Diazonaphthoquinone (DNQ) type photoresist composition containing alkali-soluble acrylic resin

Abstract

This document describes a composition comprising: an acrylic polymer comprising repeating units selected from those having structures (1), (2), (3), (4), (5), (6), and (7), wherein the repeating units are present in the acrylic polymer in a molar % range as described herein; a phenolic varnish resin having a dissolution rate of at least 50 / s in a 0.26N TMAH aqueous solution; a diazonoquinone (DNQ) photoactive compound (PAC); and an organic spin casting solvent; and a method of using the composition as a positive photoresist that can be developed in an aqueous solution.

Description

[0001] field

[0002] The disclosed subject matter relates to materials for use in photoresist imaging. More specifically, the disclosed subject matter relates to positive photosensitive materials comprising acrylic resins with high dissolution rates, exhibiting improved photospeed, development time, rehydration time, and resolution. In particular, the disclosed photoresists can be used for connecting terminals (such as metal pillars, bumps, and wiring patterns for LED applications), chip-scale packages (CSPs), and microelectromechanical systems (MEMS).

[0003] background

[0004] Photoresist compositions are used in photolithography, a process for fabricating miniaturized electronic components, such as integrated circuit devices. Generally, in these methods, a coated film of the photoresist composition is applied to a substrate (such as a silicon wafer) used for fabricating integrated circuits, circuit boards, and flat panel displays. The coated substrate is then baked to evaporate any solvents in the photoresist composition and to fix the coating onto the substrate. The baked, coated surface of the substrate is then exposed to photochemical radiation in an image-like manner. Various types of photochemical radiation are commonly used in photolithography, including visible light, ultraviolet (UV) light, far-ultraviolet (EUV) light, electron beams, and X-ray radiation energies.

[0005] Photochemical radiation exposure causes chemical transformation in the exposed areas of the coated surface. After exposure, the coated substrate is treated with a developer solution to dissolve and remove the radiation-exposed areas (for positive photoresists) or unexposed areas (for negative photoresists) of the coated surface.

[0006] Following the aforementioned development operation, the unprotected substrate can now be treated with a substrate etchant solution, plasma gas, or reactive ions, or a metal / metal composite can be deposited in the space of the substrate where the photoresist coating was removed during development. Areas of the substrate where the photoresist coating was not removed remain protected. Subsequently, the retained areas of the photoresist coating can be removed during a stripping operation, leaving a patterned substrate surface. In some cases, it is desirable to heat-treat the retained photoresist layer after the development step and before the etching step to improve its adhesion to the underlying substrate.

[0007] Positively sensitive photoresist compositions that are developable in alkaline aqueous solutions are known. These compositions generally involve (i) chemically amplified photoresists based on phenolic or (meth)acrylate resins or (ii) non-chemically amplified photoresists based on phenolic varnish resins and diazonaphthoquinone (DNQ). In phenolic varnish / DNQ photoresists, a positive image is formed through the photodecomposition of the DNQ compound (or photoactive compound—PAC), which causes the phenolic varnish resin to dissolve more rapidly in alkaline aqueous solutions in the exposed photoresist regions. These types of photoresists are used at longer UV wavelengths (such as using the i-line (365 nm)) and have been the "workhorse" photoresists in the manufacture of integrated circuits (ICs) for many years.

[0008] In standard chemically amplified (CA) positive photoresists, alkali-soluble resins (typically 4-hydroxystyrene-phenolic resins or (meth)acrylate resins) are released in areas of the photoresist exposed to radiation. The resins can be developed with an alkaline aqueous solution after acid-catalytic cleavage of the protecting groups on these resins (which initially mask the alkali-soluble portions). In these CA photoresists, the catalytic acid is formed by photodegrading a photoacid generator (PAG) component. These types of photoresists are typically used at shorter wavelengths to seek higher resolution in IC manufacturing. Some CA photoresists can cause production issues where the protecting groups masking the alkali-soluble groups require high-activation-energy acids for cleavage to remove the masking. Therefore, although these high-activation-energy groups can be removed by acid catalysis, this removal requires a time-consuming post-exposure baking step. Similarly, in high-activation-energy positive CA photoresists, there is a potential susceptibility to gaseous alkali contamination. This sensitivity arises because achieving good resolution with these photoresists requires a high nonlinearity between the degree of degradation of high-activation-energy groups and the degree of dissolution of the exposed photoresist film. Therefore, even a small depletion of acid at the surface after exposure will result in a lower degree of deprotection of these groups during the time delay between exposure and baking, causing them to behave as an insoluble photoresist surface layer. This exposure delay effect is subsequently termed a "T-top" because the resulting positive image has a large and undesirable T-shape, leading to manufacturing defects and lower device yields.

[0009] For thick-film applications, conventional phenolic varnish / DNQ photoresists produce a sloping profile, especially when the film becomes thicker due to its high absorption. On the other hand, positive chemically amplified photoresists can provide sufficient performance within a film thickness of 5 to 10 μm. However, the polymers typically used in these CA photoresists (such as 4-hydroxystyrene-based polymers) are much more expensive than conventional phenolic varnishes. Similarly, some designs requiring post-exposure baking with positive CA photoresists may negatively impact IC device yield. For display manufacturing applications, cost and device yield are also problematic, even though the required photoresist thickness is typically lower (e.g., 1 μm to 3 μm). Furthermore, conventional phenolic varnish / diazonaphthoquinone photoactive compound (DNQ-PAC) type photoresists typically exhibit slow UV sensitivity, long development times, and long rehydration times. Resolution is inferior to standard chemically amplified photoresists. The sidewall profile is sloping compared to standard CA type photoresists. Positive phenolic varnish / DNQ photoresists dissolved in conventional spin casting solvents such as propylene glycol methyl ether acetate (PGMEA; 1-methoxy-2-propanol acetate) or propylene glycol methyl ether (PGME; 1-methoxy-2-propanol) are known. Phenolic varnish polymers can also react with and combine with quinone diazides. It has been found that photoresists based solely on phenolic varnish / diazides do not possess the photosensitivity or sidewall steepness necessary for certain types of methods, especially for very thick films. Furthermore, high dark film loss in the developer is frequently observed, and such coatings can exhibit poor coating uniformity.

[0010] In contrast to the conventional phenolic varnish / diazonaphthoquinone photoactive compound (DNQ-PAC) type photoresists and standard CA photoresists described above, the composition of the present invention described below surprisingly requires no post-exposure baking, produces straight-wall L / S characteristics, does not require a long rehydration time, and also has good UV photosensitivity.

[0011] Overview

[0012] In one aspect, the present invention relates to a composition comprising components a), b), c) and d), wherein

[0013] Component a) is an acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7), wherein these repeating units are present in the acrylic polymer in a range of mol% based on the total mole number of all different repeating units present, and further wherein the sum of the individual mol% values ​​of all repeating units present in the polymer must be equal to 100 mol%.

[0014] The repeating units of structure (1) range from about 10 mol% to about 35 mol%.

[0015] The repeating units of structure (2) range from 0 mol% to approximately 20 mol%.

[0016] The repeating units of structure (3) range from about 0 mol% to about 55 mol%.

[0017] The repeating units of structure (4) range from about 0 mol% to about 30 mol%.

[0018] The repeating units of structure (5) range from about 15 mol% to about 55 mol%.

[0019] The repeating units of structure (6) range from about 0 mol% to about 40 mol%.

[0020] The repeating units of structure (7) range from about 0 mol% to about 25 mol%, and

[0021] R1, R2, R3, R4, R5, R6, and R7 are selected from H, F, C-1 to C-4 perfluoroalkyl, or C-1 to C-4 alkyl, respectively.

[0022] R8 and R9 are selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkoxyalkyl, and halogen, respectively.

[0023] R 10 It is a C-3 to C-8 cyclic alkyl or a C-7 to C-14 alicyclic alkyl.

[0024] R 11 It is a C-2 to C-8 (hydroxy) alkylene group.

[0025] R 12 It is an acid-cleavable group.

[0026] R 13 It is a C-3 to C-12 (alkoxy) alkylene group, and

[0027] The acrylic polymer described herein has at least approximately [amount missing] in a 0.26N tetramethylammonium hydroxide (TMAH) aqueous solution. And less than approximately dissolution rate,

[0028]

[0029] Component b) has at least [a certain content] in a 0.26N TMAH aqueous solution. The dissolution rate of phenolic varnish resin;

[0030] Component c) is a diazonoquinone (DNQ) photoactive compound (PAC); and

[0031] Component d) is an organic rotary casting solvent, and furthermore,

[0032] In the composition, the acrylic polymer comprises about 0.5% by weight of solids to about 70% by weight of solids, and

[0033] The DNQ PAC comprises about 5% by weight of solids to about 20% by weight of solids, and

[0034] Furthermore, the coated film of the aforementioned composition has a viscosity of less than [value missing] in a 0.26N tetramethylammonium hydroxide (TMAH) aqueous solution. Dark erosion.

[0035] Another aspect of the present invention is a method of using the composition as a positive photoresist capable of being imaged using UV radiation.

[0036] Brief description of the attached figures

[0037] The accompanying drawings, which are included to provide a further understanding of the disclosed subject matter and are incorporated into and form part of this specification, illustrate embodiments of the disclosed subject matter and, together with the specification, explain the principles of the disclosed subject matter.

[0038] Figure 1 SEM comparison of the 4 μm 1 / 1 L / S characteristics on copper for formulation examples 23, 22, 16 and 15.

[0039] Figure 2 SEM comparison of the 4 μm 1 / 1 L / S characteristics on silicon for formulation examples 26, 25 and 24.

[0040] Figure 3 The SEM images show a comparison of the 2 μm 1 / 1 L / S characteristics of formulation examples 25 and 27 on copper with different DNQ-PAC levels.

[0041] definition

[0042] Unless otherwise stated, the following terms used in the specification and claims shall have the following meanings for the purposes of this application.

[0043] In this application, unless otherwise expressly stated, the use of the singular includes the plural, and the words “a,” “an,” and “the” mean “at least one.” Furthermore, the use of the term “comprising” and other forms (such as “including” and “containing”) is non-limiting. Additionally, unless otherwise expressly stated, terms such as “element” or “component” cover elements or components comprising one unit as well as elements or components comprising more than one unit. As used herein, unless otherwise indicated, the conjunction “and” is intended to be inclusive and the conjunction “or” is not intended to be exclusive. For example, the phrase “or, alternatively” is intended to be exclusive. As used herein, the term “and / or” refers to any combination of the foregoing elements, including the use of a single element.

[0044] The terms “about” or “approximately”, when used in conjunction with a measurable numerical variable, refer to the indicated value of the variable and all values ​​of the variable within the experimental error range of the indicated value (e.g., within the 95% confidence limit of the mean) or within ±10% of the indicated value (whichever is greater).

[0045] As used herein, “CX to CY” indicates the number of carbon atoms in the chain. For example, C-1 to C-6 alkyl refers to an alkyl chain having a chain with between 1 and 6 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl). Unless otherwise explicitly stated, the chain may be straight, branched, or cyclic. Therefore, such common expressions for C-1 to C-6 alkyl also include C-1 to C-6 straight-chain alkyl, C-3 to C-6 branched alkyl, and C-3 to C-6 cyclic alkyl.

[0046] The section headings used herein are for organizational purposes and should not be construed or otherwise interpreted as limiting the subject matter described. All references or portions thereof cited in this application (including, but not limited to, patents, patent applications, articles, books, and monographs) are expressly incorporated herein by reference in their entirety for any purpose. If one or more of the incorporated references and similar materials define a term in a manner that conflicts with the definition of a term in this application, the definition in this application shall prevail.

[0047] Detailed Explanation

[0048] It should be understood that the foregoing general description and the following detailed description are illustrative and exemplary, and do not limit the subject matter as claimed. The purposes, features, advantages, and concepts of the disclosed subject matter will be apparent to those skilled in the art from the description provided herein, and based on the description appearing herein, those skilled in the art will readily be able to implement the disclosed subject matter. For the purposes of the disclosed subject matter, any descriptions and explanations including "preferred embodiments" and / or examples showing preferred modes for implementing the disclosed subject matter are not intended to limit the scope of the claims.

[0049] It will be apparent to those skilled in the art that various modifications can be made to how the disclosed subject matter is implemented based on the aspects described herein without departing from the spirit and scope of the subject matter disclosed herein.

[0050] One aspect of the present invention is a composition comprising components a), b), c), and d), wherein component a) is an acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7), wherein these repeating units are present in the acrylic polymer in a range of mol% based on the total mole number of all different repeating units present, and further wherein the sum of the individual mol% values ​​of all repeating units present in the polymer must be equal to 100 mol%.

[0051] The repeating units of structure (1) range from about 10 mol% to about 35 mol%.

[0052] The repeating units of structure (2) range from 0 mol% to approximately 20 mol%.

[0053] The repeating units of structure (3) range from about 0 mol% to about 55 mol%.

[0054] The repeating units of structure (4) range from about 0 mol% to about 30 mol%.

[0055] The repeating units of structure (5) range from about 15 mol% to about 55 mol%.

[0056] The repeating units of structure (6) range from about 0 mol% to about 40 mol%.

[0057] The repeating units of structure (7) range from about 0 mol% to about 25 mol%, and

[0058] R1, R2, R3, R4, R5, R6, and R7 are selected from H, F, C-1 to C-4 perfluoroalkyl, or C-1 to C-4 alkyl, respectively.

[0059] R8 and R9 are selected from H, C-1 to C-4 alkyl, C-1 to C-4 alkoxyalkyl, and halogen, respectively.

[0060] R 10 It is a C-3 to C-8 cyclic alkyl or a C-7 to C-14 alicyclic alkyl.

[0061] R 11 It is a C-2 to C-8 (hydroxy) alkylene group.

[0062] R 12 It is an acid-cleavable group.

[0063] R13 It is a C-3 to C-12 (alkoxy) alkylene group, and

[0064] The acrylic polymer described herein has at least approximately [amount missing] in a 0.26N tetramethylammonium hydroxide (TMAH) aqueous solution. And less than approximately dissolution rate,

[0065]

[0066]

[0067] Component b) has at least [a certain content] in a 0.26N TMAH aqueous solution. The dissolution rate of phenolic varnish resin;

[0068] Component c) is a diazonoquinone (DNQ) photoactive compound (PAC) (also known as DNQ-PAC); and

[0069] Component d) is an organic rotary casting solvent, and,

[0070] In the composition, the acrylic polymer comprises about 0.5% by weight of solids to about 70% by weight of solids, and the DNQ PAC comprises about 5% by weight of solids to about 20% by weight of solids, and

[0071] Furthermore, the coated film of the aforementioned composition has a concentration of less than 0.26 N TMAH in an aqueous solution. Dark erosion.

[0072] Component a), acrylic polymer

[0073] In one embodiment of the above-described composition of the present invention, component a) is an acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7), wherein

[0074] The repeating units of structure (1) range from about 10 mol% to about 35 mol%.

[0075] The repeating units of structure (2) range from 0 mol% to approximately 20 mol%.

[0076] The repeating units of structure (3) range from about 10 mol% to about 55 mol%.

[0077] The repeating units of structure (4) range from about 0 mol% to about 30 mol%.

[0078] The repeating units of structure (5) range from about 15 mol% to about 55 mol%.

[0079] The repeating units of structure (6) range from about 0 mol% to about 40 mol%.

[0080] The repeating units of structure (7) range from about 0 mol% to about 25 mol%.

[0081] In another embodiment of the above-described composition of the invention, component a) is an acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7), wherein these repeating units are present in the acrylic polymer in a range of mol% based on the total mole count of all different repeating units present, and further wherein the sum of the individual mol% values ​​of all repeating units present in the polymer must be equal to 100 mol%.

[0082] The repeating units of structure (1) range from about 10 mol% to about 35 mol%.

[0083] The repeating units of structure (2) are in the range of 10 mol% to about 20 mol%.

[0084] The repeating units of structure (3) range from about 0 mol% to about 55 mol%.

[0085] The repeating units of structure (4) range from about 0 mol% to about 30 mol%.

[0086] The repeating units of structure (5) range from about 15 mol% to about 55 mol%.

[0087] The repeating units of structure (6) range from about 0 mol% to about 40 mol%.

[0088] The repeating units of structure (7) range from about 0 mol% to about 25 mol%.

[0089] In one embodiment of the composition of the invention described herein, the acrylic polymer comprises about 4 to about 50% by weight of solids. In another aspect of this embodiment, the acrylic polymer comprises about 8 to about 30% by weight of solids; and in yet another aspect, about 10 to about 30% by weight of solids.

[0090] In one embodiment of the composition of the invention described herein, the dissolution rate of the acrylic polymer is from about 100 to about 100. Within the range. In another aspect of this embodiment, the dissolution rate of the acrylic polymer is between about 120 and about... Within the range. In yet another embodiment, it is approximately 120 to... In another implementation, it is approximately 120 to

[0091] In one embodiment of the composition of the invention described herein, the acrylate polymer is an acrylate polymer whose repeating units are composed of repeating units having structures (1), (3), (4), and (5). In another aspect of this embodiment, structure (1) is in the range of about 20 to about 35 mol%, structure (3) is in the range of about 30 to about 50 mol%, structure (4) is in the range of about 5 to about 20 mol%, and structure (5) is in the range of about 5 to about 20 mol%. In another aspect of this embodiment, structure (1) is in the range of about 25 to about 35 mol%, structure (3) is in the range of about 40 to about 50 mol%, structure (4) is in the range of about 7 to about 15 mol%, and structure (5) is in the range of about 10 to about 20 mol%. In yet another aspect of this embodiment, structure (1) is about 30 mol%, structure (3) is about 45 mol%, structure (4) is about 10 mol%, and structure (5) is about 15 mol%. In another aspect of this embodiment, the acrylate polymer is wherein R9 is H, and R 10 The acrylate polymer is a C-7 to C-14 alicyclic alkyl group. In another aspect of this embodiment, the acrylate polymer is more specifically an acrylate polymer composed of repeating units having structures (1), (3a), (4a), and (5a), wherein n is the number of methylene spacer groups and is an integer in the range of 1 to 4, R1, R3, R4, and R5 are selected from C-1 to C-4 alkyl groups, and R... 5’ Selected from H and C-1 to C-4 alkyl groups. In another more specific example of this embodiment, the acrylic polymer is more specifically an acrylic polymer composed of repeating units having structures (1a), (3b), (4b) and (5b).

[0092]

[0093] In one embodiment of the composition of the invention described herein, the acrylate polymer is an acrylate polymer whose repeating units are composed of repeating units having structures (1), (3), (5), and (7). In one aspect of this embodiment, structure (1) is in the range of about 16 to about 32 mol%, structure (3) is in the range of about 18 to about 35 mol%, structure (5) is in the range of about 30 to about 40 mol%, and structure (7) is in the range of about 10 to about 20 mol%. In another aspect of this embodiment, the acrylate is an acrylate in which R9 is H. In yet another aspect of this embodiment, the acrylate polymer is more specifically an acrylate polymer composed of repeating units having structures (1), (3a), (5a), and (7a), wherein n and n' are the number of methylene spacer groups and are independently in the range of 1 to 4, R1, R3, R5, and R7 are selected from C-1 to C-4 alkyl groups, R 5’ and R 7’ Each is selected from H or C-1 to C-4 alkyl groups, and R 7” It is a C-1 to C-4 alkyl group. In another more specific example of this embodiment, the acrylic polymer is more specifically an acrylic polymer composed of repeating units having structures (1a), (3b), (5b) and (7b).

[0094]

[0095] In one embodiment of the composition of the invention described herein, the acrylate polymer is an acrylate polymer whose repeating units are composed of repeating units having structures (1), (2), (5), and (6). In one aspect of this embodiment, structure (1) is in the range of about 18 to about 30 mol%, structure (2) is in the range of about 11 to about 15 mol%, structure (5) is in the range of about 25 to about 35 mol%, and structure (6) is in the range of about 25 to about 35 mol%. In another aspect of this embodiment, the acrylate polymer is more specifically an acrylate polymer composed of repeating units having structures (1), (2a), (5a), and (6), wherein n is an integer number of methylene spacer groups and is in the range of 1 to 4, R1, R5, and R6 are selected from C-1 to C-4 alkyl groups, R 5’ R8 is selected from H and C-1 to C-4 alkyl groups, and R8 is selected from H, C-1 to C-4 alkyl groups, respectively. 12 The protecting group is an acid-cleavable protecting group selected from C-4 to C-12 tertiary alkyl groups, acetal groups, and ketal groups having at least one β-hydrogen. In another more specific example of this embodiment, the acrylic polymer is more specifically an acrylic polymer composed of repeating units having structures (1a), (2b), (5b), and (6), R 12It is a C-4 to C-12 tertiary alkyl group having at least one present β-hydrogen. In another more specific example of this embodiment, the acrylic polymer is more specifically an acrylic polymer composed of repeating units having structures (1a), (2b), (5b) and (6a).

[0096]

[0097] Component b)

[0098] Phenolic varnish resin

[0099] In one embodiment of the composition of the invention described herein, the phenolic varnish resin component comprises about 10 to about 90% by weight of solids. In another aspect of this embodiment, the phenolic varnish resin is in the range of about 40 to about 90% by weight of solids.

[0100] In one embodiment of the composition of the invention described herein, the phenolic varnish resin component is a phenolic varnish resin component comprising repeating units of structure (8), wherein Ra and Rb are independently C-1 to C-4 alkyl groups, na is 0 to 3, and nb is 0 or 1. In one aspect of this embodiment, it may comprise repeating units of two or more different structures (8).

[0101]

[0102] In another embodiment of the composition of the present invention described herein, the phenolic varnish resin component is a phenolic varnish resin component comprising a repeating unit of structure (9), wherein Rc is C-1 to C-4 alkyl, Rd is C-1 to C-4 alkyl, X is -O-, C(CH3)2-, -(C=O)- or -SO2-, nc is 0 to 3, and nd is 0 or 1.

[0103]

[0104] In another embodiment of the composition of the present invention described herein, the phenolic varnish resin component is a phenolic varnish resin component comprising repeating units of structures (8) and (9). In one aspect of this embodiment, it may comprise repeating units of two or more different structures (8). In another aspect of this embodiment, it may comprise repeating units of two or more different structures (9).

[0105] In one embodiment of the composition of the present invention described herein, the phenolic varnish resin component is a phenolic varnish resin of m-cresol and formaldehyde.

[0106] The following are non-limiting examples of suitable commercially available phenolic varnish resins used as component b) in the disclosed compositions of the present invention:

[0107] Novolak The SPN-560 series products are m-cresol / formaldehyde phenolic varnish resins supplied by AllnexUSA Inc. These products are... In 300MIF developer (also known as 0.26N TMAH aqueous solution), approximately 700 to approximately It is available within a range of different dissolution rates.

[0108] The Novolak series consists of bisphenol A / m-cresol-formaldehyde varnish resins, marketed by AicaKogyo Company, Limited. These products have solubility rates as high as in AZ 300MIF developer (also known as 0.26NTMAH aqueous solution).

[0109] CL23 type phenolic varnish polymer, sold by Asahi Yukizai Corporation; for example, phenolic varnishes comprising 50% m-cresol, 20% p-cresol, 30% 2,5-xylenol, and formaldehyde, wherein M w =4,000 and dissolution rate is (In AZ 300MIF developer (also known as 0.26N TMAH aqueous solution)).

[0110] Component c)

[0111] DNQ PAC

[0112] In another embodiment of the composition of the invention described herein, the DNQ PAC is in the range of about 5 to about 20% by weight solids.

[0113] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (10) or a mixture of materials having general formula (10), wherein D 1c D 2c D 3c and D 4c They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1c D 2c D 3c Or D 4c At least one of them is a group having structure (11).

[0114]

[0115] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (10) or a mixture of materials having general formula (10), wherein D 1c D 2c D 3c and D 4c The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1c D 2c D 3c Or D 4c At least one of them is a group having structure (12).

[0116]

[0117] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (13a) or a mixture of materials having general formula (13a), wherein D 1e D 2e and D 3e They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1e D 2e Or D 3e At least one of them is a group having structure (11),

[0118]

[0119] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (13a) or a mixture of materials having general formula (13a), wherein D 1e D 2e and D 3e The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1e D 2e Or D 3e At least one of them is a group having structure (12),

[0120]

[0121] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (13b) or a mixture of materials having general formula (13b), wherein D 1e D 2e D 3e and D 4e They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1e D2e D 3e and D 4e At least one of them is a group having structure (11).

[0122]

[0123] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (13b) or a mixture of materials having general formula (13b), wherein D 1e D 2e D 3e and D 4e The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1e D 2e D 3e and D 4e At least one of them is a group having structure (12).

[0124]

[0125] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (14) or a mixture of materials having general formula (14), wherein D 1f D 2f D 3f and D 4f They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1f D 2f D 3f Or D 4f At least one of them is a group having structure (11),

[0126]

[0127] In another embodiment of the composition of the invention described herein, the DNQ PAC component is a single material having general formula (14) or a mixture of materials having general formula (14), wherein D 1f D 2f D 3f and D 4f The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1f D 2f D 3f Or D 4f At least one of them is a group having structure (12),

[0128]

[0129] In another embodiment of the composition of the present invention described herein, the DNQ PAC component is a mixture of the DNQ PAC materials described above.

[0130] The following are non-limiting examples of suitable DNQPACs used as component c) of the DNQ PAC components in the disclosed compositions of the present invention:

[0131] PW898 (CAS 107761-81-9) is 2,2'-4,4-tetrahydroxy-DNQ PAC (6-diazo-5,6-dihydro-5-oxo-1-naphthalene-sulfonate and (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl), methyl ketone), available from Accel Pharmtech LLC (East Brunswick, NJ). It is a mixture of materials having the general formula (13b), wherein D 1e D 2e D 3e and D 4e They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1e D 2e D 3e Or D 4e At least one of them is a group having structure (11).

[0132] NK-280 is DNQ-PC sold by TOYO GOSEI.,LTD under this name. It is a mixture of materials having the general formula (10), wherein D 1c D 2c D 3c and D 4c They are selected from H or groups having structure (11), wherein D 1c D 2c D 3c Or D 4c At least one of them is a group having structure (11) and the phenol is at position D. 1c D 2c D 3c and D 4c On average, about 2.8 of the groups are esterified by (11).

[0133]

[0134] Component d)

[0135] Organic spin casting solvent

[0136] The organic spin casting solvent component is an organic solvent suitable for spin casting a uniform film on a substrate. This solvent should simultaneously impart good solubility to the photoresist component at room temperature and possess volatility (vapor pressure). Its volatility should not be too high, as excessive volatility would lead to rapid evaporation and the formation of an uneven film, or too low, as excessively low volatility would result in drying times exceeding several minutes (which would increase the likelihood of particle deposition leading to defects). Examples of suitable organic solvents include, but are not limited to, butyl acetate, amyl acetate, cyclohexyl acetate, 3-methoxybutyl acetate, methyl ethyl ketone, methyl pentyl ketone, cyclohexanone, cyclopentanone, ethyl-3-ethoxypropionate, methyl-3-ethoxypropionate, methyl-3-methoxypropionate, methyl acetoacetate, ethyl acetoacetate, diacetone alcohol, methyl neopentanoate, ethyl neopentanoate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether. Propionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methyl-3-methoxybutanol, N-methylpyrrolidone, dimethyl sulfoxide, γ-butyrolactone, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, methyl lactate, ethyl lactate, propyl lactate, tetramethylene sulfone, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol dimethyl ether or diethylene glycol dimethyl ether, γ-butyrolactone. These solvents can be used alone or in mixtures of two or more. In one embodiment, the solvent component is PGMEA (1-methoxy-2-propyl acetate).

[0137] Optional components

[0138] In another embodiment of any of the above-described positive photosensitive compositions, other optional components that are compatible with and can be added to the photoresist compositions disclosed and claimed herein include heterocyclic thiols, surface leveling agents, stabilizers, auxiliary resins, plasticizers, etc., to improve the properties of the photoresist layer.

[0139] heterocyclic thiols

[0140] In one embodiment of the composition of the present invention described above, it further comprises at least one optional heterocyclic thiol component. In one aspect of this embodiment, the heterocyclic thiol component is at least one heterocyclic thiol compound comprising a ring structure selected from the general structures (15), (16), or (17), or a tautomer thereof; and

[0141]

[0142] in,

[0143] The ring structure is a monocyclic structure with 4 to 8 atoms or a polycyclic structure with 5 to 20 atoms; wherein the monocyclic or polycyclic structure comprises aromatic, non-aromatic, or heteroaromatic rings, and

[0144] In the structure (15), Xt is selected from the group consisting of C(Rt1)(Rt2), O, S, Se and Te;

[0145] In the structure (16), Y is selected from the group consisting of C(Rt3) and N;

[0146] In the structure (17), Z is selected from the group consisting of C(Rt3) and N; and

[0147] Rt1, Rt2, and Rt3 are independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted ynyl groups having 2 to 8 carbon atoms, unsubstituted ynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms.

[0148] In another embodiment, the composition of the invention comprises at least one heterocyclic thiol or its tautomer selected from the general structures (15), (16), or (17) above, which may be selected from (but is not limited to) substituted or unsubstituted triazole thiols, substituted or unsubstituted imidazolium thiols, substituted or unsubstituted triazine thiols, substituted or unsubstituted mercaptopyrimidines, substituted or unsubstituted thiadiazole thiols, substituted or unsubstituted indazole thiols, their tautomers, or combinations thereof. Substituents may include, but are not limited to, saturated or unsaturated hydrocarbon groups, substituted or unsubstituted aromatic rings, aliphatic, aromatic or heteroaromatic alcohols, amines, amides, imide carboxylic acids, esters, ethers, halogens, etc. These substituents may be used with heterocyclic thiols to improve solubility, modify interaction with the substrate, enhance light exposure, or be used as an anti-halation dye.

[0149] In another embodiment, the composition of the invention comprises at least one heterocyclic thiol or its tautomer selected from the general structures (15), (16) or (17) above, the heterocyclic thiol being selected from, but not limited to, the following compounds (18) to (34) in unsubstituted or substituted forms:

[0150]

[0151]

[0152] In another embodiment, the composition of the invention comprises at least one heterocyclic thiol or its tautomer selected from the above general structures (15), (16) or (17), the heterocyclic thiol being selected from thiouracil derivatives, such as 2-thiouracil as a further example.These include, but are not limited to, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, and 5-methoxy-6-n-propyl-2-thiouracil. 5-Bromo-2-thiouracil, 5-Chloro-2-thiouracil, 5-Fluoro-2-thiouracil, 5-Amino-2-thiouracil, 5-Amino-6-methyl-2-thiouracil, 5-Amino-6-phenyl-2-thiouracil, 5,6-Diamino-2-thiouracil, 5-Allyl-2-thiouracil, 5-Allyl-3-ethyl-2-thiouracil, 5-Allyl-6-phenyl-2-thiouracil, 5-Benzyl-2-thiouracil, 5-Benzyl-6-methyl-2-thiouracil, 5-Acetamino-2-thiouracil, 6-Methyl-5-nitro-2-thiouracil, 6-Amino-2-thiouracil, 6-Amino-5-methyl-2- Thioureapyrimidine, 6-amino-5-n-propyl-2-thiourapyrimidine, 6-bromo-2-thiourapyrimidine, 6-chloro-2-thiourapyrimidine, 6-fluoro-2-thiourapyrimidine, 6-bromo-5-methyl-2-thiourapyrimidine, 6-hydroxy-2-thiourapyrimidine, 6-acetamido-2-thiourapyrimidine, 6-n-octyl-2-thiourapyrimidine, 6-dodecyl-2-thiourapyrimidine, 6-tetra-dodecyl-2-thiourapyrimidine, 6-hexadecyl-2-thiourapyrimidine, 6-(2-hydroxyethyl)-2-thiourapyrimidine, 6-(3-isopropyloctyl)-5-methyl-2-thiourapyrimidine, 6-(m-nitrophenyl)-2-thiourapyrimidine, 6-(m-nitrophenyl)-5-n-propyl-2-thiourea Pyrimidine, 6-α-naphthyl-2-thiourea pyrimidine, 6-α-naphthyl-5-tert-butyl-2-thiourea pyrimidine, 6-(p-chlorophenyl)-2-thiourea pyrimidine, 6-(p-chlorophenyl)-2-ethyl-2-thiourea pyrimidine, 5-ethyl-6-eicosyl-2-thiourea pyrimidine, 6-acetamido-5-ethyl-2-thiourea pyrimidine, 6-eicosyl-5-allyl-2-thiourea pyrimidine, 5-amino-6-phenyl-2-thiourea pyrimidine, 5-amino-6-(p-chlorophenyl)-2-thiourea pyrimidine, 5-methoxy-6-phenyl-2-thiourea pyrimidine, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiourea pyrimidine, 6-(2-bromoethyl)-2-thiourea pyrimidine.

[0153] In another embodiment, the composition of the invention comprises at least one heterocyclic thiol selected from the general structures (15), (16) or (17) above, or a tautomer thereof, the heterocyclic thiol being selected from the group consisting of: unsubstituted triazole thiol, substituted triazole thiol, unsubstituted imidazolium thiol, substituted imidazolium thiol, substituted triazine thiol, unsubstituted triazine thiol, substituted mercaptopyrimidine, unsubstituted mercaptopyrimidine, substituted thiadiazole-thiol, unsubstituted thiadiazole-thiol, substituted indazole thiol, unsubstituted indazole thiol, tautomers thereof, and combinations thereof.

[0154] In another embodiment, the composition of the present invention comprises at least one heterocyclic thiol or its tautomer selected from the general structures (15), (16) or (17) above, wherein the heterocyclic thiol may be selected from the group consisting of: 1,3,5-triazine-2,4,6-trithiol, 2-mercapto-6-methylpyrimidin-4-ol, 3-mercapto-6-methyl-1,2,4-triazine-5-ol, 2-mercaptopyrimidin-4,6-diol, 1H-1,2,4-triazol-3-thiol, 1H-1,2,4-triazol-5-thiol. Alcohols, 1H-imidazol-2-thiol, 1H-imidazol-5-thiol, 1H-imidazol-4-thiol, 2-azabicyclo[3.2.1]oct-2-en-3-thiol, 2-azabicyclo[2.2.1]hept-2-en-3-thiol, 1H-benzo[d]imidazol-2-thiol, 2-mercapto-6-methylpyrimidin-4-ol, 2-mercaptopyrimidin-4-ol, 1-methyl-1H-imidazol-2-thiol, 1,3,4-thiadiazole-2,5-dithiol, 1H-indazole-3-thiol, their tautomers and combinations thereof.

[0155] Surface leveling agent

[0156] In one embodiment of the composition of the present invention described above, it further comprises at least one optional surface leveling agent, which may include a surfactant. In this embodiment, there are no particular limitations on the surfactant, and examples include polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oil ether; polyoxyethylene alkyl aryl ethers, such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether; polyoxyethylene polyoxypropylene block copolymers; sorbitan fatty acid esters, such as sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; nonionic surfactants of polyoxyethylene sorbitan fatty acid esters, such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate; and fluorinated surfactants, such as F-Top EF301, EF303, and EF352 (produced by Jemco). Megafac F171, F172, F173, R08, R30, R90 and R94 (manufactured by Dainippon Ink & Chemicals, Inc.), Florad FC-430, FC-431, FC-4430 and FC-4432 (manufactured by Sumitomo 3M Ltd.), Asahi Guard AG710, Surflon S-381, S-382, S-386, SC101, SC102, SC103, SC104, SC105, SC106, Surfinol E1004, KH-10, KH-20, KH-30 and KH-40 (manufactured by Asahi Glass Co., Ltd.); organosiloxane polymers, such as KP-341, X-70-092 and X-70-093 (manufactured by Shin-Etsu Co., Ltd.). (manufactured by Chemical Co., Ltd.); and acrylic or methacrylic polymers, such as Polyflow No. 75 and No. 95 (manufactured by Kyoeisha Chemical Co., Ltd.).

[0157] Another aspect of the invention is the use of any of the above-described compositions of the invention as an aqueous developable UV photoresist, preferably in the methods described below. Yet another aspect of the invention is a method comprising steps i) to iv).

[0158] i) Apply any of the above-described compositions of the present invention onto a substrate to form a coating.

[0159] ii) Bake the coating to form a baked coating.

[0160] iii) Exposing the baked coating to radiation, preferably UV radiation, through a mask to form an exposed patterned coating.

[0161] iv) Develop the exposed patterned coating using a water-based developer, remove the areas of the pattern exposed to the radiation, and form a photoresist positive image. Example

[0162] Reference will now be made to more specific embodiments of this disclosure and experimental results supporting those embodiments. However, the applicant notes that the following disclosure is for illustrative purposes only and is not intended to limit the scope of the claimed subject matter in any way.

[0163] Material

[0164] chemicals

[0165] MTA: Additive, (1H-1,2,4-triazol-3-thiol); TEA: (triethylamine); PGME (1-methoxy-2-propanol); PGMEA (1-methoxy-2-propyl acetate) and any other chemicals, unless otherwise specified, were purchased from Sigma Aldrich subsidiary of Merck KGaA (Darmstadt, Germany). NIT PAG, N-hydroxynaphthalenedicarboximide trifluoromethanesulfonate, is sold under the name (NIT PAG, 100%, Tech, pdr) by Heraeus PM NA Daychem LLC. APS-437 is a surfactant: from Shinetsu (Tokyo, Japan).

[0166] Phenolic varnish polymer

[0167] For the following formulation examples, three phenolic varnish polymers are used:

[0168] Novolak-1 is a phenolic varnish made of m-cresol and formaldehyde, and is marketed under the name "ALNOVOL". TM SPN 560 / 47MPACSLOW” was obtained from Allnex (Alpharetta, Ga), Mw 24010, D: 7.3 and exhibits good performance in 0.26N TMAH developer aqueous solution. The overall dissolution rate. Novolak-2 is a phenolic varnish of m-cresol and formaldehyde and is marketed under the name "ALNOVOL". TM SPN 560 / 47MPAC FAST” was obtained from Allnex (Alpharetta, Ga), Mw 7,245, D: 4.8 and exhibits good performance in 0.26N TMAH developer aqueous solution. The overall dissolution rate. Novolak-3 is a 1 / 1 wt / wt blend of Novolak-1 and Novolak-2, and exhibits [specific properties] in a 0.26 N TMAH developer aqueous solution. The overall dissolution rate. Novolak CL23 is a phenolic varnish polymer (sold under the name CL23F10G by Asahi Yukizai Corporation) containing 50% m-cresol, 20% p-cresol, 30% 2,5-xylenol, formaldehyde, of which M w =4,000 and the dissolution rate in 0.26N TMAH aqueous solution is

[0169] PW898 (CAS 107761-81-9) is 2,2'-4,4-tetrahydroxy-DNQ PAC (6-diazo-5,6-dihydro-5-oxo-1-naphthalenesulfonate and (4-hydroxyphenyl)-(2,3,4-trihydroxyphenyl), methyl ketone) available from Accel Pharmtech LLC (East Brunswick, NJ). It is a mixture of materials having the general formula (13b), wherein D 1e D 2e D 3e and D 4e They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1e D 2e D 3e Or D 4e At least one of them is a group having structure (11).

[0170]

[0171] NK-280 is DNQ-PC sold by TOYO GOSEI.,LTD under this name. It is a mixture of materials having the general formula (10), wherein D 1c D 2c D 3c and D 4c They are selected from H or groups having structure (11), wherein D 1c D 2c D 3c Or D 4c At least one of them is a group having structure (11) and the phenol is at position D. 1c D 2c D 3c and D 4c On average, about 2.8 groups are esterified by (11).

[0172]

[0173] Dissolution experiment

[0174] Dissolution experiments were conducted at 23°C using AZ 300MIF developer (also known as 0.26N TMAH aqueous solution) to measure the dissolution rate of acrylate polymer coatings or unexposed photoresist formulation coatings (also known as dark etching). The dissolution rate was obtained by measuring the film thickness before and after development. The dissolution rate was obtained by dividing the difference in film thickness by the development time.

[0175] Synthesis of acrylates

[0176] Synthesis Example 1: (Structure P1)

[0177]

[0178] Structure P1

[0179] 10.81 g of acrylic acid, 9.76 g of methoxyethyl acrylate, 17.62 g of benzyl methacrylate, and 25.23 g of hydroxypropyl methacrylate were mixed in 95.2 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 90 °C under nitrogen atmosphere for 18 hours in the presence of 1.35 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 63.0 g (99.3% yield) was obtained with a weight average molecular weight of 25003. Therefore, acrylic resin P1 was obtained, which exhibits [resistance / effect] in 0.26 N TMAH aqueous solution. The dissolution rate. Molecular weight can be determined by gel permeation chromatography, using a common calibration method calibrated with polystyrene standards.

[0180] Synthesis Example 2: (Structure P2)

[0181]

[0182] Structure P2

[0183] 9.00 g of acrylic acid, 9.76 g of methoxyethyl acrylate, 22.03 g of benzyl methacrylate, and 25.23 g of hydroxypropyl methacrylate were mixed in 101 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 90 °C under nitrogen atmosphere for 18 hours in the presence of 1.35 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 66.0 g (99.3% yield) was obtained with a weight average molecular weight of 30035. Therefore, acrylic resin P2 was obtained, which exhibits [resistance / effect] in 0.26 NTMAH aqueous solution. The dissolution rate.

[0184] Synthesis Example 3 (Structure P3)

[0185]

[0186] Structure P3

[0187] 28.82 g of acrylic acid, 39.04 g of methoxyethyl acrylate, 105.73 g of benzyl methacrylate, and 100.92 g of hydroxypropyl methacrylate were mixed in 419.9 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 80 °C under nitrogen atmosphere in the presence of 5.42 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 277.0 (yield 99.0%) was given, with a weight average molecular weight of 21305. Therefore, acrylic resin P3 was obtained, which has a solubility rate of: The dissolution rate.

[0188] Synthesis Example 4 (Structure P4)

[0189]

[0190] Structure P4

[0191] 25.94 g of acrylic acid, 39.04 g of methoxyethyl acrylate, 112.77 g of benzyl methacrylate, and 100.92 g of hydroxypropyl methacrylate were mixed in 426.1 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 80 °C under nitrogen atmosphere in the presence of 5.42 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 281.5 (yield 99.1%) was obtained with a weight average molecular weight of 19415. Therefore, acrylic resin P4 was obtained, which exhibits [result] in 0.26 N TMAH aqueous solution. The dissolution rate.

[0192] Synthesis Example 5 (Structure P5)

[0193]

[0194] Structure P5

[0195] 7.21 g of acrylic acid, 6.51 g of methoxyethyl acrylate, 44.05 g of benzyl methacrylate, and 14.42 g of hydroxypropyl methacrylate were mixed in 295.3 g of propylene glycol monomethyl ether (PGME) solvent. The polymerization reaction was carried out at 80 °C under nitrogen atmosphere for 18 hours in the presence of 1.64 g of AIBN. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 66.68 g (yield 90.3%) was obtained with a weight average molecular weight of 19109. Therefore, acrylic resin P5 was obtained, which exhibits [resistance / effect] in 0.26 NTMAH aqueous solution. The dissolution rate.

[0196] Synthesis Example 6 (Structure P6)

[0197]

[0198] Structure P6

[0199] 5.40 g of acrylic acid, 39.65 g of hydroxypropyl methacrylate, and 21.33 g of tert-butyl methacrylate were mixed in 126.3 g of PGME solvent. The polymerization reaction was carried out at 90 °C under nitrogen atmosphere in the presence of 1.64 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 64.58 g (97% yield) was obtained with a weight average molecular weight of 18734. Therefore, acrylic resin P6 was obtained, which exhibits [resistance / effect] in 0.26 NTMAH aqueous solution. The dissolution rate.

[0200] Synthesis Example 7 (Structure P7)

[0201]

[0202] Structure P7

[0203] 9.01 g of acrylic acid, 5.28 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 24.89 g of tert-butyl methacrylate were mixed in 115.8 g of PGME solvent. The polymerization reaction was carried out at 80 °C under nitrogen atmosphere in the presence of 1.64 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 59.67 g (98% yield) was obtained with a weight average molecular weight of 21457. Therefore, acrylic resin P7 was obtained, which exhibits [specific properties] in 0.26 N TMAH aqueous solution. The dissolution rate.

[0204] Synthesis Example 8 (Structure P8)

[0205]

[0206] Structure P8

[0207] 8.11 g of acrylic acid, 6.51 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 24.89 g of tert-butyl methacrylate were mixed in 76.2 g of PGME solvent. The polymerization reaction was carried out at 90 °C under nitrogen atmosphere in the presence of 1.23 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 60.50 g (99% yield) was obtained with a weight average molecular weight of 18672. Therefore, acrylic resin P8 was obtained, which exhibits [resistance / effect] in 0.26 N TMAH aqueous solution. The dissolution rate.

[0208] Synthesis Example 9 (Structure P9)

[0209]

[0210] Structure P9

[0211] 7.20 g of acrylic acid, 7.81 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 24.89 g of tert-butyl methacrylate were mixed in 117.3 g of PGME solvent. The polymerization reaction was carried out at 90 °C under nitrogen atmosphere in the presence of 1.64 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 60.80 g (99% yield) was obtained with a weight average molecular weight of 15542. Therefore, acrylic resin P9 was obtained, which exhibits [specific properties] in 0.26 N TMAH aqueous solution. The dissolution rate.

[0212] Synthesis Example 10 (Structure P10)

[0213]

[0214] Structure P10

[0215] 5.40 g of acrylic acid, 10.42 g of styrene, 21.62 g of hydroxypropyl methacrylate, and 24.89 g of tert-butyl methacrylate were mixed in 118.7 g of PGME solvent. The polymerization reaction was carried out at 90 °C under nitrogen atmosphere in the presence of 1.64 g of AIBN for 18 hours. After cooling to room temperature, the reaction mixture was precipitated in DI water. The white polymer solid was washed and dried under vacuum at 50 °C. 63.0 g (99% yield) was obtained with a weight average molecular weight of 14503. Therefore, acrylic resin P10 was obtained, which has a solubility rate of: [missing value] in 0.26 N TMAH aqueous solution. The dissolution rate.

[0216] Acrylic polymer P11 (structure P11) (CPR215)

[0217]

[0218] Structure P11

[0219] Poly(methacrylate-copolymer-benzyl methacrylate-copolymer-tricyclo(5.2.1.0 / 2.6)decyl methacrylate-copolymer-2-hydroxypropyl methacrylate) was obtained from Miwon Commercial Co., Ltd. (Miwon Bldg, 464 Anyang-ro, Manan-gu, Anyang-si, Gyeonggi-do, 430-806, Korea). This polymer has a solubility rate of: in 0.26 N TMAH aqueous solution.

[0220] Coatings and Formulations

[0221] All formulations were tested on 8” diameter Si and Cu wafers. The Si wafers were rehydrated and baked and then vapor-coated with hexamethyldisilazane (HMDS). Exposure was performed using a SUSS MA200 CC mask aligner or an ASML250 i-line stepper.

[0222] Photoresist coatings were prepared by spin-coating a photoresist sample and then applying a soft bake in contact mode for 300 seconds at 130°C on a standard wafer tracking hotplate. The spin speed was adjusted to obtain a 60-micrometer-thick photoresist film. All film thickness measurements were performed on the Si wafer using optical measurements.

[0223] Formulation Examples

[0224] Formulation Example 1:

[0225] 7.8 g of the polymer from Synthesis Example 1, 27.2 g of Novolak-3, 4.0 g of DNQ PAC PW898, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0226] Formulation Example 1a

[0227] 3.9 g of the polymer from Synthesis Example 1, 30.6 g of Novolak-3, 4.5 g of DNQ PAC PW898, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0228] Formulation Example 2

[0229] 11.7 g of the polymer from Synthesis Example 1, 23.8 g of Novolak-3, 3.5 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0230] Formulation Example 3

[0231] 19.5 g of the polymer synthesized in Example 1, 17.0 g of Novolak-3, 2.5 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0232] Formulation Example 4

[0233] 27.3 g of the polymer synthesized in Example 1, 10.2 g of Novolak-3, 1.5 g of DNQ PAC PW898, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0234] Formulation Example 5

[0235] 7.8 g of the polymer from Synthesis Example 2, 27.2 g of Novolak-3, 4.0 g of DNQ PAC PW898, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of PS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0236] Formulation Example 5a

[0237] 3.9 g of the polymer from Synthesis Example 2, 30.6 g of Novolak-3, 4.5 g of DNQ PAC PW898, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0238] Formulation Example 6

[0239] 11.7 g of the polymer from Synthesis Example 2, 23.8 g of Novolak-3, 3.5 g of DNQ PAC PW898, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0240] Formulation Example 7

[0241] A solution was prepared by dissolving 5.56 g of the polymer synthesized in Example 2, 23.0 g of phenolic varnish resin CL23F, 4.81 g of DNQ PACNK280, 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 in 66.58 g of PGMEA solvent. The solution was filtered for testing.

[0242] Formulation Example 8

[0243] 10.3 g of the polymer synthesized in Example 2, 19.8 g of phenolic varnish resin (CL23F resin), 4.15 g of diazonoquinone sulfonate [also known as NK280], 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 65.7 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0244] Formulation Example 9

[0245] 7.8 g of the polymer synthesized in Example 8, 27.2 g of Novolak-3, 4.0 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazol-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0246] Formulation Example 10

[0247] 11.7 g of the polymer from Synthetic Example 8, 23.8 g of Novolak-3, 3.5 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazol-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0248] Formulation Example 11

[0249] 15.6 g of the polymer from Synthetic Example 8, 20.4 g of Novolak-3, 3.0 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0250] Formulation Example 12

[0251] 19.5 g of the polymer from Synthetic Example 8, 17.0 g of Novolak-3, 2.5 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazol-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0252] Formulation Example 13

[0253] 27.3 g of the polymer from Synthetic Example 8, 10.2 g of Novolak-3, 1.5 g of diazonoquinone sulfonate [also known as PW898], 0.025 g of 1H-1,2,4-triazole-3-thiol [also known as 3-mercapto-1,2,4-triazole], and 0.023 g of APS-437 were dissolved in 61 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0254] Formulation Example 14 (Comparative Example without Acrylic Polymer):

[0255] A solution was prepared by dissolving 34.3 g Novolak-3, 4.7 g diazonoquinone sulfonate (also known as PW898), 0.025 g 1H-1,2,4-triazol-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g APS-437 in 61 g PGMEA solvent. The solution was then filtered for testing.

[0256] Formulation Example 15 (Comparative Example without Acrylic Polymer):

[0257] A solution was prepared by dissolving 27.6 g of phenolic varnish resin CL23F, 5.77 g of diazonoquinone sulfonate (also known as NK280), 0.025 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 in 66.58 g of PGMEA solvent. The solution was then filtered for testing.

[0258] Coating of the formula:

[0259] All formulations were tested on 6” or 8” diameter Si and Cu wafers. The Si wafers were rehydrated and baked and then vapor-coated with hexamethyldisilazane (HMDS). The Cu wafers were silicon wafers coated with 5,000 Å silicon dioxide, 250 Å tantalum nitride, and 3,500 Å Cu (PVD deposited).

[0260] Photoresist coatings were prepared by spin-coating a photoresist sample and then applying a soft bake in contact mode for 120 seconds at 110°C on a standard wafer tracking hotplate. The spin speed was adjusted to obtain photoresist films ranging from 5 to 10 micrometers in thickness. All film thickness measurements were performed on the Si wafer using optical measurements.

[0261] Imaging:

[0262] Expose the wafer on a SUSS MA200 CC mask aligner or an ASML 250i line stepper. Allow the photoresist to stand for 10 to 60 minutes without post-exposure baking, then develop it in AZ300MIF (0.26N tetramethylammonium hydroxide = TMAH aqueous solution) at 23°C for 120 to 360 seconds using a immersion method. Examine the developed photoresist image using a Hitachi S4700 or AMRAY 4200L electron microscope.

[0263] Imaging results

[0264] Surprisingly, it was found that by adding a combination of DNQ-PAC and phenolic varnish resin to these coatings (Tables 1 to 3), a wide range of these coatings exhibited a concentration of 100 to 100 in a 0.26 TMAH aqueous solution. The dissolution of acrylic resin coatings soluble in alkaline aqueous solutions within the range was completely suppressed. Furthermore, these completely suppressed films showed adequate dissolution upon exposure to UV light and photodecomposition by DNQ-PAC, and when exposed using a photomask targeting L / S (line and space) features, these L / S features showed no T-topping or top erosion, or showed only slight T-topping and top erosion (Table 4).

[0265] Specifically, for example, it has a very high solubility rate in alkaline aqueous solutions. The acrylate polymer P1 provides a resin that is loaded with 78.4% by weight solids of Novolak 3 and 11.5% by weight solids of DNQ PACPW898. The dissolution rate. Similarly, the dissolution rate of acrylate polymer P2 ( Provided with Novolak 3 with 78.4 wt% solids and DNQ PAC PW898 with 11.5 wt% solids. The dissolution rate. Similarly, the dissolution rate of acrylate polymer P8 ( Provided with Novolak 3 with 78.4 wt% solids and DNQ PAC PW898 with 11.5 wt% solids. The dissolution rate was found to be as high as [missing information - likely a specific value]. Therefore, it was discovered that by using a combination of phenolic varnish resin and DNQ-PAC, the dissolution rate was at least [missing information - likely a specific value]. The dissolution of the acrylate polymer was effectively suppressed. When the acrylic resin was loaded with 6.4% PAC relative to the total solids content, the film loss was at most... However, for polymer 8, when an acrylic resin with a loading of 50% solids content (relative to total solids) is loaded with the same PAC (6.4%), the film loss is to

[0266] Formulation Example 16

[0267] 2.83 g of the polymer synthesized in Example 4, 25.35 g of phenolic varnish resin CL23F, 5.94 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0268] Formulation Example 17

[0269] A solution was prepared by dissolving 5.63 g of the polymer synthesized in Example 4, 22.55 g of phenolic varnish resin CL23F, 5.94 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 in 65.83 g of PGMEA solvent. The solution was filtered for testing.

[0270] Formulation Example 18

[0271] 8.46 g of the polymer synthesized in Example 4, 19.72 g of phenolic varnish resin CL23F, 5.94 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0272] Formulation Example 19

[0273] 14.09 g of the polymer synthesized in Example 4, 14.09 g of phenolic varnish resin CL23F, 5.94 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0274] Formulation Example 20

[0275] 22.55 g of the polymer synthesized in Example 4, 5.66 g of phenolic varnish resin CL23F, 5.94 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0276] Formulation Example 21

[0277] 28.18 g of the polymer synthesized in Example 4, 5.94 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0278] Formulation Example 22

[0279] 2.83 g of the polymer from Synthetic Example 4, 27.88 g of phenolic varnish resin CL23F, 3.41 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0280] Formulation Example 23

[0281] 2.83 g of the polymer synthesized in Example 4, 28.56 g of phenolic varnish resin CL23F, 2.73 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 were dissolved in 65.83 g of PGMEA solvent to prepare a solution. The solution was filtered for testing.

[0282] Formulation Example 24

[0283] A solution was prepared by dissolving 1.71 g of CPR215 polymer, 26.85 g of phenolic varnish resin CL23F resin, 5.56 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 in 65.83 g of PGMEA solvent. The solution was then filtered for testing.

[0284] Formulation Example 25

[0285] A solution was prepared by dissolving 1.71 g of CPR215 polymer, 27.77 g of phenolic varnish resin CL23F resin, 4.64 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 in 65.83 g of PGMEA solvent. The solution was then filtered for testing.

[0286] Formulation Example 26

[0287] A solution was prepared by dissolving 1.71 g of CPR215 polymer, 29.68 g of phenolic varnish resin CL23F resin, 2.73 g of diazonoquinone sulfonate (also known as NK280), 0.024 g of 1H-1,2,4-triazole-3-thiol (also known as 3-mercapto-1,2,4-triazole), and 0.023 g of APS-437 in 65.83 g of PGMEA solvent. The solution was then filtered for testing.

[0288] Formulation Example 27 (CPR215 P11):

[0289] A solution was prepared by dissolving 1.71 g of CPR215 polymer, 27.77 g of phenolic varnish resin CL23F resin, 4.64 g of diazonaphthoquinone sulfonate (also known as NK280), and 0.023 g of APS-437 in 65.83 g of PGMEA solvent. The solution was then filtered for testing.

[0290] Table 1. Dissolution rates of formulations with varying PAC loading

[0291]

[0292] *Dissolution rate was measured by the change in film thickness after 60 seconds of development in AZ 300MIF (also known as 0.26N TMAH aqueous developer); **Comparative example without acrylate polymers.

[0293] Table 2. Dissolution rates of formulations containing P4 acrylate polymer and NK280 PAC

[0294]

[0295] *The dissolution rate was measured by the change in film thickness after 60 seconds of development in AZ 300MIF developer (also known as 0.26N TMAH aqueous solution); **Comparative example without phenolic varnish.

[0296] Table 3. Dissolution rates of formulations with P11 loading

[0297]

[0298] *Dissolution rate was measured by the change in film thickness after 60 seconds of development in AZ 300MIF developer (also known as 0.26N TMAH aqueous solution). **The formulation is MTA-free.

[0299] Table 4. CD profiles of formulations with different phenolic varnish / DNQ-PAC and acrylate polymer loadings

[0300]

[0301]

[0302] *The formulation does not contain MTA; ***Comparative formulations do not contain acrylate polymers

[0303] As can be seen from Table 1, if Novolak 3 with 69.7% by weight solids and PACPW898 with 10.3% by weight solids (Formulation Example 1a) are used, a very high solubility rate in TMAH can be achieved. The acrylate polymer P1 does not exhibit dark etching. Similarly, if formulated with 68.9% by weight solids of Novolak 3 and 16.7% by weight solids of PAC PW898 (Formulation Example 5a), the acrylate polymer P2 (dissolution rate) can be improved. It does not exhibit dark etching. Utilizing Novolak 3 with only 69.7% wt% solids and PAC PW898 (Formulation Example 9) with 10.3% wt% solids, it exhibits... The acrylate polymer P8 with the highest dissolution rate did not exhibit dark etching. Similar results were observed using a DNQ PAC NK280.

[0304] Table 2 shows the dark etching results obtained from formulation examples containing acrylate polymer P4 with varying amounts of DNQ PAC and phenolic varnish. Resin P4 has The initial dark erosion rate. In formulation examples containing P4, DNQ PAC was kept constant at 17.4 wt% solids and the acrylate polymer content was increased to a maximum of 66.1 wt% solids, only given Very slight dark etching. As seen in Comparative Formulation 21, even with DNQ PAC containing 17.4% by weight solids in the absence of phenolic varnish, very slight dark etching was observed. Large dark erosion. This confirms that when both DNQ-PAC and phenolic varnish are added together to the acrylate polymers of the compositions of the present invention, they have an unexpected synergistic effect in suppressing dark erosion on acrylate polymers (such as P4) that have a very high dark erosion rate in 0.26N TMAH aqueous solution. Similarly, the phenolic varnish component can be increased to a very large extent up to at least 83.58% by weight solids, and for formulation examples containing acrylate polymers (such as P4) with high dark erosion rates, the synergistic resistance to dark erosion is maintained.

[0305] Table 3 shows the contents containing The initial dissolution rate of the acrylate polymer P11 in the formulation examples is shown. No dark erosion of the resin was observed when various amounts of DNQ PAC and phenolic varnish were added. Furthermore, when the coatings of these formulation examples were exposed, the L / S images obtained using these formulation examples showed straight wall profiles, unlike the formulation examples containing phenolic varnish and DNQ components but without any acrylate polymer. Table 1 also shows that the formulation examples containing only phenolic varnish and DNQ-PAC also showed no dark erosion (Formulation Examples 14 and 15). However, unlike the formulations of this invention, formulations 14 and 15 showed a very sloping L / S characteristic when UV exposed under the same conditions.

[0306] Table 4 shows the resolvable doses for different 1 / 1 L / S characteristics and the properties of various formulations of the present invention. All of these formulations give very steep sidewall L / S characteristics, which is different from standard phenolic varnish formulations (Formulation Examples 14 and 15) that do not contain acrylate polymer components and give very sloping L / S characteristics when exposed under similar conditions.

[0307] Figure 1 The image shows a SEM comparison of 4 μm line and space (L / S) 1 / 1 features obtained by UV imaging of photoresist films formed on copper substrates using formulations 23, 22, 16, and 15, exposed to UV light. These results from formulations 23, 22, and 16 show that maintaining a constant acrylate polymer additive P4 preserves the steep L / S sidewalls of all these formulations of the present invention, regardless of the DNQ-PAC (NK280) and phenolic varnish (CL23F) content. Conversely, a comparative example (formulation 15) treated in the same manner but without the acrylate polymer component shows an L / S feature with a very sloping profile. Formulation 14 (another formulation with a different phenolic varnish but also without the acrylate component) also gives a very sloping L / S feature. The acrylate polymer additive P4 used in formulations 23, 22, and 16 is... An acrylate polymer additive with a very high solubility rate.

[0308] Figure 2 The image shows a SEM comparison of the 4 μm line and space (L / S) 1 / 1 features of the photoresist films formed on silicon substrates using UV exposure from Formulation Examples 26, 25, and 24. Formulation Examples 26, 25, and 24 again demonstrate that maintaining a constant acrylate polymer additive P11 maintains the steep L / S sidewalls in all these formulations when the contents of DNQ-PAC (NK280) and phenolic varnish (CL23F) are varied. The acrylate polymer additive P11 used in Formulation Examples 26, 25, and 24 is a [missing information - likely a specific type of additive]. An acrylate polymer additive with a moderate dissolution rate.

[0309] therefore, Figure 1 and Figure 2 Various acrylate polymer additives exhibiting different dissolution rates can be used in the compositions of the present invention to achieve steep L / S sidewalls, which cannot be achieved with standard phenolic varnish formulations (such as formulation examples 14 and 15) that do not contain acrylate polymer components.

[0310] Figure 3 This shows a SEM comparison of 2 μm line and space (L / S) 1 / 1 features obtained by UV imaging of photoresist films formed on copper substrates using formulations 25 and 27 (containing acrylate polymer component P11) exposed to UV light. The two formulations are identical except that one (formulation 25) contains the optional heterocyclic thiol compound MTA: additive (1H-1,2,4-triazole-3-thiol), while the other formulation (formulation 27) does not. On the copper substrate, this heterocyclic thiol compound suppresses the slight footing observed in the L / S features obtained with formulation 27. When formulation 27 was imaged on another Si substrate, no footing was observed.

[0311] Like standard phenolic varnish-DNQ photoresists, the disclosed compositions of the present invention containing acrylate polymer components do not require post-exposure baking (PEB) and have been found to be environmentally stable for the delay between exposure and development. However, the compositions of the present invention have been found to require long rehydration times, which is typically required for standard phenolic varnish photoresists [10 to 15 μm thick (20 to 30 minutes), ~5 μm thick (10 minutes)] that do not contain the acrylate polymer components as described herein. Furthermore, the novel compositions have been found to be able to image at least L / S features at an aspect ratio of 5 to 6, which is better than that achievable with comparative phenolic varnish photoresists that can only image L / S features at an aspect ratio of 3 to 4. Specifically, for example, a novel coated composition with a film thickness of 4 μm can resolve 0.65 μm L / S features (aspect ratio: 6.15 / 1). Finally, the compositions of the present invention have also been found to generally have UV sensitivity equal to or better than that of comparative standard phenolic varnish photoresist formulations that do not contain the acrylate polymer components.

Claims

1. A composition comprising components a), b), c) and d); wherein Component a) is an acrylic polymer. The acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having the structure (1), (3), (4) and (5); The acrylic polymer is an acrylic polymer whose repeating unit is an acrylic polymer having repeating units with structures (1), (3), (5) and (7); or The acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having the structure (1), (2), (5) and (6); These repeating units are present in the acrylic polymer in a range of mol% based on the total mole count of all different repeating units present, and furthermore, the sum of the individual mol% values ​​of all repeating units present in the polymer must be equal to 100 mol%. The repeating units of structure (1) range from 10 mol% to 35 mol%. The repeating units of structure (2) range from 0 mol% to 20 mol%. The repeating units of structure (3) range from 0 mol% to 55 mol%. The repeating units of structure (4) range from 0 mol% to 30 mol%. The repeating units of structure (5) range from 15 mol% to 55 mol%. The repeating units of structure (6) range from 0 mol% to 40 mol%. The repeating units of structure (7) range from 0 mol% to 25 mol%. R1, R2, R3, R4, R5, R6, and R7 are selected from H or C-1 to C-4 alkyl groups, respectively. R8 and R9 are selected from H, C-1 to C-4 alkyl, and C-1 to C-4 alkoxyalkyl, respectively. R 10 It is a C-3 to C-8 cyclic alkyl or a C-7 to C-14 alicyclic alkyl. R 11 It is a C-2 to C-8 (hydroxy) alkylene group. R 12 It is an acid-cleavable group. R 13 It is a C-3 to C-12 (alkoxy) alkylene group, and The acrylic polymer described herein has at least [a certain content] in a 0.26N tetramethylammonium hydroxide (TMAH) aqueous solution. / second and less than Dissolution rate per second Component b) has at least [a certain content] in a 0.26N TMAH aqueous solution. Phenolic varnish resin with a dissolution rate of / second; Component c) is a diazonoquinone (DNQ) photoactive compound (PAC); and Component d) is an organic rotary casting solvent, and In the composition, the acrylic polymer comprises 0.5% by weight to 70% by weight of solids, and The DNQ PAC comprises 5% to 20% solids by weight, and Furthermore, the coated film of the aforementioned composition has a concentration of less than 0.26 N TMAH in an aqueous solution. Dark erosion per second.

2. The composition according to claim 1, wherein component a) is an acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7), wherein The repeating units of structure (1) range from 10 mol% to 35 mol%. The repeating units of structure (2) range from 0 mol% to 20 mol%. The repeating units of structure (3) range from 10 mol% to 55 mol%. The repeating units of structure (4) range from 0 mol% to 30 mol%. The repeating units of structure (5) range from 15 mol% to 55 mol%. The repeating units of structure (6) range from 0 mol% to 40 mol%. The repeating units of structure (7) are in the range of 0 mol% to 25 mol%.

3. The composition according to claim 1, wherein component a) is an acrylic polymer comprising repeating units selected from repeating units having structures (1), (2), (3), (4), (5), (6), and (7), wherein these repeating units are present in the acrylic polymer in a range of mol% based on the total mole count of all different repeating units present, and further wherein the sum of the individual mol% values ​​of all repeating units present in the polymer must be equal to 100 mol%. The repeating units of structure (1) range from 10 mol% to 35 mol%. The repeating units of structure (2) are in the range of 10 mol% to 20 mol%. The repeating units of structure (3) range from 0 mol% to 55 mol%. The repeating units of structure (4) range from 0 mol% to 30 mol%. The repeating units of structure (5) range from 15 mol% to 55 mol%. The repeating units of structure (6) range from 0 mol% to 40 mol%. The repeating units of structure (7) are in the range of 0 mol% to 25 mol%.

4. The composition according to any one of claims 1 to 3, wherein the acrylic polymer comprises 4% to 50% by weight of solids.

5. The composition according to any one of claims 1 to 3, wherein the acrylic polymer comprises 10 to 30% by weight of solids.

6. The composition according to any one of claims 1 to 3, wherein the dissolution rate of said acrylic polymer is 100 to Within / second.

7. The composition according to any one of claims 1 to 3, wherein the dissolution rate of said acrylic polymer is 120 to Within / second.

8. The composition according to claim 1, wherein the acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having structures (1), (3), (4) and (5), wherein R9 is H, R 10 It is a C-7 to C-14 alicyclic alkyl group.

9. The composition according to claim 1 or 2, wherein the acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having the structure (1), (3a), (4a) and (5a), wherein n is the number of methylene spacer groups and is in the range of an integer from 1 to 4, R1, R3, R4 and R5 are selected from C-1 to C-4 alkyl groups, and R 5’ Selected from H and C-1 to C-4 alkyl groups, 10. The composition according to claim 1 or 2, wherein the acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having the structure (1a), (3b), (4b) and (5b).

11. The composition according to claim 1 or 2, wherein the acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having structures (1), (3), (5) and (7), wherein R9 is H.

12. The composition according to claim 1 or 2, wherein the acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having the structure (1), (3a), (5a) and (7a), wherein n and n' are the number of methylene spacer groups and are independently in the range of 1 to 4. R1, R3, R5, and R7 are selected from C-1 to C-4 alkyl groups, respectively. R 5’ and R 7’ Selected from H or C-1 to C-4 alkyl groups, and R 7” It is a C-1 to C-4 alkyl group.

13. The composition according to claim 1 or 2, wherein the acrylic polymer is an acrylic polymer whose repeating unit is an acrylic polymer having repeating units having structures (1a), (3b), (5b) and (7b).

14. The composition according to claim 1 or 3, wherein the acrylic polymer is an acrylic polymer whose repeating unit is a repeating unit having structures (1), (2a), (5a) and (6), wherein n is an integer number of methylene spacer groups and is in the range of 1 to 4, and R1, R5 and R6 are selected from C-1 to C-4 alkyl groups, respectively. R 5’ Selected from H and C-1 to C-4 alkyl groups, R8 is selected from H and C-1 to C-4 alkyl groups, respectively. R 12 It is an acid-degradable protecting group, selected from C-4 to C-12 tertiary alkyl groups, acetal groups, and ketal groups having at least one β-hydrogen.

15. The composition according to claim 1 or 3, wherein the acrylic polymer is an acrylic polymer whose repeating unit is an acrylic polymer having repeating units having structures (1a), (2b), (5b) and (6a).

16. The composition according to claim 1, wherein the phenolic varnish resin comprises repeating units of structure (8), wherein, Ra and Rb are independently C-1 to C-4 alkyl groups, na is 0 to 3, and nb is 0 or 1.

17. The composition according to claim 1, wherein the phenolic varnish resin comprises repeating units of structure (9), wherein, Rc is a C-1 to C-4 alkyl group, Rd is a C-1 to C-4 alkyl group, X is -O-, C(CH3)2-, -(C=O)- or -SO2-, nc is 0 to 3, and nd is 0 or 1.

18. The composition according to claim 16 or 17, wherein the phenolic varnish resin comprises the repeating units (8) and (9).

19. The composition according to any one of claims 1 to 3, wherein the phenolic varnish resin is a phenolic varnish resin of m-cresol and formaldehyde.

20. The composition according to any one of claims 1 to 3, wherein the phenolic varnish resin comprises 10 to 90% by weight of solids.

21. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single material having general formula (10) or a mixture of materials having general formula (10), wherein D 1c D 2c D 3c and D 4c They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1c D 2c D 3c Or D 4c At least one of them is a group having structure (11), 22. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single material having general formula (10) or a mixture of materials having general formula (10), wherein D 1c D 2c D 3c and D 4c The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1c D 2c D 3c Or D 4c At least one of them is a group having structure (12), 23. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single PAC compound having structure (13a) or a mixture of PAC compounds having structure (13a), wherein D 1e D 2e and D 3e They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1e D 2e Or D 3e At least one of them is a group having structure (11), 24. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single PAC compound having structure (13a) or a mixture of PAC compounds having structure (13a), wherein D 1e D 2e and D 3e The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1e D 2e Or D 3e At least one of them is a group having structure (12), 25. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single PAC compound having structure (13b) or a mixture of PAC compounds having structure (13b), wherein D 1e D 2e D 3e and D 4e They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1e D 2e D 3e Or D 4e At least one of them is a group having structure (11), 26. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single PAC compound having structure (13b) or a mixture of PAC compounds having structure (13b), wherein D 1e 、D 2e 、D 3e and D 4e The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1e 、D 2e 、D 3e Or D 4e At least one of them is a group having structure (12), 27. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single PAC compound having structure (14) or a mixture of PAC compounds having structure (14), wherein D 1f D 2f D 3f and D 4f They are respectively selected from H or groups having structure (11), and in addition, D is selected from H. 1f D 2f D 3f and D 4f At least one of them is a group having structure (11), 28. The composition according to any one of claims 1 to 3, wherein the DNQ PAC is a single PAC compound having structure (14) or a mixture of PAC compounds having structure (14), wherein D 1f D 2f D 3f and D 4f The groups are selected from H or groups having structure (12), and in addition, D is selected from H. 1f D 2f D 3f and D 4f At least one of them is a group having structure (12), 29. The composition according to any one of claims 1 to 3, wherein the diazonoquinone (DNQ) photoactive compound is in the range of 5 to 20% by weight of the photoresist composition.

30. The composition according to any one of claims 1 to 3, wherein the composition further comprises component e): at least one heterocyclic thiol compound comprising a ring structure selected from general formulas (15), (16) or (17) or a tautomer thereof; and in, The ring structure is a monocyclic structure with 4 to 8 atoms or a polycyclic structure with 5 to 20 atoms; and wherein the monocyclic structure or the polycyclic structure comprises an aromatic ring, a non-aromatic ring, or a heteroaromatic ring. In the structure (15), Xt is selected from the group consisting of C(Rt1)(Rt2), O, S, Se and Te; In the structure (16), Y is selected from the group consisting of C(Rt3) and N; In the structure (17), Z is selected from the group consisting of C(Rt3) and N; and Rt1, Rt2, and Rt3 are independently selected from the group consisting of H, substituted alkyl groups having 1 to 8 carbon atoms, unsubstituted alkyl groups having 1 to 8 carbon atoms, substituted alkenyl groups having 2 to 8 carbon atoms, unsubstituted alkenyl groups having 2 to 8 carbon atoms, substituted ynyl groups having 2 to 8 carbon atoms, unsubstituted ynyl groups having 2 to 8 carbon atoms, substituted aromatic groups having 6 to 20 carbon atoms, substituted heteroaromatic groups having 3 to 20 carbon atoms, unsubstituted aromatic groups having 6 to 20 carbon atoms, and unsubstituted heteroaromatic groups having 3 to 20 carbon atoms.

31. A method comprising steps i) to iv), i) Applying the composition according to any one of claims 1 to 30 to form a coating. ii) Bake the coating to form a baked coating. iii) Exposing the baked coating to radiation using a mask to obtain a coating with the exposed pattern. iv) Develop the exposed pattern using an aqueous alkaline developer to remove the areas of the pattern exposed to the radiation, thereby forming a photoresist positive image.

32. Use of the composition according to any one of claims 1 to 30 as an aqueous developable UV photoresist.

Images