阅读说明：本技术 一种激光蚀刻保护膜的水溶性树脂组合物 (Water-soluble resin composition for laser etching protective film ) 是由 马晓东 于 2021-04-07 设计创作，主要内容包括：本发明公开一种激光蚀刻保护膜的水溶性树脂组合物,主要包括以下重量份的组分：水性聚烯烃25～31份,水溶性高分子聚合物15～25份,水性光引发剂6～10份,附着力促进剂9～12份,助剂0.1～3份,去离子水47～55份,填料1～5份。本发明提供的激光蚀刻保护膜的水溶性树脂组合物,发挥多组分混合树脂协同作用,形成的保护膜耐热性好,激光辐照下收缩率低,渗透性高、表面粗糙度低,即使是具有凹凸结构的半导体衬底也没有缝隙,对波长小于355nm的深紫外光吸收率高,形成的开口边缘清晰；同时,本发明保护膜易于去除,能耗低,一次扫描即可清除干净不残留,对环境友好,特别适用于半导体凹凸衬底表面激光蚀刻。(The invention discloses a water-soluble resin composition of a laser etching protective film, which mainly comprises the following components in parts by weight: 25-31 parts of water-based polyolefin, 15-25 parts of water-soluble high-molecular polymer, 6-10 parts of water-based photoinitiator, 9-12 parts of adhesion promoter, 0.1-3 parts of auxiliary agent, 47-55 parts of deionized water and 1-5 parts of filler. The water-soluble resin composition of the laser etching protective film provided by the invention exerts the synergistic effect of multi-component mixed resin, the formed protective film has good heat resistance, low shrinkage rate under laser irradiation, high permeability and low surface roughness, even a semiconductor substrate with a concave-convex structure has no gap, the absorptivity to deep ultraviolet light with the wavelength less than 355nm is high, and the formed opening edge is clear; meanwhile, the protective film is easy to remove, low in energy consumption, clean and free of residue after one-time scanning, environment-friendly and particularly suitable for laser etching of the surface of the concave-convex substrate of the semiconductor.)

1. A water-soluble resin composition for laser etching protective film is prepared from water-soluble polyolefine, water-soluble high-molecular polymer, water-soluble photoinitiator, adhesion promoter, assistant, deionized water and filler.

2. The water-soluble resin composition for a laser etching protective film according to claim 1, wherein the water-soluble resin composition for a laser etching protective film comprises the following components in parts by weight: 25-31 parts of water-based polyolefin, 15-25 parts of water-soluble high-molecular polymer, 6-10 parts of water-based photoinitiator, 9-12 parts of adhesion promoter, 0.1-3 parts of auxiliary agent, 47-55 parts of deionized water and 1-5 parts of filler.

3. The water-soluble resin composition for a laser etching protective film according to claim 2, wherein the water-soluble resin composition for a laser etching protective film comprises the following components in parts by weight: 28 parts of water-based polyolefin, 20 parts of water-soluble high-molecular polymer, 8 parts of water-based photoinitiator, 10.5 parts of adhesion promoter, 1.5 parts of auxiliary agent, 51 parts of deionized water and 3 parts of filler.

4. The water-soluble resin composition for a laser-etched protective film according to claim 2 or 3, wherein the water-soluble high molecular polymer is one or more selected from the group consisting of polyacrylic acid, polymethacrylic acid, polyacrylamide, poly-2-acrylamido-2-methylpropanesulfonic acid, polyvinylpyrrolidone, and polystyrenesulfonic acid.

5. The water-soluble resin composition for a laser-etched protective film according to claim 2 or 3, wherein the aqueous photoinitiator is a BASF photoinitiator 4265.

6. The water-soluble resin composition for laser-etched protective film according to claim 2 or 3, wherein the auxiliary agent comprises a leveling agent, an antifoaming agent, an ultraviolet absorber; the filler is water-soluble graphene or silane.

7. The method for preparing the water-soluble resin composition of the laser etching protective film according to claim 1, wherein the water-soluble polyolefin and the water-soluble high molecular polymer are mixed and uniformly dispersed by high-speed stirring, and then the adhesion promoter, the auxiliary agent, the deionized water and the filler are added to continue the high-speed stirring and dispersion.

8. A method for removing the water-soluble resin composition for laser-etched protective films according to claim 1, wherein the protective film is removed by laser irradiation etching.

9. The method of claim 8, wherein the laser irradiation is performed by irradiating a laser beam having a wavelength of 355nm or less, a pulse period of 20 to 45kHz, an output of 0.1 to 2W, and a scanning speed of 100 to 200 mm/s.

10. Use of the water-soluble resin composition according to claim 1 for forming a laser etching protective film on a semiconductor element substrate.

Technical Field

The present invention relates to a water-soluble resin composition, and more particularly, to a water-soluble resin composition for a laser etching protective film.

Background

In manufacturing a semiconductor device, a micro-process of photolithography using a photoresist has been performed. The micro-processing is a processing method which includes forming a thin photoresist layer on a semiconductor substrate such as a silicon wafer, etc., etching a pattern for a semiconductor device on the mask pattern by irradiating actinic radiation such as ultraviolet rays to the mask pattern, developing it to obtain a photoresist pattern, and etching the substrate using the photoresist pattern as a protective layer, thereby forming a fine concave-convex structure corresponding to the pattern on the substrate surface.

In the micro-processing method, a planar substrate is generally used as a semiconductor substrate. When a photoresist pattern is formed on a substrate surface, if the substrate surface has low flatness, reflected light from the substrate surface is irregularly refracted, and it becomes difficult to form a pattern with high precision.

On the other hand, there are cases where it is necessary to form a concave-convex structure on the surface of the substrate. Specifically, a substrate having a concave-convex structure is formed on a surface of the substrate by using photolithography or the like, a coating layer containing, for example, silicon dioxide is further formed on the surface, and the coating layer is further processed by photolithography to form a pattern. In this case, when a layer is directly formed on the surface of a substrate having a textured structure, the textured structure on the surface of the substrate causes unevenness in the thickness of the coating layer and the pattern finally obtained has low accuracy.

In order to solve these problems, when a substrate surface having a concavo-convex structure is used, a method has been studied which includes coating a composition containing an organic polymer on the substrate surface and filling the organic polymer in the concave portion of the substrate to form a flat surface, and the layer filling the concave portion of the substrate to planarize the surface is referred to as a sacrificial layer.

Disclosure of Invention

The invention aims to provide a water-soluble resin composition for a laser etching protective film, which has the advantages of good heat resistance, high permeability, low surface roughness, easy removal and environmental protection on the basis of the prior art.

The object of the invention can be achieved by the following measures:

a water-soluble resin composition for laser etching protective film is prepared from water-soluble polyolefine, water-soluble high-molecular polymer, water-soluble photoinitiator, adhesion promoter, assistant, deionized water and filler.

The water-soluble resin composition mainly comprises the following components in parts by weight: 25-31 parts of water-based polyolefin, 15-25 parts of water-soluble high-molecular polymer, 6-10 parts of water-based photoinitiator, 9-12 parts of adhesion promoter, 0.1-3 parts of auxiliary agent, 47-55 parts of deionized water and 1-5 parts of filler.

In a preferred embodiment, the water-soluble resin composition mainly comprises the following components in parts by weight: 28 parts of water-based polyolefin, 20 parts of water-soluble high-molecular polymer, 8 parts of water-based photoinitiator, 10.5 parts of adhesion promoter, 1.5 parts of auxiliary agent, 51 parts of deionized water and 3 parts of filler.

Preferably, the water-soluble high molecular polymer is one or more of polyacrylic acid, polymethacrylic acid, polyacrylamide, poly-2-acrylamido-2-methylpropane sulfonic acid, polyvinylpyrrolidone and polystyrene sulfonic acid.

Preferably, the aqueous photoinitiator is a basf photoinitiator 4265.

Preferably, the auxiliary agent comprises a leveling agent, a defoaming agent and an ultraviolet absorbent; the leveling agent is one of Keying chemical KYC616, Okono ANK1033 and Bike chemical BYK 333; the antifoaming agent is KMT3006 or Digao 845; the ultraviolet absorber is basf 1130.

Preferably, the filler is water-soluble graphene or silane.

A preparation method of the water-soluble resin composition for the laser etching protective film comprises the following steps: firstly, mixing the water-based polyolefin and the water-soluble high molecular polymer, uniformly stirring at a high speed for dispersion, and then adding the adhesion promoter, the auxiliary agent, the deionized water and the filler for continuous high-speed stirring and dispersion.

The present invention also provides an application process of the water-soluble resin composition for forming a laser etching protective film on a semiconductor element substrate, comprising:

(1) coating a water-soluble resin composition for forming a laser etching protective film on a semiconductor substrate having a concavo-convex structure such as a silicon/silicon oxide substrate, a silicon nitride substrate, a silicon wafer substrate, a glass substrate and an ITO substrate by a spin coater;

(2) pre-baking the coating in an inert atmosphere, wherein the heating temperature is 120-180 ℃, and the curing time is 60-90 minutes, so as to form a protective film layer;

(3) exposing and developing the protective film to form a predetermined pattern;

(4) selectively performing a protective film removing step;

preferably, the developer is selected from a mixed solution of water and a surfactant or an alkaline water.

The invention also provides a method for eliminating the water-soluble resin composition of the laser etching protective film, which comprises at least one step selected from dissolution, plasma treatment, laser irradiation and thermal decomposition, and preferably removes the protective film by laser irradiation.

Preferably, the laser irradiation adopts a laser beam with the irradiation wavelength less than or equal to 355nm, a pulse period of 20-45 kHz, an output of 0.1-2W and a scanning speed of 100-200 mm/s.

In order to improve the resistance of the protective film under laser etching, the invention adopts water-based polyolefin, has excellent thermal stability, does not explode under laser etching, has almost no residue, and ensures that the edge is neat.

The invention has the beneficial effects that:

the water-soluble resin composition of the laser etching protective film provided by the invention exerts the synergistic effect of multi-component mixed resin, the formed protective film has good heat resistance, low shrinkage rate under laser irradiation, high permeability and low surface roughness, even a semiconductor substrate with a concave-convex structure has no gap, the absorptivity to deep ultraviolet light with the wavelength less than 355nm is high, and the formed opening edge is clear; meanwhile, the protective film is easy to remove, low in energy consumption, clean and free of residue after one-time scanning, environment-friendly and particularly suitable for laser etching of the surface of the concave-convex substrate of the semiconductor.

Detailed Description

The present invention will be further described with reference to the following examples. The scope of the invention is not limited to the following examples.

The preparation method of the resin composition in each example comprises the following steps: firstly, mixing the water-based polyolefin and the water-soluble high molecular polymer, uniformly stirring at a high speed for dispersion, and then adding the adhesion promoter, the auxiliary agent, the deionized water and the filler for continuous high-speed stirring and dispersion.

Example 1

The water-soluble resin composition mainly comprises the following components in parts by weight: 25 parts of water-based polyolefin, 15 parts of water-soluble high-molecular polymer, 6 parts of water-based photoinitiator, 9 parts of adhesion promoter, 0.1 part of auxiliary agent, 47 parts of deionized water and 1 part of filler.

Wherein the water-soluble high molecular polymer is polyacrylamide and poly-2-acrylamide-2-methyl propane sulfonic acid; the aqueous photoinitiator is a basf photoinitiator 4265; the leveling agent is KYC616 in chemical science filling; the antifoaming agent is KMT 3006; the ultraviolet absorbent is basf 1130; the filler is water-soluble graphene.

Example 2

The water-soluble resin composition mainly comprises the following components in parts by weight: 28 parts of water-based polyolefin, 20 parts of water-soluble high-molecular polymer, 8 parts of water-based photoinitiator, 10.5 parts of adhesion promoter, 1.5 parts of auxiliary agent, 51 parts of deionized water and 3 parts of filler.

Wherein the water-soluble high molecular polymer is polyacrylic acid or polymethacrylic acid; the aqueous photoinitiator is a basf photoinitiator 4265; the leveling agent is Okono ANK 1033; the antifoaming agent is KMT 3006; the ultraviolet absorbent is basf 1130; the filler is water-soluble graphene.

Example 3

The water-soluble resin composition mainly comprises the following components in parts by weight: 31 parts of water-based polyolefin, 25 parts of water-soluble high-molecular polymer, 10 parts of water-based photoinitiator, 12 parts of adhesion promoter, 3 parts of auxiliary agent, 55 parts of deionized water and 5 parts of filler.

Wherein the water-soluble high molecular polymer is polyvinylpyrrolidone and polystyrene sulfonic acid; the aqueous photoinitiator is a basf photoinitiator 4265; the leveling agent is a Pico chemical BYK 333; the antifoaming agent is digao 845; the ultraviolet absorbent is basf 1130; the filler is silane.

Comparative example 1

The same procedure as in example 1 was repeated except that the water-soluble polyolefin in example 1 was removed and the amount of the water-soluble high-molecular weight polymer was increased to 40 parts.

Comparative example 2

The water-soluble high molecular polymer in example 2 was removed and the amount of the water-soluble polyolefin was increased to 48 parts, as in example 2.

Comparative example 3

The aqueous photoinitiator of example 3 was replaced with a commercially available conventional photoinitiator, such as ziyue bioaqueous UV photoinitiator 2959, and the remainder of example 3.

Comparative example 4

The aqueous photoinitiator from example 3 was removed and the amount of deionized water was increased to 65 parts, as in example 3.

The application method comprises the following steps:

(1) coating a water-soluble resin composition for forming a laser etching protective film on a semiconductor substrate by a spin coater;

(2) pre-baking the coating in an inert atmosphere, heating to 150 ℃, and curing for 75 minutes to initially form a protective film layer;

(3) exposing and developing the protective film to form a predetermined pattern;

(4) removing the protective film coating by laser irradiation, and adopting a laser beam with the irradiation wavelength of 355nm, a pulse period of 45kHz, 2W output and a scanning speed of 200 mm/s;

the test results are shown in Table 1

TABLE 1

The resolution is the minimum pattern size that can form 0.1 μm line width and line spacing patterns with a line width ratio of 1: 1 after development.

After development, the protective film strips were observed by electron micrographs and rated according to the following criteria: A. the line walls are almost linear; B. bending was observed for some of the line sidewalls; C. a curve was observed across the line sidewall; D. severe bending was observed in the line sidewalls

After etching, the shape of the remaining protective film lines was observed by electron micrograph and rated according to the following criteria: A. the pattern has gaps and a twist number of 0-1/cm²(ii) a B. Having a gap in the patternAnd the number of twists is 2-3/cm²(ii) a C. The number of gaps and twists in the pattern was 4/cm²(ii) a D. The number of gaps and twists in the pattern is more than 5/cm²。

After etching, the substrate lines were observed by electron micrograph and rated as follows: A. the number of the residual protective film in the pattern is 0 to 1/cm²(ii) a B. The number of the residual protective films in the pattern is 2-3/cm²(ii) a C. The number of residual protective films in the pattern was 4/cm²(ii) a D. The number of residual protective films in the pattern is more than 5/cm²。