KR102146990B1 - Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated using the same - Google Patents

Abstract

Epoxy resin; Hardener; Inorganic fillers; And an epoxy resin composition for sealing semiconductor elements containing a phenylphenazinium compound, and a semiconductor device sealed using the same.

Description

Epoxy resin composition for sealing semiconductor devices, and a semiconductor device sealed using the same {EPOXY RESIN COMPOSITION FOR ENCAPSULATING SEMICONDUCTOR DEVICE AND SEMICONDUCTOR DEVICE ENCAPSULATED USING THE SAME}

The present invention relates to an epoxy resin composition for sealing semiconductor elements and a semiconductor device sealed using the same. More specifically, the present invention The present invention relates to an epoxy resin composition for sealing semiconductor elements capable of preventing semiconductor chip marking from occurring, and a semiconductor device sealed using the same.

Recently, the application fields of semiconductor devices are diversifying. Accordingly, the sensing capability of the sensor chip is also developing. Among them, among the biometrics for security of mobile devices or automobiles, fingerprint recognition chips are being applied due to low cost and convenience of recognition, and in particular, research on the capacitive method is rapidly progressing. The capacitive method is a method of recognizing a fingerprint based on the difference in capacitance of fingerprint irregularities when recognizing a fingerprint, and its application from mobile to automobiles and credit cards is accelerating.

Capacitive fingerprint recognition sensor semiconductor devices increase the recognition rate by reducing the sealing thickness of the epoxy resin composition for sealing semiconductor devices molded on the top of the semiconductor device, or increase the fingerprint recognition rate by using a material having a high relative dielectric constant. However, if the thickness of the epoxy resin composition for sealing a semiconductor device molded on the top surface of the semiconductor device is reduced, a chip marking phenomenon in which the semiconductor device is exposed after sealing may occur. In particular, due to the fact that the semiconductor devices are separated by a predetermined distance, the sealing thickness of the sealing composition is inevitably different between the space between the semiconductor device and the adjacent semiconductor device (i.e., the space without the semiconductor device) and the upper surface of the semiconductor device. The chip marking phenomenon may become more severe due to curing shrinkage, so improvement is urgently needed.

The object of the present invention It is to provide an epoxy resin composition for sealing semiconductor devices capable of preventing chip marking from occurring.

Another object of the present invention is that the relative dielectric constant and thermal conductivity are It is to provide an excellent epoxy resin composition for sealing semiconductor devices.

Another object of the present invention is to provide a semiconductor device sealed with the epoxy resin composition as described above.

The epoxy resin composition for sealing a semiconductor device of the present invention includes an epoxy resin; Hardener; Inorganic fillers; And a phenylphenazinium-based compound.

The phenylphenazinium compound is It may be a compound of Formula 1:

<Formula 1>

(In Formula 1, X is a monovalent anion)

The present invention provides a semiconductor device sealed using the epoxy resin composition for sealing semiconductor elements according to the present invention.

The present invention An epoxy resin composition for sealing semiconductor devices capable of preventing chip marking from occurring was provided.

In the present invention, the relative dielectric constant and thermal conductivity An excellent epoxy resin composition for sealing semiconductor devices was provided.

The present invention provides a semiconductor device sealed with the epoxy resin composition as described above.

1 is a partial cross-sectional view of a specimen for chip marking evaluation.
2 shows a ◎ state in which no chip marking has occurred.
3 shows the x state in which the chip marking has occurred considerably.

The thinner the sealing thickness of the upper surface of the fingerprint recognition semiconductor device, the better the recognition rate can be. For example, when used in a mobile display device or an automobile, the sealing thickness may be about 0.50 mm or less. Accordingly, the sealing thickness differs between the upper surface of the semiconductor device and a space between the semiconductor device and the semiconductor device (a space without a semiconductor device). Therefore, due to the difference in the degree of cure shrinkage, a chip marking phenomenon in which the semiconductor chip is exposed is inevitable.

The present inventors have secured relative dielectric constant and thermal conductivity so that they can be used for sealing semiconductor devices for fingerprint recognition sensors. In order to develop an epoxy resin for sealing semiconductor devices that can prevent chip marking from occurring, as a result of repeated research, it was found that the above object can be achieved by using a phenylphenazinium compound. The invention was completed.

The epoxy resin composition according to the present invention may include an epoxy resin, a curing agent, an inorganic filler, and a phenylphenazinium compound .

The phenylphenazinium-based compound may be a compound of Formula 1:

<Formula 1>

(In Formula 1, X is a monovalent anion).

X is F ^- may be ^-, Cl ^-, I ^- or Br.

The phenylphenazinium-based compound can eliminate the semiconductor chip marking phenomenon by flattening the final sealed surface regardless of the sealing thickness when sealing the semiconductor device.

Hereinafter, the components of the epoxy resin composition according to the present invention will be described in detail.

Epoxy resin

Epoxy resin may be used for sealing semiconductor devices 　 generally used epoxy resins, and is not particularly limited. Specifically, the epoxy resin may be an epoxy compound containing two or more epoxy groups in the molecule. For example, the epoxy resin is an epoxy resin obtained by epoxidating a condensation product of phenol or alkyl phenols and hydroxybenzaldehyde, a phenol aralkyl type epoxy resin, a phenol novolak type epoxy resin, a cresol novolak type epoxy resin, a polyfunctional type epoxy. Resin, naphthol novolak type epoxy resin, bisphenol A/bisphenol F/bisphenol AD novolak type epoxy resin, bisphenol A/bisphenol F/bisphenol AD glycidyl ether, bishydroxybiphenyl type epoxy resin, dicyclopenta Diene-based epoxy resins, biphenyl-type epoxy resins, and the like. More specifically, the epoxy resin may include at least one of a biphenyl type epoxy resin, a phenol aralkyl type epoxy resin, a cresol novolak type epoxy resin, and a polyfunctional epoxy resin. Most preferably, the epoxy resin may be one or more of a biphenyl type epoxy resin and a phenol aralkyl type epoxy resin.

Specifically, the biphenyl-type epoxy resin may be represented by Formula 2 below, but is not limited thereto.

<Formula 2>

(In Formula 2, R is an alkyl group having 1 to 4 carbon atoms, and the average value of n is 0 to 7.)

Specifically, the phenol aralkyl type epoxy resin may be represented by the following Formula 3, but is not limited thereto.

<Formula 3>

(In Chemical Formula 3, the average value of n is 1 to 7).

The epoxy resin may use an epoxy resin having an epoxy equivalent of 100 g/eq to 500 g/eq in consideration of curability. In the above range, the degree of curing can be increased.

Epoxy resin can be used alone or in combination, and it is made by pre-reaction such as a melt master batch with other components such as a curing agent, a curing accelerator, a release agent, a coupling agent, and a stress reliever in the epoxy resin. Can also be used as.

The epoxy resin may be included in an amount of 0.5% to 20% by weight, specifically 3% to 15% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, the curability of the composition may not be reduced.

Hardener

Hardener Curing agents generally used for sealing semiconductor devices may be used, and are not particularly limited. Specifically, the curing agent may be a phenolic curing agent, for example, the phenolic curing agent is a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, a polyfunctional type phenol resin, a xylok type phenol resin, a cresol novolac Including type phenolic resin, naphthol type phenolic resin, terpene type phenolic resin, dicyclopentadiene type phenolic resin, novolak type phenolic resin synthesized from bisphenol A and resol, tris(hydroxyphenyl)methane, dihydroxybiphenyl It may contain one or more of the polyhydric phenol compounds. Preferably, the phenolic curing agent is at least one of a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, and a polyfunctional type phenol resin, most preferably a phenol aralkyl type phenol resin, a phenol novolak type phenol resin, and a polyfunctional type phenol resin. Mixtures of can be used.

Specifically, the phenolaralkyl-type phenol resin may be represented by the following Formula 4, but is not limited thereto.

<Formula 4>

(The average value of n in Formula 4 is 1 to 7)

Specifically, the polyfunctional phenolic resin may be represented by the following formula (5), but is not limited thereto.

<Formula 5>

(The average value of n in Formula 5 is 1 to 7).

The curing agent may have a hydroxyl equivalent weight of 90 g/eq to 250 g/eq in consideration of curability. In the above range, the degree of curing can be increased.

The curing agent may be used alone or in combination. In addition, it may be used as an additive compound made by subjecting the curing agent to a pre-reaction such as a melt master batch with other components such as an epoxy resin, a curing accelerator, a release agent and a stress reliever.

The curing agent may be included in an amount of 0.1% to 13% by weight, preferably 0.1% to 10% by weight of the epoxy resin composition for sealing semiconductor devices. Within the above range, there may be an effect of not reducing the curability of the composition.

The blending ratio of the epoxy resin and the curing agent can be adjusted according to the requirements of mechanical properties and moisture resistance reliability in the package. For example, the chemical equivalent ratio of the epoxy resin to the curing agent may be 0.95 to 3, specifically 1 to 2, and more specifically 1 to 1.75. When the equivalent ratio of the epoxy resin and the curing agent satisfies the above range, excellent strength may be realized after curing of the epoxy resin composition.

Inorganic filler

The inorganic filler is for improving the mechanical properties and low stress of the epoxy resin composition. As the inorganic filler, general inorganic fillers used for semiconductor sealing materials may be used without limitation, and are not particularly limited. For example, as the inorganic filler, molten silica, crystalline silica, calcium carbonate, magnesium carbonate, alumina, magnesia, clay, talc, calcium silicate, titanium oxide, antimony oxide, glass fiber, etc. may be used. I can. These may be used alone or in combination. Preferably, alumina alone as an inorganic filler in order to ensure the relative dielectric constant and thermal conductivity; Alternatively, a mixture of at least one of alumina and molten silica and crystalline silica may be used. When molten silica and crystalline silica are used in combination with alumina, the relative dielectric constant and thermal conductivity can be improved by using molten silica and crystalline silica in an amount of 10% by weight or less of the total inorganic filler.

The shape of the alumina is not limited, but the spherical alumina can improve fluidity. The average particle diameter (D50) of alumina is preferably 1 µm to 30 µm, and has good fluidity in the above range and may have good thermal conductivity and relative dielectric constant. Alumina may be coated in advance with a coupling agent, an epoxy resin, or a curing agent, if necessary.

The amount of inorganic filler used depends on the required physical properties such as moldability, low stress, and high temperature strength. In a specific embodiment, the inorganic filler may be included in an amount of 70% to 95% by weight, for example, 75% to 94% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, there may be an effect of securing the fluidity, reliability, relative dielectric constant and thermal conductivity of the composition.

Phenylphenazinium compound

Phenylphenazinium-based compounds can be prepared using commercially available products or using conventional synthetic methods known to those skilled in the art.

The phenylphenazinium-based compound may be included in an amount of 0.1% to 3% by weight, for example, 0.1% to 1% by weight, in the epoxy resin composition for sealing semiconductor devices. In the above range, it is possible to eliminate the chip marking phenomenon and to prevent a decrease in adhesion and reliability in the semiconductor device.

Silicone oil

The epoxy resin composition according to the present invention may include a silicone oil together with a phenylphenazinium compound within a range that does not impair the object of the present invention. Silicone oil can suppress the occurrence of voids.

The silicone oil may be included in an amount of 0.1% to 3% by weight, for example, 0.1% to 1% by weight of the epoxy resin composition for sealing semiconductor devices. Within the above range, void generation can be eliminated.

The sum of the phenylphenazinium-based compound and the silicone oil may be contained in an amount of 0.1% to 3% by weight, for example, 0.2% to 1% by weight, in the epoxy resin composition for sealing semiconductor devices. Within the above range, void generation can be eliminated.

Meanwhile, in addition to the above components, the epoxy resin composition according to the present invention may further include at least one of a curing accelerator, a coupling agent, a release agent, and a colorant.

Hardening accelerator

The curing accelerator is a substance that accelerates the reaction between the epoxy resin and the curing agent. As the curing accelerator, for example, tertiary amines, organometallic compounds, organophosphorus compounds, imidazoles, boron compounds, and the like can be used.

Tertiary amines include benzyldimethylamine, triethanolamine, triethylenediamine, diethylaminoethanol, tri(dimethylaminomethyl)phenol, 2-2-(dimethylaminomethyl)phenol, 2,4,6-tris(diaminomethyl) )Phenol and tri-2-ethylhexyl acid salt. Specific examples of organometallic compounds include chromium acetylacetonate, zinc acetylacetonate, and nickel acetylacetonate. Organophosphorus compounds include tris-4-methoxyphosphine, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, phenylphosphine, diphenylphosphine, triphenylphosphine, triphenylphosphine triphenylborane, triphenylphosphine Pin-1,4-benzoquinone and adducts. Examples of imidazoles include 2-phenyl-4-methylimidazole, 2-methylimidazole, 　2-phenylimidazole, 　2-aminoimidazole, 2-methyl-1-vinylimidazole, and 2-ethyl- 4-methylimidazole, 2-heptadecylimidazole, and the like, but are not limited thereto. Specific examples of the boron compound include tetraphenylphosphonium-tetraphenylborate, triphenylphosphine tetraphenylborate, tetraphenylboron salt, trifluoroborane-n-hexylamine, trifluoroboranemonoethylamine, tetrafluoro Boranetriethylamine, tetrafluoroboranamine, and the like. In addition, 1,5-diazabicyclo[4.3.0]non-5-ene (1,5-diazabicyclo[4.3.0]non-5-ene:DBN), 1,8-diazabicyclo[5.4. 0]undec-7-ene (1,8-diazabicyclo[5.4.0]undec-7-ene: DBU) and 　phenol novolac resin salt　, but are not limited thereto.

The curing accelerator may be an epoxy resin or an adduct made by pre-reacting with the curing agent.

The curing accelerator may be included in an amount of 0.01% to 2% by weight, specifically 0.02% to 1.5% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, curing of the epoxy resin composition is accelerated, and curing is also advantageous.

Coupling agent

The coupling agent is for improving the interfacial strength by reacting between the epoxy resin and the inorganic filler, and may be, for example, a silane coupling agent. The silane coupling agent may react between the epoxy resin and the inorganic filler to improve the interfacial strength between the epoxy resin and the inorganic filler, and the kind is not particularly limited. Specific examples of the silane coupling agent include epoxysilane, aminosilane, ureidosilane, mercaptosilane, and alkylsilane. The coupling agent may be used alone or in combination.

The coupling agent may be included in an amount of 0.01% to 5% by weight, preferably 0.05% to 3% by weight of the epoxy resin composition for sealing semiconductor devices. In the above range, the strength of the cured epoxy resin composition may be improved.

Release agent

As the release agent, at least one selected from the group consisting of paraffin wax, ester wax, higher fatty acid, higher fatty acid metal salt, natural fatty acid and natural fatty acid metal salt may be used.

The release agent may be included in an amount of 0.1% to 1% by weight of the epoxy resin composition for sealing semiconductor devices.

coloring agent

The colorant is for laser marking of the semiconductor device sealing material, and colorants well known in the art may be used, and there is no particular limitation. For example, the colorant may include one or more of carbon black, titanium black, titanium nitride, copper hydroxide phosphate, iron oxide, and mica.

The colorant may be included in an amount of 0.01% to 5% by weight, preferably 0.05% to 3% by weight of the epoxy resin composition for sealing semiconductor devices.

In addition, the epoxy resin composition of the present invention may include antioxidants such as Tetrakis[methylene-3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate]methane, etc., within a range that does not impair the object of the present invention; Flame retardants such as aluminum hydroxide 　 can be additionally included as needed.

The epoxy resin composition is uniformly and sufficiently mixed at a predetermined mixing ratio using a Hensel mixer or Lodige mixer, and then using a roll-mill or a kneader. After melt-kneading, cooling and grinding may be performed to obtain a final powder product.

The epoxy resin composition of the present invention as described above can be usefully applied to a semiconductor device, particularly a semiconductor device mounted on a mobile display or a fingerprint recognition sensor of an automobile. As a method of sealing a semiconductor device by using the epoxy resin composition obtained in the present invention, a low pressure transfer molding method can be generally used. However, it is also possible to form by a method such as injection molding or casting.

The semiconductor device according to the present invention can be sealed with the epoxy resin composition for sealing semiconductor elements of the present invention. For example, the semiconductor device may include a capacitive semiconductor device for fingerprint recognition.

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this has been presented as a preferred example of the present invention and cannot be construed as limiting the present invention in any sense.

Specific specifications of the components used in the following Examples and Comparative Examples are as follows.

Epoxy resin

1) Biphenyl type epoxy resin: YX-4000H (JER, epoxy equivalent: 196g/eq)

2) Phenol aralkyl type epoxy resin: NC-3000 (Japanese explosives, epoxy equivalent: 270g/eq)

Hardener

3) Multifunctional phenolic resin: MEH-7500-3S (Meiwa Chem., hydroxyl group equivalent: 95g/eq)

4) Phenolaralkyl-type phenol resin: MEH-7851-SS (Meiwa Chem., hydroxyl group equivalent: 203g/eq)

5) Phenol novolak type phenol resin: H-4 (Meiwa Chem., hydroxyl group equivalent: 106 g/eq)

weapon Filler

6) Alumina: DAB-05MS (Denka Denki, average particle diameter (D50): 7.6㎛)

Phenylphenazinium compound

7) CTK6E7420 (ChemTik, molecular weight: 470 to 550 g/mol, 3-(diethylamino)-7[{(4-dimethylamino)phenyl}azo]-5-phenylphenazinium salt (compound of Formula 1)

Silicone oil

8) FZ-3736 (DOW corning, viscosity: 2,240cp @25℃)

Hardening accelerator

9) 2-phenyl-4-methylimidazole

coloring agent

10) Carbon black: Nubian Black TH-807 (Orient Chemical, pH 7.0)

Release agent

11) Carnauba wax

Coupling agent

12) KBM-403, a trimethoxysilane containing an epoxy group (Shin-Etsu)

Example And Comparative example

Each component was weighed according to the composition (unit: parts by weight) of Table 1, and then uniformly mixed using a Henschel mixer to prepare a powdery primary composition. Thereafter, melt-kneading at 90 to 110°C using a continuous kneader was performed, followed by cooling and pulverizing to prepare an epoxy resin composition for sealing semiconductor devices.

Example Comparative example One 2 3 4 One 2 3 Epoxy resin One) 3.28 3.28 3.28 3.28 3.28 3.44 3.55 2) 3.28 3.28 3.28 3.28 3.28 3.43 3.54 Hardener 3) 1.12 1.12 1.12 1.12 1.12 1.18 1.21 4) 0.98 0.98 0.98 0.98 0.98 1.03 1.06 5) 0.71 0.71 0.71 0.71 0.71 0.74 0.76 Inorganic filler 6) 89.0 89.0 89.0 89.0 89.0 89.0 89.0 Phenylphenazinium compound 7) 0.75 0.25 0.45 0.65 0 0 0 Silicone oil 8) 0 0.50 0.30 0.10 0.75 0.30 0 Hardening accelerator 9) 0.10 0.10 0.10 0.10 0.10 0.10 0.10 coloring agent 10) 0.30 0.30 0.30 0.30 0.30 0.30 0.30 Release agent 11) 0.23 0.23 0.23 0.23 0.23 0.23 0.23 Coupling agent 12) 0.25 0.25 0.25 0.25 0.25 0.25 0.25 total 100 100 100 100 100 100 100

The physical properties of the epoxy resin compositions of Examples and Comparative Examples prepared as described above were measured according to the following physical property evaluation method. The measurement results are shown in Table 2.

Property evaluation method

(1) Fluidity (inch, spiral flow): Using a low pressure transfer molding press, an epoxy resin composition was injected into a mold for measuring spiral flow according to EMMI-1-66 at a molding temperature of 175°C and a molding pressure of 70 kgf/cm ² Then, the flow field (unit: inch) was measured. The higher the measured value, the better the fluidity.

(2) Relative dielectric constant: The epoxy resin composition was cured at 175° C. for 120 seconds to prepare a specimen having a thickness of 3.26 mm and measured using an LCR meter (Agilent).

(3) Thermal conductivity (W/mK): A specimen for evaluation was prepared with an epoxy resin composition according to ASTM D5470 and measured at 25°C.

(4) Chip marking: The epoxy resin composition was granulated by a conventional method.

Referring to FIG. 1, a plurality of Cu chips of length x width x thickness (620 µm x 360 µm x 200 µm) on a Cu PCB (Printed Circuit Board) of length x width x thickness (240mm x 74mm x 220㎛) x length x It was attached with a 40㎛-thick die attach film (DAF) with a width (7 rows x 13 rows). Using the semiconductor device molding compression equipment TOWA PMC-1040D, the prepared granules were The specimen was obtained by compression molding at 175° C. for 120 seconds. Visually, the specimen was evaluated for chip marking.

2 shows a ◎ state in which no chip marking has occurred. Referring to FIG. 2, a square-shaped Cu chip is not recognized at all. 3 shows the x state in which the chip marking has occurred considerably. Referring to FIG. 3, it can be seen visually that the Cu chips of the square shape are spaced apart from each other. The △ state indicates a state in which a lot of chip marking has occurred, and the ○ state indicates a state in which a little chip marking has occurred.

(5) Fingerprint recognition: A semiconductor package was molded using an epoxy resin composition, and recognition for each package was evaluated.

Example Comparative example One 2 3 4 One 2 3 Spiral flow
(inch) 62 65 65 67 65 62 58 Relative permittivity 8.7 8.6 8.4 8.6 8.5 8.3 8.6 Thermal conductivity (W/mK) 3.3 3.3 3.4 3.2 3.3 3.3 3.2 Chip marking ◎ ○ ○ ◎ △ × × Fingerprint recognition
Recognition rate
(%)
(Up to 5 times) 99.8 99.6 99.7 99.6 99.4 99.4 99.5 Total number of packages tested 120 120 120 120 120 120 120

As shown in Table 2, the epoxy resin composition of the present invention can prevent the occurrence of chip marking and has high fingerprint recognition power. In addition, the epoxy resin composition of the present invention has excellent relative dielectric constant and thermal conductivity.

On the other hand, in Comparative Examples 1 to 3 not including the phenylphenazinium compound, a lot of chip marking occurred.

Simple modifications or changes of the present invention can be easily implemented by those of ordinary skill in the art, and all such modifications or changes can be considered to be included in the scope of the present invention.

Claims (9)

0.5% to 20% by weight of epoxy resin; 0.1% to 13% by weight of a curing agent; 70% to 95% by weight of inorganic filler; And 0.1% to 3% by weight of a phenylphenazinium-based compound.
The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the phenylphenazinium-based compound is a compound represented by the following formula (1):
<Formula 1>

(In Formula 1, X is a monovalent anion).
delete The epoxy resin composition for sealing a semiconductor device according to claim 1, wherein the epoxy resin composition for sealing a semiconductor device further comprises silicone oil.
The epoxy resin composition for sealing a semiconductor device according to claim 4, wherein the total of the phenylphenazinium-based compound and the silicone oil is contained in an amount of 0.1% to 3% by weight of the epoxy resin composition for sealing a semiconductor device.
The epoxy resin composition according to claim 1, wherein the inorganic filler contains alumina.
The epoxy resin composition for sealing semiconductor devices according to claim 6, wherein the inorganic filler further comprises silica.
delete A semiconductor device sealed by using the epoxy resin composition for sealing semiconductor elements according to any one of claims 1, 2, and 4 to 7.

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