CN115793391A - Photoresist and application thereof - Google Patents
Photoresist and application thereof Download PDFInfo
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- CN115793391A CN115793391A CN202211513745.9A CN202211513745A CN115793391A CN 115793391 A CN115793391 A CN 115793391A CN 202211513745 A CN202211513745 A CN 202211513745A CN 115793391 A CN115793391 A CN 115793391A
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- leveling agent
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Abstract
The application provides a photoresist and an application thereof, belonging to the technical field of semiconductors and integrated circuits. The photoresist comprises 10wt% -30 wt% of phenolic resin, 2wt% -10 wt% of diazonaphthoquinone sensitizer and 0.1wt% -10 wt% of additive. According to the application, the additive containing halogen is added into the diazonaphthoquinone type photoresist, and the additive can interact with other components in the photoresist, so that the light sensitivity of the photoresist is improved, the photoresist can have better photoetching performance, and the photoresist is particularly in a shape with a more vertical side wall.
Description
Technical Field
The application relates to the technical field of semiconductors and integrated circuits, in particular to a photoresist and application thereof.
Background
With the vigorous development of new infrastructure such as cloud computing, internet of things, 5G communication, artificial intelligence and the like, an integrated circuit is taken as one of core industries of the information industry, and a high-speed development road is followed.
The 365nm (i-line) photoresist is based on main materials such as phenolic resin and diazonaphthoquinone, and the patterns of the mask are transferred and copied to a silicon chip through photoetching process procedures such as exposure, development and the like, and the 365nm (i-line) photoresist is widely applied to the manufacturing process of hundreds of nanometers to microns in integrated manufacturing circuits.
In the chip packaging process, a thick film photoresist with the thickness of 7-20 microns needs to be used for manufacturing various dot and line patterns on the surface of a substrate, the light sensitivity of the photoresist greatly influences the production efficiency of the packaging process, and the thick film photoresist based on the phenolic resin/diazonaphthoquinone at present has the main problem of insufficient light sensitivity.
Disclosure of Invention
The application provides a photoresist and application thereof, which can improve the light sensitivity of the photoresist and enable the photoresist to have better photoetching performance.
The embodiment of the application is realized as follows:
in a first aspect, the present examples provide a photoresist comprising: 10 to 30 weight percent of phenolic resin, 2 to 10 weight percent of diazonaphthoquinone sensitizer and 0.1 to 10 weight percent of additive.
The structural formula of the additive is as follows:
wherein R is 1 Selected from X, C 1～6 alkyl-X or (ph) m -X。
R 2 Selected from H, Y, C 1～6 alkyl-Y, (ph) n -Y or C 1～4 -(ph) n -Y。
X and Y are independently selected from F, cl, br or I, and m and n are integers from 1 to 3.
R 3 Is selected from
In the technical scheme, the additive containing the halogen is added into the diazonaphthoquinone type photoresist, and the additive can interact with other components in the photoresist, so that the photosensitivity of the photoresist is improved, and the photoresist has better photoetching performance, and is particularly represented by a shape with a vertical side wall.
In a first possible example of the first aspect of the present application, in combination with the first aspect, the above R 1 Selected from X, C 1～6 alkyl-X or (ph) m -X。
R 2 Selected from H, Y, C 1～6 alkyl-Y or (ph) n -Y。
In a second possible example of the first aspect of the present application in combination with the first aspect, the above R 2 Selected from H, Y or C 1～6 An alkyl group-Y.
In a third possible example of the first aspect of the present application in combination with the first aspect, R is as described above 1 Selected from X or C 1～6 An alkyl group-X.
In a fourth possible example of the first aspect of the present application in combination with the first aspect, the phenolic resin has a molecular weight of 4000 to 10000.
Alternatively, the phenolic resin has the following structural formula:
wherein a, b or c can be 0.
In a fifth possible example of the first aspect of the present application in combination with the first aspect, the diazonaphthoquinone sensitizer described above includes a 2,1,4-type diazonaphthoquinone sensitizer and/or a 2,1,5-type diazonaphthoquinone sensitizer.
In a sixth possible example of the first aspect of the present application, in combination with the first aspect, the photoresist further includes 0.1wt% to 5wt% of a leveling agent.
Optionally, the leveling agent includes any one or more of a siloxane-based leveling agent, a polyether-based leveling agent, and a fluorine-containing polymethyl methacrylate-based leveling agent.
Optionally, the leveling agent is a siloxane-based leveling agent.
With reference to the first aspect, in a seventh possible example of the first aspect of the present application, the photoresist further includes 40wt% to 80wt% of a solvent.
Alternatively, the solvent comprises any one or more of propylene glycol methyl ether acetate, 2-heptanone, and ethyl lactate.
In an eighth possible example of the first aspect of the present application, in combination with the first aspect, the photoresist includes 20wt% to 30wt% of a phenolic resin, 5wt% to 8wt% of a diazonaphthoquinone sensitizer, 0.1wt% to 2wt% of a leveling agent, 40wt% to 80wt% of a solvent, and 0.1wt% to 3wt% of an additive.
In a second aspect, the present application provides a use of the photoresist in integrated circuits and chip packages.
Optionally, the photoresist has a thickness of 7 μm to 20 μm.
Alternatively, the developer solution used for the photoresist is a potassium hydroxide solution.
In the technical scheme, the photoresist can be applied to integrated circuits and chip packaging processes in a thick coating mode.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic view of a photoresist of example 1 of the present application after being developed with KOH developer;
FIG. 2 is a schematic diagram of the photoresist of example 2 of the present application after being developed with KOH developer;
FIG. 3 is a schematic view of the photoresist of example 3 of the present application after being developed with KOH developer;
FIG. 4 is a schematic representation showing the photoresist of example 4 of the present application after being developed with KOH developer;
FIG. 5 is a schematic representation of the photoresist of example 5 after being developed with KOH developer;
FIG. 6 is a schematic representation of the photoresist of example 6 of the present application after being developed with KOH developer;
FIG. 7 is a schematic representation of the photoresist of example 7 after being developed with KOH developer;
FIG. 8 is a schematic representation of the photoresist of example 8 after being developed with KOH developer;
FIG. 9 is a schematic representation of the photoresist of example 9 of the present application after development with KOH developer;
FIG. 10 is a graphical representation of the photoresist of comparative example 1 of the present application after development with KOH developer;
FIG. 11 is a schematic representation of the photoresist of comparative example 2 of the present application after development with KOH developer;
FIG. 12 is a topographical view of a photoresist of example 1 of the present application after developing with TMAH developer.
Detailed Description
Embodiments of the present application will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
At present, with the vigorous development of new infrastructure such as cloud computing, internet of things, 5G communication, artificial intelligence and the like, an integrated circuit is taken as one of core industries of an information industry, and a high-speed development road is followed. The 365nm (i-line) photoresist is based on main materials such as phenolic resin and diazonaphthoquinone, and the patterns of the mask are transferred and copied to a silicon chip through photoetching process procedures such as exposure, development and the like, and the 365nm (i-line) photoresist is widely applied to the manufacturing process of hundreds of nanometers to microns in integrated manufacturing circuits.
The inventor notices that in the chip packaging process, a thick film photoresist with the thickness of 7-20 μm is required to be used for manufacturing various dot and line patterns on the surface of a substrate, the light sensitivity of the photoresist greatly influences the production efficiency of the packaging process, but the existing thick film photoresist of phenolic resin/diazonaphthoquinone has the problems of insufficient light sensitivity, side wall inclination and the like.
In order to solve the problem of insufficient light sensitivity of the thick film photoresist of the phenolic resin/diazonaphthoquinone, the inventor researches and discovers that the photosensitive resist can be realized by adjusting two main materials of a photosensitizer and resin, but due to structural change and physicochemical property variety limitation of the two main materials, the comprehensive performance of the photoresist, such as light sensitivity, heat resistance, resolution, a process window and the like, usually needs to adjust the addition amount and the structure for multiple times to balance optimization of performances such as resolution, light sensitivity and the like, and the actual operation is difficult to realize.
Based on the consideration, in order to solve the problem of insufficient light sensitivity of the phenolic resin/diazonaphthoquinone thick film photoresist, the inventor designs a photoresist through intensive research, and the additive containing halogen is added into the diazonaphthoquinone type photoresist and can interact with other components in the photoresist, so that the light sensitivity of the photoresist is improved, the photoresist has better photoetching performance and the specific appearance shows that the side wall is more vertical.
The following is a detailed description of a photoresist according to an embodiment of the present application:
the present application provides a photoresist comprising: 10 to 30 weight percent of phenolic resin, 2 to 10 weight percent of diazonaphthoquinone sensitizer, 0.1 to 10 weight percent of additive, 0.1 to 5 weight percent of flatting agent and 40 to 80 weight percent of solvent.
Wherein, the structural formula of the phenolic resin is as follows:
a. b or c can both be 0.
As an example, a may be 0, b, c may not be 0; or b may be 0, a, c is not 0; or c is 0, a, b is 0; or a and b may both be 0 and c may not be 0; or a and c are both 0 and b is not 0; or b, c are not 0, a is 0; or a, b and c may be all not 0.
Molecular weight M of phenolic resin w 4000 to 10000.
The diazonaphthoquinone sensitizer comprises 2,1,4 types of diazonaphthoquinone sensitizers and/or 2,1,5 types of diazonaphthoquinone sensitizers, and the selectable structure is as follows:
PAC-1
PAC-2: r = H, or
The additive is a halogen-containing compound, and the structural formula of the additive is as follows:
wherein R is 1 Selected from X, C 1～6 alkyl-X or (ph) m -X。
R 2 Selected from H, Y, C 1～6 alkyl-Y, (ph) n -Y or C 1～4 -(ph) n -Y。
X and Y are respectively selected from F, cl, br or I, and m and n are integers from 1 to 3.
R 3 Is selected from
Alternatively, R 1 Selected from X or C 1～6 An alkyl group-X.
Alternatively, R 1 Is selected from X.
Alternatively, R 1 Selected from Cl.
Alternatively, R 2 Selected from H, Y, C 1～6 alkyl-Y or (ph) n -Y。
Alternatively, R 2 Selected from H, Y or C 1～6 alkyl-Y.
Alternatively, R 2 Is selected from H.
The leveling agent comprises any one or more of a siloxane leveling agent, a polyether leveling agent and a fluorine-containing polymethyl methacrylate leveling agent.
Optionally, the leveling agent is a siloxane-based leveling agent.
The solvent comprises any one or more of propylene glycol methyl ether acetate, 2-heptanone and ethyl lactate.
As an example, the solvent may be propylene glycol methyl ether acetate, 2-heptanone, or ethyl lactate alone, or may be a mixture of propylene glycol methyl ether acetate and 2-heptanone, or may be a mixture of propylene glycol methyl ether acetate and ethyl lactate, or may be a mixture of 2-heptanone and ethyl lactate, or may be a mixture of propylene glycol methyl ether acetate, 2-heptanone, and ethyl lactate.
By way of example, the photoresist may include 10wt%, 12wt%, 15wt%, 18wt%, 20wt%, 22wt%, 25wt%, 28wt%, or 30wt% of a phenolic resin, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, or 10wt% of a diazonaphthoquinone sensitizer, 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 2wt%, 5wt%, 8wt%, 10wt% of an additive, 0.1wt%, 0.2wt%, 0.5wt%, 0.8wt%, 1wt%, 2wt%, 3wt%, 4wt%, or 5wt% of a leveling agent, and 40wt%, 45wt%, 50wt%, 55wt%, 60wt%, 65wt%, 70wt%, 75wt%, or 80wt% of a solvent.
Optionally, the photoresist comprises 20wt% -30 wt% of phenolic resin, 5wt% -8 wt% of diazonaphthoquinone sensitizer, 0.1wt% -2 wt% of leveling agent, 40wt% -80 wt% of solvent and 0.1wt% -3 wt% of additive.
According to the application, the additive containing halogen is added into the diazonaphthoquinone type photoresist, and the additive can interact with other components in the photoresist, so that the light sensitivity of the photoresist is improved, the photoresist can have better photoetching performance, and the photoresist is particularly in a shape with a more vertical side wall.
The application also provides an application of the photoresist in integrated circuit and chip packaging.
The preparation method of the photoresist comprises the following steps: mixing phenolic resin, diazonaphthoquinone photosensitizer, a leveling agent, an additive and a solvent according to a ratio, placing the mixture on a light-shielding shaking table at 5-30 ℃ and mixing the mixture at a constant speed for 12 hours to obtain a mixed solution, and filtering the mixed solution by using a microporous filter membrane with the aperture of 0.2 mu m to obtain the photoresist.
Optionally, when the photoresist is coated on the silicon wafer, the thickness of the photoresist is 7 μm to 20 μm.
Alternatively, the developer solution used for the photoresist is a potassium hydroxide solution.
A photoresist of the present application and its use are described in further detail below with reference to examples.
Example 1
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of p-chlorobenzoic acid (22 g) containing 0.5mL DMF in dichloromethane (200 mL), and the reaction mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃ and the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 min, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 20.1g of the product (80% yield) as a dark oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，7.61(d，2H)，7.99(d，2H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone sensitizer, flatting agent, additive and solvent according to a certain proportion, placing on a light-shielding table at 25 deg.C, uniformly mixing for 12h to obtain a mixed solution, and filtering the mixed solution with a 0.2 μm-aperture microporous filter membrane to obtain the photoresist.
Example 2
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of p-bromobenzoic acid (23.7 g) containing 0.5mL DMF in dichloromethane (200 mL), the reaction mixture was stirred at 40 ℃ for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃, the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 minutes, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 19.23g of the product (76% yield) as an oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，7.71ppm(d，2H)，7.74ppm(d，2H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 3
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has m/p-cresol 6/4 structure and molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of p-chloromethylbenzoic acid (24 g) in dichloromethane (200 mL) containing 0.5mL DMF, and the reaction mixture was stirred at 40 ℃ for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃ and the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 minutes, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 20.4g of product (77.3% yield) as an oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，4.61ppm(s，2H)，7.41ppm(d，2H)，7.99ppm(d，2H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 4
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of 4' -chloro-4-diphenic acid (33 g) in dichloromethane (200 mL) containing 0.5mL DMF, the reaction mixture was stirred at 50 ℃ for 24 hours, concentrated under reduced pressure and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃, the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 minutes, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 24.4g of product (72% yield) as an oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，7.62ppm(s，2H)，7.76ppm(d，2H)，8.04ppm(d，2H)，8.11ppm(d，2H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 5
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of 4-chloro-2-fluorobenzoic acid (24.7 g) in dichloromethane (200 mL) containing 0.5mL DMF, and the reaction mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃ and the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 minutes, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 20.4g of product (72% yield) as an oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，7.37ppm(s，1H)，7.75ppm(d，1H)，7.89ppm(d，1H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 6
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has m/p-cresol 6/4 structure and molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of 2, 4-dichlorobenzoic acid (27 g) in dichloromethane (200 mL) containing 0.5mL DMF, the reaction mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃ and the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 minutes, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 20.8g of product (71.5% yield) as an oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，7.48ppm(s，1H)，7.64ppm(d，1H)，7.91ppm(d，1H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 7
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of 2-bromomethyl 4-chlorobenzoic acid (35.4 g) in dichloromethane (200 mL) containing 0.5mL DMF, and the reaction mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃ and the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 minutes, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 24.5g of product (68% yield) as an oil.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，4.55ppm(s，2H)，7.57ppm(s，2H)，8.00ppm(d，1H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 8
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has m/p-cresol 6/4 structure and molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of 4', 5-dichloro- [1,1' -biphenyl ] -2-carboxylic acid (38 g) in dichloromethane (200 mL) containing 0.5mL DMF, and the reaction mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃, the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 min, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution and dried over magnesium sulfate and concentrated to give 23.6g of product (62% yield) as a brown solid.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，7.63ppm(d，2H)，7.71ppm(s，1H),7.78ppm(s，2H)，8.08ppm(d，1H),8.17ppm(d，1H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone photosensitizer, flatting agent, additive and solvent according to a ratio, placing on a light-shielding shaker at 25 ℃ and mixing at a constant speed for 12h to obtain a mixed solution, and filtering the mixed solution by using a 0.2-micron-aperture microporous filter membrane to obtain the photoresist.
Example 9
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additive is prepared by the following method:
oxalyl chloride (10 mL) was added dropwise over 30 minutes to a slurry of 4', 5-dichloro-3 ' -methyl- [1,1' -biphenyl ] -2-carboxylic acid (46 g) in dichloromethane (200 mL) containing 0.5mL DMF, and the reaction mixture was stirred at room temperature for 24 hours, concentrated under reduced pressure, and then co-evaporated with toluene. To the residue was added 14mL of tert-butanol, the mixture was cooled to 0 ℃ and the reaction mixture was stirred for a further 1 hour and then treated with 500mL of saturated sodium bicarbonate solution. After stirring for 5 min, the precipitate was separated and the organic phase was washed with saturated sodium chloride solution, dried over magnesium sulfate and concentrated to give 24.5g of the product (61.8% yield) as a brown solid.
HNMR：CDCl 3 ，400MHz，1.43ppm(s，9H)，2.26ppm(s，3H)7.56ppm(d，1H)，7.68ppm(s，1H),7.70ppm(d，1H)，7.72ppm(s，1H),8.08ppm(s，2H)，8.16ppm(d，1H)。
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone sensitizer, flatting agent, additive and solvent according to a certain proportion, placing on a light-shielding table at 25 deg.C, uniformly mixing for 12h to obtain a mixed solution, and filtering the mixed solution with a 0.2 μm-aperture microporous filter membrane to obtain the photoresist.
Comparative example 1
The comparative example of the present application provides a photoresist comprising: 28wt% of a phenol resin, 4wt% of a 2,1,4 type diazonaphthoquinone sensitizer (PAC-1), 1wt% of a silicone leveling agent and 67wt% of a solvent.
Wherein the phenolic resin has m/p-cresol 6/4 structure and molecular weight of 6220.
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone sensitizer, flatting agent and solvent according to a certain proportion, placing on a light-shielding table at 25 deg.C, uniformly mixing for 12h to obtain a mixed solution, and filtering the mixed solution with a 0.2 μm pore size microporous filter membrane to obtain the photoresist.
Comparative example 2
The embodiment of the application provides a photoresist, which comprises: 28wt% of a phenol resin, 4wt% of a diazonaphthoquinone sensitizer (PAC-1) of 2,1,4 types, 1wt% of a silicone leveling agent, 65wt% of a solvent, and 2wt% of an additive.
Wherein the phenolic resin has a structure of m/p-cresol 6/4 and a molecular weight of 6220.
The structural formula of the additive is as follows:
the additives were purchased from Bailingwei technologies, beijing.
The photoresist is prepared by the following method:
mixing phenolic resin, diazonaphthoquinone sensitizer, flatting agent, additive and solvent according to a certain proportion, placing on a light-shielding table at 25 deg.C, uniformly mixing for 12h to obtain a mixed solution, and filtering the mixed solution with a 0.2 μm-aperture microporous filter membrane to obtain the photoresist.
Test example 1
The photoresists prepared in the embodiments 1 to 10 and the comparative examples 1 to 2 are taken, the photoresists are uniformly coated on bare silicon wafers in a spin coating mode, evaluation indexes of the photoresists mainly comprise light sensitivity and cross-sectional morphology performance besides resolution and photosensitivity, the results are shown in table 1, and the developed morphology graphs of the photoresists in the embodiments 1 to 10 and the comparative examples 1 to 2 are shown in tables 1 to 11.
The process conditions of the photoresist are as follows:
substrate: 6' optical silicon wafer;
pre-baking: 90C60s, CHP;
post-baking: 115C60s, CHP;
and (3) developing: 60s, single development, KOH (0.75 wt%);
an exposure apparatus: nikon i9;
film thickness: 7 μm.
The test mode of the photosensitivity value is as follows: coating photoresist on a substrate, reducing solvent residue through prebaking, placing the substrate in a photoetching machine, setting different areas corresponding to different exposure energies, developing the substrate for 60s by using a KOH developing solution, testing the film thickness after the development, wherein the film thickness can be reduced to zero along with the increase of the exposure energy because the designed system is a positive photoresist system, and reading the first exposure energy for developing the photoresist (namely the film thickness is 0) to obtain the light sensitivity value.
The contrast test mode is as follows: and (3) drawing the residual film thickness and the corresponding exposure energy of the different areas, wherein the slope is the contrast, and the higher the contrast is, the straighter the appearance and the better photoetching performance are corresponding to.
The side wall test mode is as follows: and after a mask is added to form a pattern, measuring the angle between the photoresist of the cross section of the pattern and the substrate.
TABLE 1 developing Effect of examples 1 to 10 and comparative examples 1 to 2
From the above, it can be seen from examples 1 to 9 that the photoresist of the present application exhibits high photosensitivity and lithographic performance, and the specific photosensitivity value is only 215mj/cm 2 ～250mj/cm 2 The angle of the side wall is 85.1-88.2 degrees, and the contrast is 3.91-5.02 degrees. And the sidewall angle of the photoresist of example 1 is closest to 90 °, and the steric hindrance is larger in example 4 and examples 8 to 9 because at least two benzene rings exist in the structure of the additive, and the sidewall angle is lower compared to that of example 1.
As can be seen from the comparison of comparative example 1 and example 1, the photoresist of comparative example 1 has no additive, the photosensitivity value is 420mj/cm2, the sidewall angle is 63.3, and the contrast is 1.24. The photoresist of comparative example 1 has a photosensitivity value much greater than that of the photoresist of example 1, the sidewall angle of the photoresist of comparative example 1 is much smaller than that of the photoresist of example 1, and the contrast of the photoresist of comparative example 1 is much smaller than that of the photoresist of example 1. That is, the photoresist of comparative example 1 was inferior in both light sensitivity and lithography performance.
As can be seen from the comparison between comparative example 2 and example 1, the photoresist of comparative example 2, to which the conventional additives were added, had a photosensitivity value of 390mj/cm2, a sidewall angle of 72.0 deg., and a contrast of 1.63. The photo sensitivity value of the photoresist of comparative example 2 is much greater than that of the photoresist of example 1, the sidewall angle of the photoresist of comparative example 2 is much smaller than that of the photoresist of example 1, and the contrast of the photoresist of comparative example 2 is much smaller than that of the photoresist of example 1. That is, the photoresist of comparative example 2 was inferior in both light sensitivity and lithographic performance.
Test example 2
The photoresist prepared in example 1 was uniformly coated on a bare silicon wafer by spin coating, and the evaluation index of the photoresist mainly included photosensitivity and cross-sectional profile properties in addition to resolution and photosensitivity, and the result is shown in table 2, and the developed profile of the photoresist of example 1 is shown in table 12.
The process conditions of the photoresist are as follows:
substrate: 6' optical silicon wafer;
pre-baking: 90C60s, CHP;
post-baking: 115C60s, CHP;
and (3) developing: 60s, single development, TMAH (2.38 wt%);
an exposure apparatus: nikon i9;
film thickness: 7 μm.
Table 2 developing effect of example 1
| Item | Light sensitivity value (mj/cm) 2 ) | Side wall angle (°) | Contrast ratio |
| Example 1 | 415 | 59.3 | 2.05 |
As can be seen from the above, the photoresist of example 1 is developed by using a TMAH developing solution, the photosensitivity value is 415mj/cm2, the sidewall angle is 59.3 °, and the contrast is 2.05, compared with the KOH developing method, the photosensitivity is reduced by using the TMAH developing solution, and the sidewall angle and the contrast are greatly reduced.
The foregoing description is given for the purpose of illustrating particular embodiments of the present application and is not in any way intended to limit the invention, as numerous modifications and variations will be apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. A photoresist, wherein the photoresist comprises: 10 to 30 weight percent of phenolic resin, 2 to 10 weight percent of diazonaphthoquinone sensitizer and 0.1 to 10 weight percent of additive;
the additive has the following structural formula:
wherein R is 1 Selected from X, C 1～6 alkyl-X or (ph) m -X；
R 2 Selected from H, Y, C 1～6 alkyl-Y, (ph) n -Y or C 1～4 -(ph) n -Y；
X and Y are respectively selected from F, cl, br or I, m and n are integers from 1 to 3;
R 3 is selected from
2. The photoresist of claim 1, wherein R is 1 Selected from X, C 1～6 alkyl-X or (ph) m -X；
R 2 Selected from H, Y, C 1～6 alkyl-Y or (ph) n -Y。
3. The photoresist of claim 2, wherein R is 2 Selected from H, Y or C 1～6 An alkyl group-Y.
4. The photoresist of claim 3, wherein R is 1 Selected from X or C 1～6 An alkyl group-X.
5. The photoresist according to any one of claims 1 to 4, wherein the phenolic resin has a molecular weight of 4000 to 10000;
alternatively, the phenolic resin has the following structural formula:
wherein a, b or c can be 0.
6. The photoresist of any one of claims 1 to 4, wherein the diazonaphthoquinone sensitizer comprises a 2,1,4 class diazonaphthoquinone sensitizer and/or a 2,1,5 class diazonaphthoquinone sensitizer.
7. The photoresist of any one of claims 1 to 4, further comprising 0.1wt% to 5wt% of a leveling agent;
optionally, the leveling agent comprises any one or more of a siloxane leveling agent, a polyether leveling agent and a fluorine-containing polymethyl methacrylate leveling agent;
optionally, the leveling agent is a siloxane-based leveling agent.
8. The photoresist of any one of claims 1 to 4, further comprising 40 to 80wt% of a solvent;
optionally, the solvent comprises any one or more of propylene glycol methyl ether acetate, 2-heptanone, and ethyl lactate.
9. The photoresist according to any one of claims 1 to 4, wherein the photoresist comprises 20 to 30wt% of phenolic resin, 5 to 8wt% of diazonaphthoquinone sensitizer, 0.1 to 2wt% of leveling agent, 40 to 80wt% of solvent and 0.1 to 3wt% of the additive.
10. Use of a photoresist according to any one of claims 1 to 9 in integrated circuits and chip packaging;
optionally, the thickness of the photoresist is 7 μm to 20 μm;
optionally, the developing solution for the photoresist is a potassium hydroxide solution.
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| CN202211513745.9A CN115793391A (en) | 2022-11-29 | 2022-11-29 | Photoresist and application thereof |
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