Monomolecular weight photoresist, method of making and using same

Abstract

The present disclosure provides a preparation method of a single molecular weight photoresist, comprising: preparing a single molecular weight compound by reacting a compound containing a hydroxyl group and a capping group with a compound having a TBS-protected hydroxyl group and an acyl azide group as end groups; connecting the capping group to one end of the single molecular weight compound and connecting the TBS-protected group to the other end; when chain extension is required, performing a deprotection reaction on the single molecular weight compound, and then reacting it with a group containing an acyl azide; and through iterative deprotection and chain extension of the single molecular weight compound, a target compound is prepared. The single molecular weight photoresist prepared by the preparation method provided by the present disclosure, under the action of an electron beam or EUV, causes the main chain of the exposed region to break or further polymerize, so that the dissolution rate of the exposed and non-exposed regions is significantly different, thus it is expected to shorten the development time, avoid overexposure and achieve a synergistic improvement in resolution and sensitivity.

Description

Technical Field

[0001] This disclosure relates to the field of semiconductor technology, and in particular to a single molecular weight photoresist, its preparation method, and its application. Background Technology

[0002] Large-scale integrated circuits and semiconductor chip technology have become the core foundation of advanced manufacturing and information technology. The integrated circuit industry involves several core processes, such as photolithography, etching, and ion implantation; among them, photolithography is a prerequisite for subsequent etching and ion implantation. Besides specialized photolithography equipment, the success of the photolithography process heavily depends on the quality and performance of the photoresist material. Simply optimizing process parameters and processing conditions is no longer sufficient to meet the current demands of photoresist materials. Furthermore, shorter wavelength light beams place more stringent requirements on the performance of photoresist materials.

[0003] Traditional photoresists only involve reactions of polymer side chain functional groups, resulting in a less significant difference in dissolution rates between exposed and unexposed areas. This necessitates longer development times, negatively impacting the synergistic improvement of photoresist resolution and sensitivity. Furthermore, traditional photoresists are typically multi-component systems, which often exhibit uneven dispersion and interactions between different components, affecting development performance. Summary of the Invention

[0004] In view of the above, in order to solve at least one technical problem described in the related art and in order to achieve the above objectives, the technical solution of this disclosure is as follows:

[0005] This disclosure discloses a method for preparing a single molecular weight photoresist, comprising:

[0006] Compound J was prepared from compounds shown in formula G and H.

[0007]

[0008] Where 0≤m≤2, R1, R2, and R3 are independently selected from -F, -Cl, -Br, -I, -NO2, -H, Cl~C 20 alkane group, C2-C 20 olefinic group, C2-C 20 alkyne group, C1-C 20 alkoxy groups, C2-C 20 The olefinic group or C2~C 20 One of the alkynyl groups, where R is a functional group used to regulate the film-forming properties of single molecular weight photoresists;

[0009] With compounds Using the compound shown in formula H or formula J as a starting material, the compound shown in formula K is prepared, where i is 1 or 2, and T is a capping group;

[0010]

[0011] The compound shown in formula K was subjected to a deprotection reaction to obtain the compound shown in formula L.

[0012]

[0013] Iterate the compound shown in formula L to obtain a new compound. Repeat the rearrangement and deprotection reactions until a single molecular weight photoresist with the target molecular weight is obtained.

[0014] According to embodiments of this disclosure, it further includes: a compound of formula G, wherein the compound of formula G comprises:

[0015] The compound shown in formula D was reduced by sodium borohydride as a reducing agent to obtain the compound shown in formula E.

[0016]

[0017] The compound shown in formula E was reacted to obtain the compound shown in formula F.

[0018]

[0019] The compound shown in formula F was reacted to obtain the compound shown in formula G.

[0020]

[0021] According to embodiments of this disclosure, it further includes: preparing the compound represented by formula H, wherein the compound represented by formula H comprises:

[0022] Using the compound shown in formula G as a raw material, the hydroxyl group in the compound shown in formula G is protected to prepare the compound shown in formula H.

[0023]

[0024] According to embodiments of this disclosure, it further includes: preparing the compound shown in formula D, wherein the compound shown in formula D comprises:

[0025] The compound shown in formula A and compound RBr were reacted as raw materials to prepare the compound shown in formula B.

[0026]

[0027] The compound shown in formula B was reacted to obtain the compound shown in formula C.

[0028]

[0029] The compound shown in formula C was reacted to obtain the compound shown in formula D.

[0030]

[0031] According to embodiments of this disclosure, R is any one of the following structures:

[0032]

[0033] Where 1≤a≤20.

[0034] According to embodiments of this disclosure, wherein, It can be any of the following structures:

[0035]

[0036] Among them, R4, R5, and R6 are independently selected from -F, -Cl, -Br, -I, -NO2, -H, Cl~C 20 alkane group, C2~C 20 olefinic group, C2~C 20 Alkyne group, C1~C 20 alkoxy groups, C2~C 20 The olefinic group or C2~C 20 One of the alkynyl groups.

[0037] According to embodiments of this disclosure, wherein,

[0038] After the rearrangement reaction, column chromatography is required to obtain the compound.

[0039] According to embodiments of this disclosure, wherein,

[0040] The compound shown in formula J was obtained by column chromatography purification;

[0041] The compound shown in formula K was obtained by column chromatography purification.

[0042] In another aspect of this disclosure, a single molecular weight photoresist is disclosed, having the structure shown in formula (I):

[0043]

[0044] Where n is 0 to 20.

[0045] In another aspect of this disclosure, a method for preparing a film layer using photoresist is disclosed, comprising:

[0046] The photoresist is added to the solvent, shaken, dissolved, and filtered to obtain a photoresist solution;

[0047] A photoresist solution is coated onto a substrate, and after drying, a film is obtained.

[0048] According to embodiments of this disclosure, wherein,

[0049] The concentration of the photoresist solution is 4 mg / mL to 80 mg / mL;

[0050] The thickness of the film is 10nm-5000nm.

[0051] In another aspect of this disclosure, the application of a single molecular weight photoresist in electron beam photoresist or extreme ultraviolet photoresist is disclosed.

[0052] Based on the above technical solution, the beneficial effects of this disclosure are as follows:

[0053] The single-molecular-weight photoresist disclosed herein causes chain growth or breakage of the polymer backbone in the exposed region under the action of an electron beam or EUV, resulting in a significant difference in the dissolution rate between the exposed and unexposed regions. Therefore, it is expected to shorten the development time, avoid overexposure, and achieve a synergistic improvement in resolution and sensitivity.

[0054] The single-molecule photoresist disclosed herein has a defined chain structure and chain length, thus possessing a precise molecular weight. Each molecular chain is identical, allowing for precise control of the monomer, resulting in superior stability during exposure and development steps, facilitating improved development resolution. Furthermore, the photoresist, controlled by development parameters, can be used as both positive and negative photoresist. The developer solution is acid- and alkali-free, making it substrate-friendly. Attached Figure Description

[0055] Figure 1 The 1H NMR spectrum of the compound shown in B-1 prepared according to Example 1;

[0056] Figure 2 The 1H NMR spectrum of the compound shown in D-1 prepared according to Example 1;

[0057] Figure 3 The 1H NMR spectrum of the compound E-1 prepared according to Example 1;

[0058] Figure 4 The 1H NMR spectrum of the compound shown in F-1 prepared according to Example 1;

[0059] Figure 5 The 1H NMR spectrum of the compound G-1 prepared according to Example 1;

[0060] Figure 6The 1H NMR spectrum of the compound shown in H-1 prepared according to Example 1;

[0061] Figure 7 The 1H NMR spectrum of the compound J-1 prepared according to Example 1;

[0062] Figure 8 The 1H NMR spectrum of the compound shown in L-1 prepared according to Example 1;

[0063] Figure 9 The 1H NMR spectrum of the compound M-1 prepared according to Example 1;

[0064] Figure 10a The electron beam exposure and development pattern obtained according to Application Example 1 is a positive photoresist atomic force microscopy characterization pattern.

[0065] Figure 10b The negative photoresist atomic force microscopy characterization pattern obtained after electron beam exposure and development according to Application Example 1;

[0066] Figure 11a The positive photoresist atomic force microscopy characterization pattern obtained according to Application Example 2 after EUV exposure and development.

[0067] Figure 11b The image shows the negative photoresist atomic force microscopy characterization pattern obtained after EUV exposure and development according to Application Example 2. Detailed Implementation

[0068] To make the objectives, technical solutions, and advantages of this disclosure clearer, the following detailed description is provided in conjunction with specific embodiments and the accompanying drawings.

[0069] The endpoints and any values ​​of the ranges disclosed in this disclosure are not limited to the precise ranges or values, and such ranges or values ​​should be understood to include values ​​close to such ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this disclosure.

[0070] The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit this disclosure. The terms “comprising,” “including,” etc., as used herein indicate the presence of the stated features, steps, operations, and / or components, but do not exclude the presence or addition of one or more other features, steps, operations, or components.

[0071] All terms used herein (including technical and scientific terms) have the meanings commonly understood by those skilled in the art, unless otherwise defined. It should be noted that the terms used herein are to be interpreted in a manner consistent with the context of this specification, and not in an idealized or overly rigid way.

[0072] Traditional photoresists typically use resin and photoacid as raw materials. When exposed to an electron beam or light, the photoacid causes the functional groups to break down. This disclosure provides a single-molecular-weight photoresist. Its single component avoids the imbalance between resolution, line edge roughness, and sensitivity caused by reactions between multiple organic components. Furthermore, since it does not contain photoacid, it will not cause corrosion or other damage to the substrate.

[0073] Based on this, the method for preparing a single molecular weight photoresist disclosed herein effectively controls the chain length of the photoresist. It uses end-capping groups and compounds containing TBS groups as raw materials to react and form functional groups with end-capping groups at one end and TBS protection at the other. During the preparation process, a cyclical iterative process of chain growth and deprotection is utilized to control the molecular weight of the resulting compound, resulting in greater stability and controllability of the photoresist during exposure and development.

[0074] This disclosure discloses a method for preparing a single molecular weight photoresist, comprising:

[0075] Step 1: Using the compounds shown in formula G and formula H as raw materials, the compound shown in formula J is prepared.

[0076]

[0077] Where 0 ≤ m ≤ 2 (e.g., it can be 0, 1, or 2), and R1, R2, and R3 are independently selected from -F, -Cl, -Br, -I, -NO2, -H, Cl~C 20 alkane group, C2-C 20 olefinic group, C2-C 20 alkyne group, C1-C 20 alkoxy groups, C2-C 20 The olefinic group or C2~C 20 One of the alkynyl groups, where R is a functional group used to regulate the film-forming properties of single molecular weight photoresists;

[0078] Step 2: Using compounds Using the compound shown in formula H or formula J as a starting material, a rearrangement reaction is carried out to obtain the compound shown in formula K, where i is 1 or 2, and T is a capping group;

[0079]

[0080] Step 3: Perform a deprotection reaction on the compound shown in formula K to obtain the compound shown in formula L;

[0081]

[0082] Step 4: Iterate the compound shown in formula L to obtain a new compound. Repeat the rearrangement and deprotection reactions until a single molecular weight photoresist with the target molecular weight is obtained.

[0083] According to embodiments of this disclosure, a compound containing a TBS group is reacted with a capping group to form a functional group with a capping group at one end and TBS protection at the other end. Based on a protection-deprotection strategy, a single molecular weight photoresist with controllable molecular weight and structure is formed during the preparation process using a cyclic iterative process of chain growth-deprotection. The photoresist provided by this disclosure has a precise single molecular weight structure, which makes it exhibit superior stability in exposure, development, and other steps, and synergistically improves development resolution and sensitivity.

[0084] According to the embodiments of this disclosure, step one specifically includes sub-steps (i) to (ii):

[0085] Sub-step (1): Dissolve the compound shown in formula H in anhydrous toluene, remove water by azeotropic reaction, then add anhydrous toluene as solvent and react at 60-110℃ for 3-8h, then restore to room temperature; wherein, the reaction temperature can be 60℃, 80℃, 100℃, or 110℃; and the reaction time can be 3h, 5h, 6h, or 8h.

[0086] Sub-step (II): In another reaction vessel, add the compound shown in formula G and 0.5% DBTL (dibutyltin dilaurate). After azeotropic dehydration using anhydrous toluene, dissolve the compound in anhydrous THF (tetrahydrofuran). Transfer the solution to the reaction vessel previously containing the compound shown in formula H and react at room temperature for 5–15 hours. The reaction time can be 5 hours, 7 hours, 9 hours, 12 hours, or 15 hours. After the reaction is complete, use petroleum ether-ethyl acetate as eluent for column chromatography to obtain a single compound shown in formula J.

[0087] According to embodiments of this disclosure, THF can be replaced with 2-methyltetrahydrofuran, chloroform, etc.

[0088] According to an embodiment of this disclosure, the hydroxyl group in the compound shown in Formula G reacts with the azide group in the compound shown in Formula H to generate the compound shown in Formula J, wherein the compound shown in Formula J is connected to an azide group at one end and to TBS at the other end, forming a compound that can be used for a stepwise increase in reaction at one end.

[0089] According to the embodiments of this disclosure, step two specifically includes:

[0090] Hydroxyl raw materials without repeating units The compound represented by formula H or formula J, 0.5% DBTL, is dissolved in anhydrous toluene, and after azeotropic dehydration, NMP (N-methylpyrrolidone) is added as a solvent. The reaction is carried out at 60-110℃ for 3-8 hours. The reaction temperature can be 60℃, 80℃, 100℃, or 110℃; the reaction time can be 3 hours, 5 hours, 6 hours, or 8 hours.

[0091] According to the embodiments of this disclosure, step three specifically includes:

[0092] Methanol was added to dilute the reaction solution obtained in step two, and p-toluenesulfonic acid was added to remove TBS protection. The deprotected O atoms were then linked to H atoms to form exposed hydroxyl groups, allowing for polymerization. After the reaction was complete, EA (ethyl acrylate) and deionized water were added to the system for extraction. The organic phase was washed three times with saturated brine, dried, and concentrated to obtain the compound shown in formula L. Column chromatography using petroleum ether-ethyl acetate as eluent yielded the compound with a single molecular weight, as shown in formula L.

[0093] According to embodiments of this disclosure, methanol can be replaced with water or saturated brine.

[0094] According to an embodiment of this disclosure, in step four,

[0095] If compound When reacted with the compound shown in formula H, the resulting compound grows by one repeating unit; if the compound The compound shown in formula J reacts with the resulting compound, which grows two repeating units. This yields a compound shown in formula K with a capping group at one end and OTBS at the other, preventing it from undergoing further polymerization.

[0096] The single-molecule photoresist prepared by this method has a defined chain structure and chain length, thus possessing a precise molecular weight. Each molecular chain is identical, resulting in superior stability during exposure and development steps, which facilitates improved development resolution and sensitivity adjustment. Simultaneously, the single-component or single-molecule photoresist can reduce the dispersion inhomogeneity and phase separation of multi-component systems, avoiding mutual interference between different components.

[0097] It should be noted that the above expression of Ca to Cb represents that the number of carbon atoms in the group is a to b.

[0098] As C1~C 20 Examples of alkane groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecane, dodecane, etc., with methyl being preferred.

[0099] As C1~C20 Examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentooxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, etc., among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentoxy, and isopentoxy are preferred, and methoxy is more preferred.

[0100] As C2~C 20 Examples of olefin groups include vinyl, allyl, 2-methylpropyl-2-enyl, etc., with allyl being preferred.

[0101] As C2~C 20 Examples of alkyne groups include: ethynyl, propynyl, 2-methylprop-2-ynyl, etc.

[0102] As C2~C 20 Examples of olefins include ethyleneoxy, allyloxy, 2-methylprop-2-olefin, etc.

[0103] As C2~C 20 Examples of alkynyloxy groups include: acetylenoxy, propynoxy, 2-methylprop-2-alkynoxy, etc.

[0104] According to embodiments of this disclosure, the above preparation method further includes: preparing the compound represented by formula G, wherein preparing the compound represented by formula G includes:

[0105] Step 101: The compound shown in formula D is reduced using sodium borohydride as a reducing agent to obtain the compound shown in formula E.

[0106]

[0107] Step 102: Using the compound shown in Formula E as a starting material, react to obtain the compound shown in Formula F;

[0108]

[0109] Step 103: Using the compound shown in formula F as a starting material, react to obtain the compound shown in formula G;

[0110]

[0111] According to an embodiment of this disclosure, step 101 specifically includes:

[0112] The compound shown in formula D is dissolved in THF, and sodium borohydride is added in batches at 0–30°C. The reaction is carried out at room temperature for 2–12 h. The reaction temperature can be 0°C, 10°C, 20°C, or 30°C, and the reaction time can be 2 h, 5 h, 8 h, 10 h, or 12 h.

[0113] After removing THF from the system, EA and deionized water were added, followed by extraction. The organic phase was washed three times with saturated brine, and after drying and concentration, the compound shown in formula E was obtained.

[0114] According to an embodiment of this disclosure, step 102 specifically includes:

[0115] The compound shown in formula E is dissolved in methanol, potassium hydroxide is added to the system, and the mixture is refluxed for 6 to 10 hours; the reaction time can be 6 hours, 8 hours, or 10 hours.

[0116] Methanol was removed by rotary evaporation, deionized water was added, and the pH was adjusted to approximately 3 using hydrochloric acid. Extraction was performed by adding EA, and the organic phase was washed three times with saturated brine. After drying and concentration, the organic phase was given as the compound represented by formula F.

[0117] According to an embodiment of this disclosure, step 103 specifically includes:

[0118] The compound shown in formula F is dissolved in THF, and triethylamine is added to the system at 0-30°C. After stirring for 10 minutes, DPPA (azidating agent) is added dropwise to the system and the reaction is carried out at room temperature for 6-10 hours. The reaction temperature can be 0°C, 10°C, 20°C, or 30°C, and the reaction time can be 6 hours, 8 hours, or 10 hours.

[0119] After removing THF, column chromatography using petroleum ether-ethyl acetate as eluent yielded the compound shown in formula G.

[0120] According to embodiments of this disclosure, the above preparation method further includes: preparing the compound represented by formula H, wherein preparing the compound represented by formula H includes:

[0121] Using the compound shown in formula G as a raw material, the hydroxyl group in the compound shown in formula G is protected to prepare the compound shown in formula H.

[0122]

[0123] According to embodiments of this disclosure, the steps for preparing the compound represented by formula H specifically include:

[0124] The compound shown in formula G is dissolved in DCM (dichloromethane), and imidazole is added to the system at 0-30°C. After stirring for 10 minutes, TBSCl (tert-butyldimethylchlorosilane) is added to the system, and the reaction is carried out at room temperature for 5-8 hours. The reaction temperature can be 0°C, 10°C, 20°C, or 30°C, and the reaction time can be 5 hours, 6 hours, 7 hours, or 8 hours.

[0125] DCM (dichloromethane) was added to the system for dilution, followed by the addition of deionized water. The mixture was then extracted, and the organic phase was washed three times with saturated brine. After drying and concentrating the organic phase, the compound represented by formula H was obtained.

[0126] According to embodiments of this disclosure, the above preparation method further includes: preparing the compound represented by formula D, wherein preparing the compound represented by formula D includes:

[0127] Step 201: React the compound shown in Formula A and compound RBr as raw materials to obtain the compound shown in Formula B;

[0128]

[0129] Step 202: Using the compound shown in Formula B as a raw material, react to obtain the compound shown in Formula C;

[0130]

[0131] Step 203: Using the compound shown in Formula C as a raw material, react to obtain the compound shown in Formula D;

[0132]

[0133] According to an embodiment of this disclosure, step 201 further includes:

[0134] The compound shown in Formula A, compound R-Br, and potassium carbonate are dissolved in DMF and reacted under nitrogen protection at 50–85 °C for 6–15 h; wherein the reaction temperature can be 50 °C, 60 °C, 75 °C, or 85 °C; and the reaction time can be 6 h, 8 h, 10 h, 12 h, or 15 h.

[0135] The solvent DMF was removed by evaporation, and the organic phase was dissolved in ethyl acetate. The organic phase was washed with saturated brine, dried and concentrated, and then column chromatography was performed using petroleum ether-ethyl acetate as eluent to obtain the compound shown in formula B.

[0136] According to embodiments of this disclosure, the Br in R-Br can be replaced with groups such as F, I, OTs, etc., that can achieve equivalent efficacy (etherification with phenolic hydroxyl groups).

[0137] According to an embodiment of this disclosure, step 202 further includes:

[0138] The compound shown in Formula B, NBS (N-bromosuccinimide), and AIBN (azobisisobutyronitrile) were dissolved in CCl4 and refluxed under nitrogen protection for 8–24 h; wherein the reaction time could be 8 h, 10 h, 15 h, 20 h, 22 h, or 24 h.

[0139] After the reaction was completed, the insoluble solids were removed by filtration, the filtrate was washed three times with saturated brine, and the organic phase was dried and concentrated to obtain the compound shown in formula C.

[0140] According to an embodiment of this disclosure, step 203 further includes:

[0141] The compound shown in formula C is slowly added to morpholine, using morpholine as both a solvent and a reactant, and the reaction is carried out at 30–60°C for 8–16 h; wherein the reaction temperature can be 30°C, 40°C, 50°C, or 60°C; and the reaction time can be 8 h, 10 h, 12 h, 14 h, or 16 h.

[0142] Excess morpholine was removed by rotation, and the mixture was extracted with a large amount of ethyl acetate and water. The organic phase was washed multiple times with 1 mol / L hydrochloric acid and then three times with saturated brine. After drying and concentrating the organic phase, column chromatography with petroleum ether-ethyl acetate as eluent was used to obtain the compound shown in formula D.

[0143] According to embodiments of this disclosure, wherein,

[0144] R can be any of the following structures:

[0145]

[0146] Where 1≤a≤20, for example, a can be 1, 2, 4, 6, 8, 12, 16, 20, etc.

[0147] According to embodiments of this disclosure, the aforementioned R groups in the single molecular weight photoresist can adjust the physical and chemical properties of the photoresist, such as improving the coating effect, promoting microphase separation during patterning, and enabling further cross-linking of the photoresist or providing space for post-modification.

[0148] According to embodiments of this disclosure, wherein,

[0149] It can be any of the following structures:

[0150]

[0151] Among them, R4, R5, and R6 are independently selected from -F, -Cl, -Br, -I, -NO2, -H, Cl~C 20 alkane group, C2~C 20 olefinic group, C2~C 20Alkyne group, C1~C 20 alkoxy groups, C2~C 20 The olefinic group or C2~C 20 One of the alkynyloxy groups. According to embodiments of this disclosure, wherein...

[0152] Following the rearrangement reaction, column chromatography is required to obtain the compound.

[0153] According to embodiments of this disclosure, wherein,

[0154] The compound represented by formula J was obtained by column chromatography purification.

[0155] The compound represented by formula K was obtained by column chromatography purification.

[0156] Another aspect of this disclosure also discloses a single molecular weight photoresist having the structure shown in formula (I):

[0157]

[0158] Where n ranges from 0 to 20, and m, R1 to R3, and R have the same meanings as described above. This single-molecule photoresist has a defined chain structure and chain length, thus possessing a precise molecular weight. Each molecular chain is identical, resulting in superior stability during exposure and development steps, facilitating improved development resolution and sensitivity adjustment. Simultaneously, the single-component or single-molecule photoresist can reduce dispersion inhomogeneity and phase separation in multi-component systems, avoiding mutual interference between different components.

[0159] According to embodiments of this disclosure, m can be 0, 1, or 2. Increasing the value of m will increase the difficulty of preparation and make the raw materials more expensive.

[0160] According to embodiments of this disclosure, wherein,

[0161] n can be 1, 5, 6, 8, 10, 12, 15, or 20. A value that is too small or too large will significantly alter the physical properties of the photoresist, thus worsening the coating and other processing effects.

[0162] Another aspect of this disclosure also discloses a method for preparing a photoresist film, comprising:

[0163] The photoresist solvent is added to the solvent, shaken, dissolved, and filtered to obtain a photoresist solution;

[0164] The photoresist solution is coated onto the substrate and then dried to obtain the film layer.

[0165] The solvent can be THF, ethylene glycol dimethyl ether, NMP (N-methylpyrrolidone), DMF, acetone, butanone, or methyl isobutyl ketone; the organic filter membrane is used to filter insoluble impurities such as dust with a wavelength ≤450 nm; the shaking time can be 30s-30mins, for example: 30s, 1min, 5mins, 15mins, 20mins, 30mins; the shaking temperature can be 12-45℃, for example: 12℃, 25℃, 28℃, 35℃, 45℃.

[0166] The photoresist can be applied by spin coating, with a spin coating speed of 500 r / min to 8000 r / min, for example: 500 r / min, 2000 r / min, 5000 r / min, 8000 r / min; the substrate must be hydrophobically treated before coating; the drying temperature can be 40-120℃, for example: 40℃, 60℃, 80℃, 120℃; the drying time can be 1-30 mins, for example: 1 min, 5 mins, 10 mins, 20 mins, 30 mins.

[0167] According to embodiments of this disclosure, the substrate is a silicon wafer, but it can also be other materials with a smooth surface, such as glass or metal.

[0168] According to embodiments of this disclosure, wherein,

[0169] The concentration of the photoresist solution is 4 mg / mL to 80 mg / mL;

[0170] The thickness of the film is 10nm-5000nm.

[0171] The concentration of the photoresist solution is 4 mg / mL to 80 mg / mL, for example: 4 mg / mL, 15 mg / mL, 35 mg / mL, 55 mg / mL, 70 mg / mL, 80 mg / mL; the thickness of the film is 10 nm to 5000 nm, for example: 10 nm, 100 nm, 1000 nm, 3000 nm, 5000 nm.

[0172] In another aspect of this disclosure, the application of a single molecular weight photoresist in electron beam photoresist or extreme ultraviolet (EUV) photoresist is disclosed. Upon irradiation with an electron beam or EUV light to a certain intensity, the photoresist self-degrades to form a positive photoresist. When further irradiation with the electron beam or EUV light reaches another intensity range, further polymerization and crosslinking occur to form a negative photoresist, which is then developed. Specifically, when the voltage is 100 kV, the electron beam dose is ≤200 μC / cm². 2 When the voltage is 100kV, the electron beam dose is ≥4000μC / cm. 2 When the EUV energy density is ≤5mJ / cm³, a negative gel is formed. 2When the EUV energy density is ≥35mJ / cm³, a positive gel is formed; 2 When the time is right, a negative gel is formed. The development time is 20s-300s. Preferably, the compound shown in formula (I) has m=0; n=8 or n=10 or n=12.

[0173] The technical solution of this disclosure will be further described below with reference to specific embodiments. However, it should be noted that the following embodiments are only used to illustrate the technical solution of this disclosure, but this disclosure is not limited thereto. The raw materials used in the embodiments are described as follows:

[0174] Isooctane bromo, NBS, AIBN, morpholine, sodium borohydride, DPPA, and N-methylpyrrolidone (NMP) were purchased from Sigma-Aldrich and used without further purification. Tetrahydrofuran was dried under reflux with sodium wire and then distilled before use. Petroleum ether, ethyl acetate, dibutyltin laurate, potassium carbonate, zinc powder, acetic acid, methanol, triethylamine, potassium hydroxide, and other reagents were all analytical grade and purchased from Sinopharm Chemical Reagent Co., Ltd., and used directly without further purification. The ultrapure water used in the experiment was prepared by the Milli-QSP intelligent ultrapure water system with a resistivity of 18.4 MΩ·cm.

[0175] Example 1: Synthesis of self-degrading photoresist with a single molecular weight

[0176] Step 1: Preparation of the compound shown in B-1

[0177]

[0178] Figure 1 The figure shows the 1H NMR spectrum of compound B-1. 5.0 g (30.09 mmol) of compound A-1, 6.97 g (36.11 mmol) of isobutane bromo, and 12.48 g (390.27 mmol) of potassium carbonate were dissolved in 50 mL of DMF. The reaction was carried out under nitrogen protection at 50–85 °C for 6–15 h. After removing the DMF solvent by rotation, 100 mL of ethyl acetate was added to dissolve the compound. The organic phase was washed with saturated brine, dried, and concentrated. The compound B-1 was obtained by column chromatography using petroleum ether-ethyl acetate as eluent, with a yield of 88%.

[0179] Step 2: Preparation of the compound shown in C-1

[0180]

[0181] 5.0 g (17.96 mmol) of the compound shown in B-1, 3.2 g (17.96 mmol) of NBS (N-bromosuccinimide), and 0.03 g (0.18 mmol) of AIBN were dissolved in 50 mL of CCl4 and refluxed under nitrogen protection for 8–24 h. After the reaction was completed, the insoluble solids were removed by filtration, and the filtrate was washed three times with saturated brine. The organic phase was dried and concentrated to give the compound shown in C-1. The yield was 92%, and it was used directly in the next step without further purification.

[0182] Step 3: Preparation of the compound shown in D-1

[0183]

[0184] Figure 2 The figure shows the 1H NMR spectrum of compound D-1. 5g of compound C-1 was slowly added to 50mL of morpholine, using morpholine as both the solvent and reactant. The reaction was carried out at 30–60℃ for 8–16 h. Excess morpholine was removed by rotary evaporation, followed by extraction with a large amount of ethyl acetate and water. The organic phase was washed multiple times with 1mol / L hydrochloric acid, then three times with saturated brine. After drying and concentrating the organic phase, column chromatography using petroleum ether-ethyl acetate as the eluent was performed to obtain compound D-1 in 85% yield.

[0185] Step 4: Preparation of the compound shown in E-1

[0186]

[0187] Figure 3 The 1H NMR spectrum of compound E-1 is shown. 5.0 g (17.10 mmol) of compound D-1 was dissolved in 50 mL of THF. 0.65 g (17.10 mmol) of sodium borohydride was added in portions at 0–30 °C, and the reaction was carried out at room temperature for 2–12 h. After removing THF from the system, 100 mL of EA and 100 mL of deionized water were added, and the mixture was extracted. The organic phase was washed three times with saturated brine, dried, and concentrated to obtain compound E-1 in 95% yield.

[0188] Step 5: Preparation of the compound shown in F-1

[0189]

[0190] Figure 4The figure shows the 1H NMR spectrum of the compound represented by F-1. 5.0 g (16.98 mmol) of the compound represented by E-1 was dissolved in 50 mL of methanol. 2.86 g (50.95 mmol) of potassium hydroxide was added to the system, and the mixture was refluxed for 6–10 h. After the reaction was complete, methanol was removed by rotary evaporation, 100 mL of deionized water was added, and the pH was adjusted to approximately 3 using hydrochloric acid. 100 mL of EA was added for extraction. The organic phase was washed three times with saturated brine, dried, and concentrated to obtain the compound represented by formula F-1, with a yield of 95%.

[0191] Step Six: Preparation of the compound shown in G-1

[0192]

[0193] Figure 5 The figure shows the 1H NMR spectrum of compound G-1. 5.0 g (17.83 mmol) of compound F-1 was dissolved in 50 mL of THF. 1.99 g (19.62 mmol) of triethylamine was added to the system at 0–30 °C, and the mixture was stirred for 10 minutes. Then, 5.4 g (19.62 mmol) of DPPA was added dropwise, and the reaction was allowed to proceed at room temperature for 6–10 h. After the reaction was complete, THF was removed by rotation, and column chromatography using petroleum ether-ethyl acetate as eluent yielded compound G-1 in 88% yield.

[0194] Step 7: Preparation of the compound shown in H-1

[0195]

[0196] Figure 6 The figure shows the 1H NMR spectrum of compound H-1. 5.0 g (16.37 mmol) of compound G-1 was dissolved in 50 mL of DCM. 1.23 g (18.01 mmol) of imidazole was added to the system at 0–30 °C, and the mixture was stirred for 10 minutes. Then, 2.71 g (18.01 mmol) of TBSCl was added, and the reaction was carried out at room temperature for 5–8 h. After the reaction was complete, the system was diluted with DCM and deionized water was added. Extraction was performed, and the organic phase was washed three times with saturated brine. The organic phase was dried and concentrated to give compound H; the yield was 88%.

[0197] Step 8: Preparation of the compound shown in J-1

[0198]

[0199] Figure 7The figure shows the 1H NMR spectrum of compound J-1. 5.0 g (11.91 mmol) of compound H-1 was dissolved in 50 mL of anhydrous toluene. After azeotropic dehydration, another 50 mL of anhydrous toluene was added as solvent, and the reaction was carried out at 60–110 °C for 3–8 h, followed by a return to room temperature. In another reaction flask, 3.64 g (11.91 mmol) of compound G-1 and 0.5% DBTL were added. After azeotropic dehydration with 30 mL of anhydrous toluene, 40 mL of anhydrous THF was added to dissolve the compound. The solution was transferred to the reaction flask containing compound H-1 and reacted at room temperature for 5–15 h. After the reaction was complete, column chromatography using petroleum ether-ethyl acetate as eluent yielded compound J; the yield was 85%.

[0200] Step Nine: Preparation of the compound shown in K-1

[0201]

[0202] 1.15 g (10.63 mmol) of hydroxyl starting material T-OH (without repeating units), 5.0 g (10.63 mmol) of the compound shown in J-1, and 0.5% DBTL were dissolved in 50 mL of anhydrous toluene. After azeotropic dehydration, 50 mL of NMP was added as a solvent, and the reaction was carried out at 60 °C for 8 h. After the reaction was completed, the compound shown in K-1 was obtained. No further purification was performed, and the compound was directly proceeded to the next step of deprotection.

[0203] Step 10: Deprotection reaction of the compound shown in K-1

[0204]

[0205] Figure 8 The figure shows the 1H NMR spectrum of the compound shown in L-1. The compound shown in K-1 was diluted with 30 mL of methanol, and 0.2 g of 1.063 mmol of p-toluenesulfonic acid was added to remove TBS protection. After the reaction was complete, 100 mL of EA and 100 mL of deionized water were added to the system for extraction. The organic phase was washed three times with saturated brine, dried and concentrated, and then subjected to column chromatography using petroleum ether-ethyl acetate as eluent to obtain the compound shown in L-1.

[0206] Step 11: Using the compound shown in formula L-1 and the compound shown in formula H or formula J as raw materials, a rearrangement reaction is carried out to obtain the compound shown in formula M-1.

[0207] The above-mentioned growth-deprotection iterative cycle is continuously carried out until the precise molecule M-1 with a degree of polymerization of 10 is reached; Figure 9 The figure shows the 1H NMR spectrum of the compound shown in M-1.

[0208]

[0209] in,

[0210] Application Example 1: Electron Beam Exposure and Development of Single Molecular Weight Self-Degrading Photoresist

[0211]

[0212] The compound shown in M-1 was dissolved in the organic solvent ethylene glycol dimethyl ether and spin-coated onto a silicon wafer to form a film of approximately 50 nm. The film was then subjected to an electron beam dose of 150 μC / cm at a voltage of 100 kV. 2 The voltage is 100kV and the electron beam dose is 4000μC / cm. 2 After exposure, toluene and ethylene glycol dimethyl ether were used for development to obtain positive and negative patterns, respectively. Figure 10a Based on the electron beam exposure and development pattern obtained in Application Example 1, lines with linewidths of 45nm, 90nm, 120nm and 220nm were obtained, with a development time of 60s. Figure 10b To characterize the negative photoresist pattern obtained after electron beam exposure and development according to Application Example 1, lines with linewidths of 30 nm, 80 nm, 120 nm, and 200 nm were obtained, with a development time of 60 s. Application Example 1 demonstrates that this type of polymer can be used as both positive and negative photoresist under electron beam exposure.

[0213] Application Example 2: EUV Exposure and Development of Single Molecular Weight Self-Degrading Photoresist

[0214]

[0215] The compound shown in M-1 was dissolved in the organic solvent ethylene glycol dimethyl ether and spin-coated onto a silicon wafer to form a film of approximately 50 nm. The film was then subjected to EUV at an energy density of 5 mJ / cm². 2 EUV energy density is 45 mJ / cm² 2 After exposure, toluene and ethylene glycol dimethyl ether were used for development to obtain positive and negative patterns, respectively. Figure 11a Based on the EUV exposure and development pattern obtained in Application Example 2, lines with a linewidth of approximately 60 nm were obtained, and the development time was 60 s. Figure 11b To characterize the negative adhesive pattern after EUV exposure and development according to Application Example 2, lines with a linewidth of approximately 33 nm were obtained, with a development time of 60 s. Application Example 2 demonstrates that this type of polymer can be used as both positive and negative adhesives under EUV.

[0216] The specific embodiments described above further illustrate the purpose, technical solutions, and beneficial effects of this disclosure. It should be understood that the above descriptions are merely specific embodiments of this disclosure and are not intended to limit this disclosure. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the protection scope of this disclosure.

Claims

1. An application of a single molecular weight photoresist as an electron beam photoresist or extreme ultraviolet photoresist, wherein, The single molecular weight photoresist has the structure shown in formula (I): Equation (I), Wherein, n is 0~20, and by controlling the exposure metering, the single molecular weight photoresist can switch between positive and negative photoresist. Specifically, under a 100kV electron beam, it exhibits positive photoresist characteristics when the dose is ≤200μC / cm², and negative photoresist characteristics when the dose is ≥4000μC / cm². Under extreme ultraviolet light, it exhibits positive photoresist characteristics when the energy density is ≤5mJ / cm², and negative photoresist characteristics when the energy density is ≥35mJ / cm². The single molecular weight photoresist is prepared by the following method: Compound J was prepared from compounds shown in formula G and H. Where 0≤m≤2, R1, R2, and R3 are independently selected from -F, -Cl, -Br, -I, -NO2, -H, Cl~C 20 alkane group, C2-C 20 olefinic group, C2-C 20 alkyne group, C1-C 20 alkoxy groups, C2-C 20 The olefinic group or C2~C 20 One of the alkynyl groups, where R is a functional group used to regulate the film-forming properties of single molecular weight photoresists; With compounds Using the compound shown in formula H or formula J as a starting material, a rearrangement reaction is carried out to obtain the compound shown in formula K, where i is 1 or 2, and T is a capping group; The compound represented by formula K was subjected to a deprotection reaction to obtain the compound represented by formula L; Iterate the compound represented by formula L to obtain a new compound. Repeat the rearrangement and deprotection reactions until a single molecular weight photoresist with the target molecular weight is obtained. Where R has the following structure: , 1≤a≤20.

2. The application according to claim 1, wherein, The compound represented by formula G is prepared by the following method: The compound shown in formula D was reduced by sodium borohydride as a reducing agent to obtain the compound shown in formula E. The compound shown in formula E was reacted to obtain the compound shown in formula F; The compound shown in formula F was reacted as a raw material to obtain the compound shown in formula G; 。 3. The application according to claim 2, wherein, The compound represented by formula H is prepared by the following method: Using the compound shown in formula G as a raw material, the hydroxyl group in the compound shown in formula G is protected to prepare the compound shown in formula H; 。 4. The application according to claim 2, wherein, The compound represented by formula D is prepared by the following method: The compound shown in formula A and compound RBr were reacted as raw materials to prepare the compound shown in formula B. The compound shown in formula B was reacted as a raw material to obtain the compound shown in formula C. The compound shown in formula C was reacted as a raw material to obtain the compound shown in formula D; 。 5. The application according to any one of claims 1-4, wherein, It can be any of the following structures: Among them, R4, R5, and R6 are independently selected from -F, -Cl, -Br, -I, -NO2, -H, Cl~C 20 alkane group, C2~C 20 olefinic group, C2~C 20 Alkyne group, C1~C 20 alkoxy groups, C2~C 20 The olefinic group or C2~C 20 One of the alkynyl groups.

6. The application according to claim 1, wherein, Following the rearrangement reaction, column chromatography is required to obtain the compound.

7. The application according to claim 6, wherein, The compound represented by formula J was obtained by column chromatography. The compound represented by formula K was obtained by column chromatography.

8. In the application according to any one of claims 1 to 7, the single molecular weight photoresist is used to prepare the film layer by the following method: The single molecular weight photoresist is added to a solvent, shaken, dissolved, and filtered to obtain a photoresist solution; The single molecular weight photoresist solution is coated onto the substrate and then dried to obtain the film layer.

9. The application according to claim 8, wherein, The concentration of the photoresist solution is 4 mg / mL to 80 mg / mL; The thickness of the film is 10 nm to 5000 nm.

Images