JP2016065226A - Thermosetting resin composition, resin film with carrier, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve reliability of a semiconductor device.SOLUTION: A thermosetting resin composition for forming a solder resist is provided, which comprises an epoxy resin and silica particles. When a resin film obtained by using the thermosetting resin composition is subjected to a dynamic viscoelasticity test under the conditions of 62.83 rad/sec measurement frequency and 3°C/min temperature elevation rate, a minimum complex viscosity of the resin film at 50 to 150°C is 0.1 Pa sec or more and 5000 Pa sec or less.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a thermosetting resin composition, a resin film with a carrier, and a semiconductor device, for example, a thermosetting resin composition for forming a solder resist.

  The use of a cured film formed using a thermosetting resin composition has been studied as a solder resist constituting a semiconductor device. As a technique regarding such a thermosetting resin composition, the technique of patent documents 1-3 is mentioned, for example.

  In Patent Document 1, a structure having a circuit board and a solder resist layer formed on the circuit board is prepared, and then a plastic film is adhered to the surface of the solder resist layer. Describes a method of manufacturing a circuit board including a step of forming a via hole by irradiating a laser beam from above. Patent Document 2 describes a method for manufacturing a printed wiring board having a solder resist having an opening on its surface. Patent Document 3 describes a solder resist resin composition containing a naphthol resin and a blue colorant.

JP 2010-62478 A JP2013-84816A JP 2012-136893 A

  About the semiconductor device provided with the soldering resist formed using a thermosetting resin composition, improving the reliability is calculated | required.

According to the present invention,
A thermosetting resin composition for forming a solder resist,
An epoxy resin and silica particles,
When a dynamic viscoelasticity test was performed on a resin film obtained using the thermosetting resin composition under the conditions of a measurement frequency of 62.83 rad / sec and a temperature increase rate of 3 ° C./min, There is provided a thermosetting resin composition having a minimum complex viscosity of 0.1 Pa · sec to 5000 Pa · sec at 150 ° C.

According to the present invention,
A carrier substrate;
A resin film provided on the carrier substrate and formed using the thermosetting resin composition described above;
A resin film with a carrier is provided.

According to the present invention,
A semiconductor device including a solder resist composed of a cured product of the above-described thermosetting resin composition is provided.

  According to the present invention, the reliability of a semiconductor device can be improved.

It is sectional drawing which shows an example of the resin film with a carrier which concerns on this embodiment. It is sectional drawing which shows an example of the semiconductor device which concerns on this embodiment.

  Hereinafter, embodiments will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

  The thermosetting resin composition according to this embodiment is a thermosetting resin composition that forms a solder resist, and includes an epoxy resin and silica. Further, the thermosetting resin composition has a measurement frequency of 62.83 rad / sec and a temperature increase rate of 3 ° C./min with respect to a resin film (hereinafter simply referred to as “resin film”) obtained using the thermosetting resin composition. When the dynamic viscoelasticity test is performed, the lowest complex viscosity of the resin film at 50 to 150 ° C. is 0.1 Pa · sec or more and 5000 Pa · sec or less.

  In order to improve the reliability of a semiconductor device provided with a solder resist, for example, it is required to improve the embedding property of a solder resist between conductor circuit patterns (hereinafter, also simply referred to as “solder resist embedding property”). However, in the case of forming a solder resist using a thermosetting resin composition, it may be difficult to realize a semiconductor device with excellent moisture absorption reliability while improving the solder resist embedding property.

  As a result of intensive studies, the present inventor has improved the embedding property of the solder resist obtained using the thermosetting resin composition by controlling the minimum complex viscosity at 50 to 150 ° C. of the thermosetting resin composition. It has been found that a semiconductor device having excellent moisture absorption reliability can be realized. In the present embodiment, based on such knowledge, the lowest complex viscosity of the resin film at 50 to 150 ° C. is set to 0.1 Pa · sec or more and 5000 Pa · sec or less. By using a thermosetting resin composition that satisfies the above conditions as the constituent material of the solder resist, the reliability of the semiconductor device can be improved.

  Hereinafter, the thermosetting resin composition, the resin film with carrier 100, and the semiconductor device 102 according to the present embodiment will be described in detail.

First, the thermosetting resin composition will be described.
The thermosetting resin composition is used for forming a solder resist. In the present embodiment, for example, a thermosetting resin film formed using a thermosetting resin composition is laminated on a circuit board, and the solder resist is formed by thermosetting the film.

A thermosetting resin composition can be made into the varnish shape containing a solvent, for example.
On the other hand, the thermosetting resin composition may be in the form of a film. In this case, for example, a film-like thermosetting resin composition can be obtained by performing a solvent removal treatment on a resin film obtained by applying a varnish-like thermosetting resin composition. The film-like thermosetting resin composition has a solvent content of 5% by weight or less with respect to the entire thermosetting resin composition. Further, the film-like thermosetting resin composition has a weight change rate of 5% by weight or less before and after heat treatment at 170 ° C. for 2 minutes. In addition, the film-like thermosetting resin composition can be laminated | stacked on a carrier base material, and can comprise the resin film with a carrier.

In the solder resist formed using the thermosetting resin composition, an opening for exposing the conductor circuit pattern is formed by, for example, laser irradiation, plasma etching, chemical etching, or lithography processing. The thermosetting resin composition according to this embodiment has excellent laser processability, and is particularly suitable for use in forming a solder resist in which openings are formed by laser irradiation.
The thermosetting resin composition contains an epoxy resin (A) and silica (B).

(Epoxy resin (A))
The epoxy resin (A) is, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol M type epoxy resin (4,4 ′-(1,3-phenylenedioxide). Isopropylene) bisphenol type epoxy resin), bisphenol P type epoxy resin (4,4 ′-(1,4-phenylenediisopridiene) bisphenol type epoxy resin), bisphenol Z type epoxy resin (4,4′-cyclohexene) Bisphenol type epoxy resins such as sidiene bisphenol type epoxy resins; phenol novolak type epoxy resins, cresol novolak type epoxy resins, tetraphenol group ethane type novolak type epoxy resins, novola having a condensed ring aromatic hydrocarbon structure Novolak type epoxy resins such as epoxy resins; biphenyl type epoxy resins; aralkyl type epoxy resins such as xylylene type epoxy resins and biphenyl aralkyl type epoxy resins; naphthylene ether type epoxy resins, naphthol type epoxy resins, naphthalenediol type epoxy resins Epoxy resins having a naphthalene skeleton such as bifunctional to tetrafunctional epoxy naphthalene resins, binaphthyl epoxy resins, naphthalene aralkyl epoxy resins; anthracene epoxy resins; phenoxy epoxy resins; dicyclopentadiene epoxy resins; norbornene epoxy Resin; adamantane type epoxy resin; 1 type or 2 types or more selected from a fluorene type epoxy resin can be included. Among these, it is more preferable to include an epoxy resin having a naphthalene skeleton from the viewpoint of improving the embedding property of the solder resist and the surface smoothness. Thereby, while being able to reduce the linear expansion coefficient of a soldering resist, the elasticity modulus can also be improved. It is also possible to improve the workability by improving the rigidity of the circuit board, and to improve the reflow resistance and suppress the warpage in the semiconductor package. In addition, from the viewpoint of improving the embedding property of the solder resist, it is particularly preferable to include an epoxy resin having a trifunctional or higher functional naphthalene skeleton.

  In this embodiment, it is mentioned as an example of a preferable aspect that the epoxy resin shown to the following formula | equation (1) is included as an epoxy resin (A).

（式（１）中、ｎは０〜１０の整数であり、Ｒ_１およびＲ_２は互いに独立して水素原子、炭素数１〜６のアルキル基、または炭素数１〜６のアルコキシ基である）

(In the formula (1), n is an integer of 0, _{R 1} and _{R 2} independently of one another are hydrogen atom, is an alkyl group or an alkoxy group having 1 to 6 carbon atoms, 1 to 6 carbon atoms )

  The content of the epoxy resin (A) is, for example, preferably 3% by weight or more and more preferably 5% by weight or more with respect to the total solid content of the thermosetting resin composition. By making content of an epoxy resin (A) more than the said lower limit, it can contribute to the improvement of the embedding property and smoothness of the soldering resist formed using a thermosetting resin composition. On the other hand, the content of the epoxy resin (A) is preferably 40% by weight or less, and more preferably 35% by weight or less, for example, based on the total solid content of the thermosetting resin composition. By making content of an epoxy resin (A) below the said upper limit, the heat resistance and moisture resistance of a solder resist formed using a thermosetting resin composition can be improved. In addition, the total solid content of a thermosetting resin composition refers to the whole component except the solvent contained in a thermosetting resin composition. The same applies hereinafter.

(Silica (B))
Silica (B) contains at least one of spherical silica particles and crushed silica particles, for example. From the viewpoint of improving the embedding property and surface smoothness of the solder resist, it is more preferable to include spherical silica. Silica (B) is, for example, fused silica.

As the silica (B), more preferably contains first silica particles having an average particle diameter D ₅₀ is 2nm or 100nm or less (fine silica) in the thermosetting resin composition. Thereby, the embedding property and surface smoothness of a solder resist can be improved more effectively. Further, the average particle diameter D ₅₀ of the first silica particles is preferably 10 nm or more and 80 nm or less, and more preferably 20 nm or more and 70 nm or less. Thereby, the effect mentioned above becomes more remarkable.

Furthermore, in the present embodiment, the first and silica particles having an average particle diameter _{D 50} is 2nm or 100nm or less, the silica particles having an average particle size _{D 50} is greater than 100nm (second silica particles), both thermosetting It is preferable to include in a functional resin composition. When the thermosetting resin composition includes the first silica particles and the second silica particles having such an average particle diameter D ₅₀ , the minimum complex viscosity of the resin film at 50 to 150 ° C. is more surely reduced to 0. It can be set to 1 Pa · sec or more and 5000 Pa · sec or less. Moreover, the surface smoothness of the formed solder resist improves by arrange | positioning a 1st silica particle between 2nd silica particles. Thus, the embedding property and surface smoothness of the solder resist can be further improved by using the first silica particles and the second silica particles in combination. The average particle diameter D ₅₀ of the second silica particles is preferably 400 nm or more and 5 μm or less, and more preferably 600 nm or more and 3 μm or less. Thereby, the effect mentioned above becomes more remarkable.
Further, the average particle diameter _{D 50} of the first silica particles and D1 ([mu] m), when the average particle diameter _{D 50} of the second silica particles was D2 ([mu] m), the value of D2-D1 is, 0.35 .mu.m It is preferably 4 μm or less, more preferably 0.5 μm or more and 2 μm or less. When the first silica particles and the second silica particles satisfy the above relationship, the minimum complex viscosity of the resin film at 50 to 150 ° C. is more reliably set to 0.1 Pa · sec to 5000 Pa · sec. In addition, the surface smoothness of the solder resist to be formed can be further improved.

The average particle diameter _{D 50} of the silica (B), for example a laser diffraction particle size distribution analyzer (HORIBA Ltd., LA-500) can be measured using a.
The content of the first silica particles is preferably 1% by weight to 15% by weight and preferably 3% by weight to 8% by weight with respect to the total solid content of the thermosetting resin composition. Is more preferable. By setting the content of the first silica particles within the above range, the fluidity of the thermosetting resin composition can be controlled. Thereby, the lowest complex viscosity of the resin film at 50 to 150 ° C. can be set within the above range more reliably.
The content of the second silica particles is preferably 25% by weight to 75% by weight and more preferably 29% by weight to 70% by weight with respect to the total solid content of the thermosetting resin composition. Is more preferable. By making content of a 2nd silica particle in the said range, the heat resistance and moisture resistance of the soldering resist obtained using a thermosetting resin composition can be improved more. Moreover, if content of the 1st silica particle is in the said range, while being able to improve the surface smoothness of the soldering resist formed more, the minimum complex viscosity of the resin film in 50-150 degreeC is more reliable. Can be controlled.

  In preparing the thermosetting resin composition, the silica (B) is more preferably obtained by using, for example, a silica raw material having a silica concentration of 10 wt% or more and 90 wt% or less. From the viewpoint of improving the mechanical strength of the circuit board, it is particularly preferable to use a silica raw material having a silica concentration of 50% by weight or more and 90% by weight or less, for example. Further, from the viewpoint of suppressing the deflection of the circuit board and improving the moisture absorption reliability of the semiconductor device, for example, a silica raw material having a silica concentration of 50% by weight to 90% by weight and a silica concentration of 10% by weight to 50% by weight. It is particularly preferable to use a silica raw material that is not more than%. In particular, when the silica (B) includes the first silica particles and the second silica particles, as the silica raw material having a silica concentration of 10 wt% or more and 50 wt% or less, the first silica particles are used, It is preferable to use the second silica particles as a silica raw material having a silica concentration of 50 wt% or more and 90 wt% or less. Thereby, the dispersibility of the silica particles (the first silica particles and the second silica particles) in the thermosetting resin composition can be maintained, so that the circuit embedding property and the smoothness can be improved. it can. As a result, the deflection of the circuit board can be further suppressed, and the moisture absorption reliability of the semiconductor device can be further improved.

  The content of silica (B) is, for example, preferably 30% by weight or more, and more preferably 50% by weight or more based on the total solid content of the thermosetting resin composition. By making content of a silica (B) more than the said lower limit, the heat resistance and moisture resistance of the soldering resist obtained using a thermosetting resin composition can be improved effectively. Further, the linear expansion coefficient of the solder resist can be lowered and the elastic modulus can be improved. Thereby, it is possible to contribute to the reduction of warpage of the obtained semiconductor package. On the other hand, the content of silica (B) is, for example, preferably 90% by weight or less, and more preferably 85% by weight or less, based on the total solid content of the thermosetting resin composition. By making the content of silica (B) not more than the above upper limit value, it becomes possible to more effectively improve the embedding property of the solder resist.

(Cyanate resin (C))
A thermosetting resin composition can contain cyanate resin (C), for example. As a result, the linear expansion coefficient of the solder resist can be lowered, and the elastic modulus and rigidity can be improved. It is also possible to contribute to improvement of heat resistance and moisture resistance of the obtained semiconductor device.
The cyanate resin (C) is, for example, a novolak-type cyanate resin; a bisphenol-type cyanate resin such as a bisphenol A-type cyanate resin, a bisphenol E-type cyanate resin, or a tetramethylbisphenol F-type cyanate resin; a naphthol aralkyl-type phenol resin; 1 type or 2 types or more selected from naphthol aralkyl type cyanate resin obtained by reaction of this; dicyclopentadiene type cyanate resin; biphenyl alkyl type cyanate resin can be included. Among these, from the viewpoint of lowering the linear expansion coefficient of the solder resist and improving the elastic modulus and rigidity, it is more preferable to include at least one of a novolak type cyanate resin and a naphthol aralkyl type cyanate resin. It is particularly preferable to include a resin.

The content of the cyanate resin (C) is, for example, preferably 3% by weight or more and more preferably 5% by weight or more with respect to the total solid content of the thermosetting resin composition. By making content of cyanate resin (C) more than the said lower limit, the linear expansion coefficient of the soldering resist formed using a thermosetting resin composition can be reduced more effectively, and the elasticity The rate can be improved. Moreover, it can contribute to the improvement of embedding property and smoothness.
On the other hand, the content of the cyanate resin (C) is, for example, preferably 40% by weight or less, and more preferably 35% by weight or less, based on the total solid content of the thermosetting resin composition. By making content of cyanate resin (C) below the said upper limit, the heat resistance and moisture resistance of a solder resist formed using a thermosetting resin composition can be improved.

(Curing accelerator (D))
A thermosetting resin composition can contain a hardening accelerator (D), for example. Thereby, the sclerosis | hardenability of a thermosetting resin composition can be improved.
As a hardening accelerator (D), the hardening accelerator which accelerates | stimulates hardening reaction of an epoxy resin (A) can be used, The kind in particular is not limited. In the present embodiment, examples of the curing accelerator (D) include zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, zinc octylate, bisacetylacetonate cobalt (II), and trisacetylacetonate cobalt. Organometallic salts such as (III), tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole, 2- Imidazoles such as phenyl-4-ethylimidazole, 2-phenyl-4-methyl-5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, acetic acid, benzoic acid , Salicy Acid may include an organic acid such as p-toluenesulfonic acid, and the one or more selected from an onium salt compound. Among these, it is more preferable to include an onium salt compound from the viewpoint of more effectively improving curability.

  Although the onium salt compound used as a hardening accelerator (D) is not specifically limited, For example, the compound represented by following General formula (2) can be used.

（式（２）中、Ｐはリン原子、Ｒ^３、Ｒ^４、Ｒ^５およびＲ^６は、それぞれ、置換もしくは無置換の芳香環または複素環を有する有機基、あるいは置換もしくは無置換の脂肪族基を示し、互いに同一であっても異なっていてもよい。Ａ⁻は分子外に放出しうるプロトンを少なくとも１個以上分子内に有するｎ（ｎ≧１）価のプロトン供与体のアニオン、またはその錯アニオンを示す）

(In formula (2), P is a phosphorus atom, R ³ , R ⁴ , R ⁵ and R ⁶ are each an organic group having a substituted or unsubstituted aromatic ring or heterocyclic ring, or a substituted or unsubstituted aliphatic group. Each of which may be the same as or different from each other, and A ⁻ represents an anion of an n-valent proton donor having at least one proton that can be released to the outside of the molecule in the molecule, or Indicates the complex anion)

The content of the curing accelerator (D) is, for example, preferably 0.1% by weight or more, and more preferably 0.3% by weight or more with respect to the total solid content of the thermosetting resin composition. By making content of a hardening accelerator (D) more than the said lower limit, sclerosis | hardenability of a thermosetting resin composition can be improved more effectively.
On the other hand, the content of the curing accelerator (D) is, for example, preferably 10% by weight or less, and more preferably 5% by weight or less, based on the total solid content of the thermosetting resin composition. By making content of a hardening accelerator (D) below the said upper limit, the preservability of a thermosetting resin composition can be improved.

(Colorant (E))
A thermosetting resin composition can contain a coloring agent (E), for example. The colorant (E) includes one or more selected from dyes, pigments, and pigments such as green, red, blue, yellow, and black. Among these, from the viewpoint of improving the visibility of the opening and the like, it is more preferable to include a green colorant, and it is particularly preferable to include a green dye. As the green colorant, for example, one or more known colorants such as anthraquinone, phthalocyanine, and perylene can be contained.

The content of the colorant (E) is, for example, preferably 0.05% by weight or more and more preferably 0.1% by weight or more with respect to the total solid content of the thermosetting resin composition. By making content of a coloring agent (E) more than the said lower limit, the visibility and concealment of the opening part of the soldering resist obtained using a thermosetting resin composition can be improved more effectively. .
On the other hand, the content of the colorant (E) is, for example, preferably 5% by weight or less, and more preferably 3% by weight or less based on the total solid content of the thermosetting resin composition. By making content of a coloring agent (E) below the said upper limit, it becomes possible to improve sclerosis | hardenability etc. of a thermosetting resin composition more effectively.

(Other ingredients (F))
In addition to the above components, the thermosetting resin composition includes a coupling agent, a leveling agent, a curing agent, a photosensitizer, an antifoaming agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, One or two or more additives selected from ion trapping agents and the like may be added.
Examples of the coupling agent include silane coupling agents such as epoxy silane coupling agents, cationic silane coupling agents and aminosilane coupling agents, titanate coupling agents and silicone oil type coupling agents.
Examples of the leveling agent include acrylic copolymers. As a hardening | curing agent, a phenol resin etc. are mentioned, for example. Examples of the photosensitive agent include photosensitive diazoquinone compounds.

(solvent)
The thermosetting resin composition can contain a solvent, for example. Examples of the solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, toluene, ethyl acetate, cyclohexane, heptane, cyclohexane, cyclohexanone, tetrahydrofuran, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, ethylene glycol, cellosolve, carbitol, anisole, and One or more selected from organic solvents such as N-methylpyrrolidone can be included.

  When the thermosetting resin composition is varnished, the solid content of the thermosetting resin composition is preferably, for example, 30% by weight to 80% by weight, and preferably 40% by weight to 70% by weight. It is more preferable that Thereby, the thermosetting resin composition excellent in workability | operativity and film formability is obtained. In addition, the varnish-like thermosetting resin composition includes, for example, the above-described components, an ultrasonic dispersion method, a high-pressure collision dispersion method, a high-speed rotation dispersion method, a bead mill method, a high-speed shear dispersion method, and a rotation and revolution dispersion. It can prepare by melt | dissolving, mixing, and stirring in a solvent using various mixers, such as a system.

  In addition, the thermosetting resin composition which concerns on this embodiment can be made into the composition which does not contain fiber base materials, such as a glass fiber base material, and a paper base material, for example. Thereby, it is possible to realize a thermosetting resin composition particularly suitable for forming a solder resist.

As described above, the thermosetting resin composition was subjected to a dynamic viscoelasticity test on a resin film obtained using the thermosetting resin composition under the conditions of a measurement frequency of 62.83 rad / sec and a temperature increase rate of 3 ° C./min. When performed, the lowest complex viscosity of the resin film at 50 to 150 ° C. is 0.1 Pa · sec to 5000 Pa · sec. As a result, it is possible to realize a semiconductor device having excellent moisture absorption reliability while improving the embedding property of the solder resist as described above. Thereby, the surface smoothness of the solder resist can also be improved. The dynamic viscoelasticity test can be performed under the following conditions using, for example, a dynamic viscoelasticity measuring apparatus. The dynamic viscoelasticity measuring apparatus is not particularly limited, but for example, Physica MCR-301 manufactured by Anton Paar can be used.
Frequency: 62.83 rad / sec
Measurement temperature: 50-200 ° C
Temperature increase rate: 3 ° C / min
Geometry: Parallel plate Plate diameter: 10mm
Plate spacing: 0.1mm
Load (normal force): 0N (constant)
Strain: 0.3%
Measurement atmosphere: Air

  When the thermosetting resin composition is in the form of a film, the film-like thermosetting resin composition is used as it is as a resin film obtained using the thermosetting resin composition in the dynamic viscoelasticity test. be able to. On the other hand, when the thermosetting resin composition is varnished, a resin obtained by subjecting the thermosetting resin film obtained by forming the varnish-like thermosetting resin composition to a solvent removal treatment. The film can be used as a resin film for the dynamic viscoelasticity test. This solvent removal treatment is performed under the condition that the solvent content of the thermosetting resin film is 5% by weight or less with respect to the entire thermosetting resin film. In addition, the thermosetting resin film after treatment has a weight change rate of 5% by weight or less before and after heat treatment at 170 ° C. for 2 minutes. In the present embodiment, for example, the solvent removal treatment can be performed under conditions of 100 ° C. to 150 ° C. and 1 minute to 5 minutes. This makes it possible to sufficiently remove the solvent while suppressing the curing of the thermosetting resin film.

  From the viewpoint of more effectively improving the embedding property and surface smoothness of the solder resist and the moisture absorption reliability of the semiconductor device formed using the solder resist, the resin film obtained using the thermosetting resin composition The minimum complex viscosity is more preferably 0.5 Pa · sec to 4500 Pa · sec, and particularly preferably 1 Pa · sec to 4000 Pa · sec.

  In this embodiment, for example, the minimum complex viscosity is controlled by appropriately selecting the type and amount of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, and the like. Is possible. Among these, for example, appropriately adjusting the type and content of the epoxy resin (A) and silica (B), appropriately blending other components, and performing surface treatment on silica (B) Are particularly important factors in order to bring the minimum complex viscosity into the desired numerical range.

  When the thermosetting resin composition is heat-treated at 200 ° C. for 1 hour to obtain a cured product, the storage modulus at 25 ° C. of the obtained cured product is, for example, 7 GPa or more. As a result, it is possible to suppress the deflection and strength of the circuit board including the solder resist obtained by using the thermosetting resin composition, suppress the warpage of the semiconductor package including the circuit board, and the like. The storage elastic modulus is more preferably 10 GPa or more. On the other hand, the upper limit value of the storage elastic modulus is not particularly limited, but can be set to, for example, 50 GPa.

  When the thermosetting resin composition is heat treated at 200 ° C. for 1 hour to obtain a cured product, the glass transition temperature of the obtained cured product is, for example, 160 ° C. or higher. Thereby, it becomes possible to improve the heat resistance and reflow resistance of the solder resist obtained using the thermosetting resin composition. The glass transition temperature is more preferably 200 ° C. or higher. On the other hand, the upper limit value of the glass transition temperature is not particularly limited, but can be set to 350 ° C., for example.

  In the present embodiment, the storage elastic modulus and the glass transition temperature are obtained, for example, by performing a dynamic viscoelasticity test using a dynamic viscoelasticity measuring device under conditions of a frequency of 1 Hz and a heating rate of 5 ° C./min. It can be calculated from the measurement result. Although it does not specifically limit as a dynamic viscoelasticity measuring apparatus, For example, the Seiko Instruments make and DMS6100 can be used.

When the thermosetting resin composition is heat-treated at 200 ° C. for 1 hour to obtain a cured product, the linear expansion coefficient of the obtained cured product below the glass transition temperature is, for example, 30 ppm / ° C. or less. Thereby, it becomes possible to suppress warpage of a semiconductor package including a solder resist obtained using the thermosetting resin composition. The linear expansion coefficient is particularly preferably 28 ppm / ° C. or less. On the other hand, the lower limit value of the linear expansion coefficient is not particularly limited, but may be 3 ppm / ° C., for example.
In the present embodiment, for example, an average at 25 to 50 ° C. of the linear expansion coefficient obtained by measuring at a temperature rising rate of 10 ° C./min using TMA (thermal analyzer) is calculated, and this is calculated. The linear expansion coefficient at a temperature lower than the glass transition temperature can be obtained.

  In the present embodiment, for example, by appropriately selecting the type and blending amount of each component contained in the thermosetting resin composition, the preparation method of the thermosetting resin composition, etc., the storage elastic modulus, the above It is possible to control the glass transition temperature and the linear expansion coefficient.

Next, the resin film with carrier 100 will be described.
FIG. 1 is a cross-sectional view showing an example of a resin film with carrier 100 according to the present embodiment. The resin film with carrier 100 is used to form a solder resist. As shown in FIG. 1, the resin film with carrier 100 includes, for example, a carrier substrate 12 and a resin film (thermosetting resin film) 10 provided on the carrier substrate 12. The resin film 10 is formed using the thermosetting resin composition according to the present embodiment. For this reason, as described above, the reliability of a semiconductor device including a solder resist formed using the resin film with carrier 100 can be improved.

  The resin film with carrier 100 is formed, for example, by applying a varnish-like thermosetting resin composition on the carrier substrate 12 to form a coating film, and then performing a solvent removal process on the coating film. 10 can be produced. The solvent removal treatment is performed, for example, under conditions where the solvent content of the coating film is 5% by weight or less with respect to the entire coating film. Moreover, the coating film after a process will be 5 weight% or less of the weight change rate before and behind heat processing, for example at 170 degreeC for 2 minutes. The carrier substrate 12 is not particularly limited, and is made of, for example, PET (Polyethylene terephthalate) or copper foil. Moreover, the film thickness of the resin film 10 is not particularly limited, but can be, for example, 5 μm or more and 300 μm or less. Thereby, the resin film 10 suitable for formation of a solder resist can be realized.

  In the present embodiment, for example, the solder resist can be formed using the resin film with carrier 100 as follows. First, the resin film with carrier 100 is stuck on the surface of the circuit board on which the conductor circuit pattern is provided so that the resin film 10 faces the circuit board. The application of the resin film with carrier 100 can be performed by, for example, laminating the resin film with carrier 100 on a circuit board and then vacuum-pressing it. Next, the carrier substrate 12 is peeled from the resin film 10. Thereafter, the resin film 10 remaining on the circuit board is thermally cured. As a result, a solder resist made of a cured film obtained by curing the resin film 10 is formed on the circuit board so as to cover the conductor circuit pattern.

Next, the semiconductor device 102 will be described.
FIG. 2 is a cross-sectional view showing an example of the semiconductor device 102 according to the present embodiment. As shown in FIG. 2, the semiconductor device 102 includes a solder resist 26. The solder resist 26 is composed of a cured product of the thermosetting resin composition according to this embodiment. Therefore, as described above, the semiconductor device 102 having excellent reliability can be realized. The film thickness of the solder resist 26 is not particularly limited, but can be, for example, 5 μm or more and 300 μm or less.

  The semiconductor device 102 includes, for example, a circuit board 20 and a semiconductor element 60 mounted on the circuit board 20. The circuit board 20 is an organic substrate such as an interposer. Further, the semiconductor element 60 is mounted on the circuit board 20 via a die attach material 62, for example. In FIG. 2, the circuit board 20 in which the conductor circuit pattern 24 is provided on one surface of the core base material 22 and the other surface opposite to the one surface is illustrated. In this case, a solder resist 26 is formed on each of the one surface and the other surface of the core base material 22 so as to cover the conductor circuit pattern 24.

  The core base material 22 is a resin base material formed by impregnating a fiber base material with a resin composition, for example. Although the thickness of the core base material 22 is not specifically limited, For example, it can be 10 micrometers or more and 1000 micrometers or less. In the present embodiment, one or more buildup layers may be laminated on at least one of the one surface and the other surface of the core base material 22. In this case, the solder resist 26 is formed on the uppermost buildup layer.

In the solder resist 26, an opening 28 for exposing the conductor circuit pattern 24 is formed. The bonding wire 50 that connects the semiconductor element 60 and the circuit board 20 is bonded to, for example, the conductor circuit pattern 24 exposed in the opening 28. In the example in which the solder balls 30 that are external connection terminals are provided on the circuit board 20, the solder balls 30 are formed on the conductor circuit pattern 24 exposed in the opening 28, for example. The opening 28 is formed by, for example, laser irradiation or lithography processing.
The semiconductor element 60 and the bonding wire 50 are sealed with, for example, a sealing resin 40. The sealing resin 40 can be formed using, for example, an epoxy resin composition.

  The semiconductor device 102 is formed as follows, for example. First, the conductor circuit pattern 24 is formed on the one surface and the other surface of the core substrate 22. Next, a solder resist 26 is formed on each of the one surface and the other surface of the core substrate 22. The solder resist 26 can be formed using, for example, the above-described resin film with carrier 100. Next, an opening 28 is formed in the solder resist 26 by laser irradiation. In addition, when forming the opening 28 by lithography processing by exposure and development, the solder resist 26 is thermally cured after the exposure and development are performed and the opening 28 is formed before the solder resist 26 is thermally cured. It becomes. In addition, after the opening 28 is formed, desmear treatment and plasma treatment can be performed on the one surface and the other surface of the circuit board 20. A semiconductor element 60 is mounted on one surface of the circuit board 20 obtained in this way via a die attach material 62. Next, the semiconductor element 60 and the conductor circuit pattern 24 provided on the one surface side of the circuit board 20 and exposed from the opening 28 are connected by a bonding wire 50. Next, the semiconductor element 60 and the bonding wire 50 are sealed with a sealing resin 40. Thereafter, a solder ball 30 is formed on the conductor circuit pattern 24 provided on the other surface opposite to the one surface of the circuit board 20 and exposed from the opening 28. In the present embodiment, for example, the semiconductor device 102 can be manufactured as described above.

  It should be noted that the present invention is not limited to the above-described embodiments, and modifications, improvements, and the like within the scope that can achieve the object of the present invention are included in the present invention.

  Next, examples of the present invention will be described. The present invention is not limited to this.

(Examples 1 to 10 and Comparative Examples 1 and 2)
[1] Preparation of Thermosetting Resin Composition A varnish-like thermosetting resin composition was prepared for each Example and each Comparative Example having the composition shown in Table 1. The thermosetting resin composition was obtained by dissolving and dispersing the raw materials of each component blended according to Table 1 in methyl ethyl ketone as a solvent, and then stirring for 1 hour using a high-speed stirring device. The detail of the raw material of each component in Table 1 is as follows. Among the numerical values indicating the mixing ratios in Table 1, the numerical values outside the parentheses indicate the mixing ratio (wt%) of the raw materials of each component, and the numerical values in parentheses indicate the solid content ratio (wt%) of each component, respectively. Yes.

Epoxy resin (A)
Epoxy resin 1: Epoxy resin having a naphthalene skeleton (HP-5000, manufactured by DIC Corporation)
Epoxy resin 2: Epoxy resin having a naphthalene skeleton (HP-6000, manufactured by DIC Corporation)

Silica (B)
Silica 1: Admanano, manufactured by Admatechs Co., Ltd. (average particle diameter D ₅₀ = 0.05 μm, silica concentration 40% by weight)
Silica 2: SC1050-HLA, manufactured by Admatechs Co., Ltd. (average particle diameter D ₅₀ = 0.35 μm, silica concentration 60% by weight)
Silica 3: SC2050-KNO, manufactured by Admatechs Co., Ltd. (average particle diameter D ₅₀ = 0.5 μm, silica concentration 70% by weight)
Silica 4: SC4050-KNR, manufactured by Admatechs Co., Ltd. (average particle diameter D ₅₀ = 1 μm, silica concentration 70% by weight)
Silica 5: SC5050-KNR, manufactured by Admatechs Co., Ltd. (average particle diameter D ₅₀ = 1.5 μm, silica concentration 70% by weight)

Cyanate resin (C)
A phenol novolac type cyanate resin (PT30, manufactured by Lonza Japan Co., Ltd.) was dissolved in methyl isobutyl ketone to use a cyanate resin concentration of 90% by weight.

Curing accelerator (D)
An adduct of tetraphenylphosphonium and bis (naphthalene-2,3-dioxy) phenylsilicate dispersed in cyclohexanone at 40% by weight was used.

Colorant (E)
Green dye (Kayaset Green AB, manufactured by Nippon Kayaku Co., Ltd.)

Other ingredients (F)
Coupling agent: 3-glycidoxypropyltrimethoxysilane (A-187, manufactured by Momentive Performance Materials Japan)
Leveling agent: BYK-361N, manufactured by Big Chemie Japan Co., Ltd.

[2] Production of resin film with carrier For each example and each comparative example, after the obtained thermosetting resin composition was applied on a PET film as a carrier substrate, the solvent was used at 140 ° C. for 2 minutes. Then, a thermosetting resin film having a thickness of 30 μm was formed. Thereby, a resin film with a carrier was obtained.

  In addition, about the obtained thermosetting resin film, it confirmed that the solvent content rate was 5 weight% or less with respect to the whole thermosetting resin film. Moreover, about the obtained thermosetting resin film | membrane, it confirmed that the weight change rate before and behind 170 degreeC and the heat processing for 2 minutes was 5 weight% or less.

[Minimum complex viscosity]
For each example and each comparative example, the lowest complex viscosity was measured as follows. First, from the resin film with a carrier obtained above, a sample obtained by peeling off a PET film as a carrier substrate was prepared as a measurement sample. Subsequently, the complex viscosity was measured on the measurement sample under the following conditions using a dynamic viscoelasticity measuring device (manufactured by Anton Paar, device name Physica MCR-301). From the obtained measurement results, the lowest complex viscosity (Pa · sec) of the measurement sample at 50 to 150 ° C. was calculated. The results are shown in Table 1.
Frequency: 62.83 rad / sec
Measurement temperature: 50-200 ° C
Temperature increase rate: 3 ° C / min
Geometry: Parallel plate Plate diameter: 10mm
Plate spacing: 0.1mm
Load (normal force): 0N (constant)
Strain: 0.3%
Measurement atmosphere: Air

[Storage modulus, glass transition temperature]
About each Example and each comparative example, three resin films which peeled PET film which is a carrier base material from the obtained resin film with a carrier were laminated | stacked, and the 90-micrometer-thick resin sheet was produced. Next, the resin sheet was heat-treated at 200 ° C. for 1 hour, and then cut into a width of 8 mm × a length of 50 mm × a thickness of 90 μm to obtain a measurement sample. A dynamic viscoelasticity test was performed on the measurement sample using a dynamic viscoelasticity measurement apparatus (Seiko Instruments, DMS6100) under conditions of a frequency of 1 Hz and a temperature increase rate of 5 ° C./min. Next, the glass transition temperature (° C.) and the storage elastic modulus (GPa) at 25 ° C. were calculated from the obtained measurement results. The glass transition temperature was determined from the peak value of tan δ. The results are shown in Table 1.

[Linear expansion coefficient]
About each Example and each comparative example, three resin films which peeled PET film which is a carrier base material from the obtained resin film with a carrier were laminated | stacked, and the 90-micrometer-thick resin sheet was produced. Next, the resin sheet was heat treated at 200 ° C. for 1 hour, and then cut into a width of 4 mm × a length of 20 mm × a thickness of 90 μm to obtain a measurement sample. The linear expansion coefficient was measured on the measurement sample using TMA (manufactured by TA Instruments Co., Ltd.) under the condition of a temperature increase rate of 10 ° C./min. Subsequently, the average of the measurement result in 25-50 degreeC was computed, and this was made into the linear expansion coefficient (ppm / degreeC) in less than a glass transition temperature (Tg). The results are shown in Table 1.

[Evaluation of circuit embeddability, evaluation of smoothness, evaluation of deflection]
About each Example and each comparative example, circuit embedding evaluation, smoothness evaluation, and deflection amount evaluation were performed as follows.
First, a double-sided copper-clad laminate (LαZ-4785GH-J, manufactured by Sumitomo Bakelite Co., Ltd.) prepared by laminating 11 μm-thick copper foil on one surface and the other surface of a core substrate (40 mm × 85 mm, 60 μmt) is prepared. did. Subsequently, the copper foil of the said copper clad laminated board was etched, and the conductor circuit pattern was formed, and the circuit board by which the said conductor circuit pattern was formed in the one surface and the other surface was obtained. Subsequently, the resin film with a carrier obtained above was laminated on each of the one surface and the other surface of the circuit board so that the thermosetting resin film opposed to the circuit board. Thereafter, vacuum hot press molding was performed using a vacuum pressurizing laminator apparatus under conditions of a temperature of 100 ° C., a pressure of 0.8 MPa, and 30 seconds. Subsequently, after peeling off the carrier base material from the resin film with carrier, the thermosetting resin film on the circuit board was cured at 200 ° C. for 1 hour to form a solder resist film. In this way, a sample was obtained.

1. Circuit Embedding Evaluation The surface of the solder resist film formed on one surface of the circuit board was observed with a microscope at any 10 positions of the sample obtained above. The evaluation of the circuit embedding property was performed according to the following criteria by confirming whether or not a void was present, whether or not the solder resist film was embedded between the conductor circuit patterns.
A: There were no voids in all the observed locations.
B: In the observed 1 to 5 locations, there were voids to the extent that no problem occurred in actual use.
C: In the observed 6 to 9 locations, there were voids to the extent that no problem occurred in actual use.
D: Voids causing problems in actual use existed at all the observed locations.

2. Smoothness evaluation About the sample obtained above, arbitrary 10 places of the surface of the soldering resist film formed on one surface of a circuit board were scanned with the laser microscope, and surface roughness Ra was measured. The smoothness was evaluated according to the following criteria.
A: The average value of Ra at 10 locations is less than 0.90 μm B: The average value of Ra at 10 locations is 0.90 μm or more and less than 0.95 μm C: The average value of Ra at 10 locations is 0.95 μm or more and less than 1 μm D: The average value of Ra at 10 locations is 1 μm or more

3. Evaluation of deflection amount About the sample obtained above, the other side was used as a free end while supporting a 10 mm portion from the end of one side of the pair of short sides of the sample. In this state, the deflection amount of the other side was measured. The amount of deflection was evaluated according to the following criteria.
A: Deflection amount is less than 6 mm B: Deflection amount is 6 mm or more and less than 6.5 mm C: Deflection amount is 6.5 mm or more and less than 7 mm D: Deflection amount is 7 mm or more

[3] Production of Semiconductor Package For each example and each comparative example, a semiconductor package was produced as follows. First, a double-sided copper-clad laminate obtained by laminating a 12 μm-thick copper foil on one surface and the other surface of a 240 μm-thick core base material (LαZ-4785TH-G, manufactured by Sumitomo Bakelite Co., Ltd.) was prepared. Subsequently, the copper foil of the said copper clad laminated board was etched, and the conductor circuit pattern was formed, and the circuit board by which the said conductor circuit pattern was formed in the one surface and the other surface was obtained. Next, after laminating the resin film with a carrier obtained above so that the thermosetting resin film faces the circuit board on each of the one surface and the other surface of the circuit board, a vacuum pressure laminator device is used. Then, vacuum heating and pressing were performed under conditions of a temperature of 100 ° C., a pressure of 0.8 MPa, and 30 seconds. Subsequently, after peeling off the carrier base material from the resin film with carrier, the thermosetting resin film on the circuit board was cured at 200 ° C. for 1 hour to form a solder resist film.

  Next, an opening is formed in the solder resist film provided on one surface of the circuit board by a carbon dioxide laser so that a part of the conductor circuit pattern is exposed, and then desmear treatment and plasma treatment are performed on the one surface of the circuit board. gave. Next, after mounting a semiconductor element on one surface of the circuit board via a die attach material, the conductor pattern exposed from the opening and the semiconductor element were connected by a bonding wire. Next, the semiconductor element and the bonding wire were encapsulated with an epoxy resin composition to obtain a semiconductor package (16 mm × 16 mm).

[Moisture absorption reliability]
About each Example and each comparative example, moisture absorption reliability was evaluated as follows.
First, the semiconductor package obtained above was subjected to moisture absorption treatment at 85 ° C. and relative humidity 60% for 168 hours, followed by IR reflow treatment (260 ° C., 10 seconds, 3 times reflow). Next, the solder resist film of the semiconductor package after the reflow treatment was observed with an ultrasonic imaging apparatus SAT. The moisture absorption reliability was evaluated according to the following criteria.
A: No peeling occurred on the solder resist film.
B: Peeling occurred in the solder resist film so as not to cause a problem in actual use.
C: The solder resist film was peeled to such an extent that a slight problem occurred in actual use.
D: Peeling unsuitable for actual use occurred in the solder resist film.

[Package warpage evaluation]
About each Example and each comparative example, the curvature amount in 25 degreeC of the obtained semiconductor package was measured, and it evaluated according to the following references | standards. The package warpage amount is defined by the distance between the center point of the upper surface of the semiconductor package and the outer peripheral portion of the upper surface in the stacking direction of the semiconductor element and the circuit board. A: Package warpage amount is less than 90 μm B: Package warpage amount is 90 μm or more and less than 95 μm C: Package warpage amount is 95 μm or more and less than 100 μm D: Package warpage amount is 100 μm or more

100 resin film with carrier 102 semiconductor device 10 resin film (thermosetting resin film)
12 carrier base material 20 circuit board 22 core base material 24 conductor circuit pattern 26 solder resist 30 solder ball 40 sealing resin 50 bonding wire 60 semiconductor element 62 die attach material

Claims (11)

A thermosetting resin composition for forming a solder resist,
An epoxy resin and silica particles,
When a dynamic viscoelasticity test was performed on a resin film obtained using the thermosetting resin composition under the conditions of a measurement frequency of 62.83 rad / sec and a temperature increase rate of 3 ° C./min, The thermosetting resin composition whose minimum complex viscosity of the said resin film in 150 degreeC is 0.1 Pa.sec or more and 5000 Pa.sec or less.   The storage elastic modulus at 25 ° C of the obtained cured product is 7 GPa or more when the cured product is obtained by heat-treating the thermosetting resin composition at 200 ° C for 1 hour. Thermosetting resin composition.   The glass transition temperature of the obtained cured product is 160 ° C or higher when the cured product is obtained by heat-treating the thermosetting resin composition at 200 ° C for 1 hour. Thermosetting resin composition.   When the thermosetting resin composition is heat-treated at 200 ° C for 1 hour to obtain a cured product, the linear expansion coefficient of the obtained cured product below the glass transition temperature is 30 ppm / ° C or less. The thermosetting resin composition according to any one of 1 to 3.   The thermosetting resin composition according to any one of claims 1 to 4, further comprising a cyanate resin.   The thermosetting resin composition according to any one of claims 1 to 5, wherein the epoxy resin includes an epoxy resin having a naphthalene skeleton. The silica particles have an average particle diameter D ₅₀ of claims 1 to thermosetting resin composition according to any one of 6 including a first silica particles is 2nm or 100nm or less. The silica particles are first and silica particles having an average particle diameter _{D 50} is 2nm or 100nm or less, an average particle diameter _{D 50} any one of claims 1 to 7 comprising the a second silica particles greater than 100nm The thermosetting resin composition according to item.   The thermosetting resin composition according to any one of claims 1 to 8, further comprising a green dye. A carrier substrate;
A resin film provided on the carrier substrate and formed using the thermosetting resin composition according to any one of claims 1 to 9,
A resin film with a carrier.   A semiconductor device provided with the soldering resist comprised by the hardened | cured material of the thermosetting resin composition as described in any one of Claims 1 thru | or 9.

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