片狀樹脂組合物之製作> <Production of sheet-like resin composition>

將以下成分以表1所示之比率溶解於甲基乙基酮中，製備固形物成分濃度成為45~60重量%之接著劑組合物之溶液。 The following components were dissolved in methyl ethyl ketone at a ratio shown in Table 1 to prepare a solution of an adhesive composition having a solid content concentration of 45 to 60% by weight.

丙烯酸系樹脂：以丙烯酸乙酯-甲基丙烯酸甲酯作為主成分之丙烯酸酯系聚合物(商品名「Paracron W-197CM」，根上工業股份有限公司製造) Acrylic resin: an acrylate-based polymer containing ethyl acrylate-methyl methacrylate as a main component (trade name "Paracron W-197CM", manufactured by Gensei Industrial Co., Ltd.)

環氧樹脂1：商品名「Epikote 1004」，JER股份有限公司製造 Epoxy resin 1: trade name "Epikote 1004", manufactured by JER Co., Ltd.

環氧樹脂2：商品名「Epikote 828」，JER股份有限公司製造 Epoxy resin 2: trade name "Epikote 828", manufactured by JER Co., Ltd.

硬化劑1：酚系樹脂(商品名「MEH-7851H」，明和化成股份有限公司製造) Hardener 1: phenolic resin (trade name "MEH-7851H", manufactured by Minghe Chemical Co., Ltd.)

硬化劑2：酸酐(商品名「RIKACID HH」，新日本理化股份有限公司製造) Hardener 2: Anhydride (trade name "RIKACID HH", manufactured by New Japan Physical and Chemical Co., Ltd.)

無機填充劑：球狀二氧化矽(商品名「SO-25R」，Admatechs股份有限公司製造) Inorganic filler: spherical cerium oxide (trade name "SO-25R", manufactured by Admatechs Co., Ltd.)

熱硬化促進觸媒：咪唑觸媒(商品名「2PHZ-PW」，四國化成股份有限公司製造) Thermal hardening promoting catalyst: Imidazole catalyst (trade name "2PHZ-PW", manufactured by Shikoku Chemicals Co., Ltd.)

助焊劑：鄰大茴香酸(商品名「orthoanisic acid」，東京化成股份有限公司製造) Flux: o-anisic acid (trade name "orthoanisic acid", manufactured by Tokyo Chemical Industry Co., Ltd.)

將該接著劑組合物之溶液塗佈於作為剝離襯墊(隔離件)進行聚矽氧脫模處理過之厚度為38μm、由聚對苯二甲酸乙二酯膜形成的脫模處理膜上後，於130℃下乾燥2分鐘，藉此製作厚度40μm之片狀樹脂組合物。 The solution of the adhesive composition was applied onto a release-treated film formed of a polyethylene terephthalate film having a thickness of 38 μm which was subjected to polyfluorene stripping treatment as a release liner (separator). It was dried at 130 ° C for 2 minutes to prepare a sheet-like resin composition having a thickness of 40 μm.

[評價] [Evaluation]

使用所製作之片狀樹脂組合物對以下項目進行評價。將各評價結果示於表1。 The following items were evaluated using the produced sheet-like resin composition. The results of each evaluation are shown in Table 1.

<黏度之測定方法> <Method for measuring viscosity>

使用黏彈性測定裝置ARES(Rheometric Scientific公司製造)測定所製作之片狀樹脂組合物之黏度。將片狀樹脂組合物以不產生空隙且成為500~1000μm之厚度之方式積層，將所積層之樣品沖裁成8mm，夾於8mm之平行板，於頻率：1Hz、測定起始溫度：50℃、測定結束溫度：250℃、升溫速度：10℃/min之測定條件下進行測定，讀取80℃、150℃、200℃下之黏度之值，藉此求出黏度η80、黏度η150、黏度η200。 The viscosity of the produced sheet-like resin composition was measured using a viscoelasticity measuring apparatus ARES (manufactured by Rheometric Scientific Co., Ltd.). The sheet-like resin composition was laminated so as to have a thickness of 500 to 1000 μm without generating voids, and the sample of the laminated layer was punched into 8 mm. , clipped to 8mm The parallel plate was measured under the measurement conditions of frequency: 1 Hz, measurement start temperature: 50 ° C, measurement end temperature: 250 ° C, and temperature increase rate: 10 ° C / min, and reading at 80 ° C, 150 ° C, and 200 ° C The viscosity value is used to obtain the viscosity η 80 , the viscosity η 150 , and the viscosity η 200 .

<安裝評價> <Installation Evaluation>

於WALTS股份有限公司之測試載具(於厚度725μm之晶圓形成有高度40μm之凸塊者)，貼附厚度40μm之片狀樹脂組合物，設為樣品A。貼附條件係於真空度：100Pa之條件下設為溫度：80℃、貼附壓力：0.5MPa。 A test piece of WALTS Co., Ltd. (a bump having a height of 40 μm was formed on a wafer having a thickness of 725 μm), and a sheet-like resin composition having a thickness of 40 μm was attached to sample A. The attachment conditions were set to a temperature of 80 ° C under vacuum: 100 Pa, and a pressure of 0.5 MPa.

繼而，於切晶帶(商品名「WS-01」，日東電工公司製造)貼合樣品A之晶圓側並固定，對樣品A進行切晶，藉此製作附有片狀樹脂組合物之半導體晶片(晶片尺寸：7mm見方)，設為樣品B。 Then, the dicing tape (trade name "WS-01", manufactured by Nitto Denko Corporation) was bonded to the wafer side of sample A and fixed, and sample A was subjected to dicing to prepare a semiconductor having a sheet-like resin composition. Wafer (wafer size: 7 mm square), set to sample B.

其次，將所拾取之樣品B安裝於具有電極之安裝用基板(電極之高度：15μm)。安裝係使用TORAY ENGINEERING公司之覆晶接合機(FC3000W)進行。安裝條件係於荷重：0.5MPa之條件下，於200℃下保持10秒鐘後，於260℃下保持10秒。 Next, the sample B picked up was attached to a mounting substrate having electrodes (the height of the electrodes: 15 μm). The installation was carried out using a flip chip bonding machine (FC3000W) from TORAY ENGINEERING. The mounting conditions were maintained at 200 ° C for 10 seconds under a load of 0.5 MPa and then held at 260 ° C for 10 seconds.

(空隙評價) (void evaluation)

將所獲得之安裝後之樣品與晶片平行地進行研磨，使片狀樹脂組合物露出。利用光學顯微鏡(200倍)確認所露出之樹脂部分之空隙狀態，將未確認到產生空隙(最大直徑：超過3μm)之情形設為「○」，將哪怕於1個部位確認到產生空隙之情形設為「×」，而進行評價。 The obtained sample after mounting was polished in parallel with the wafer to expose the sheet-like resin composition. When the void state of the exposed resin portion was confirmed by an optical microscope (200 times), the case where voids (maximum diameter: more than 3 μm) were not confirmed was set to "○", and even if one space was confirmed to have a void, It is evaluated as "X".

(接合狀態評價) (joining state evaluation)

對所獲得之安裝後之樣品通電，實際地進行動作確認，藉此確認接合狀態。將已導通而正常地作動且於接合截面無破裂等之良好接合狀態之情形設為「○」，將未導通、或導通不充分而未正常地作動之情形、或於接合截面產生破裂等不良情況之情形設為「×」，而進行評價。 The obtained sample after the installation was energized, and the operation was confirmed in actuality, thereby confirming the joined state. In the case of a good bonding state in which the bonding section is normally turned on and the bonding section is not broken, etc., it is set to "○", and the case where the conduction is not performed or the conduction is insufficient, the operation is not performed normally, or the joint cross section is broken. In the case of the situation, it is set to "X" and the evaluation is performed.

根據表1可知，於所有實施例中均可製造出空隙之產生或膨脹得到抑制、並且半導體晶片與基板之接合良好、連接可靠性良好的半導體裝置。另一方面，於比較例1中，雖然空隙評價良好，但接合狀態不充分。認為其原因在於：150℃下之黏度η150過高，晶片之凸塊與基板之電極之接合不充分。於比較例2及3中，雖然接合狀態良好，但確認到空隙。認為其原因在於：於比較例2中，150℃下之黏度η150過低，於比較例3中，除黏度η150過低以外，200℃下之黏度η200亦過低，空隙之膨脹未得到充分抑制。 As can be seen from Table 1, in all of the examples, a semiconductor device in which generation or expansion of voids was suppressed, bonding between a semiconductor wafer and a substrate was good, and connection reliability was good. On the other hand, in Comparative Example 1, although the void evaluation was good, the joined state was insufficient. The reason is that: the viscosity at 150 ℃ η 150 is too high, the bump electrodes bonded wafer of the substrate is not sufficient. In Comparative Examples 2 and 3, although the joined state was good, voids were confirmed. The reason is that: in Comparative Example 2, the viscosity at 150 ℃ η 150 is too low, in Comparative Example 3, except outside low viscosity η 150, the viscosity at 200 ℃ η 200 is also low, the void expanded is not It is fully suppressed.

2‧‧‧片狀樹脂組合物 2‧‧‧Flake resin composition

4‧‧‧連接構件 4‧‧‧Connecting components

5‧‧‧半導體晶片(半導體元件) 5‧‧‧Semiconductor wafer (semiconductor component)

16‧‧‧被黏著體 16‧‧‧Adhesive body

17‧‧‧導電材 17‧‧‧Electrical materials

20‧‧‧半導體裝置 20‧‧‧Semiconductor device

Claims (10)

一種片狀樹脂組合物，其係用以填充被黏著體與電性連接於該被黏著體之半導體元件之間之空間的熱硬化性片狀樹脂組合物，且於溫度範圍50℃~250℃、升溫速度10℃/min、頻率1Hz之測定條件下測定上述片狀樹脂組合物之黏度時，溫度150℃下之黏度η150為0.05MPa‧s≦η150≦2.2MPa‧s，溫度200℃下之黏度η200為1.0MPa‧s≦η200≦100.0MPa‧s。 A sheet-like resin composition for filling a thermosetting sheet-like resin composition which is a space between an adherend and a semiconductor element electrically connected to the adherend, and is in a temperature range of 50 ° C to 250 ° C When the viscosity of the sheet-like resin composition is measured under the measurement conditions of a heating rate of 10 ° C / min and a frequency of 1 Hz, the viscosity η 150 at a temperature of 150 ° C is 0.05 MPa ‧ ≦ 150 150 ≦ 2.2 MPa ‧ s, temperature 200 ° C The lower viscosity η 200 is 1.0 MPa ‧ s ≦ 200 ≦ 100.0 MPa ‧ s. 如請求項1之片狀樹脂組合物，其中於上述測定條件下測定上述片狀樹脂組合物之黏度時，進而，溫度80℃下之黏度η80為0.001MPa‧s≦η80≦1.0MPa‧s。 The sheet-like resin composition of claim 1, wherein when the viscosity of the sheet-like resin composition is measured under the above-mentioned measurement conditions, the viscosity η 80 at a temperature of 80 ° C is 0.001 MPa ‧ s 80 80 ≦ 1.0 MPa ‧ s. 如請求項2之片狀樹脂組合物，其中上述黏度η80為0.01MPa‧s≦η80≦0.1MPa‧s，上述黏度η150為0.1MPa‧s≦η150≦2.2MPa‧s，上述黏度η200為1.0MPa‧s≦η200≦50.0MPa‧s。 The sheet-like resin composition of claim 2, wherein the viscosity η 80 is 0.01 MPa ‧ ≦ 80 80 ≦ 0.1 MPa ‧ and the viscosity η 150 is 0.1 MPa ‧ ≦ 150 150 ≦ 2.2 MPa ‧ s, the viscosity η 200 is 1.0 MPa ‧ s 200 200 ≦ 50.0 MPa ‧ s. 如請求項1至3中任一項之片狀樹脂組合物，其含有環氧樹脂、硬化劑、熱塑性樹脂、無機填充劑及熱硬化促進觸媒。 The sheet-like resin composition according to any one of claims 1 to 3, which comprises an epoxy resin, a curing agent, a thermoplastic resin, an inorganic filler, and a thermosetting-promoting catalyst. 如請求項4之片狀樹脂組合物，其中上述熱塑性樹脂係重量平均分子量為5×105以上之丙烯酸系樹脂。 The sheet-like resin composition of claim 4, wherein the thermoplastic resin is an acrylic resin having a weight average molecular weight of 5 × 10 5 or more. 如請求項4之片狀樹脂組合物，其中上述無機填充劑之平均粒徑為10nm以上且500nm以下。 The sheet-like resin composition of claim 4, wherein the inorganic filler has an average particle diameter of 10 nm or more and 500 nm or less. 如請求項4之片狀樹脂組合物，其中上述熱硬化促進觸媒係於分子內含有氮原子之有機化合物，該有機化合物之分子量為50~500。 The sheet-like resin composition of claim 4, wherein the thermosetting-promoting catalyst is an organic compound containing a nitrogen atom in the molecule, and the molecular weight of the organic compound is 50 to 500. 一種積層片，其包括： 黏著帶，其具有基材及設置於該基材上之黏著劑層；及如請求項1至7中任一項之片狀樹脂組合物，其積層於上述黏著劑層上。 A laminated sheet comprising: An adhesive tape having a substrate and an adhesive layer provided on the substrate; and the sheet-like resin composition according to any one of claims 1 to 7, which is laminated on the above adhesive layer. 如請求項8之積層片，其中上述黏著帶係半導體晶圓之背面研削用帶或切晶帶。 The laminate of claim 8, wherein the adhesive tape is a back-grinding tape or a dicing tape of a semiconductor wafer. 一種半導體裝置之製造方法，其係包括被黏著體、與該被黏著體電性連接之半導體元件、及填充該被黏著體與該半導體元件之間之空間之片狀樹脂組合物的半導體裝置之製造方法，且包括如下步驟：準備附有片狀樹脂組合物之半導體元件，其係將如請求項1至7中任一項之片狀樹脂組合物貼合於上述半導體元件而成；及連接步驟，其係將上述被黏著體與上述半導體元件之間之空間以上述片狀樹脂組合物予以填充，並且將上述半導體元件與上述被黏著體電性連接。 A method of manufacturing a semiconductor device comprising: a semiconductor device to which an adherend, a semiconductor element electrically connected to the adherend, and a sheet-like resin composition filling a space between the adherend and the semiconductor element; a manufacturing method, comprising the steps of: preparing a semiconductor element with a sheet-like resin composition, which is obtained by laminating the sheet-like resin composition according to any one of claims 1 to 7 to the above-mentioned semiconductor element; In the step of filling the space between the adherend and the semiconductor element with the sheet-like resin composition, the semiconductor element is electrically connected to the adherend.
TW104114939A 2014-05-13 2015-05-11 Sheet-like resin composition, multilayer sheet and method for manufacturing semiconductor device TW201546230A (en)

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