High-tolerance photoresist capable of long-time baking and preparation process thereof

Abstract

The application provides a high-tolerance photoresist capable of resisting long-time baking, which comprises the following components in percentage by mass: 20-30% of anhydride modified acrylic resin; 2-5% of a macromolecular photoinitiator; 0.1-0.5% of a pigment; 20-30% of quartz powder; 4-8% of extinction powder; 18-25% of an organic solvent; 5-10% of a functional additive; 10-15% of an epoxy resin; and 0.5-2.5% of melamine; wherein the macromolecular photoinitiator is a POSS photoinitiator containing benzophenone. Maleic anhydride is used as a functional monomer to introduce an anhydride into the molecular chain of the acrylic resin, thereby improving the curing efficiency and the performance of the photoresist and increasing the baking time of the photoresist; and the POSS containing benzophenone is used as the macromolecular photoinitiator to further increase the rigidity of the photoresist, increase the baking time of the photoresist and improve the tolerance of the photoresist.

Description

Technical Field

[0001] This invention relates to the field of photoresist preparation, and more specifically to a highly tolerant photoresist that can withstand long-term baking and its preparation process. Background Technology

[0002] With the continuous development of integrated circuit manufacturing processes, linewidths are constantly shrinking, thus the package size of devices is also gradually decreasing. From early integrated circuits to large-scale integrated circuits and very large-scale integrated circuits, and now to ultra-large-scale integrated circuits, devices are showing a trend of further reduction in size, more complete functions, and stronger performance. The development of photolithography technology is a crucial link in the development of integrated circuits. The photolithography process is roughly divided into two stages. The first stage uses an exposure machine to transfer the desired pattern onto the surface photoresist of a silicon wafer or mask. The second stage is the development stage, where the pattern generated in the first stage is revealed through the chemical reaction between the developer and the photoresist.

[0003] Photoresist, also known as photoresist, is a gel-like liquid composed of photosensitive compounds, matrix resins, and organic solvents. When photoresist is exposed to light of a specific wavelength, its chemical structure changes, altering its solubility in a specific solution. Photoresist requires baking before use; the longer the baking time, the higher the process tolerance and the better the quality. Currently, the baking time of existing photoresists on the market does not meet the requirements of technological development. Summary of the Invention

[0004] To further increase the baking time of the ink and improve its process tolerance during use, this invention provides a highly tolerant photoresist that can withstand long-term baking and its preparation process, as detailed below:

[0005] A highly tolerant photoresist that can withstand long-term baking, comprising the following components in weight percentages:

[0006] Anhydride-modified acrylic resin 20-30%; macromolecular photoinitiator 2-5%; pigment 0.1-0.5%;

[0007] Quartz powder 20-30%; matting agent 4-8%; organic solvent 18-25%; functional additives 5-10%;

[0008] The epoxy resin is 10-15%; melamine is 0.5-2.5%; and the macromolecular photoinitiator is a POSS photoinitiator containing benzophenone.

[0009] Furthermore, the preparation method of the anhydride-modified acrylic resin is as follows:

[0010] S1: Mix maleic anhydride, oxetane methacrylate, methyl methacrylate, styrene, and dicumyl peroxide evenly to obtain a mixed solution;

[0011] S2: Mix ethyl acetate and dicumyl peroxide evenly, and divide them into 3 parts according to mass, which are respectively used as components a, b and c;

[0012] S3: Add the remaining ethyl acetate, propylene glycol methyl ether acetate, and ethylene glycol butyl ether to the reactor, heat to reflux, and add the mixed solution prepared in S1 dropwise over 3 hours. After the addition is complete, keep the mixture at reflux temperature for 2 hours. After the reflux temperature is complete, add component a dropwise and keep the mixture at reflux temperature for 1 hour.

[0013] S4: After the heat preservation is completed, add component b and heat at reflux temperature for 1 hour; after the heat preservation is completed, add component c and heat at reflux temperature for 1 hour; after the heat preservation is completed, cool down to 90℃, filter, and discharge to obtain material E.

[0014] S5: Add epoxy resin, material E, and dibutyltin dilaurate sequentially to a four-necked flask, heat to 90°C and keep warm for a period of time. After the reaction is complete, anhydride-modified epoxy acrylate resin is obtained.

[0015] Furthermore, the method for synthesizing the benzophenone-containing POSS photoinitiator includes the following steps:

[0016] Using 1,6-hexanediol diacrylate as the active substrate, 4-benzoylphenoxypropyl silsesquioxane, 1,6-hexanediol diacrylate, and DMA dissolved in THF were mixed and reacted at 100°C for 5–10 h, followed by polymerization under ultraviolet light of a certain intensity.

[0017] Furthermore, the functional additives include defoamers, rheology modifiers, and photosensitive monomers, wherein the photosensitive monomers are acryloyl groups.

[0018] A process for preparing a highly tolerant photoresist that can withstand long-term baking includes the following steps:

[0019] S1. Ingredients: Weigh the materials according to their mass percentage;

[0020] S2, Pre-dispersion: Dispersing materials using a disperser;

[0021] S3. Grinding: Use a three-roll mill to grind the dispersed material;

[0022] S4. Stirring: Disperse the material again using a disperser;

[0023] S5. Viscosity Adjustment: Adjust the viscosity of the material to a suitable range;

[0024] S6. Filtering and filling: Use a sieve to filter the material.

[0025] Beneficial effects:

[0026] This invention provides a highly tolerant photoresist capable of withstanding long-term baking and its preparation process. First, acrylic resin is modified with anhydride, using maleic anhydride as a functional monomer. Introducing the anhydride into the acrylic resin molecular chain improves the curing efficiency of the acrylic resin. Simultaneously, the introduction of the anhydride enhances the performance of the photoresist, increasing its baking time. Then, benzophenone-containing POSS is used as a macromolecular photoinitiator. On one hand, benzophenone-containing POSS has high initiation efficiency; under light irradiation, it can locally generate high concentrations of active free radicals, rapidly initiating monomer polymerization and reducing the inhibitory effect of oxygen. On the other hand, the benzene ring structure of the polymerized benzophenone-containing POSS increases the rigidity of the photoresist, further increasing its baking time and improving its tolerance. Detailed Implementation

[0027] To enhance understanding of the present invention, the present invention will be further described in detail below with reference to embodiments. These embodiments are only used to explain the present invention and do not constitute a limitation on the scope of protection of the present invention.

[0028] Example 1:

[0029] A process for preparing a highly tolerant photoresist that can withstand long-term baking includes the following steps:

[0030] (1) Preparation of anhydride-modified acrylic resin, the steps are as follows:

[0031] S1: Mix maleic anhydride, oxetane methacrylate, methyl methacrylate, styrene, and dicumyl peroxide evenly to obtain a mixed solution;

[0032] S2: Mix ethyl acetate and dicumyl peroxide evenly, and divide them into 3 parts according to mass, which are respectively used as components a, b and c;

[0033] S3: Add the remaining ethyl acetate, propylene glycol methyl ether acetate, and ethylene glycol butyl ether to the reactor, heat to reflux, and add the mixed solution prepared in S1 dropwise over 3 hours. After the addition is complete, keep the mixture at reflux temperature for 2 hours. After the reflux temperature is complete, add component a dropwise and keep the mixture at reflux temperature for 1 hour.

[0034] S4: After the heat preservation is completed, add component b and heat at reflux temperature for 1 hour; after the heat preservation is completed, add component c and heat at reflux temperature for 1 hour; after the heat preservation is completed, cool down to 90℃, filter, and discharge to obtain material E.

[0035] S5: Add epoxy resin, material E, and dibutyltin dilaurate sequentially to a four-necked flask, heat to 90°C and keep warm for a period of time. After the reaction is complete, anhydride-modified epoxy acrylate resin is obtained.

[0036] (2) Prepare the ingredients according to the following mass percentages of each component:

[0037] Anhydride-modified acrylic resin 20%; benzophenone-containing POSS photoinitiator 2%; pigment 0.5%; quartz powder 30%; matting agent 8%; organic solvent 24%; epoxy resin 10%; melamine 0.5%; defoamer 1%; rheology modifier 0.5%; acryloyl group 3.5%.

[0038] (3) Pre-dispersion: Dispersing the material using a disperser;

[0039] (4) Grinding: The dispersed material is ground using a three-roll mill;

[0040] (5) Stirring: Disperse the material again using a disperser;

[0041] (6) Viscosity adjustment: Adjust the viscosity of the material to a suitable range.

[0042] (7) Filtering and filling: Use a sieve to filter the material.

[0043] Example 2:

[0044] A process for preparing a highly tolerant photoresist that can withstand long-term baking includes the following steps:

[0045] (1) Preparation of anhydride-modified acrylic resin, the steps are as follows:

[0046] S1: Mix maleic anhydride, oxetane methacrylate, methyl methacrylate, styrene, and dicumyl peroxide evenly to obtain a mixed solution;

[0047] S2: Mix ethyl acetate and dicumyl peroxide evenly, and divide them into 3 parts according to mass, which are respectively used as components a, b and c;

[0048] S3: Add the remaining ethyl acetate, propylene glycol methyl ether acetate, and ethylene glycol butyl ether to the reactor, heat to reflux, and add the mixed solution prepared in S1 dropwise over 3 hours. After the addition is complete, keep the mixture at reflux temperature for 2 hours. After the reflux temperature is complete, add component a dropwise and keep the mixture at reflux temperature for 1 hour.

[0049] S4: After the heat preservation is completed, add component b and heat at reflux temperature for 1 hour; after the heat preservation is completed, add component c and heat at reflux temperature for 1 hour; after the heat preservation is completed, cool down to 90℃, filter, and discharge to obtain material E.

[0050] S5: Add epoxy resin, material E, and dibutyltin dilaurate sequentially to a four-necked flask, heat to 90°C and keep warm for a period of time. After the reaction is complete, anhydride-modified epoxy acrylate resin is obtained.

[0051] (2) Prepare the ingredients according to the following mass percentages of each component:

[0052] Anhydride-modified acrylic resin 25%; benzophenone-containing POSS photoinitiator 3%; pigment 0.2%; quartz powder 25%; matting agent 6%; organic solvent 20%; epoxy resin 13%; melamine 2%; defoamer 2%; rheology modifier 2%; acryloyl group 1.8%;

[0053] (3) Pre-dispersion: Dispersing the material using a disperser;

[0054] (4) Grinding: The dispersed material is ground using a three-roll mill;

[0055] (5) Stirring: Disperse the material again using a disperser;

[0056] (6) Viscosity adjustment: Adjust the viscosity of the material to a suitable range.

[0057] (7) Filtering and filling: Use a sieve to filter the material.

[0058] Example 3:

[0059] A process for preparing a highly tolerant photoresist that can withstand long-term baking includes the following steps:

[0060] (1) Preparation of anhydride-modified acrylic resin, the steps are as follows:

[0061] S1: Mix maleic anhydride, oxetane methacrylate, methyl methacrylate, styrene, and dicumyl peroxide evenly to obtain a mixed solution;

[0062] S2: Mix ethyl acetate and dicumyl peroxide evenly, and divide them into 3 parts according to mass, which are respectively used as components a, b and c;

[0063] S3: Add the remaining ethyl acetate, propylene glycol methyl ether acetate, and ethylene glycol butyl ether to the reactor, heat to reflux, and add the mixed solution prepared in S1 dropwise over 3 hours. After the addition is complete, keep the mixture at reflux temperature for 2 hours. After the reflux temperature is complete, add component a dropwise and keep the mixture at reflux temperature for 1 hour.

[0064] S4: After the heat preservation is completed, add component b and heat at reflux temperature for 1 hour; after the heat preservation is completed, add component c and heat at reflux temperature for 1 hour; after the heat preservation is completed, cool down to 90℃, filter, and discharge to obtain material E.

[0065] S5: Add epoxy resin, material E, and dibutyltin dilaurate sequentially to a four-necked flask, heat to 90°C and keep warm for a period of time. After the reaction is complete, anhydride-modified epoxy acrylate resin is obtained.

[0066] (2) Prepare the ingredients according to the following mass percentages of each component:

[0067] Anhydride-modified acrylic resin 30%; benzophenone-containing POSS photoinitiator 2%; pigment 0.1%; quartz powder 25%; matting agent 4%; organic solvent 18%; epoxy resin 10%; melamine 2%; defoamer 3%; rheology modifier 5%; acryloyl group 0.9%.

[0068] (3) Pre-dispersion: Dispersing the material using a disperser;

[0069] (4) Grinding: The dispersed material is ground using a three-roll mill;

[0070] (5) Stirring: Disperse the material again using a disperser;

[0071] (6) Viscosity adjustment: Adjust the viscosity of the material to a suitable range.

[0072] (7) Filtering and filling: Use a sieve to filter the material.

[0073] The photoresists prepared in Examples 1-3 were subjected to performance tests, and the test results are as follows:

[0074] Temperature / °C Time / min Can the ink be cleaned by chemicals? Example 1 75 60 Okay Example 2 80 70 Okay Example 3 85 80 OK

[0075] Therefore, the photoresist prepared by this process can withstand long-term baking and has high tolerance.

[0076] As a further improvement, the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A highly tolerant photoresist capable of withstanding prolonged baking, characterized in that, The components include the following mass percentages: Anhydride-modified acrylic resin 20-30%; macromolecular photoinitiator 2-5%; pigment 0.1-0.5%; Quartz powder 20-30%; matting agent 4-8%; organic solvent 18-25%; functional additives 5-10%; Epoxy resin 10-15%; melamine 0.5-2.5%; the macromolecular photoinitiator is a POSS photoinitiator containing benzophenone; The preparation method of anhydride-modified acrylic resin is as follows: S1: Mix maleic anhydride, oxetane methacrylate, methyl methacrylate, styrene, and dicumyl peroxide evenly to obtain a mixed solution; S2: Mix ethyl acetate and dicumyl peroxide evenly, and divide them into 3 parts according to mass, which are respectively used as components a, b and c; S3: Add the remaining ethyl acetate, propylene glycol methyl ether acetate, and ethylene glycol butyl ether to the reactor, heat to reflux, and add the mixed solution prepared in S1 dropwise over 3 hours. After the addition is complete, keep the mixture at reflux temperature for 2 hours. After the reflux temperature is complete, add component a dropwise and keep the mixture at reflux temperature for 1 hour. S4: After the heat preservation is completed, add component b and heat at reflux temperature for 1 hour; after the heat preservation is completed, add component c and heat at reflux temperature for 1 hour; after the heat preservation is completed, cool down to 90℃, filter, and discharge to obtain material E. S5: Add epoxy resin, material E, and dibutyltin dilaurate sequentially to a four-necked flask, heat to 90°C and keep warm for a period of time. After the reaction is complete, anhydride-modified epoxy acrylate resin is obtained.

2. The highly tolerant photoresist capable of withstanding long-term baking according to claim 1, characterized in that, The method for synthesizing the benzophenone-containing POSS photoinitiator includes the following steps: Using 1,6-hexanediol diacrylate as the active substrate, 4-benzoylphenoxypropyl silsesquioxane, 1,6-hexanediol diacrylate, and DMA dissolved in THF were mixed and reacted at 100°C for 5-10 hours, followed by polymerization under ultraviolet light of a certain intensity.

3. The highly tolerant photoresist capable of withstanding long-term baking according to claim 1, characterized in that, The functional additives include defoamers, rheology modifiers, and photosensitive monomers, wherein the photosensitive monomers are acryloyl groups.

4. The preparation process of a highly tolerant photoresist capable of withstanding long-term baking according to any one of claims 1 to 3, characterized in that, Includes the following steps: S1. Ingredients: Weigh the materials according to their mass percentage; S2, Pre-dispersion: Dispersing materials using a disperser; S3. Grinding: Use a three-roll mill to grind the dispersed material; S4. Stirring: Disperse the material again using a disperser; S5. Viscosity Adjustment: Adjust the viscosity of the material to a suitable range; S6. Filtering and filling: Use a sieve to filter the material.