KR100651475B1 - Resin for substrate used in imprinting lithography process - Google Patents

Abstract

Provided is a resin composition for an interlayer dielectric of a substrate, which has an optimized curing degree and an optimized curing rate, and realizes a micropattern with high reliability and high precision when applied to an imprinting lithographic process. The resin composition for an interlayer dielectric of a substrate applied to an imprinting lithographic process comprises an epoxy resin, an inorganic filler, a curing agent and a curing accelerator. The resin composition comprises the curing accelerator in an amount of 0.1-2.0 wt% based on the weight of the resin composition, and has a curing degree of 10-70%. The curing accelerator is selected from the group consisting of imidazole compounds, phosphine compounds and mixtures thereof.

Description

Resin for substrate used in imprinting lithography process

1A to 1F are cross-sectional views for explaining a method of forming a circuit pattern on a substrate by a photolithography method of the related art.

2 is a graph showing FT-IR measurement data for evaluating the degree of curing of the resin.

3 is a graph showing the viscosity change of the resin for the substrate according to the content of the curing accelerator in the embodiment of the present invention.

4A to 4C are photographs showing the results of imprinting using the resin for a substrate according to Example 1 of the present invention.

5 is a photograph showing the result of imprinting using the resin for a substrate according to Comparative Example 1 of the present invention.

6 is a photograph showing the result of imprinting using the resin for a substrate according to Comparative Example 2 of the present invention.

※ Explanation of code about main part of drawing ※

1: Insulation layer

2: metal plating layer

3: copper foil

4: photoresist film

5: artwork film

6: window for circuit pattern formation

7: Window for forming via hole fill plating layer

8: metal plating layer

The present invention relates to an interlayer insulating layer resin for a substrate for application to an imprinting lithography process. More specifically, the present invention is an interlayer insulating layer resin for a substrate to be applied to an imprinting lithography process, which can realize a fine pattern with high reliability and high precision when applied to an imprinting lithography method by controlling the degree of curing and curing rate. It is about.

Today, electronic and electric technology is rapidly evolving for more information storage, faster information processing and transmission, and simpler communication network to keep pace with the 21st century's high information and communication society.

In particular, under the condition of the finiteness of a given information transmission rate, as a method capable of meeting these requirements, a method for implementing the components as small as possible while increasing reliability and providing new functionality has been proposed.

As described above, in accordance with the trend of light and short size of electronic products, fine patterns, miniaturization, and packaging of printed circuit boards are also progressing simultaneously. Accordingly, a circuit having excellent signal processing capability in a smaller area may be implemented. For this purpose, there is a need for manufacturing high density substrates (line / space ≦ 10 μm / 10 μm, microvia <30 μm).

In particular, FCBGA, which serves as a medium between the semiconductor and the main board according to high speed, high capacity, and mobile of the semiconductor, is also increasingly required for a thin substrate and a high density circuit.

In the prior art, a photolithography method is used as a method of forming a circuit pattern of such a high density substrate.

1A to 1F are schematic cross-sectional views illustrating a method of forming a circuit pattern on a substrate according to the conventional photolithography method.

First, after forming the metal plating layer 2 on the board | substrate which consists of the insulating layer 1 and the copper foil layer 3 (FIG. 1A), the photoresist film, for example, the dry film 4 is apply | coated on it. (B) using the artwork film 5 designed according to which the circuit pattern is to be formed (Fig. 1c), a window 6 and a via hole peel plating layer for forming the circuit pattern through a normal exposure and development process are formed. The window 7 for forming is formed (FIG. 1D). After forming the metal plating layer 8 on the windows 6 and 7 formed from this through a normal plating process (FIG. 1E), the dry film 4 is peeled off and a circuit pattern is formed.

In the prior art as described above, a pattern having a desired shape is formed through a general photolithography method using an insulating material having an appropriate degree of curing (generally B-stage). However, when applying this method, it is known that there are many problems to form a fine pattern of about 10 μm.

In order to solve these problems, imprinting lithography methods have been tried in recent years. In order to form the circuit pattern by applying the imprinting lithography method, a resin for a substrate also needs an imprintable material suitable for this method.

In particular, it is expected that the general interlayer insulating material products commonly used as the substrate resin of FCBGA may be manufactured through the plating process after forming the fine pattern, but the degree of curing of the substrate resin supplied is always Since it is determined, there are limitations in the imprinting lithography process and problems in release property arise. This is because in order to apply the imprinting lithography method, the degree of curing of the resin for the substrate must be within a certain range that is advantageous for the process, and the curing rate is also within the optimum range, which is advantageous to realize the pattern completely. .

In addition, since most of the resin for the substrate is an epoxy-based thermosetting polymer, it is a partially cured state (B-stage) having a certain degree of curing, and the lower the degree of curing, the more favorable the pattern formation, but the deformation of the pattern during post-cure The higher the degree of hardening, the higher the degree of curing, the lower the possibility of deformation of the pattern, but harder to form a fine pattern is difficult to form a lot.

Therefore, there is an urgent need for a resin for a substrate that can satisfy the specific physical properties required for imprinting for the imprinting lithography method.

Accordingly, in the present invention, extensive research has been conducted to solve the problems described above. As a result, an interlayer insulating layer resin for an imprint-enabled substrate is controlled by controlling the curing degree and curing rate to an appropriate level so as to be suitable for forming patterns through an imprinting lithography method. The present invention was completed based on this.

Accordingly, it is an object of the present invention to provide an interlayer insulating layer resin for a substrate having an appropriate degree of curing when the imprinting method is applied, so that a fine circuit pattern can be easily implemented.

Another object of the present invention is an interlayer for a substrate having an appropriate curing speed so that deformation of the pattern due to shrinkage phenomenon due to crosslinking does not occur during post-curing process when the imprinting method is applied. An insulating layer resin is provided.

According to an aspect of the present invention, in the interlayer insulating layer resin for a substrate for application to an imprinting lithography process, including an epoxy resin, an inorganic filler, a curing agent and a curing accelerator, wherein the curing accelerator is 0.1 to 2.0 of the insulating layer resin An interlayer insulating layer resin for a substrate for application to an imprinting lithography process comprising an amount by weight and having a curing degree of 10 to 70% is provided.

Here, the epoxy resin may be selected from the group consisting of bisphenol A epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, rubber modified epoxy resin, phosphorus flame retardant epoxy resin and mixtures thereof.

The curing accelerator may be selected from the group consisting of imidazole compounds, phosphine compounds and mixtures thereof.

The inorganic filler may be contained in an amount of 20 to 70% by weight of the insulating layer resin.

According to another aspect of the present invention, there is provided a copper foil laminate in which copper foil (Cu Foil) is laminated on at least one surface of the insulating layer resin.

According to yet another aspect of the present invention, it comprises an insulating layer including an outer circuit layer, at least one inner circuit layer, and a conductive hole formed for electrical conduction between each circuit layer, wherein the insulating layer is A printed circuit board is provided, which is the insulating layer resin.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

As described above, according to the present invention, the degree of curing (%) and curing rate of the resin are controlled so that the micropattern can be easily realized with high reliability and high precision when the imprinting method is applied as compared to the resin for the substrate. It is characterized by controlling the amount of curing accelerator used and B-stage manufacturing conditions.

In the present invention, an imprintable material having an appropriate level of curing and an appropriate curing rate has been invented in order to form a pattern by applying imprinting lithography, and the identification of the degree of curing of a resin for a substrate for an optimal imprinting process, and -The optimum curing rate and the curing rate at which deformation of the pattern does not occur due to shrinkage due to crosslinking during post-curing were investigated.

In particular, what is different from the conventional imprinting lithography substrate is that the present invention has been described with an emphasis on the imprintable degree of curing (%) and the curing rate of the resin for the substrate.

Substrate resin according to the present invention contains an epoxy resin, an inorganic filler, a curing agent and a curing accelerator as essential components.

The epoxy resin usable in the present invention may be selected from the group consisting of bisphenol A epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, rubber modified epoxy resin, phosphorus flame retardant epoxy resin, and mixtures thereof. It is not specifically limited to this.

The inorganic filler usable in the present invention is not particularly limited as long as it is known in the art. The amount of the inorganic filler used is 20 to 70% by weight of the insulating layer resin is most suitable in consideration of strength characteristics, CT, modulus characteristics and the like.

The curing agent usable in the present invention is not particularly limited as long as it is known in the art, and its amount is typically such that the equivalent ratio of the curing agent equivalent: epoxy resin is 0.5: 1 to 2: 1.

The curing accelerator usable in the present invention may be selected from the group consisting of imidazole compounds such as 2-methyl imidazole, phosphine compounds such as 3-phenyl phosphine and mixtures thereof, but are not particularly limited thereto. no.

In particular, the imidazole compound, 2-ethyl-4-methyl imidazole, 1- (2-cyanoethyl) -2-alkyl imidazole, 2-phenyl imidazole, 2-phenyl imidazole, 1-methyl Imidazole, 2-methyl imidazole, 2-phenyl-4-methyl imidazole, cyanoethylation derivatives thereof, carboxylic acid derivatives, hydroxyl group derivatives, etc. may be exemplified as exemplary components, but is not particularly limited thereto. It is not.

Content of the hardening accelerator in the resin for board | substrates of this invention is 0.1 to 2.0 weight%.

When the content of the curing accelerator is less than 0.1% by weight, the curing rate is excessively lowered and hardening does not proceed much, so that the molecular weight of the resin is not sufficiently high due to the curing reaction, and thus the mechanical strength is low and brittleness is large.

When the content of the curing accelerator exceeds 2.0% by weight, the curing proceeds too much, the initial viscosity is too high, the resin flow is relatively insufficient, the pattern transfer is not complete, and the imprinting method is applied. There is a disadvantage that excessive process pressure is required.

The resin for the substrate of the present invention should also have a degree of curing of 10 to 70%, preferably 15 to 30%.

When the degree of curing of the resin is less than 10%, the imprinting process takes a long time, and the flowability is high and flows out of the stage during imprinting and the deformation of the pattern is severe. In addition, in the case of more than 70%, the flowability of the resin composition is lowered, so that the transfer of the pattern is not effective, and defects are likely to occur, and residues are left when vias are formed. It is necessary.

The degree of curing is not particularly limited and may be performed according to what is known in the art.

For example, there is a method of adjusting the curing temperature, a method of adjusting the amount of curing accelerator, a method of adjusting the curing time, and the like.

The substrate resin of the present invention may further include other additives such as fillers added to a conventional substrate resin within a range that does not impair the specific physical properties desired in the present invention.

The above-described interlayer insulating layer resin for a substrate of the present invention can be used as a resin laminated plate by laminating a plurality of sheets in accordance with a conventional lamination step according to the application purpose. Such an interlayer insulating layer resin may also produce a copper foil laminate by laminating copper foil (Cu Foil) together on one or both sides of the resin laminate as known by a person skilled in the art in manufacturing the resin laminate.

In addition, the copper-clad laminate or the resin laminated plate may be applied to a conventional printed circuit board manufacturing process and may be used as an outer layer or an inner layer substrate, or an insulating layer between each circuit layer.

As described above, in the present invention, when applied to the imprinting lithography method, to have an optimum degree of curing (%) by adjusting the manufacturing conditions of the B-stage film to facilitate the implementation of the fine circuit pattern with high reliability and high precision. There is provided a resin for an imprint-able substrate which is controlled to adjust the initial viscosity and at the same time adjust the content of the curing accelerator to have an optimum curing rate.

In particular, in the present invention, unlike the conventional use of the curing accelerator merely to cure the resin, in the control of the content of the curing accelerator, the imprinting property that is sensitively changed depending on the curing accelerator of the resin and the content of the curing accelerator In consideration of the above, the specific amount of the curing accelerator added must be selected.

The resin for a substrate of the present invention described above is applicable not only to a normal substrate but also to an imprinting lithography process for producing a substrate for FCBGA having a fine pattern of about 10 μm.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.

Example 1

To prepare a resin solution for the substrate as shown in the composition shown in Table 1 and 2 as follows, it was film cast on a PET film and treated for 30 minutes at 80 ℃, 110 minutes 5 ℃ in a convection oven (convection oven) To produce a semi-cured resin.

Base resin composition (% by weight) Total amount of mixture (g) Solvent (g) Solution (g) YD-011 YDPN- 638 YDCN- 500-10P KDP- 550 KR-207 B6-A 20.00 13.30 13.30 40.30 13.1 100 31 131.03 B6-B 20.00 13.30 13.30 40.30 13.1 100 31 131.03

YD-011 (bisphenol A type epoxy resin, Kukdo Chemical)

YDPN-638 (phenol phenolic epoxy resin, Kukdo Chemical)

YDCN-500-10P (Cresol novolac epoxy resin, Kukdo Chemical)

KDP-550 (Phosphorus Flame Retardant Epoxy Resin, Kukdo Chemical)

KR-207 (Rubber modified epoxy resin, Kukdo Chemical)

Hardener type Curing agent addition amount (g) Curing accelerator added amount (wt%) equivalent weight Softening point (℃) B6-A Bisphenol- Noble 38.14 0.5 120 ± 2 129.1 B6-B Bisphenol- Noble 38.14 0.25 120 ± 2 129.1

1) 0.5 ~ 2.0㎛ spherical filler was used to improve the physical properties of the epoxy resin, 38% by weight of the resin was used.

2) 2-Methyl imidazole, a curing accelerator, was added by diluting 20% by weight in 2-methoxy ethanol (methyl-cellulose solution).

3) B6-A and B6-B are the same under all conditions, and only the amount of 2-methyl imidazole which is a curing accelerator is different.

4) The above example is just one embodiment, and the resin composition, the amount of the solvent, the type and amount of the curing agent can be variously changed.

The quantitative measurement of the degree of cure was analyzed by comparing the peak intensity of the epoxy ring of the FT-IR before curing and during curing as shown in FIG.

※ Viscosity change measurement of resin for substrate according to amount of curing accelerator

Curing progress was determined by removing the semi-cured epoxy resin cast on PET film and observing the viscosity increase with time at 110 ° C. using an ARES reometer from TA instruments.

In case of B6-A, a high viscosity was reached in a shorter time, and this increased the curing rate due to the addition of a hardening accelerator, and it can be seen that rapid curing occurred quickly.

Comparative Example 1

As the thermosetting conditions, except that the treatment for 30 minutes at 80 ℃, 10 minutes at 110 ℃ was carried out in the same manner as B6-A of Example 1 to prepare a semi-cured resin.

Comparative Example 2

A semi-cured resin was prepared in the same manner as B6-A of Example 1, except that 0.05 wt% of a curing accelerator was used.

Various physical properties of the resins obtained in Example 1 B6-A and Comparative Examples 1 and 2 were measured, and the results are shown in Table 3 below.

Curing accelerator Curing condition Sec (at G '?? G ") Cure Speed (Tilt) Gel time (sec) Example 1 Spl. 1 (standard) 0.5% by weight 80 ° C (30 minutes) / 110 ° C (5 minutes) 233 73 262 Comparative Example 1 Spl. 2 (over hardening) 0.5% by weight 80 ° C (30 minutes) / 110 ° C (10 minutes) 70 100 18 Comparative Example 2 Spl. 3 (Use a small amount of hardening accelerator) 0.1% by weight 80 ° C (30 minutes) / 110 ° C (5 minutes) * 1.7 2109

* Not measurable due to high degree of cure

On the other hand, micropattern scanning micrographs obtained by applying the resin obtained in Example 1 B6-A to the imprinting lithography process and patterning are shown in FIGS. 4A to 4C, respectively. 4A to 4C are SEM images of substrates obtained from an imprinting process performed to fabricate test patterns, respectively.

In addition, micropattern scanning micrographs obtained by applying the resins obtained in Comparative Examples 1 and 2 to the imprinting lithography process, respectively, are shown in FIGS. 5 and 6, respectively.

Referring to Table 3 and Figures 4 to 6, Comparative Example 1 (Spl. 2) on the basis of the embodiment (Spl. 1) of the present invention is the same amount of the curing accelerator, but the heat treatment at 110 ℃ for a long time Compared to Example 2 (Spl. 3), but the heat treatment conditions were the same as in Example, but the amount of the curing accelerator was added to only 0.05% by weight of the curing accelerator, so that the curing was not progressed much. It is a state.

As shown in Figures 4a to 4c, the resin for the substrate according to the present invention was applied to the imprint lithography method, even if the line / space to implement a fine pattern of 10㎛ / 10㎛ fine circuit pattern was formed very precisely You can check it.

On the other hand, as a result of imprinting using a resin having undergone much hardening (Comparative Example 1), imprinting was performed due to the high imprinting pressure, but the initial viscosity was too high, so that the resin flow was relatively low, so that the pattern transfer was completely completed. You can see that it does not.

In addition, as a result of imprinting using a resin (Comparative Example 2) containing a relatively small amount of a curing accelerator, the curing rate was slowed and the curing proceeded slightly, indicating a degree of curing of about 3%. Therefore, the molecular weight of the resin was not sufficiently high due to the curing reaction, the brittleness was large, and the following results were obtained. That is, the curing rate was too slow, the curing did not proceed sufficiently, the brittleness of the resin (brittle) was torn apart.

Although the present invention has been described in detail through specific examples, this is for explaining the present invention in detail, and a resin for a substrate for applying to an imprinting lithography process according to the present invention is not limited thereto. It is apparent that modifications and improvements are possible by those skilled in the art.

As described above, according to the present invention, the optimum degree of curing (%) through the control of the manufacturing conditions of the B-stage film to facilitate the implementation of the fine circuit pattern with high reliability and high precision when applied to the imprinting lithography method There is provided a resin for an imprint-enabled substrate which is controlled to have an initial viscosity to control the initial viscosity, and at the same time to adjust the content of the curing accelerator to have an optimum curing speed.

The resin for a substrate according to the present invention is imprinted for forming a fine pattern by controlling the degree of curing and the content of the curing accelerator appropriately in consideration of the imprinting property which is sensitively changed according to the change in the content of the curing accelerator along with the degree of curing of the resin. In addition to this easy, it is possible to prevent the deformation of the pattern due to the shrinkage phenomenon during the post-curing process when applying the imprinting method.

In particular, since the resin for a board | substrate of this invention is applicable not only to a normal board | substrate but also to the imprinting lithography process for manufacturing the board | substrate for FCBGA which has a fine pattern about 10 micrometers, the utility is anticipated.

All modifications and variations of the present invention fall within the scope of the present invention, and the specific scope of protection of the present invention will be apparent from the appended claims.

Claims (6)

An interlayer insulating layer resin for a substrate for application to an imprinting lithography process, comprising an epoxy resin, an inorganic filler, a curing agent and a curing accelerator, wherein the curing accelerator is included in an amount of 0.1 to 2.0% by weight of the insulating layer resin, An interlayer insulating layer resin for a substrate for application to an imprinting lithography process, wherein the degree of curing is 10 to 70%. The method of claim 1, wherein the epoxy resin is selected from the group consisting of bisphenol A epoxy resin, cresol novolac epoxy resin, phenol novolac epoxy resin, rubber modified epoxy resin, phosphorus flame retardant epoxy resin, and mixtures thereof. An interlayer insulating layer resin for a substrate to be applied to an imprinting lithography step. The interlayer insulating layer resin for a substrate for application to an imprinting lithography process according to claim 1, wherein the curing accelerator is selected from the group consisting of imidazole compounds, phosphine compounds and mixtures thereof. The interlayer insulating layer resin for a substrate for application to an imprinting lithography process according to claim 1, wherein the inorganic filler is contained in an amount of 20 to 70% by weight of the insulating layer resin. Copper foil laminated board in which copper foil (Cu Foil) was laminated | stacked on at least one surface of the insulating-layer resin in any one of Claims 1-4. And an insulating layer including an outer circuit layer, at least one inner circuit layer, and a conductive hole formed for electrical conduction between the respective circuit layers, wherein the insulating layer is any one of claims 1 to 4. Printed circuit board, characterized in that the insulating layer resin according to claim.

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