WO1999034434A1 - Epoxy bleeding inhibitor and method of preventing epoxy bleeding - Google Patents

Abstract

A method of epoxy bleeding prevention which adversely affects neither die bonding strength nor assembling and impairs neither discoloration preventive effect nor sealing effect. The epoxy bleeding inhibitor to be used for die-bonding in a semiconductor production process is characterized by containing at least one organic compound selected among carboxylic acids and thiols each having a linear part having three or more carbon atoms, carboxylic acids and thiols each having a benzene ring, carboxylic acids each having a mercapto or hydroxyl group, polyhydric unsaturated alcohols, nitrogenous heterocyclic compounds each containing sulfur in the molecule, and derivatives of these.

Description

 Description Epoxy bleedout inhibitor and prevention method

Technical field

 TECHNICAL FIELD The present invention relates to an epoxy pre-dating agent and a method for preventing a semiconductor device such as a lead frame or a printed wiring board from being bonded to an IC chip with an epoxy resin in a die bonding step. Background art

 In a die bonding process in which an IC chip is bonded and fixed to a semiconductor device such as a lead frame or a printed wiring board with an epoxy resin, the bonding surface (usually plated with gold, silver, copper, palladium, etc.). If the surface roughness is too large, or if the surface is contaminated with an organic substance such as a discoloration inhibitor or a sealing agent, the resin or additive oozes out when the epoxy resin is applied (epoxy bleed out). ) Occurs. This epoxy bleed-out lowers the die bonding strength and causes a defect in the subsequent wire bonding process.

 Conventionally, in order to prevent such epoxy bleed out, the surface roughness of the bonding surface has been reduced to suppress the capillary phenomenon, and the surface has been cleaned to remove contaminants. However, since the surface roughness of the bonding surface affects the die-bonding strength and the image recognition ability of the assembly machine, it cannot be reduced unconditionally. In addition, cleaning the surface is a problem because it impairs the discoloration prevention treatment and the sealing effect.

 An object of the present invention is to establish a method of preventing epoxy pre-dating which does not adversely affect die bonding strength and assembly characteristics and does not impair the discoloration prevention treatment / sealing treatment effect. Disclosure of the invention

As a result of intensive studies, the present inventors have found that a solution containing a specific organic compound It has been found that epoxy bleeding can be effectively prevented by immersing the coating and adsorbing the organic coating on the surface of the plating surface. .

 The present invention is based on this finding,

 1. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mercapto group or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule. An epoxy predout inhibitor in a die bonding process in a semiconductor manufacturing process, characterized by containing a nitrogen-containing heterocyclic compound containing the compound or one or more organic compounds selected from these derivatives.

 2. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain portion, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mechabutate or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule The wiring substrate is immersed in an epoxy bleed-gate inhibitor in the die bonding step of the semiconductor manufacturing process, which contains a nitrogen-containing heterocyclic compound containing at least one or an organic compound selected from these derivatives. Or a method for preventing epoxy bleeding, which comprises spraying the epoxy bleeding inhibitor on a wiring substrate.

 3. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain part, carboxylic acid or thiol having benzene group, carboxylic acid having mercapto group or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule. The wiring substrate is immersed in an epoxy bleed-gate inhibitor in the die-bonding step of the semiconductor manufacturing process, which contains a nitrogen-containing heterocyclic compound or one or more organic compounds selected from these derivatives. A wiring base material and a semiconductor package, which have been subjected to an epoxy bleed out prevention treatment by spraying an agent to the wiring base material.

4. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain portion, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mechabutate or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule A wiring base material and a semiconductor package, characterized in that at least one organic compound selected from nitrogen-containing heterocyclic compounds containing these or derivatives thereof is adsorbed on the surface. PT / JP98 / 05897

5. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mechabutate or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule A discoloration-preventing solution or a pore-sealing solution containing an epoxy pre-dosing inhibitor comprising a nitrogen-containing heterocyclic compound containing at least one or an organic compound selected from these derivatives. Is provided. Embodiment of the Invention

 The epoxy pre-drying inhibitor of the present invention is particularly applicable to semiconductor devices such as a lead frame and a printed wiring board, but is not necessarily limited thereto, and may be used in an epoxy bonding step in a die bonding step. Applicable to any product that may cause a blowout.

Examples of the organic compound having the epoxy pre-dite prevention function contained in the epoxy pre-dite prevention agent of the present invention include the following organic compounds. _C A: carbon atom in a linear portion A carboxylic acid or thiol having at least 3

For example, Kaburo phosphate (C s H ii COOH), butyric acid (C ₃ H ₇ COOH), E Nan preparative acid _{(C E H 1 3 COOH)} , pelargonic acid _{(C S H: L 7 COOH} ), turnip Li down acid _{(C s H 1 9 COOH)} , Undeshiru acid _{(C lc »H 2 1 COOH} ), Lau-phosphate (C ii H sa COOH), preparative Rideshiru acid _{(C 1 2 H 2 S COOH} ), millimeter cystine acid _{(C 1 3 H 2 7 COOH} ), pentamethylene 'decyl acid _{(C 1 4 H 2 9 COOH} ), palmitic acid _{(C 1 5 H 3 1 COOH} ), heptadecyl acid (C is H ss COOH), stearic Li down acid _{(C 1 7 H 3 5 COOH} ), nonadecanoic _{(C 1 S H 3 τ COOH} ), behenic acid _{(C 2 1 H 4 3 COOH} ), Orei phosphate _{(C 1 7 H 3 a COOH} ), El force acid _{(C 2 1 H 4 1 COO} HV, Li Nord acid _{(C i 7 H 3 1 COOH} ), carboxylic acids such as Li Bruno Len acid (C i H ss COOH),

Pentane thiol (C s H ii SH), octanethiol _{(C S H: L 7 SH} ), decane thiol _{(C 1 0 H 2 1 SH} ) ' hexadecyl mercaptan _{(C ie H 3 a SH)} , mercaptopropyl main Tokishishiran (HS (CH 2) a S i (OCH

3) Thiols such as 3). B: Carboxylic acid or thiol having a benzene ring

For example, two collected by filtration benzoate (〇 2 NC ₆ H ₄ COOH), Benjirume Rukabuta emissions _{(C e H 5 CH 2 SH} ) and the like.

 C: a carboxylic acid having a mercapto group or a hydroxyl group,

For example, mercapto acid (HSCH s COOH) and mucinic acid (HOOC (CHOH) ₄ COOH).

D: Polyunsaturated Anoleco

For example, butynediol (HOCH ₂ C ® CH ₂ OH), such as butenediol _{(HOCH 2 CH = CHCH 2 OH} ).

E: Nitrogen-containing heterocyclic compound containing sulfur in the molecule

 For example, thiobarbituric acid.

 An epoxy pre-outout inhibitor containing one or more organic compounds selected from the above organic compounds or derivatives thereof is included in the present invention.

 The epoxy bleeding inhibitor of the present invention contains the above organic compound in an amount of 0.1 mg / L to 100 g_L, preferably 10 mg / L to 10 g "L. If the concentration of the compound is too low, there is no effect of preventing epoxy bleeding, and if the concentration is too high, no further effect can be expected, which is not preferable.

 When the organic compound is hardly soluble in water, an organic solvent such as alcohol and ketone is added as necessary.

 If necessary, a boric acid-based, phosphate-based, or organic acid-based pH buffer is added in an amount of 0.1 to 100 g / L, preferably 1 to 50 g / L.

 Further, if necessary, any one of anionic, cationic, and nonionic surfactants or a mixture thereof is used in an amount of 1 βg / L to 10 g / L, preferably 1. Add β g / L to 1 g / L.

 The pH of the epoxy bleed inhibitor solution does not need to be particularly limited.

The temperature of the epoxy bleedout inhibitor solution should be 580 ° C, preferably 10 to 50 ° C. If the temperature is too low, the epoxy bleed-out effect is low, and if the temperature is too high, no further effect can be expected, which is not preferable. The method for preventing epoxy bleed out is to immerse the wiring substrate in an epoxy bleed out inhibitor solution or to spray the epoxy bleed out inhibitor solution onto the substrate (shower, spray, etc.). After contacting with water, wash and dry. Further, the same effect can be exerted by adding the above-mentioned organic compound which is a main component of the epoxy bleeding inhibitor to the discoloration inhibitor and the sealing agent. By performing the above-described epoxy bleed out prevention treatment, the above organic compound is adsorbed on the adhered surface of the wiring base material, and a film made of an organic compound having a thickness of about one to several molecules is formed. Is done. Therefore, it is possible to increase the contact angle between the plating surface and the epoxy resin, and to suppress the bleeding of the epoxy resin. Since the organic compound film to be adsorbed is very thin, it does not adversely affect the assembly characteristics such as wire bonding and molding. In addition, the effect of preventing discoloration and the effect of sealing treatment are not impaired.

 Wiring substrates and semiconductor packages that have been subjected to the epoxy bleedout prevention treatment by the above method are also included in the present invention.

Example

 Hereinafter, the present invention will be described based on examples, but the present invention is not limited to these examples.

 (Examples 1 to 15)

 Copper alloy (Cu: 97.7% -Sn: 2.0% -Ni: 0.2% -Ρ: 0 · 03%) After performing the trike plating, the tip part and inner part are plated with silver on the spot or copper plating, gold plating or palladium plating on the entire lead frame. did.

After that, the epoxy pre-drying prevention treatment described in Tables 1 to 3 was performed. 【table 1 】

 Epoxy bleed-art evaluation

 O: 0 II m, m: ≤ 1 0 0 y m X 0 0 «m Evaluation of discoloration prevention effect

 〇: No discoloration, X: Discoloration

 Evaluation of sealing effect

O: No corrosion, X: Corrosion [Table 2]

 Epoxy bleed-out evaluation

 0: 0 «m. Δ: ≤ 1 0 0 u X: ≥ 1 0 0 w m Evaluation of discoloration prevention effect

 〇: No discoloration, X: Discoloration

 Evaluation of sealing effect

0: No corrosion, X: Corrosion [Table 3]

 O: 0 M m, Δ: ≤ 1 0 0 w m 1 0 0 w Evaluation of discoloration prevention effect

 〇: No color, X: Discolored

 Evaluation of sealing effect

〇: No rot, X: Corrosion Before the epoxy bleed out prevention treatment, some samples were subjected to a discoloration prevention treatment or a sealing treatment.

 The discoloration prevention treatment was performed under the following conditions.

 Anti-tarnish liquid: Main component Benzotriazole 0 g / L

 pH: 9-0

 Bath temperature: 25 ° C

 Time: 10 s

 Method: Immersion

 The sealing treatment was performed under the following conditions.

 Sealing solution Main component Triethanolamine 0 g / L

 P H 9.0

 Bath temperature 25 ° C

 Time 1 0 s

 Method Immersion

 Die-bonding and wire-bonding were performed on these base materials, and epoxide pre-dout, wire-bonding characteristics, and molding characteristics were evaluated.

 The evaluation of the epoxy bleed was performed by the following method.

 After applying a commercially available epoxy resin for low stress die bonding to the plated surface, heat-curing at 200 ° C for 60 min, observe the epoxy-applied part with a microscope (30 times), and use epoxy resin. The door lift was measured.

 The evaluation of the wire bonding characteristics was performed by the following method.

 After bonding the wires with a thermocompression bonding method using ultrasonic waves (temperature: 200 ° (:, load: 50 g, time: .10 ms)), the pull strength was measured with a bull tester.

 The evaluation of the molding characteristics was performed by the following method.

 After applying a commercially available epoxy resin for molding to the surface to be plated, it was cured by heating at 175 ° C for 5 hours, and the shear strength was measured.

In addition, the samples subjected to the discoloration prevention treatment or the sealing treatment were evaluated for the discoloration prevention effect or the sealing treatment effect. The discoloration prevention effect was evaluated by the following method for spot-plated parts and copper strike-plated parts for spot silver-plated products, and for plated parts for whole-plated products.

 The plating surface after immersion in 1 O min in boiling pure water was visually observed.

 The evaluation of the sealing effect was performed on the plated surface of each of the spot-plated product and the fully-plated product by the following method.

 The plating surface after immersion in the following artificial sweat solution at 40 ° C. for 24 hours was visually observed.

 Artificial sweat composition

 Sodium chloride: 9.9 g / L

 Sodium sulfide: 0.8 g / L

 Urea: 1.7 g / L

 Lactic acid: 1.1 mL / L

 Ammonia water: 0.27 mL / L

 PH: 5

 The results are shown in Table 13.

 (Examples 16 to 20)

 鋦 Alloy (.Cu: 97.7% -Sn: 2.0% -Ni: 0.2% -Ρ: 0 03%) Lead frame base material with silver, gold, copper, or palladium plating Was applied.

These wiring substrates were subjected to a discoloration prevention treatment or a sealing treatment. At that time, as described in Table 4, the epoxy predite inhibitor of the present invention was added to the discoloration preventing solution or the sealing treatment solution.

[Table 4]

 Epoxy bleed-out comment

 0: 0 w m, Δ: ≤ 1 0 0 w m X: ≥ 1 0 0 / Evaluation of discoloration prevention effect

 〇: No discoloration, X: Discoloration

 Evaluation of sealing effect

O: No corrosion, X: Corrosion Die-bonding and wire-bonding were performed on these base materials, and epoxy bleed-out, wire-bonding properties, molding properties, and a discoloration preventing or sealing effect were performed in the same manner as in Examples 1 to 15. Was evaluated. Table 4 shows the results.

 (Comparative Examples 1 to 5)

 Copper alloy (Cu: 97.7%-Sn: 2.0% -Ni: 0.2% -Ρ: 0 03%) lead frame base material with silver, gold, copper or palladium plating Either was given.

 The sample in the — part was subjected to a discoloration prevention treatment or a sealing treatment.

 The discoloration prevention treatment was performed under the following conditions.

 Anti-discoloration liquid: Main component Benzotriazole 0. g ZL

 ρ 9.: 9.0

 Bath temperature: 2 5

 Time: 10 s

 Method: Immersion

 The sealing treatment was performed under the following conditions.

 Sealing solution Main ingredient Triethanolamine 0 g / L

 P H 9.0

 Bath temperature 25 ° C

 Time 1 0 s

 Method Immersion

 Die-bonding and wire-bonding were performed on these substrates, and evaluation of epoxy pre-out, wire-bonding characteristics, molding characteristics, and the effect of preventing discoloration or sealing treatment was performed in the same manner as in the examples. went.

The results are shown in Table 5. [Table 5]

 Epoxy bleed-art evaluation

 0: 0 t m, mm: ≤ 100 m X: ≥ 100 μm Evaluation of discoloration prevention effect

 〇: No discoloration, X: Discoloration

 Evaluation of sealing effect

O: No corrosion, X

(Result)

 In the wiring base material (Examples 1 to 15) on which the epoxy bleeding prevention treatment was performed using the epoxy pre-dipping prevention agent of the present invention, generation of epoxy bleedout was not observed in the die bonding step. Was. Similarly, when the epoxy bleedout inhibitor of the present invention was added to the anti-tarnish solution or the sealing solution (Examples 16 to 20), the occurrence of epoxy pre-dout in the die bonding step was also reduced. I couldn't see it. In all of the examples, the wire bonding characteristics and the molding characteristics were good. The base material having the discoloration preventing effect or the sealing treatment effect had the expected discoloration preventing effect and the sealing treatment effect.

 On the other hand, when the epoxy bleed out prevention treatment was not performed (Comparative Examples 1 to 5), the occurrence of epoxy bleed out in the die bonding step was observed. The invention's effect

 An epoxy bleeding prevention treatment for adsorbing an organic compound having an epoxy prepreg prevention function onto the surface of a semiconductor device such as a lead frame or a brim kneading plate using the epoxy bleeding preventing agent of the present invention. By doing so, it is possible to prevent epoxy bridging in the die bonding step without impairing the discoloration prevention effect and the sealing effect. Also, there is no adverse effect on wire bonding characteristics and assembly characteristics such as molding characteristics.

Claims

The scope of the claims 1. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mercapto group or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule An epoxy bleedout inhibitor in a die bonding step of a semiconductor manufacturing process, characterized by containing a nitrogen-containing heterocyclic compound containing at least one or an organic compound selected from these derivatives.  2. Carboxylic acid or thiol having 3 or more carbon atoms in the linear chain, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mercapto group or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule Whether the wiring substrate is immersed in an epoxy bleedout inhibitor in the die bonding step of the semiconductor manufacturing process, which contains a nitrogen-containing heterocyclic compound or one or more organic compounds selected from these derivatives. Alternatively, a method for preventing epoxy bleed out, comprising spraying the epoxy bleed out preventive agent on a wiring base material.  3. Carboxylic acid or thiol having 3 or more carbon atoms in the straight chain, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mercapto group or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule Whether the wiring substrate is immersed in an epoxy bleed-gate inhibitor in the die-bonding step of the semiconductor manufacturing process, which contains a nitrogen-containing heterocyclic compound containing one or more organic compounds selected from these derivatives. Alternatively, a wiring base material and a semiconductor package which are subjected to an epoxy bleed out prevention treatment by spraying the epoxy bleed out preventing agent on the wiring base material.  4. Carboxylic acid or thiol having 3 or more carbon atoms in the linear chain, carboxylic acid or thiol having a benzene ring, carboxylic acid having a mercapto group or hydroxyl group, polyunsaturated alcohol, sulfur in the molecule A wiring base material and a semiconductor package, characterized in that at least one organic compound selected from nitrogen-containing heterocyclic compounds or derivatives thereof is adsorbed on the surface. 5. Carboxylic acids or thiols with 3 or more carbon atoms in the linear chain, benzene One selected from a carboxylic acid or thiol having a ring, a carboxylic acid having a mercapto group or a hydroxyl group, a polyunsaturated alcohol, a nitrogen-containing heterocyclic compound containing a yellow acid in a molecule, or a derivative thereof. A discoloration preventing liquid or a pore-sealing liquid, comprising an epoxy pre-outout agent comprising the above organic compound.