TWI495956B - Photosensitive resin composition, electronic element and method of fabricating the same - Google Patents

Description

Photosensitive resin composition, electronic component and method of producing the same

The present invention relates to a photosensitive resin composition, and particularly to a photosensitive resin composition containing a decane compound and an orthoester, a method of producing an electronic component using the photosensitive resin composition, and a method obtained by the method Electronic components.

Generally, the process of the semiconductor integrated circuit is basically carried out by: forming a material layer on the substrate; coating the photosensitive resin composition on the material layer; selectively exposing the photosensitive resin composition and Developing to form a mask pattern; etching the material layer in the presence of the mask pattern to transfer the pattern to the material layer; finally, removing the unnecessary photosensitive resin composition using a stripping agent.

In addition to the photoinitiator, polymerizable monomer, and alkali-soluble resin necessary for exposure and development, the photosensitive resin composition may further contain other components to modulate its properties, such as adhesion promoters, interfaces. Active agents, antioxidants, plasticizers or dyes, and the like. The adhesion promoter can improve the adhesion ability of the photosensitive resin composition to the underlying material layer. However, when the photosensitive resin composition is taken out from the sealed environment and used, the effect of the adhesion promoter may gradually become longer with time. Getting worse. This issue remains to be further studied and revised. good.

The present invention provides a photosensitive resin composition which has excellent stability.

The photosensitive resin composition of the present invention comprises a photoinitiator, an alkali soluble resin, a polymerizable monomer, a adhesion promoter, an orthoester, and a solvent, wherein the adhesion promoter is a decane having a molecular weight of 100 to 30,000. Compound.

In one embodiment of the present invention, the adhesion promoter is a decane compound represented by R ¹ Si(OR ² ) _3-n R ³ _n wherein R ¹ is an alkyl group or has a vinyl group, an epoxy group, an amine group An alkyl group of (amino), (meth)acryloxy, mercapto, decyl or isobutenyl, and R ² is a C ₁ -C ₃ alkyl group, respectively, R ³ is C ₁ -C ₃ alkyl, respectively, and n is 0, 1, or 2.

In one embodiment of the invention, n is zero.

In one embodiment of the invention, the adhesion promoter is γ-(methacryloxy)propyltrimethoxydecane, γ-aminopropyltriethoxydecane or γ-glycidylpropyltrimethoxy. Decane.

In one embodiment of the invention, the orthoester is a compound represented by R ⁴ C(OR ⁵ ) ₃ wherein R ⁴ is hydrogen or C ₁ -C ₃ alkyl, and R ^{5 is} independently C ₁ -C ₄ alkyl.

In one embodiment of the present invention, the content of the adhesion promoter is from 0.1% by weight to 10% by weight based on the total amount of the photosensitive resin composition.

In one embodiment of the present invention, the orthoester content is from 0.1% by weight to 35% by weight based on the total amount of the photosensitive resin composition.

In one embodiment of the present invention, the content of the photoinitiator is from 1% by weight to 10% by weight based on the total amount of the photosensitive resin composition, and the content of the alkali-soluble resin is from 1% by weight to 40% by weight, the content of the polymerizable monomer is from 1% by weight to 40% by weight, and the content of the solvent is from 20% by weight to 80% by weight.

The method of manufacturing an electronic component of the present invention includes the following steps. The substrate is first provided. Next, the aforementioned photosensitive resin composition is applied onto the substrate. Then, the photosensitive resin composition coated on the substrate is cured by light irradiation.

The electronic component of the present invention is produced by the aforementioned method of manufacturing an electronic component.

As described above, the present invention provides a photosensitive resin composition, a method of producing an electronic component using the photosensitive resin composition, and an electronic component obtained by the method. Since the decane compound is contained in the photosensitive resin composition, the adhesion to the substrate is improved, and since the orthoester is further contained, it can be stored in a general environment for a while and maintains adhesion to the substrate.

The above described features and advantages of the present invention will be more apparent from the following description.

In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, a particular numerical range is recited and is equivalent to the disclosure of any numerical value in the range of the value and the numerical range defined by any value in the numerical range, as the The smaller value range is the same. For example, the description of the "content of 10 to 80%" is equivalent to exposing the range of "20% to 50%", regardless of whether it is listed in the manual. Give other values.

Herein, if a group is not specifically indicated to be substituted, the group may represent a substituted or unsubstituted group. For example, "alkyl" can mean a substituted or unsubstituted alkyl group. Further, when a group crown is described by "C _X ", it means that the group has X carbon atoms.

A first embodiment of the present invention provides a photosensitive resin composition comprising a photoinitiator, an alkali soluble resin, a polymerizable monomer, a adhesion promoter, an orthoester, and a solvent, wherein adhesion promotion The agent is a decane compound having a molecular weight of 100 to 30,000. When irradiated, the photoinitiator in the photosensitive resin composition is excited to cause the polymerizable monomer to start polymerization; for example, the photoinitiator may generate radicals upon irradiation, thereby promoting the free radical of the polymerizable monomer. Base polymerization. Thereby, the portion of the photosensitive resin composition that is exposed to light is insoluble in the alkaline solvent, and the portion that is not exposed to light is dissolved in the alkaline solvent, thereby being used as a photoresist.

The photoinitiator can be any suitable compound known in the art. The photoinitiator may be included in an amount of from 1% by weight to 10% by weight, based on the total amount of the photosensitive resin composition, preferably from 1% by weight to 5% by weight, and examples thereof may include, for example, 2,4-trichloro a triazine compound of 2,4-trichloromethyl-(4'-methoxyphenyl)-6-triazine; such as 2,2'-di 2-chlorophenyl)-4,4'-5,5'-tetraphenyl non-imidazole (2,2'-bis(2-chlorophenyl)-4,4'-5,5'-tetraphenyl non-imidazole) a non-imidazole compound; an acetophenone-like compound such as 2-hydroxy-2-methyl-1-phenylpropane-1-one; a diphenyl ketone such as 4,4'-bis(dimethylamino)benzo-phenone; such as 2,4-diethyl thioxene A thioxanthone compound of 2,4-diethyl thioxanthone; such as phosphorus oxidation of 2,4,6-trimethylbenzoyl diphenylphosphine oxide a compound such as 3,3'-carbonylvinyl-7-(diethylamine) (3,3'-carbovinyl-7- A coumarin compound of (diethylamino)), and an O-acyloxime compound such as Irgacure OXE-01 and OXE-02 available from BASF Corporation. A photoinitiator may be used alone or in combination of two or more photoinitiators.

The alkali-soluble resin may be an acid group-containing binder resin, and the structure thereof is not particularly limited, and any alkali-soluble binder resin known in the art to which the present invention pertains may be used, and the content thereof is based on the total amount of the photosensitive resin composition. It may be between 1% and 40% by weight, preferably between 2% and 20% by weight. Further, one alkali-soluble resin may be used alone, or two or more kinds of alkali-soluble resins may be used in combination. For example, the binder resin may be an acrylic resin or an epoxy resin.

The polymerizable monomer may be a monomer which starts the polymerization reaction by the catalysis of the photoinitiator, and the structure thereof is not particularly limited, and any polymerizable monomer known in the art to which the present invention pertains may be used, and the content thereof is photosensitive. The total amount of the resin composition may be between 1% by weight and 40% by weight, and examples thereof may include tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (trimethylolpropane) Triacrylate, TMPTA), pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), 4-methyltetrahydrophthalic anhydride, 3,4-epoxycyclohexylmethyl 3,4- Compounds such as 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexane carboxylate, hexamethoxymethylmelamine, and isophorone diisocyanate. One type of polymerizable monomer may be used alone or two or more types of polymerizable monomers may be used in combination.

The solvent may be any solvent known in the art to which the photosensitive resin composition is dissolved, and the solvent is contained in an amount of 20% by weight to 80% by weight based on the total amount of the photosensitive resin composition. Examples of the solvent may include methyl ethyl ketone (methylethylketone), methylcellosolve, ethylcellosolve, propylcellosolve, ethylene glycol dimethylether, ethylene glycol diethyl ether (ethylene) Glycol diethylether), ethylene glycol methylethylether, propylene glycol dimethylether, propylglycol diethylether, propylene glycol methylethylether, 2-ethoxypropanol 2-ethoxypropanol), 2-methoxypropanol, 3-methoxybutanol, cyclopentanone, cyclohexanone, propylene glycol methyl ether acetate (propyleneglycol methylether acetate, PGMEA), propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, ethoxyethylpropionate (EEP), Ethyl 3-ethoxy propionate, ethyl cellosolve acetate, methyl cetoacetate Llosolve acetate), butyl acetate or dipropylene glycol monomethylether. One solvent may be used alone or two or more solvents may be used in combination.

In order to enhance the adhesion strength between the photosensitive resin composition and the object to be coated (for example, an inorganic material substrate), the photosensitive resin composition of the first embodiment further contains a decane compound as a adhesion promoter. The molecular weight of the decane compound is between 100 and 30,000. However, the adhesion promoter having a small molecular weight can make the development effect better, so the preferred molecular weight of the decane compound is 100 to 1000.

Specifically, the adhesion promoter may be a decane compound represented by R ¹ Si(OR ² ) _3-n R ³ _n wherein R ¹ is an alkyl group or has a vinyl group, an epoxy group, an amine group, or (methyl group) An alkyl group of a propylene methoxy, thiol, decyl or isobutenyl group. R ² is a C ₁ -C ₃ alkyl group, respectively, R ³ is a C ₁ -C ₃ alkyl group, and n is 0, 1 or 2, that is, at least one -OR ² group in one molecule of the decane compound .

In one embodiment, n is 0, that is, the adhesion promoter is a trialkoxydecane.

In one embodiment, the adhesion promoter is gamma-(methacryloxy)propyltrimethoxydecane, gamma-aminopropyltriethoxydecane or gamma-glycidylpropyltrimethoxydecane.

When R ¹ has a decyl group, the adhesion promoter is a decane compound containing two or more decyl groups in one molecule. In this regard, R ¹ may be represented by the formula -R ¹ 'Si(OR ² ) _3-n R ³ _n wherein R ¹ 'is a divalent alkyl group or has a vinyl group, an epoxy group, an amine group, (A) The alkyl group of the acryloxy, thiol or isobutenyl group, and R ² , R ³ and n are as defined in paragraph 0026.

Further, only one type of adhesion promoter may be used, or a plurality of adhesion promoters may be used in combination. For example, a mixture of Silane compound R ¹ is unsubstituted alkyl and R ¹ is a vinyl group, an epoxy group, an amino group, (meth) Bing Xixi group, a thiol group, an alkyl silicon or isobutenyl a decane compound of an alkyl group. The content of the adhesion promoter may be from 0.1% by weight to 10% by weight based on the total amount of the photosensitive resin composition.

In the present embodiment, one possible mechanism by which the adhesion promoter acts in the photosensitive resin composition is as follows. After the photosensitive resin composition is applied onto the inorganic material substrate, the alkoxy group on the partial decane compound may react with moisture in the environment to form a sterol group, and the alkoxy or decyl group may be on the surface of the substrate and/or The functional groups of other decane compounds react to form a covalent bond; the functional groups on the other side of the decane compound form a chemical bond with other components in the resin composition, such as a binder resin or a polymerizable monomer. Therefore, the decane compound can serve as a bridge between the substrate and the resin composition, and enhance the adhesion of the photosensitive resin composition to the inorganic material substrate.

However, the inventors have found that the photosensitive resin composition absorbs a trace amount of moisture in the air or a trace amount of moisture originally present in the solvent, and hydrolyzes the alkoxy group of the decane compound to form hydrazine. The alcohol group, an increase in the sterol group, causes a condensation reaction between the decane compounds to be converted into a polymer. The polymerization that occurs during this period consumes the alkoxy group on the decane compound, detracting from its ability to promote adhesion.

For this reason, the inventors have found that the addition of the orthoester to the photosensitive resin composition contributes to the suppression of the reaction between the decane compound and the water vapor, and the photosensitive resin composition coated on the substrate can remain attached for a long period of time. Therefore, the stability of the photosensitive resin composition is greatly improved, or the photosensitive resin composition can be used for a long period of time after opening, and the adhesion can be maintained, and the use of the photosensitive resin composition can be prolonged. the term.

The orthoester may be a compound represented by R ⁴ C(OR ⁵ ) ₃ wherein R ⁴ is hydrogen or a C ₁ -C ₃ alkyl group, and R ^{5 is} each independently a C ₁ -C ₄ alkyl group. Specifically, the orthoester may be trimethyl orthoformate, trimethyl orthopropionate or tributyl orthoformate, and the content thereof is a photosensitive resin composition. The total amount is from 0.1% by weight to 35% by weight.

It is to be noted that the orthoester is one of the water scavengers, however, it is not the effect of adding any water scavenger to the photosensitive resin composition to improve the stability. In this regard, the following will be proved by experiments.

Other embodiments of the present invention also provide a method of manufacturing an electronic component and an electronic component obtained by the foregoing method. The foregoing manufacturing method includes a lithography step using the aforementioned photosensitive resin composition. Specifically, the substrate is first provided, and then the photosensitive resin composition described above is applied onto the substrate, and then the photosensitive resin composition coated on the substrate is cured by light irradiation. Next, the developing step may be further performed to remove the unexposed portion of the photosensitive resin composition. The foregoing substrate may include any material that may be used in a general semiconductor device process, such as an ITO substrate or a molybdenum (Mo) substrate.

<experiment>

The invention will be described more specifically hereinafter with reference to the embodiments. Although the following experiments are described, the materials used, the amounts and ratios thereof, the processing details, the processing flow, and the like can be appropriately changed without departing from the scope of the invention. Therefore, the invention should not be construed restrictively based on the experiments described below.

The photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 3 were prepared according to the ratio (% by weight) shown in Table 1, wherein the description of each component is as follows: alkali-soluble resin: acrylic resin manufactured by Daxing Materials A binder resin which is a polymer comprising three or more co-blocks, and the co-blocks are structures derived from the following monomers: (A-1) an ethylenically unsaturated monomer having an acid group, (A- 2) an ethylenically unsaturated monomer other than (A-1) and (A-3) an epoxy group-containing unsaturated monomer; a polymerizable monomer: a product of the company UN-904, a product of Changxing Chemical Co., Ltd. Pentaerythritol pentaacrylate (DPHA), 4-methyltetrahydrophthalic anhydride produced by Waterstone, 3,4-epoxycyclohexylmethyl 3,4 -epoxycyclohexane carboxylate), hexamethoxymethylmelamine and isophorone diisocyanate; leveling agent: product F-479 of DIC; photoinitiator: product Irgacure® 907 of BASF Adhesion promoter: γ-(methacryloxy)propyltrimethoxydecane (gamma-methacryl) Oxypropyltrimethoxysilane) or gamma-aminopropyltriethoxysilane or γ-glycidylpropyltrimethoxydecane; Solvent: propylene glycol methyl ether acetate (PGMEA) and 3-B produced by Sanfu Chemical Company Ethoxyethylpropionate (EEP); Original acid ester: trimethyl orthoformate, trimethyl orthopropionate, tributyl orthoformate; other water scavengers: butyl cellosolve and 3-methyl- 3-methyl-3-methoxybutanol.

Each of the photosensitive resin compositions of each of the examples and each of the comparative examples was coated on the ITO substrate and the Mo substrate at the following three time points, and then the adhesion strength was tested: (1) the test was performed immediately after the coating was completed (ie, ("Initial" in Table 2); (2) After the coating is completed, it is allowed to stand at 25 ° C for three days, and then subjected to ultrasonic vibration treatment; (3) After the coating is completed, it is allowed to stand at 45 ° C for 12 hours, and then ultrasonically oscillated. deal with.

The ultrasonic oscillating treatment was performed using a Transonic 300H ultrasonic oscillator at a frequency of 37 kHz for 60 minutes at 50 ° C to test the adhesion of each sample under deteriorating conditions.

The adhesion strength test is performed by a cross-cut method. This is the easiest way to test the adhesion of a coating. The adhesion of the coating was known by a 90-degree cross-cut of the surface of the coating with a standard multi-blade (ZCC 2087 knives manufactured by ZEHNTNER) to observe the peeling of the coating. The test results are also shown in Table 2, where "5B", "4B", "2B", "1B" and "0B" respectively indicate: 5B: the cutting edge is smooth and complete, the coating is completely free of peeling; 4B: cutting line intersection There are small debris, the peeling area is less than 5% of the total area; 2B: the edge of the cutting line, the small square has some or all of the peeling, accounting for 15~35% of the total area; 1B: the edge of the cutting line, some or all of the small square Exfoliation, accounting for 35~65% of the total area; 0B: The edge of the cutting line, the small square has some or all of the peeling, accounting for more than 65% of the total area.

Referring to Table 2, Comparative Example 1 did not add any water scavenger, and therefore the adhesion of the photosensitive resin composition to the substrate after being applied to the substrate and after being left in a general environment for a while, became very poor. Comparative Example 2 and Comparative Example 3 added other water-removing agents, so the degree of adhesion deterioration with the idle time was not as serious as in Comparative Example 1, but it was degraded from "5B" or "4B" immediately after the preparation was completed. Poor "2B" and "1B". As for Experimental Examples 1 to 7 in which an orthoester was added, the photosensitive composition remained even after being placed under a relatively harsh condition for 12 hours. Excellent substrate adhesion, and the effect does not change even if the content of orthoester is greatly changed.

As described above, the present invention provides a photosensitive resin composition, a method for producing an electronic component using the photosensitive resin composition, and an electronic component obtained by the method. Since the decane compound is contained in the photosensitive resin composition, the adhesion to the substrate is improved, and since the orthoester is further contained, the photosensitive resin composition can be stored in a general environment for a while, and is maintained in a pair. Adhesion of the substrate. In this way, the flexibility of the application can be increased.

Although the present invention has been described above by way of examples, it is not intended to limit the invention. Any changes and modifications may be made without departing from the spirit and scope of the invention. Therefore, the scope of protection of this application is subject to the definition of the scope of the patent application attached.

Claims (10)

A photosensitive resin composition comprising: a photoinitiator; an alkali-soluble resin; a polymerizable monomer; a adhesion promoter which is a decane compound having a molecular weight of 100 to 30,000; an orthoester; and a solvent. The photosensitive resin composition according to claim 1, wherein the adhesion promoter is a decane compound represented by R ¹ Si(OR ² ) _3-n R ³ _n , wherein R ¹ is an alkyl group or has ethylene An alkyl group of an epoxy group, an epoxy group, an amino group, a (meth) acryloxy group, a mercapto group, a decyl group or an isobutenyl group, and R ² is C, respectively. ₁ -C ₃ alkyl, R ³ is C ₁ -C ₃ alkyl, respectively, and n is 0, 1 or 2. The photosensitive resin composition as described in claim 2, wherein n is 0. The photosensitive resin composition according to claim 1, wherein the adhesion promoter is γ-(methacryloxy)propyltrimethoxydecane, γ-aminopropyltriethoxydecane or Γ-glycidylpropyltrimethoxydecane. The photosensitive resin composition according to claim 1, wherein the orthoester is a compound represented by R ⁴ C(OR ⁵ ) ₃ , wherein R ⁴ is hydrogen or a C ₁ -C ₃ alkyl group, and R ^{5 is} each independently C ₁ -C ₄ alkyl. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition The adhesion promoter is contained in an amount of from 0.1% by weight to 10% by weight based on the total of the resin composition. The photosensitive resin composition according to claim 1, wherein the orthoester content is from 0.1% by weight to 35% by weight based on the total amount of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the photoinitiator is contained in an amount of from 1% by weight to 10% by weight based on the total of the photosensitive resin composition, and the alkali-soluble resin The content is from 1% by weight to 40% by weight, the content of the polymerizable monomer is from 1% by weight to 40% by weight, and the content of the solvent is from 20% by weight to 80% by weight. A method of producing an electronic component, comprising: providing a substrate; coating the photosensitive resin composition according to any one of claims 1 to 8 on the substrate; and applying the photosensitive film coated on the substrate The resin composition is hardened by irradiation with light. An electronic component produced by the method of manufacturing an electronic component according to claim 9.