阅读说明：本技术 正型光阻组成物及图案化聚酰亚胺层的形成方法 (Positive photoresist composition and method for forming patterned polyimide layer ) 是由 张庭玮 鍾明哲 于 2018-09-13 设计创作，主要内容包括：本发明提供一种正型光阻组成物及图案化聚酰亚胺层的形成方法,正型光阻组成物包括甲酚型酚醛树脂、重氮萘醌类感光剂以及有机溶剂；以100重量份的该甲酚型酚醛树脂为基准,该重氮萘醌类感光剂的用量为40重量份至60重量份,该甲酚型酚醛树脂中游离甲酚的含量低于2重量百分比,且该甲酚型酚醛树脂以3.5重量百分比至7重量百分比的四甲基氢氧化铵水溶液溶解的碱性溶解速率低于285埃/秒。本发明的正型光阻组成物对聚酰亚胺剥除剂具有优异的耐化学性,能具体提升光阻层对低介电性的聚酰亚胺层的保护能力,从而优化图案化聚酰亚胺层的工艺与品质。(The invention provides a positive photoresist composition and a method for forming a patterned polyimide layer, wherein the positive photoresist composition comprises a cresol-type phenolic resin, a diazonaphthoquinone photosensitizer and an organic solvent; the diazonaphthoquinone sensitizer is used in an amount of 40 to 60 parts by weight based on 100 parts by weight of the cresol-type phenol resin, the content of free cresol in the cresol-type phenol resin is less than 2% by weight, and the alkaline dissolution rate of the cresol-type phenol resin dissolved in an aqueous tetramethylammonium hydroxide solution of 3.5 to 7% by weight is less than 285 angstrom/sec. The positive photoresist composition has excellent chemical resistance to the polyimide stripper, and can specifically improve the protective capability of the photoresist layer to the polyimide layer with low dielectric property, thereby optimizing the process and the quality of the patterned polyimide layer.)

1. A positive photoresist composition is characterized in that the positive photoresist composition comprises a cresol-type phenolic resin, a diazonaphthoquinone photosensitizer and an organic solvent; the diazonaphthoquinone sensitizer is used in an amount of 40 to 60 parts by weight based on 100 parts by weight of the cresol-type phenol resin, the content of free cresol in the cresol-type phenol resin is less than 2% by weight, and the alkaline dissolution rate of the cresol-type phenol resin dissolved in an aqueous tetramethylammonium hydroxide solution of 3.5 to 7% by weight is less than 285 angstrom/sec.

2. The positive resist composition according to claim 1, wherein the cresol-type phenol resin has a weight average molecular weight of 10000 to 40000.

3. The positive resist composition according to claim 1, wherein the diazonaphthoquinone sensitizer is used in an amount of 45 to 55 parts by weight based on 100 parts by weight of the cresol-type phenol resin.

4. The positive resist composition according to claim 1, wherein the positive resist composition comprises a fluorine-based surfactant.

5. The positive resist composition according to any one of claims 1 to 4, wherein the organic solvent is used in an amount of 100 to 500 parts by weight based on 100 parts by weight of the cresol novolak resin.

6. The positive photoresist composition of claim 5, wherein the organic solvent comprises 2-heptanone, propylene glycol monomethyl ether acetate, ethyl lactate, methyl ethyl ketone, or a combination thereof.

7. A method of forming a patterned polyimide layer, the method comprising:

coating the positive photoresist composition of any one of claims 1 to 6 on a polyimide layer to form a photoresist layer;

exposing and developing the photoresist layer with a developer to obtain a patterned photoresist layer covering a portion of the polyimide layer;

stripping the polyimide layer uncovered by the patterned photoresist layer by using a polyimide stripping agent;

the patterned photoresist layer is removed by using a photoresist remover to form a patterned polyimide layer.

8. The method of claim 7, wherein the developer is an aqueous solution of 3.5 to 7 weight percent tetramethylammonium hydroxide.

9. The method of claim 7, wherein between the developing step and the stripping step, the method comprises hard baking the patterned photoresist layer and the polyimide layer at a temperature of 80 ℃ to 120 ℃.

10. The method of claim 7, wherein the photoresist remover comprises acetone, butanone, 2-pentanone, 3-pentanone, propylene glycol monomethyl ether acetate, ethyl lactate, or combinations thereof.

11. The method of any of claims 7 to 10, wherein the polyimide stripper comprises 1 to 20 weight percent of organic amine compound, 5 to 30 weight percent of organic nitrogen-containing compound, and 50 to 90 weight percent of ethylene glycol aqueous solution.

Technical Field

The present invention relates to a photoresist composition and a patterning method thereof, and more particularly, to a positive photoresist composition and a method for patterning a polyimide layer using the same.

Background

In the RDL (redistribution layer) process in the semiconductor industry, an IC can be applied to different device modules by coating a polyimide film on a silicon wafer, and changing the contact position of an originally designed contact position (I/O pad) through a wafer level metal wiring process and a bump process.

In semiconductor processing, the patterning of the polyimide film can be achieved by dry etching (dry etching) or wet etching (wet etching). Wherein, the dry etching process can remove the polyimide film in the predetermined area by using plasma to realize the purpose of patterning; however, etching a polyimide film with low dielectric constant by plasma changes its electrical properties and causes short circuits.

The wet etching process can be performed by selecting a positive photoresist (positive photoresist) or a negative photoresist (negative photoresist) according to different requirements. Taking a positive photoresist as an example, in a wet etching process, a polyimide film in a specific region can be protected by a positive photoresist film, and after exposure and development steps, a polyimide film which is not protected by the positive photoresist film is stripped by using a specific polyimide stripper, and then the positive photoresist film is stripped to realize the purpose of patterning. However, most of the currently available positive photoresist films have a problem of poor chemical resistance to the polyimide stripper, so that the positive photoresist films cannot protect the polyimide film as expected, and the quality of the patterned polyimide film is affected.

Disclosure of Invention

One of the objectives of the present invention is to improve a positive photoresist composition, which can greatly improve the chemical resistance of the photoresist layer to the existing polyimide stripper, and further improve the protection capability of the photoresist layer to the polyimide layer with low dielectric property, so as to achieve the purpose of patterning the polyimide layer.

In addition, another objective of the present invention is to completely and easily strip the photoresist layer formed by the positive photoresist composition by the photoresist remover, so as to ensure its easy stripping property and avoid the problem of photoresist residue after wet etching.

To achieve the above object, the present invention provides a positive photoresist composition, which comprises: it includes cresol type phenolic resin (cresol-type novolak resin) and diazonaphthoquinoneA light agent and an organic solvent; the diazonaphthoquinone sensitizer is used in an amount of 40 to 60 parts by weight based on 100 parts by weight of the cresol-type phenol resin, the free cresol (free cresol) content of the cresol-type phenol resin is less than 2% by weight, and the cresol-type phenol resin has an Alkaline Dissolution Rate (ADR) of less than 3.5 to 7% by weight of an aqueous tetramethylammonium hydroxide solution

Preferably, in the positive photoresist composition of the present invention, the organic solvent is used in an amount of 100 to 500 parts by weight, preferably 170 to 230 parts by weight, based on 100 parts by weight of the cresol novolak resin; the dosage of the diazonaphthoquinone sensitizer is 45 to 55 weight portions. By controlling the amount of each component in the positive resist composition, the positive resist composition can be prevented from precipitating the photosensitizer, thereby ensuring its applicability.

Preferably, in the positive photoresist composition of the invention, the cresol-type novolac resin is dissolved in 3.5 wt% to 5 wt% of tetramethylammonium hydroxide water solution with ADR lower than that of the cresol-type novolac resin

More specifically, the cresol-type phenol resin has an ADR lower than that when dissolved in a 3.5 wt% aqueous solution of tetramethylammonium hydroxide

Preferably, in the positive photoresist composition of the invention, the content of free cresol in the cresol-type phenolic resin may be less than 1.8 wt%, more preferably between 1 wt% and 1.8 wt%, and still more preferably between 1.5 wt% and 1.7 wt%.

Preferably, in the positive photoresist composition of the invention, the cresol novolac resin has a weight average molecular weight of 10000 to 40000.

Preferably, in the positive resist composition of the present invention, the cresol type novolac resin m-cresol: the molar ratio of p-cresol may be between 3: 7 to 7: 3, or less.

Preferably, the diazonaphthoquinone sensitizer of the present invention is an ester compound obtained by reacting a diazonaphthoquinone compound with a phenol group-containing compound, for example: 1-phenolic-4- (1- (4- (2- (4- (phenolmethyl) phenyl) propyl-2) phenyl) -1- (4-phenolphenyl) ethyl) phenyl diazonaphthoquinone derivatives, tris (4-hydroxyphenyl) methyl diazonaphthoquinone derivatives, tris (4-hydroxyphenyl) ethyl diazonaphthoquinone derivatives, 1, 4-bis [1- (4-hydroxyphenyl) -1-methylethyl ] phenyl diazonaphthoquinone derivatives, but not limited thereto.

Preferably, the positive photoresist composition of the present invention may further comprise an additive such as, but not limited to, fluorine-based surfactant (fluorosurfactant), surface planarization agent, plasticizer, stabilizer, etc., according to different requirements. In the case of a fluorine-based surfactant, when the positive photoresist composition contains a fluorine-based surfactant, the fluorine-based surfactant is used in an amount of 0.1 to 0.5 parts by weight, preferably 0.18 to 0.22 parts by weight, based on 100 parts by weight of the cresol novolak resin. The fluorine-based surfactant may be an oligomer containing a fluorine group, a hydrophilic group and a lipophilic group, for example: commercially available Novec FC-4430 (from 3M), FC-4434 (from 3M), MEGAFAC F-477 (from DIC), and the like, but is not limited thereto.

Preferably, in the positive photoresist composition of the present invention, the applicable organic solvent includes 2-heptanone, propylene glycol monomethyl ether acetate, ethyl lactate, methyl ethyl ketone, or a combination thereof, but is not limited thereto. Preferably, the organic solvent applicable to the scheme is 2-heptanone.

The invention also provides a method for forming a patterned polyimide layer, which comprises the following steps:

coating the positive photoresist composition on a polyimide layer to form a photoresist layer;

exposing and developing the photoresist layer with a developer to obtain a patterned photoresist layer covering a portion of the polyimide layer;

stripping the polyimide layer uncovered by the patterned photoresist layer by using a polyimide stripper (stripper); and

the patterned photoresist layer is removed by using a photoresist remover to form a patterned polyimide layer.

Preferably, in the patterning process of the present invention, the method for coating the positive photoresist composition can be selected from spin coating, spray coating, tape coating, or roll coating, but is not limited thereto. In addition, after the coating step, the positive photoresist composition can be baked at a temperature of 80 ℃ to 120 ℃ to dry it into a photoresist layer.

Preferably, in the patterning process of the present invention, a mask having a specific pattern may be used, and the mask is irradiated with light having an appropriate energy to perform the exposure step; then, a developing step is performed using a developer of an appropriate concentration. The developing method may be a dip developing method or a spray developing method, but is not limited thereto. In addition, after the developing step and before the stripping step, the patterned photoresist layer and the polyimide layer disposed under the patterned photoresist layer may be hard baked at a temperature of 80 ℃ to 120 ℃, preferably at a temperature of 100 ℃ to 110 ℃.

In the patterning process of the present invention, the developing step can be performed by using an existing developer. Preferably, the developer applicable to the present invention may be an aqueous tetramethylammonium hydroxide solution, and the concentration of the tetramethylammonium hydroxide in the aqueous tetramethylammonium hydroxide solution may be 3.5 wt% to 7 wt%, preferably 3.5 wt% to 5 wt%, and more preferably 3.5 wt% or 5 wt%. According to the present invention, if the concentration of the developer is less than 3.5 wt%, the time required for the development step is long, and problems of too narrow line width and photoresist residue are liable to occur; on the contrary, if the concentration of the developer exceeds 7 wt%, defects such as peeling off of the photoresist layer, too wide line width, or poor pattern edge may occur. Therefore, by controlling the concentration of the developer, it is possible to contribute to improving the effect and quality of patterning to obtain a desired line width dimension.

Preferably, after the exposing and developing steps, the polyimide layer not covered with the patterned photoresist layer may be further stripped using a polyimide stripper. Preferably, the polyimide stripper is not particularly limited, and may be selected from various commercially available polyimide strippers, for example: PIC 01-PIC 06 (available from Changlie liter), the composition of the polyimide stripper basically comprises 1-20 wt% of organic amine compounds, 5-30 wt% of organic nitrogen-containing compounds and 50-90 wt% of ethylene glycol aqueous solution.

Preferably, the photoresist remover applicable to the present invention comprises acetone, butanone, 2-pentanone, 3-pentanone, propylene glycol monomethyl ether acetate, ethyl lactate, or a combination thereof, but is not limited thereto.

The positive photoresist composition has excellent chemical resistance to a polyimide stripper, can specifically improve the protection capability of a photoresist layer to a polyimide layer with low dielectric property, has easy stripping performance, and can avoid the problem of photoresist residue in a patterning process. Accordingly, the positive photoresist composition of the present invention can specifically improve the disadvantages of the conventional photoresist composition, thereby optimizing the process and quality of the patterned polyimide layer.

The method for forming the patterned polyimide layer adopts the positive photoresist composition, so the patterned photoresist layer can provide good protection effect for the polyimide layer with low dielectric property in the process, and the unprotected polyimide layer is stripped by the polyimide stripper, thereby optimizing the process and the quality of the patterned polyimide layer.

Drawings

Fig. 1 is a schematic diagram of a process for patterning a polyimide layer according to the present invention.

Wherein, the reference numbers:

10 silicon wafer

20 polyimide layer

20A patterned polyimide layer

30a photoresist layer

30A patterned photoresist layer

Total film thickness of T1, T2 polyimide layer and patterned photoresist layer

M light shield

Detailed Description

The following describes embodiments of the present invention with reference to several examples; those skilled in the art can readily appreciate from the disclosure of the present invention that many modifications and variations can be made to implement or use the present invention without departing from the spirit thereof.

Preparation of positive photoresist composition

Cresol-type novolak resin (cresol-type novolak resin), diazonaphthoquinone derivative of diazonaphthoquinone sensitizer (1-phenol-4- (1- (4- (2- (4- (phenolmethyl) phenyl) propyl-2) phenyl) -1- (4-phenolphenyl) ethyl) phenyl), fluorine-based surfactant (MEGAFAC F-477 available from DIC corporation), and organic solvent (2-heptanone) were mixed in the amounts shown in table 1 below to prepare positive resist compositions of examples 1 to 3 and comparative examples 1 to 4, respectively. The characteristics of the cresol-type phenol resin used in each example and comparative example are described in table 1 below.

The positive resist compositions of the examples and comparative examples differ in that: the amount of cresol-type phenol resin used, the amount of diazonaphthoquinone sensitizer used, and the molar ratio of cresol-type phenol resin intermediate-cresol to p-cresol (shown as "m-cresol: p-cresol molar ratio" in table 1 below), the content of free cresol in the cresol-type phenol resin, the alkaline dissolution rate at which the cresol-type phenol resin was dissolved in a 3.5 wt% aqueous tetramethylammonium hydroxide solution (shown as "ADR (TMAH 3.5%)" in table 1 below), and the weight average molecular weight (Mw) of the cresol-type phenol resin.

Table 1: the amounts of the respective components in the positive resist compositions of examples 1 to 3 and comparative examples 1 to 4 and the cresol-type novolac resin mid-cresol: molar ratio of p-cresol, free cresol content, ADR and Mw.

Method for patterning polyimide layer

The positive photoresist compositions prepared in the above examples 1 to 3 and comparative examples 1 to 4 were selected and sequentially subjected to the following steps of coating, exposure, development, stripping, removal of the photoresist, etc., to form a patterned polyimide layer.

The methods for patterning the polyimide layer in the examples and the comparative examples are substantially the same, and the differences are only that the positive photoresist compositions used are different from each other, so as to compare the effects of the positive photoresist compositions of the different examples and comparative examples applied to the patterned polyimide layer. The detailed method for patterning the polyimide layer is described with reference to fig. 1 and the following steps.

As shown in fig. 1, an 8-inch silicon wafer 10 is prepared, and a low dielectric polyimide layer 20 with a thickness of 100 nm is formed on the 8-inch silicon wafer 10; then spin-coating each positive photoresist composition on the polyimide layer 20 using a spin coater, and heating at 100 ℃ for 2.5 minutes using a baking plate to obtain a uniform photoresist layer 30 having a thickness of 15 μm; then, an exposure step is performed by irradiating appropriate energy on the mask M using an exposure machine, and a development step is performed using a 5% tetramethylammonium hydroxide aqueous solution (developer) to obtain a patterned photoresist layer 30A, the patterned photoresist layer 30A covers a portion of the polyimide layer 20, and the total film thickness of the polyimide layer 20 and the patterned photoresist layer 30A is measured and recorded as "T1"; then, the total film thickness of the polyimide layer 20 and the patterned photoresist layer 30A was measured and recorded as "T2" when it was heated at 110 ℃ for 5 minutes using a baking plate and then immersed in a polyimide stripper (available from changlier as PIC01) previously heated to 50 ℃ for about 3 minutes until a portion of the polyimide layer 20 (i.e., the polyimide layer not covered with the patterned photoresist layer 30A) was stripped; finally, the whole of the silicon wafer 10 whose film residue rate has been measured is immersed in acetone (resist remover) for 1 minute, and then the process of patterning a polyimide layer is completed, thereby forming a patterned polyimide layer 20A on the silicon wafer 10.

The film thicknesses T1 and T2 measured in the foregoing method of patterning a polyimide layer of the respective examples and comparative examples are recorded in the following table 2, respectively, and defined as "residual film ratio" in a ratio of T2/T1, and the results are also shown in the following table 2. The higher the residual film rate, the better chemical resistance of the photoresist layer to the polyimide stripper can be represented, and the protective capability of the photoresist layer to the polyimide layer thereunder can be improved.

In addition, after the patterning process of the polyimide layer was completed in each of examples and comparative examples, the surface of each of the patterned polyimide layers was observed using an optical microscope to confirm whether or not the patterned polyimide layers of examples 1 to 3 and comparative examples 1 to 4 have a photo-resist residual defect, and the observation results are also shown in table 2 below. Observing whether the surface of the patterned polyimide layer has residual photoresist layer can confirm whether the photoresist layer can be completely removed by the photoresist remover commonly used in the market at present so as to confirm the film quality of the patterned polyimide layer.

Table 2: film thicknesses T1, T2 and residual film ratios measured for the polyimide layer patterned using the positive photoresist compositions of examples 1 to 3 and comparative examples 1 to 4.

	T1(μm)	T2(μm)	T2/T1(％)	Photoresist residue analysis
					Example 1	15.0	13.9	93	Is free of
Example 2	15.2	13.1	86	Is free of
					Example 3	15.2	13.3	88	Is free of
Comparative example 1	15.0	9.9	66	Is free of
					Comparative example 2	15.1	9.1	60	Is free of
Comparative example 3	-	-	-	Is free of
					Comparative example 4	15.0	5.7	38	Is free of

According to the results shown in the above tables 1 and 2, the positive photoresist composition simultaneously has (1) 100 parts by weight of cresol-type phenolic resin and 40 to 60 parts by weight of diazonaphthoquinone sensitizer, (2) the content of free cresol in the cresol-type phenolic resin is less than 2 wt%, and (3) the ADR (TMAH 3.5%) of the cresol-type phenolic resin is less than

In the case of the three characteristics, for example, the positive photoresist compositions of examples 1 to 3, the residual film ratio measured can be at least 80%, and the entire photoresist layer can be easily removed by using the photoresist remover commonly used in the market in the patterning process without the problem of photoresist residue. On the contrary, if at least one of the above features is absent, for example, the positive photoresist compositions of the above comparative examples 1 to 4 have a significantly poor residual film ratio, which indicates that the chemical resistance of the photoresist layer formed by using the positive photoresist compositions of the comparative examples 1 to 4 to the polyimide stripper is insufficient, and the underlying polyimide layer cannot be protected as desired, so that the polyimide stripper can etch the polyimide layer covered by the patterned photoresist layer, thereby significantly reducing the residual film ratio, and even more causing the problem of film cracking in the comparative example 3.

As can be seen from further elaboration of the positive resist compositions of the comparative examples, the residual film ratio was only 66% since the content of free cresol in the cresol-type phenol resin in the positive resist composition of comparative example 1 exceeded 2 wt%; the cresol type phenolic resin in the positive photoresist compositions of comparative examples 2 and 3 is the same as that in example 1, but the dosage of the diazonaphthoquinone sensitizer in the positive photoresist composition of comparative example 2 is lower than the limit value of 40 wt%, so the residual film rate of comparative example 2 is only 60%, and the dosage of the diazonaphthoquinone sensitizer in the positive photoresist composition of comparative example 3 exceeds the limit value of 60 wt%, so that the positive photoresist composition of comparative example 3 has the problem of photosensitizer precipitation in the process, and the use is not good; the positive photoresist composition of comparative example 4 had a residual film ratio of only 38% due to the excessively high ADR of the cresol novolak resin.

The experimental results prove that the invention passes the orderThe resist composition simultaneously comprises (1) 100 parts by weight of cresol-type phenolic resin and 40-60 parts by weight of diazonaphthoquinone sensitizer, (2) the content of free cresol in the cresol-type phenolic resin is less than 2 wt%, and (3) the ADR (TMAH 3.5%) of the cresol-type phenolic resin is less than

The three characteristics that the formed photoresist layer has easy stripping performance in the process, avoids the problem of photoresist residue, and can optimize the chemical resistance of the photoresist layer to the polyimide stripping agent, so that the photoresist layer can effectively protect the polyimide layer below the photoresist layer in wet etching, thereby realizing the purpose of patterning the low-dielectric-property polyimide layer.

The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.