Extreme ultraviolet non-chemically amplified photoresist and preparation method and application thereof

Abstract

The application relates to an extreme ultraviolet non-chemical amplification photoresist as well as a preparation method and application thereof. The extreme ultraviolet non-chemical amplification photoresist has excellent indexes and processing performance, and meets the use in the EUV photoetching field. The extreme ultraviolet non-chemical amplification photoresist has the characteristics of simple preparation, easy availability of raw materials, small operation difficulty and wide applicability.

Description

Technical Field

[0001] This invention relates to the field of photoresist technology, and in particular to an extreme ultraviolet non-chemical amplification photoresist, its preparation method, and its application. Background Technology

[0002] Photoresist, also known as photoresist, undergoes a change in solubility under irradiation by light sources such as ultraviolet light and electron beams, thus becoming either soluble or insoluble in developer. Based on the changes in its properties after light exposure, photoresists are mainly divided into two categories: photoresists that are insoluble in developer become soluble under light irradiation and are called positive photoresists; while photoresists that are soluble in developer become insoluble under irradiation and are called negative photoresists.

[0003] Photoresist is one of the key materials in the photolithography process, and its quality directly affects the manufacturing precision of semiconductor integrated circuits and devices. With the development of the semiconductor manufacturing industry, photolithography technology, categorized by exposure wavelength, has successively evolved through G-line (436nm), I-line (365nm), KrF (248nm), ArF (193nm, including dry and immersion methods), and extreme ultraviolet (EUV, 13.5nm) lithography. EUV lithography is considered the primary choice for mass production of 10–16nm node chips, but this requires photoresist with higher sensitivity and resolution to ensure accurate transfer of the pattern from the photomask to the silicon wafer.

[0004] Currently, polymer materials used in EUV photoresists are divided into chemically amplified photoresists (CAR) and non-chemically amplified photoresists (non-CAR). The former requires the use of photoacid generators (PAG) to generate a large number of strong acid hydrogen ions, but photoacid diffusion will cause a large linewidth roughness. Although attaching PAG molecular bonds to the polymer molecular chain can greatly reduce acid diffusion, it cannot completely eliminate it.

[0005] CN107991842A discloses an application of polycarbonate as an electron beam photoresist material, wherein the polycarbonate is formed by alternating copolymerization of carbon dioxide and at least one epoxy alkane. The disclosed polycarbonate exhibits high sensitivity, high resolution, and high contrast. However, the synthesis method for this type of polycarbonate requires the use of an autoclave, a reaction under a 3MPa carbon dioxide atmosphere for up to 48 hours, and the product needs to be dissolved in carbon dichloride followed by purification by methanol precipitation and filtration. The reaction conditions and steps are complex.

[0006] CN111253563A discloses an application of polycarbonate as an ultraviolet photoresist material. The disclosed polycarbonate incorporates photosensitive groups and / or acid-generating groups into its side chains, reducing the diffusion of photoacids into unexposed areas. This causes the photoresist to undergo both polarity reversal and main chain breakage after exposure, resulting in low line edge roughness, high sensitivity, high resolution, and high contrast. However, this type of polycarbonate photoresist material is essentially a chemically amplified photoresist (CAR), requiring the use of a photoacid-generating agent (PAG) to produce a large number of strong acid hydrogen ions. Although it introduces photoacid groups into the polymer side chains, as mentioned earlier, chemically amplified photoresists always suffer from photoacid diffusion problems, resulting in inferior sensitivity and line width roughness compared to non-chemically amplified photoresists.

[0007] In summary, it is of great significance to develop a novel polycarbonate resin as a non-chemically amplified photoresist material and apply it to the field of extreme ultraviolet (EUV) lithography. Summary of the Invention

[0008] To address the shortcomings of existing technologies, the present invention aims to provide an extreme ultraviolet (EUV) non-chemical amplification photoresist, its preparation method, and its applications. The EUV non-chemical amplification photoresist possesses excellent properties and processing performance, meeting the requirements for applications in the EUV lithography field. Furthermore, the EUV non-chemical amplification photoresist is characterized by its simple preparation, readily available raw materials, low operational difficulty, and wide applicability.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, wherein the EUV non-chemical amplification photoresist comprises a polycarbonate resin having the structure shown in Formula I:

[0011]

[0012] Where m and n are each an independent integer between 1 and 200 (e.g., 5, 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, etc.);

[0013] R1 is the structural unit formed by the first monomer, which is a diol;

[0014] R2 is the structural unit formed by the second monomer, which has the following structure:

[0015]

[0016] Where x is an integer from 2 to 12 (e.g., 4, 6, 8, 10, etc.).

[0017] In this invention, the polycarbonate resin contains easily dissociable carbonate and sulfone groups. Under EUV irradiation, the polymer decomposes into CO2, SO2, and many low-molecular-weight fragments. These fragments increase solubility in the developer and are removed during development, resulting in high resolution and low line edge roughness. Furthermore, due to its excellent properties and processing performance, it can be used as an extreme ultraviolet non-chemical amplification photoresist, meeting the requirements of EUV lithography applications.

[0018] Preferably, the first monomer is selected from any one or a combination of at least two of the following structures:

[0019]

[0020] Preferably, the raw materials for preparing the second monomer include 4-hydroxystyrene and dithiol.

[0021] Preferably, the dithiol includes any one of ethylenedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, or n-dodecylthiol.

[0022] Preferably, the polycarbonate resin comprises any one or a combination of at least two of the following compounds:

[0023]

[0024]

[0025]

[0026]

[0027]

[0028] Where each m is an independent integer between 1 and 200, such as 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, etc.

[0029] n is an independent integer between 1 and 200, such as 10, 20, 40, 60, 80, 100, 120, 140, 160, 180, etc.

[0030] Preferably, the intrinsic viscosity of the polycarbonate resin is 0.52-1.01 dL / g, such as 0.6 dL / g, 0.7 dL / g, 0.8 dL / g, 0.9 dL / g, etc.

[0031] Preferably, the number average molecular weight of the polycarbonate resin is 9657-25896 g / mol, such as 10000 g / mol, 12000 g / mol, 14000 g / mol, 16000 g / mol, 18000 g / mol, 20000 g / mol, 22000 g / mol, 24000 g / mol, etc.

[0032] Preferably, the polycarbonate resin has a molecular weight distribution index of 1.6-2.4, such as 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, etc.

[0033] Preferably, the glass transition temperature of the polycarbonate resin is 127-151°C, such as 130°C, 135°C, 140°C, 145°C, 150°C, etc.

[0034] Preferably, the thermal decomposition temperature of the polycarbonate resin is ≥229℃, such as 240℃, 260℃, 280℃, etc.

[0035] In a second aspect, the present invention provides a method for preparing the extreme ultraviolet non-chemical amplification photoresist described in the first aspect, the method comprising the following steps:

[0036] Diphenyl carbonate, the first monomer forming the R1 structural unit, and the second monomer forming the R2 structural unit are mixed and subjected to bulk melt polymerization to obtain a polycarbonate resin, namely the extreme ultraviolet non-chemical amplification photoresist.

[0037] The extreme ultraviolet non-chemical amplification photoresist described in this invention has the characteristics of simple preparation, readily available raw materials, low operational difficulty, and wide applicability.

[0038] Preferably, the method for preparing the second monomer includes the following steps:

[0039] (a) 4-hydroxystyrene, dithiol, initiator and solvent are mixed and crosslinked to obtain a bisphenol monomer with a thioether structure;

[0040] (b) The bisphenol monomer with thioether structure, m-chloroperoxybenzoic acid and solvent are mixed and reacted to obtain the bisphenol monomer with sulfone structure, which is the second monomer.

[0041] Preferably, in step (a), the initiator includes a photoinitiator.

[0042] Preferably, the initiator comprises any one or a combination of at least two of benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin butyl ether, wherein typical but non-limiting combinations include: a combination of benzoin dimethyl ether and benzoin ethyl ether, a combination of benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether, a combination of benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin butyl ether, etc.

[0043] Preferably, the solvent comprises any one or a combination of at least two of tetrahydrofuran, butanone, or cyclopentanone, wherein typical but non-limiting combinations include: a combination of tetrahydrofuran and butanone, a combination of butanone and cyclopentanone, a combination of tetrahydrofuran, butanone, and cyclopentanone, etc.

[0044] Preferably, the crosslinking reaction is followed by separation and drying.

[0045] Preferably, in step (b), the reaction temperature is 10-40°C, such as 15°C, 20°C, 25°C, 30°C, 35°C, etc.

[0046] Preferably, the reaction is followed by washing and drying.

[0047] Preferably, the ratio of the molar number of diphenyl carbonate to the total molar number of the first monomer and the second monomer is (1.05-1.1):1, wherein 1.05-1.1 can be 1.06, 1.07, 1.08, 1.09, etc.

[0048] Preferably, the raw materials for the bulk melt polymerization preparation further include a catalyst, and optionally, additional agents.

[0049] Preferably, the catalyst comprises any one or a combination of at least two of tetrabutyl titanate, lithium acetylacetonate, lithium carbonate, or cesium carbonate, wherein typical but non-limiting combinations include: a combination of tetrabutyl titanate and lithium acetylacetonate, a combination of lithium acetylacetonate, lithium carbonate, and cesium carbonate, a combination of tetrabutyl titanate, lithium acetylacetonate, lithium carbonate, and cesium carbonate, etc.

[0050] Preferably, the adjuvant comprises any one or a combination of at least two of tetramethylguanidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, 7-methylhexabicycloguanidine, or tetrabutylammonium hydroxide, wherein typical but non-limiting combinations include: a combination of tetramethylguanidine and 4-dimethylaminopyridine, a combination of 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, and 7-methylhexabicycloguanidine, a combination of 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, 7-methylhexabicycloguanidine, and tetrabutylammonium hydroxide, etc.

[0051] Preferably, the bulk melt polymerization is carried out under a protective atmosphere.

[0052] Preferably, the bulk melt polymerization includes a first polymerization reaction, a second polymerization reaction, a third polymerization reaction, and a fourth polymerization reaction.

[0053] Preferably, the temperature of the first polymerization reaction is 150-160℃, such as 152℃, 154℃, 156℃, 158℃, etc.

[0054] Preferably, the system temperature is set to 150-160°C (e.g., 152°C, 154°C, 156°C, 158°C, etc.), and a protective atmosphere is provided to the bottom of the reactor.

[0055] Preferably, the flow rate of the protective atmosphere for the first polymerization reaction is 0.5-3 mL / min, such as 1 mL / min, 1.5 mL / min, 2 mL / min, 2.5 mL / min, etc.

[0056] Preferably, the temperature of the second polymerization reaction is 235-255℃, such as 240℃, 245℃, 250℃, etc.

[0057] Preferably, the second polymerization reaction takes 1-10 hours, such as 2 hours, 4 hours, 6 hours, 8 hours, etc.

[0058] Preferably, the rotation speed of the first polymerization reaction and the second polymerization reaction is 70-150 rpm, such as 80 rpm, 100 rpm, 120 rpm, 140 rpm, etc.

[0059] Preferably, the temperature of the third polymerization reaction is ≤260℃, such as 258℃, 256℃, 254℃, etc.

[0060] Preferably, the rotation speed of the third polymerization reaction is 50-70 rpm, such as 55 rpm, 60 rpm, 65 rpm, etc.

[0061] Preferably, the pressure of the third polymerization reaction is ≤1.5kPa, such as 1.4kPa, 1.3kPa, 1.2kPa, 1.1kPa, 1.0kPa, etc.

[0062] Preferably, the temperature of the fourth polymerization reaction is 265-275℃, such as 266℃, 268℃, 270℃, 272℃, 274℃, etc.

[0063] Preferably, the rotation speed of the fourth polymerization reaction is 100-150 rpm, such as 110 rpm, 120 rpm, 130 rpm, 140 rpm, etc.

[0064] Preferably, the pressure of the fourth polymerization reaction is ≤30Pa, for example, 25Pa, 20Pa, 15Pa, etc.

[0065] As a preferred technical solution, the preparation method includes the following steps:

[0066] (1) Mix 4-hydroxystyrene, dithiol, initiator and solvent, carry out cross-linking reaction, separate and dry to obtain bisphenol monomer with thioether structure;

[0067] A sulfone-structured bisphenol monomer, m-chloroperoxybenzoic acid, and a solvent were mixed and reacted at 10-40°C. The mixture was then washed and dried to obtain a sulfone-structured bisphenol monomer, which was the second monomer.

[0068] (2) Mix diphenyl carbonate, the first monomer, the second monomer and the catalyst. Under a protective atmosphere, heat the mixture at 70-150 rpm to 150-160°C, and introduce the protective atmosphere to the bottom of the reaction vessel. Control the flow rate of the protective atmosphere to be 0.5-3.0 mL / min.

[0069] Then raise the temperature to 235-255℃ and react for 1-10 hours;

[0070] Then adjust the speed to 50-70 rpm, reduce the system pressure to ≤1.5 kPa, and maintain the temperature at ≤260℃;

[0071] The rotation speed was then adjusted to 100-150 rpm, the system pressure was reduced to ≤30 Pa, and the temperature was maintained at 265-275℃. Polycondensation was then carried out to obtain the extreme ultraviolet non-chemical amplification photoresist.

[0072] Thirdly, the present invention provides a display device comprising the extreme ultraviolet non-chemical amplification photoresist described in the first aspect.

[0073] Compared with the prior art, the present invention has the following beneficial effects:

[0074] (1) The method for synthesizing extreme ultraviolet non-chemical amplification photoresist described in this invention is simple, the raw materials are readily available, the operation is easy, and the applicability is wide.

[0075] (2) The sensitivity of the extreme ultraviolet non-chemical amplification photoresist described in this invention is 14-98 mJ / cm. 2 The resolution ranges from 19.6 to 51.8 nm. It possesses excellent specifications and processing performance, meeting the requirements for applications in EUV lithography. Detailed Implementation

[0076] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0077] Example 1

[0078] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0079]

[0080] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0081] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0082] (1) Preparation of the second monomer:

[0083] Weigh 360.45 g (3 mol) of 4-hydroxystyrene and 141.3 g (1.5 mol) of ethylenedithiol into a glass bottle, add 0.38 g (5 mol%) of benzoin dimethyl ether (photoinitiator), and dissolve thoroughly in 100 mL of THF. Place the glass bottle in an ultraviolet crosslinker and irradiate at a wavelength of λ = 365 nm for 24 h. After the reaction is complete, separate by column chromatography using an eluent of V (petroleum ether):V (cyclopentanone) = 2:1, and dry under vacuum at 40 °C for 24 h to obtain the bisphenol monomer with a thioether structure.

[0084] Weigh out 334.11 g (1 mol) of thioether-structured bisphenol monomer, dissolve it in THF, add m-CPBA (690.28 g, 4 mol), and stir at room temperature for 10 h. After the reaction is complete, precipitate is precipitated by adding cold methanol dropwise, washed three times, and dried in a vacuum drying oven at 40 °C for 24 h to obtain the second monomer.

[0085] The preparation process of the second monomer is shown in the following formula:

[0086]

[0087] (2) Preparation of polycarbonate materials

[0088] 989.7 g (4.62 mol) of diphenyl carbonate, 211.5 g (0.88 mol) of hydrogenated bisphenol A, 441.3 g (3.02 mol) of isosorbide, 199.05 g (0.5 mol) of the second monomer, 0.073 g of cesium carbonate, and 0.13 g of 4-dimethylaminopyridine were added to a 2 L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, with stirring at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor, with a flow rate of 0.6 mL / min. The temperature was then gradually increased to 240 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0089] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 272℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 0.61 dL / g, the vacuum was removed, and the material was discharged under pressure to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist with a number-average molecular weight of 13065 g / mol.

[0090] Example 2

[0091] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0092]

[0093] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0094] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0095] (1) The second monomer in this embodiment is the same as that in Example 1.

[0096] (2) Preparation of polycarbonate materials

[0097] 989.7 g (4.62 mol) of diphenyl carbonate, 321.5 g (2.2 mol) of isosorbide, 197.5 g (1.7 mol) of 1,4-cyclohexanediol, 199.05 g (0.5 mol) of the second monomer, 0.06 g of lithium acetylacetonate, and 0.10 g of 4-dimethylaminopyridine were added to a 2 L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, with stirring at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor at a flow rate of 0.5 mL / min. The temperature was then gradually increased to 245 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0098] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 270℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 0.52 dL / g, the vacuum was removed, and the material was discharged under pressure to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist, with a number-average molecular weight of 9657 g / mol.

[0099] Example 3

[0100] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0101]

[0102] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0103] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0104] (1) The second monomer in this embodiment is the same as that in Example 1.

[0105] (2) Preparation of polycarbonate materials

[0106] 989.7 g (4.62 mol) of diphenyl carbonate, 321.5 g (2.2 mol) of isosorbide, 333.7 g (1.7 mol) of dicyclohexanediol, 199.05 g (0.5 mol) of the second monomer, 0.08 g of tetrabutyl titanate, and 0.14 g of tetramethylguanidine were added to a 2 L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, with stirring at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor, with a flow rate of 0.8 mL / min. The temperature was then gradually increased to 245 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0107] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 275℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 0.77 dL / g, the vacuum was removed, and the material was discharged under pressure to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist, with a number-average molecular weight of 17326 g / mol.

[0108] Example 4

[0109] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0110]

[0111] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0112] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0113] (1) The second monomer in this embodiment is the same as that in Example 1.

[0114] (2) Preparation of polycarbonate materials

[0115] 989.7 g (4.62 mol) of diphenyl carbonate, 440.7 g (2.2 mol) of spirodiol, 333.7 g (1.7 mol) of 4,8-tricyclo[5.2.1.O2,6]decanediethanol, 199.05 g (0.5 mol) of the second monomer, 0.09 g of lithium acetylacetonate, and 0.16 g of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to a 2L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, and the reactor was stirred at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor, with the nitrogen flow rate controlled at 0.8 mL / min. The temperature was then gradually increased to 245 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0116] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 270℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 0.69 dL / g, the vacuum was removed, and the material was discharged under pressure to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist, with a number-average molecular weight of 15389 g / mol.

[0117] Example 5

[0118] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0119]

[0120] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0121] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0122] (1) The second monomer in this embodiment is the same as that in Example 1.

[0123] (2) Preparation of polycarbonate materials

[0124] 989.7 g (4.62 mol) of diphenyl carbonate, 440.7 g (2.2 mol) of spirodiol, 333.7 g (1.7 mol) of 1,3-adamantimil, 199.05 g (0.5 mol) of the second monomer, 0.09 g of lithium acetylacetonate, and 0.16 g of 7-methylhexacyclic bicyclic guanidine were added to a 2 L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, with stirring at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor, with a flow rate controlled at 1.0 mL / min. The temperature was then gradually increased to 245 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0125] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 270℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 1.01 dL / g, the vacuum was removed, and the material was discharged under pressure to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist with a number-average molecular weight of 25896 g / mol.

[0126] Example 6

[0127] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0128]

[0129] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0130] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0131] (1) The second monomer in this embodiment is the same as that in Example 1.

[0132] (2) Preparation of polycarbonate materials

[0133] 989.7 g (4.62 mol) of diphenyl carbonate, 440.7 g (2.2 mol) of spirodiol, 285.9 g (1.7 mol) of 1,3-adamantanediol, 199.05 g (0.5 mol) of the second monomer, 0.08 g of tetrabutyl titanate, and 0.15 g of 1,8-diazabicyclo[5.4.0]undec-7-ene were added to a 2L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, and the reactor was stirred at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor, with the nitrogen flow rate controlled at 0.8 mL / min. The temperature was then gradually increased to 250 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0134] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 275℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 0.8 dL / g, the vacuum was removed, and the material was pressurized and discharged to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist, with a number-average molecular weight of 18979 g / mol.

[0135] Example 7

[0136] This embodiment provides an extreme ultraviolet (EUV) non-chemical amplification photoresist, which is a polycarbonate-based material. The structural formula of the polycarbonate material is as follows:

[0137]

[0138] The ratio of m to n is determined by the feeding ratio of each raw material and the preparation process described below.

[0139] The preparation method of the extreme ultraviolet non-chemical amplification photoresist includes the following steps:

[0140] (1) The second monomer in this embodiment is the same as that in Example 1.

[0141] (2) Preparation of polycarbonate materials

[0142] 989.7 g (4.62 mol) of diphenyl carbonate, 440.7 g (2.2 mol) of spirodiol, 197.5 g (1.7 mol) of 1,4-cyclohexanediol, 199.05 g (0.5 mol) of the second monomer, 0.07 g of cesium carbonate, and 0.13 g of tetramethylguanidine were added to a 2 L stainless steel reactor. After the raw materials and catalyst were added, the air inside the stainless steel reactor was purged with nitrogen three times. The temperature was then gradually increased at a rate of 5 °C / min, with stirring at 100 rpm. When the reactor temperature reached 155 °C, nitrogen was introduced to the bottom of the reactor at a flow rate of 0.7 mL / min. The temperature was then gradually increased to 245 °C at a rate of 4 °C / min, and the reaction was carried out for 5 hours. The mass of the byproduct phenol was collected to calculate the conversion rate. The reaction was terminated when the conversion rate was >95%.

[0143] Continue heating and adjust the rotation speed to 60 rpm. Slowly reduce the pressure to 1 kPa within 30 minutes, maintaining the reactor temperature at 260℃. Then, gradually reduce the pressure to below 30 Pa within 30 minutes and adjust the rotation speed to 120 rpm for a high-vacuum polycondensation reaction, maintaining the reactor temperature at 270℃. Sampling and analysis were performed. Stirring was stopped when the polymer viscosity reached 0.89 dL / g, the vacuum was removed, and the material was discharged under pressure to obtain a polycarbonate sample, which is the extreme ultraviolet non-chemically amplified photoresist, with a number-average molecular weight of 21668 g / mol.

[0144] Performance testing

[0145] 1. The extreme ultraviolet non-chemical amplification photoresists described in Examples 1-7 were subjected to the following tests:

[0146] (1) IV (Intrinsic Viscosity): GB / T 14190-2008 Test Method for Fiber Grade Polyester Chips (PET).

[0147] (2) Mn (number average molecular weight): Detected by Waters e2695 gel chromatography with a 2414RI detector, a Styragel HR3 5μm 7.8×300mm (THF) column, and chloroform as the mobile phase.

[0148] (3)T g (Glass transition temperature): GB / T 19466.2-2004 Plastics. Differential scanning calorimetry (DSC).

[0149] (4) Molecular weight distribution index: Same as the reference standard for number-average molecular weight test.

[0150] (5)T d GB / T 31850-2015 Method for determining the thermal decomposition temperature of non-metallic sealing materials.

[0151] The test results are summarized in Table 1.

[0152] Table 1

[0153]

[0154] Analysis of the data in Table 1 shows that the intrinsic viscosity of the extreme ultraviolet non-chemical amplification photoresist described in this invention is between 0.52 and 1.01 dL / g, the number-average molecular weight is between 9657 and 25896 g / mol, the glass transition temperature is between 127 and 151℃, the molecular weight distribution index is between 1.6 and 2.4, and the thermal decomposition temperature is above 229℃. The extreme ultraviolet non-chemical amplification photoresist described in this invention has the advantages of simple synthesis method, readily available raw materials, low operation difficulty, and wide applicability.

[0155] 2. Evaluation of the extreme ultraviolet non-chemical amplification photoresists described in Examples 1-7 using EUV photoresist:

[0156] The polycarbonate prepared above was dissolved in methyl isobutyl ketone. After complete dissolution, it was coated onto a silicon wafer and baked at 150°C for 200 seconds to remove the solvent. The film thickness was 50 nm. The dosage was 10–150 mJ / cm². 2 The silicon wafer is exposed to light and then developed using a mixture of isopropanol and 5% methyl isobutyl ketone. Technical parameters such as exposure dose and critical linewidth at a 100nm half-pitch are statistically analyzed. The exposure dose reflects sensitivity; a lower exposure dose results in higher sensitivity. The critical linewidth reflects resolution; a smaller critical linewidth results in higher resolution.

[0157] The test results are summarized in Table 2.

[0158] Table 2

[0159] <![CDATA[Exposure dose, mJ / cm 2 > Critical linewidth, nm Example 1 50 27.5 Example 2 83 48.2 Example 3 98 51.8 Example 4 20 19.6 Example 5 25 28.8 Example 6 20 29.5 Example 7 14 37.3

[0160] Analysis of the data in Table 2 shows that the exposure dose of the extreme ultraviolet non-chemical amplification photoresist described in this invention is between 14 and 98 mJ / cm². 2 The critical linewidth is between 19.6 and 51.8 nm; further, it was found that the sensitivity of the extreme ultraviolet non-chemical amplification photoresist described in this invention can reach 15 mJ / cm. 2 The highest sensitivity is 14 mJ / cm. 2 Meanwhile, the resolution can reach below 20nm, with a maximum resolution of 19.6nm; this is comparable to the level of non-CAR photoresists used in EUV applications. For example, the mainstream non-CAR photoresist PMMA has a sensitivity of 20mJ / cm. 2For resolutions below 20nm, the carbonate-based photoresist described in this invention achieves the performance of mainstream photoresists. Furthermore, the extreme ultraviolet (EUV) non-chemically amplified photoresist described in this invention possesses excellent properties and processing performance, meeting the requirements for applications in the EUV lithography field.

[0161] The present invention has been illustrated with the above embodiments to explain the detailed method of the present invention. However, the present invention is not limited to the detailed method described above, that is, it does not mean that the present invention must rely on the detailed method described above to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. An extreme ultraviolet non-chemical amplification photoresist, characterized in that, The extreme ultraviolet non-chemically amplified photoresist is a polycarbonate resin, and the polycarbonate resin has the structure shown in Formula I: Formula I; Where m and n are independent integers between 1 and 200; R1 is the structural unit formed by the first monomer, which is a diol; R2 is the structural unit formed by the second monomer, which has the following structure: ； Where x is an integer from 2 to 12; The first monomer is selected from any one or a combination of at least two of the following structures: 。 2. The extreme ultraviolet non-chemical amplification photoresist according to claim 1, characterized in that, The raw materials for preparing the second monomer include 4-hydroxystyrene and dithiol.

3. The extreme ultraviolet non-chemical amplification photoresist according to claim 2, characterized in that, The dithiol includes any one of ethylenedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 2,3-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol, or n-dodecylthiol.

4. The extreme ultraviolet non-chemical amplification photoresist according to claim 1, characterized in that, The polycarbonate resin includes any one or a combination of at least two of the following compounds: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； Where each m is an independent integer between 1 and 200; n is an integer between 1 and 200, each of which is independent.

5. The extreme ultraviolet non-chemical amplification photoresist according to claim 1, characterized in that, The intrinsic viscosity of the polycarbonate resin is 0.52-1.01 dL / g.

6. The extreme ultraviolet non-chemical amplification photoresist according to claim 1, characterized in that, The number-average molecular weight of the polycarbonate resin is 9657-25896 g / mol.

7. The extreme ultraviolet non-chemical amplification photoresist according to claim 1, characterized in that, The molecular weight distribution index of the polycarbonate resin is 1.6-2.

4.

8. The extreme ultraviolet non-chemically amplified photoresist according to claim 1, characterized in that, The glass transition temperature of the polycarbonate resin is 127-151℃.

9. The extreme ultraviolet non-chemical amplification photoresist according to claim 1, characterized in that, The thermal decomposition temperature of the polycarbonate resin is ≥229℃.

10. A method for preparing the extreme ultraviolet non-chemically amplified photoresist according to any one of claims 1-9, characterized in that, The preparation method includes the following steps: Diphenyl carbonate, the first monomer forming the R1 structural unit, and the second monomer forming the R2 structural unit are mixed and subjected to bulk melt polymerization to obtain a polycarbonate resin, namely the extreme ultraviolet non-chemical amplification photoresist.

11. The preparation method according to claim 10, characterized in that, The preparation method of the second monomer includes the following steps: (a) 4-hydroxystyrene, dithiol, initiator and solvent are mixed and crosslinked to obtain a bisphenol monomer with a thioether structure; (b) The bisphenol monomer with thioether structure, m-chloroperoxybenzoic acid and solvent are mixed and reacted to obtain the bisphenol monomer with sulfone structure, which is the second monomer.

12. The preparation method according to claim 11, characterized in that, In step (a), the initiator includes a photoinitiator.

13. The preparation method according to claim 11, characterized in that, The initiator includes any one or a combination of at least two of the following: benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin butyl ether.

14. The preparation method according to claim 11, characterized in that, The solvent in steps (a) and (b) includes any one or a combination of at least two of tetrahydrofuran, butanone, or cyclopentanone.

15. The preparation method according to claim 11, characterized in that, The crosslinking reaction is followed by separation and drying.

16. The preparation method according to claim 11, characterized in that, In step (b), the reaction temperature is 10-40°C.

17. The preparation method according to claim 11, characterized in that, In step (b), the reaction is followed by washing and drying.

18. The preparation method according to claim 10, characterized in that, The ratio of the molar number of diphenyl carbonate to the total molar number of the first and second monomers is (1.05-1.1):

1.

19. The preparation method according to claim 10, characterized in that, The raw materials for the bulk melt polymerization preparation also include a catalyst.

20. The preparation method according to claim 10, characterized in that, The raw materials for the bulk melt polymerization preparation also include additives.

21. The preparation method according to claim 19, characterized in that, The catalyst comprises any one or a combination of at least two of tetrabutyl titanate, lithium acetylacetonate, lithium carbonate, or cesium carbonate.

22. The preparation method according to claim 20, characterized in that, The adjuvant includes any one or a combination of at least two of the following: tetramethylguanidine, 4-dimethylaminopyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 1,5,7-triazidobicyclo(4.4.0)dec-5-ene, 7-methylhexabicycloguanidine, or tetrabutylammonium hydroxide.

23. The preparation method according to claim 10, characterized in that, The bulk melt polymerization is carried out under a protective atmosphere.

24. The preparation method according to claim 10, characterized in that, The bulk melt polymerization includes a first polymerization reaction, a second polymerization reaction, a third polymerization reaction, and a fourth polymerization reaction.

25. The preparation method according to claim 24, characterized in that, The temperature of the first polymerization reaction is 150-160℃.

26. The preparation method according to claim 10, characterized in that, The system temperature is raised to 150-160℃, and a protective atmosphere is introduced to the bottom of the reactor.

27. The preparation method according to claim 24, characterized in that, The flow rate of the protective atmosphere for the first polymerization reaction is 0.5-3 mL / min.

28. The preparation method according to claim 24, characterized in that, The temperature of the second stage polymerization reaction is 235-255℃.

29. The preparation method according to claim 24, characterized in that, The second stage of polymerization reaction takes 1-10 hours.

30. The preparation method according to claim 24, characterized in that, The rotation speeds of the first and second polymerization reactions are 70-150 rpm.

31. The preparation method according to claim 24, characterized in that, The temperature of the third polymerization reaction is ≤260℃.

32. The preparation method according to claim 24, characterized in that, The rotation speed of the third polymerization reaction is 50-70 rpm.

33. The preparation method according to claim 24, characterized in that, The pressure of the third polymerization reaction is ≤1.5 kPa.

34. The preparation method according to claim 24, characterized in that, The temperature of the fourth polymerization reaction is 265-275℃.

35. The preparation method according to claim 24, characterized in that, The rotation speed of the fourth polymerization reaction is 100-150 rpm.

36. The preparation method according to claim 24, characterized in that, The pressure of the fourth polymerization reaction is ≤30Pa.

37. The preparation method according to claim 10, characterized in that, The preparation method includes the following steps: (1) Mix 4-hydroxystyrene, dithiol, initiator and solvent, carry out cross-linking reaction, separate and dry to obtain bisphenol monomer with thioether structure; A sulfone-structured bisphenol monomer, m-chloroperoxybenzoic acid, and a solvent were mixed and reacted at 10-40°C. The mixture was then washed and dried to obtain a sulfone-structured bisphenol monomer, which was the second monomer. (2) Mix diphenyl carbonate, the first monomer, the second monomer and the catalyst. Under a protective atmosphere, heat the mixture at 70-150 rpm to 150-160°C, and introduce the protective atmosphere to the bottom of the reaction vessel. Control the flow rate of the protective atmosphere to be 0.5-3.0 mL / min. Then raise the temperature to 235-255℃ and react for 1-10 h; Then adjust the rotation speed to 50-70 rpm, reduce the system pressure to ≤1.5 kPa, and maintain the temperature at ≤260℃; The rotation speed was then adjusted to 100-150 rpm, the system pressure was reduced to ≤30 Pa, and the temperature was maintained at 265-275℃ to induce condensation and obtain the extreme ultraviolet non-chemical amplification photoresist.

38. A display device, characterized in that, The display device includes the extreme ultraviolet non-chemical amplification photoresist according to any one of claims 1-9.

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