Method for manufacturing insulating film and semiconductor package

Abstract

The present invention relates to a method for manufacturing an insulating layer which can minimize the degree of warpage caused by polymer shrinkage at the time of curing and secure the stability of a semiconductor chip located therein, and a method for manufacturing a semiconductor package using an insulating layer obtained from the manufacturing method of the insulating layer.

Claims

1. A method for manufacturing an insulating layer, comprising: sealing at least two or more semiconductor elements between a photosensitive resin layer and a polymer resin layer, wherein the polymer resin layer is formed on a substrate and contains an alkali-soluble resin and a heat-curable binder; exposing to light and alkali-developing the photosensitive resin layer to form a photosensitive resin block, alkali-developing an exposed polymer resin layer by the photosensitive resin block to form a polymer resin block; and curing the polymer resin block to form the insulating layer, wherein in the alkali developing step, at least one semiconductor element is sealed between the photosensitive resin block and the polymer resin block which are in contact with each other, and wherein a maximum longitudinal cross-sectional diameter of the polymer resin block is 50% or less with respect to a maximum longitudinal cross-sectional length of the polymer resin layer.

2. The method for manufacturing an insulating layer according to claim 1, wherein a maximum longitudinal cross-sectional length of the polymer resin block is 100 mm or less.

3. The method for manufacturing an insulating layer according to claim 1, wherein in the alkali developing step, the photosensitive resin layer or the polymer resin layer located at 10% to 90% of a distance between adjacent semiconductor elements is removed wherein the distance between adjacent semiconductor elements is a minimum distance from the end of one semiconductor element to the end of another semiconductor element in two adjacent semiconductor elements.

4. The method for manufacturing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one acidic functional group, and at least one cyclic imide functional group substituted with an amino group.

5. The method for manufacturing an insulating layer according to claim 4, wherein the cyclic imide functional group substituted with an amino group includes a functional group represented by the following Chemical Formula 1: ##STR00007## in Chemical Formula 1, R1 is an alkylene group or an alkenyl group having 1 to 10 carbon atoms forming an imide ring, and “*” means a bonding point.

6. The method for manufacturing an insulating layer according to claim 4, wherein the alkali-soluble resin is produced through reaction of a cyclic unsaturated imide compound and an amine compound, and the at least one of the cyclic unsaturated imide compound and the amine compound contains an acidic functional group substituted at its terminal.

7. The method for manufacturing an insulating layer according to claim 6, wherein the amine compound includes at least one selected from the group consisting of a carboxylic acid compound substituted with an amino group and a polyfunctional amine compound containing two or more amino groups.

8. The method for manufacturing an insulating layer according to claim 1, wherein the alkali-soluble resin includes at least one repeating unit represented by the following Chemical Formula 3 and at least one repeating unit represented by the following Chemical Formula 4: ##STR00008## in Chemical Formula 3, R2 is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, and “*” means a bonding point, ##STR00009## in Chemical Formula 4, R3 is a direct bond, an alkylene group having 1 to 20 carbon atoms, an alkenyl group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms, R4 is —H, —OH, —NR5R6, a halogen, or an alkyl group having 1 to 20 carbon atoms, R5 and R6 are each independently be hydrogen, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and “*” means a bonding point.

9. The method for manufacturing an insulating layer according to claim 8, wherein the alkali-soluble resin is produced by reaction of a polymer containing a repeating unit represented by the following Chemical Formula 5, an amine represented by the following Chemical Formula 6, and an amine represented by the following Chemical Formula 7: ##STR00010## in Chemical Formulas 5 to 7, R2 to R4 are as defined in claim 8, and “*” means a bonding point.

10. The method for manufacturing an insulating layer according to claim 8, wherein the alkali-soluble resin is produced by reaction of a compound represented by the following Chemical Formula 8 and a compound represented by the following Chemical Formula 9: ##STR00011## in Chemical Formulas 8 and 9, R2 to R4 are as defined in claim 9.

11. The method for manufacturing an insulating layer according to claim 1, wherein the alkali-soluble resin has an acid value of 50 mgKOH/g to 250 mgKOH/g, as determined by KOH titration.

12. The method for manufacturing an insulating layer according to claim 1, wherein the polymer resin layer contains 1 parts by weight to 150 parts by weight of a heat-curable binder with respect to 100 parts by weight of the alkali-soluble resin.

13. The method for manufacturing an insulating layer according to claim 1, wherein the heat-curable binder includes at least one functional group selected from the group consisting of an oxetanyl group, a cyclic ether group, a cyclic thioether group, a cyanide group, a maleimide group, a benzoxazine group, and an epoxy group.

14. The method for manufacturing an insulating layer according to claim 1, wherein the curing is performed at a temperature of 50° C. to 150° C. for 0.1 hours to 2 hours.

15. The method for manufacturing an insulating layer according to claim 1, further comprising removing the photosensitive resin block after curing the polymer resin block.

16. The method for manufacturing an insulating layer according to claim 15, further comprising a step of curing the polymer resin block at a temperature of 150° C. to 250° C. for 0.1 hours to 10 hours, after the step of removing the photosensitive resin block.

17. The method for manufacturing an insulating layer according to claim 1, wherein the step of sealing includes: a step of forming at least two or more semiconductor elements on an adhesive film; a step of forming the polymer resin layer on the substrate; a step of contacting the adhesive film with the polymer resin layer; and a step of peeling the adhesive film and forming the photosensitive resin layer.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 schematically illustrates a manufacturing process of an insulating layer of Example 1.

(2) FIG. 2 schematically illustrates a manufacturing process of a semiconductor package of Example 1.

DETAILED DESCRIPTION OF THE EMBODIMENTS

(3) The present invention will be described below in more detail by way of examples. However, these examples are provided for illustrative purposes only, and should not be construed as limiting the scope of the present invention.

PRODUCTION EXAMPLES: PRODUCTION OF ALKALI-SOLUBLE RESIN

Production Example 1

(4) 632 g of dimethylformamide (DMF) as a solvent, 358 g of BMI-1100 (manufactured by Daiwakasei Industry Co., Ltd.) as an N-substituted maleimide compound, and 274 g of 4-aminophenylacetic acid as an amine compound were placed and mixed in a 2-liter reaction vessel with heating and cooling capability and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and stirred at 85° C. for 96 hours to produce an alkali-soluble resin solution having a solid content of 50%.

Production Example 2

(5) 632 g of dimethylformamide (DMF) as a solvent, 434 g of p-carboxyphenylmaleimide as an N-substituted maleimide compound, and 198 g of 4,4-diaminodiphenyl methane as an amine compound were placed and mixed in a 2-liter reaction vessel with heating and cooling capability and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and stirred at 85° C. for 96 hours to produce an alkali-soluble resin solution having a solid content of 50%.

Production Example 3

(6) 543 g of dimethylacetamide (DMAc) as a solvent was placed in a 2-liter reaction vessel with heating and cooling capability and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and 350 g of SMA1000 (Cray Valley), 144 g of 4-aminobenzoic acid (PABA), and 49 g of 4-aminophenol (PAP) were added thereto and mixed. After the temperature of the reactor was set to 80° C. under a nitrogen atmosphere, the acid anhydride and the aniline derivative were reacted continuously for 24 hours to form an amic acid. Then, the temperature of the reactor was set to 150° C., and the imidization reaction was continued for 24 hours to produce an alkali-soluble resin solution having a solid content of 50%.

Production Example 4

(7) 516 g of methylethylketone (MEK) as a solvent was placed in a 2-liter reaction vessel with heating and cooling capability and equipped with a thermometer, a stirrer, a reflux condenser, and a quantitative moisture analyzer, and 228 g of p-carboxyphenylmaleimide, 85 g of p-hydroxyphenylmaleimide, 203 g of styrene, and 0.12 g of azobisisobutyronitrile (AIBN) were added thereto and then mixed. The temperature of the reactor was gradually raised to 70° C. under a nitrogen atmosphere, and then the reaction was continued for 24 hours to produce an alkali-soluble resin solution having a solid content of 50%.

Example: Manufacture of Insulating Layer and Semiconductor Package

Example 1

(8) (1) Manufacture of Insulating Layer

(9) As shown in FIG. 1 below, an insulating layer was manufactured in the order of the following steps <1> to <10>.

(10) <1> A plurality (10 or more) of semiconductor chips (2) with a size of 8 mm×8 mm×80 μm were separately arranged on a UV-release adhesive film (1) at intervals of 10 mm on the top, bottom, left, and right sides.

(11) <2> A Debondable Temporary Adhesive (4) (LG Chem) was formed on a silicon wafer (3) having a thickness of 200 μm. Then, a polymer resin composition prepared by mixing 16 g of the alkali-soluble resin synthesized in Production Example 1, 6 g of MY-510 (manufactured by Huntsman) as a heat-curable binder, and 43 g of SC2050 MTO (solid content 70%, manufactured by Adamatech) was coated onto the Debondable Temporary Adhesive (4) at a thickness of 100 μm and dried to prepare a structure in which the silicon wafer (3)—Debondable Temporary Adhesive (4)—polymer resin layer (5) were sequentially laminated. At this time, the maximum longitudinal cross-sectional length of the polymer resin layer was 200 mm.

(12) Thereafter, the adhesive film (1) of step <1> and the polymer resin layer (5) were vacuum laminated at 85° C. to form a structure in which the silicon wafer (3)—Debondable Temporary Adhesive (4)—polymer resin layer (5)—semiconductor chip (2)—adhesive film (1) were sequentially laminated to seal the semiconductor chip (2).

(13) <3> The adhesive surface of the adhesive film (1) was irradiated with UV to eliminate the adhesive property, and then the adhesive film (1) was peeled and removed.

(14) <4> The adhesive film (1) was removed and simultaneously a photosensitive dry film resist (6) (KL1015, manufactured by KOLON Industries) having a thickness of 15 μm was laminated on the exposed polymer resin layer (5) and the surface of the semiconductor chip (2) at a temperature of 110° C.

(15) <5> A negative type of photomask was brought into contact with the photosensitive dry film resist (6), and then irradiated with ultraviolet light (light amount of 25 mJ/cm.sup.2). The photosensitive dry film resist (6) and the polymer resin layer (5) were simultaneously developed through a 1% sodium carbonate developer at 30° C. to form a photosensitive resin block (7) and a polymer resin block (8).

(16) At this time, the polymer resin layer (5) and the photosensitive dry film resist (6) located at 40% to 60% of the distance between adjacent semiconductor chips (2) were removed by development, and simultaneously one semiconductor chip was included in the polymer resin block, and the maximum longitudinal cross-sectional length of the polymer resin block was 16 mm.

(17) <6> The polymer resin block (8) was heat-cured at a temperature of 100° C. for 1 hour.

(18) <7> The etchant was treated to remove the photosensitive resin block (7) remaining on the polymer resin block (8).

(19) <8> The polymer resin block (8) was heat-cured at a temperature of 200° C. for 1 hour to manufacture an insulating layer.

(20) (2) Manufacture of Semiconductor Package

(21) As shown in FIG. 2 below, a semiconductor package was manufactured in the order of the following steps <9> to <11>.

(22) <9> A polymer resin composition prepared by mixing 16 g of the alkali-soluble resin synthesized in Production Example 1, 5 g of MY-510 (manufactured by Huntsman) as a heat-curable binder, and 35 g of SC2050 MTO (manufactured by Adamatech) was coated onto the PET film and dried to prepare a polymer resin layer having a thickness of 15 μm. Then, the polymer resin layer was vacuum laminated on the polymer resin block (8) of the prepared insulating layer and the semiconductor chip (2) at 85° C., and the PET film was removed. A photosensitive dry film resist KL1015 (manufactured by KOLON Industries) having a thickness of 15 μm was laminated on the polymer resin layer at 110° C. A negative type of photomask was brought into contact with the photosensitive dry film resist and then irradiated with ultraviolet light (light amount of 25 mJ/cm.sup.2). The photosensitive dry film resist and the polymer resin layer were simultaneously developed through a 1% sodium carbonate developer at 30° C.

(23) At this time, the photosensitive dry film resist on which the pattern was formed acted as a protective layer of the polymer resin layer, so that the same pattern as that of the photosensitive dry film resist was also formed on the polymer resin layer.

(24) Subsequently, after heat-curing at a temperature of 100° C. for 1 hour, the photosensitive dry film resist was removed using a 3% sodium hydroxide resist peeling liquid at a temperature of 50° C. and heat-cured at a temperature of 200° C. for 1 hour to form a first insulating pattern layer (9) having a certain pattern.

(25) <10> A titanium-copper thin film was deposited on the first insulation pattern layer (9) using a sputterer, and heated at a temperature of 100° C. for 30 minutes to improve adhesion with the sputter layer. Then, a dry film (RY-5319, Hitachi Kasei) was laminated to form a pattern, and electroplating was performed to form a circuit in the form of a metal pattern and at the same time the via hole was filled with metal to form a metal pattern layer (10).

(26) <11> A second insulating pattern layer (11) having a predetermined pattern was formed on the metal pattern layer (10) in the same manner as in <9>, thereby manufacturing a semiconductor package.

Example 2

(27) An insulating layer and a semiconductor package were manufactured in the same manner as in Example 1, except that in the manufacturing stage <5> of the insulating layer of Example 1, four semiconductor chips were included in the polymer resin block, and the maximum longitudinal cross-sectional length of the polymer resin block was 34 mm.

Example 3

(28) An insulating layer and a semiconductor package were manufactured in the same manner as in Example 1, except that in the manufacturing stage <2> of the insulating layer of Example 1, the alkali-soluble resin synthesized in Production Example 2 was used instead of the alkali-soluble resin synthesized in Production Example 1.

Example 4

(29) An insulating layer and a semiconductor package were manufactured in the same manner as in Example 1, except that in the manufacturing step <2> of the insulating layer of Example 1, the alkali-soluble resin synthesized in Production Example 3 was used instead of the alkali-soluble resin synthesized in Production Example 1.

Example 5

(30) An insulating layer and a semiconductor package were manufactured in the same manner as in Example 1, except that in the manufacturing step <2> of the insulating layer of Example 1, the alkali-soluble resin synthesized in Production Example 4 was used instead of the alkali-soluble resin synthesized in Production Example 1.

Comparative Examples 1 to 3: Manufacture of Insulating Layer and Semiconductor Package

Comparative Example 1

(31) <1> A plurality of semiconductor chips with a size of 8 mm×8 mm×80 μm were separately arranged on the thermal-release adhesive film at intervals of 10 mm on the top, bottom, left, and right sides.

(32) <2> A Debondable Temporary Adhesive (LG Chem) was formed on a silicon wafer having a thickness of 200 μm. Then, a photosensitive resin composition prepared by mixing 30 g of CCR-1291H (manufactured by Nippon Kayaku) as an acid-modified acrylate resin, 5 g of TMPTA (manufactured by ETNIS) as a polyfunctional acrylate monomer, 2 g of Irgacure TPO-L (manufactured by BASF) as a photoinitiator, 6 g of YDCN-500-8P (Kukdo Chemical) as a polyfunctional epoxy, 0.2 g of 2E4MZ (manufactured by Shikoku Chem) as a heat-curable catalyst, and 49 g of SC2050 MTO (solid content 70%, manufactured by Adamatech) was coated onto the debondable temporary adhesive at a thickness of 100 μm and dried to prepare a structure in which silicon wafer—Debondable Temporary Adhesive-polymer resin layer were sequentially laminated.

(33) Subsequently, the adhesive film 1 of step <1> and the polymer resin layer were vacuum laminated at 85° C. to form a structure in which silicon wafer-Debondable Temporary Adhesive-polymer resin layer-semiconductor chip-adhesive film were sequentially laminated to seal the semiconductor chip.

(34) <3> The adhesive film was heated at 100° C. for 1 minute to eliminate the adhesive property, and then the adhesive film was peeled and removed.

(35) <4> A negative type of photomask was brought into contact with the surface on which the semiconductor chip was mounted, irradiated with ultraviolet rays (light amount of 400 mJ/cm.sup.2), and developed through a 1% sodium carbonate developer at 30° C. to form a photosensitive resin block and a polymer resin block.

(36) <5> The polymer resin block (8) was irradiated with ultraviolet rays (light amount of 1500 mJ/cm.sup.2) and then heat-cured at a temperature of 200° C. for 1 hour to manufacture an insulating layer.

Comparative Example 2

(37) An insulating layer was manufactured in the same manner as in Example 1, except that the step of forming the photosensitive resin block and the polymer resin block in step <5> of Example 1 was omitted.

Comparative Example 3

(38) An insulating layer was manufactured in the same manner as in Example 1, except that step <4> and step <5> of Example 1 were omitted and the polymer resin block was formed by dicing the polymer resin layer.

(39) Herein, in the case of Comparative Example 3, burrs were generated in the polymer resin block formed after the dicing of the polymer resin layer, and there was a technical limitation that it was difficult to handle, for example defects were generated in subsequent processes or the silicon wafer was broken due to warpage.

Experimental Example: Measurement of Physical Properties of Insulating Layers and Semiconductor Packages Obtained in Examples and Comparative Examples

(40) The physical properties of the insulating layers and the semiconductor packages obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

(41) 1. Degree of Warpage

(42) When the semiconductor packages obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were placed on a flat surface, the height from the curved or bent tip to the bottom of the semiconductor package was measured.

(43) 2. Delamination

(44) When the semiconductor packages obtained in Examples 1 to 5 and Comparative Examples 1 and 2 were separated from the debondable temporary adhesive (4), thermal stresses were applied three times under the reflow condition of TM6502.6.27. Then, using scanning acoustic tomography (SAT), the delamination of the semiconductor package was confirmed under the following criteria.

(45) OK: No delamination was observed.

(46) NG: Delamination was observed

(47) TABLE-US-00001 TABLE 1 Results of Experimental Examples of Examples and Comparative Examples Category Degree of warpage(mm) Delamination Example 1 3 OK Example 2 5 OK Example 3 3 OK Example 4 4 OK Example 5 4 OK Comparative 2 NG Example 1 Comparative 124 OK Example 2

(48) As shown in Table 1, it was confirmed that in the case of the semiconductor packages obtained in Examples 1 to 5, while the degree of warpage was as small as 10 mm or less, delamination did not occur and so excellent durability was exhibited.

(49) On the other hand, it was confirmed that in the case of the semiconductor package obtained in Comparative Example 1, as a well-known novolac-based oligomer was used as an acid-modified resin, the delamination occurred and the durability was deteriorated.

(50) In addition, it was confirmed that in the case of the semiconductor package obtained in Comparative Example 2, as the polymer resin layer having the maximum longitudinal cross-sectional length of 200 mm was cured without forming a polymer resin block, the degree of warpage was as high as 124 mm.

EXPLANATION OF SIGN

(51) 1: Adhesive film 2: Semiconductor chip 3: Silicon wafer, or copper-clad laminate 4: Debondable temporary adhesive or die bonding film 5: Polymer resin layer 6: Photosensitive dry film resist 7: Photosensitive resin block 8: Polymer resin block 9: First insulating pattern layer 10: Metal pattern layer 11: Second insulating layer <1> to <11>: Order of progress of process