Photo-base generators, patterned compositions, patterned methods, patterned films, and applications thereof

Abstract

Photobase generators, patterning compositions, patterning methods, patterned films, and uses thereof are disclosed. The photobase generators are used for patterning, the photobase generators are selected from at least one of the compounds shown in Formula I, wherein A and B are each independently selected from an aromatic or heteroaromatic ring; each R1 is independently selected from halogen, optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl; each R2 and R3 is independently selected from halogen, optionally substituted alkyl, optionally substituted cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein each R0 is independently selected from hydrogen, optionally substituted alkyl, or optionally substituted aryl; each of m and n is independently selected from an integer from 0 to 8; at least one of m and n is other than 0; x is selected from an integer from 0 to 5. Formula I.

Description

Technical Field

[0001] This application relates to the manufacture of microelectronic devices, and more particularly to photo-induced alkali-generating agents, patterning compositions, patterning methods, patterned films, and their applications. Background Technology

[0002] In the field of microelectronic device manufacturing, patterning materials are key functional materials for transferring patterns from photomasks to substrates, a trend particularly driven by the expansion of the memory market and the increase in storage capacity. Currently, in advanced semiconductor processes, chemically amplified resists (CARs) have become mainstream due to their significant reduction in the energy required for exposure in patterning processes. For advanced patterning technologies, the shorter wavelengths or higher energies of their exposure sources place higher demands on the absorption characteristics and pattern performance of the patterning materials. In this context, optimizing the critical dimension (CD) and line width roughness (LWR) of the patterning process becomes particularly important, enabling high-resolution patterning materials to provide finer patterns. Summary of the Invention

[0003] This application discloses a photo-induced alkali-generating agent, a patterning composition, a patterning method, a patterned film, and their applications, for optimizing the critical dimensions and line width roughness of the patterning process, and providing finer patterns in the manufacture of microelectronic devices.

[0004] In a first aspect, this application provides a photo-induced alkali-generating agent for patterning, wherein the photo-induced alkali-generating agent is selected from at least one of the compounds represented by Formula I:

[0005] Formula I, Wherein, A and B are each independently selected from aromatic rings or heteroaromatic rings; R1 is each independently selected from halogens, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, or optionally substituted aryl groups; R2 and R3 are each independently selected from halogens, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen, optionally substituted alkyl groups, or optionally substituted aryl groups; m and n are each independently selected from integers from 0 to 8; at least one of m and n is not 0; x is selected from integers from 0 to 5.

[0006] The photo-induced alkali-generating agent described in this disclosure, when used in positive patterning compositions for charged particle beam exposure, can enable the positive patterning compositions to exhibit excellent line width roughness and high resolution.

[0007] In one possible implementation, A and B are each independently selected from C6-C. 14 Aromatic rings or C2-C 14 Mixed fragrance ring.

[0008] In one possible implementation, A and B are each independently selected from benzene rings, naphthalene rings, anthracene rings, or phenanthrene rings.

[0009] In one possible implementation, A and B are each independently selected from benzene rings, naphthalene rings, or anthracene rings.

[0010] In one possible implementation, both A and B are benzene rings.

[0011] In one possible implementation, R2 and R3 are each independently selected from halogens, optionally substituted C1-C8 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, or -N(RO)2, provided that at least one of R2 and R3 is -N(RO)2, wherein R0 is each independently selected from hydrogen, optionally substituted C1-C6 alkyl groups, or optionally substituted C6-C... 14 Aryl.

[0012] In one possible implementation, R2 and R3 are each independently selected from iodine, C1-C6 alkyl, C3-C8 cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C6 alkyl.

[0013] In one possible implementation, R2 and R3 are each independently selected from iodine, C1-C4 alkyl, C3-C6 cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C4 alkyl.

[0014] In one possible implementation, R2 and R3 are each independently selected from C1-C4 alkyl or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C4 alkyl.

[0015] In one possible implementation, at least two of R2 and R3 are -N(R0)2; wherein each R0 is independently selected from hydrogen or C1-C6 alkyl.

[0016] In one possible implementation, at least one R2 and at least one R3 are -N(R0)2; wherein each R0 is independently selected from hydrogen or C1-C6 alkyl.

[0017] In one possible implementation, R2 and R3 each have one of the following components: -N(R0)2; wherein each of R0 is independently selected from hydrogen or C1-C6 alkyl groups.

[0018] In one possible implementation, m and n are each independently selected from integers from 1 to 6.

[0019] In one possible implementation, m and n are each independently selected from integers from 1 to 4.

[0020] In one possible implementation, m and n are each independently selected from 1 or 2.

[0021] In one possible implementation, both m and n are 1.

[0022] In one possible implementation, -N(RO)2 is -N(CH3)2.

[0023] Since -N(CH3)2 is a strong electron-donating group, its conjugated electron donation (+M) is much stronger than its induced electron donation (+I), thus significantly increasing the electron cloud density of the benzene ring in the photo-induced alkalization agent. This strong electron donation drives the π–π... Conjugation increases the molar absorptivity, which is beneficial for improving the photoresponsibility of the photoalkalizing agent, thereby further improving the resolution of the patterned composition containing the photoalkalizing agent and improving the line width roughness.

[0024] In one possible implementation, R1 is independently selected from halogens, optionally substituted C1-C8 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, or optionally substituted C6-C4 alkyl groups. 14 Aryl.

[0025] In one possible implementation, R1 is independently selected from fluorine, iodine, C1-C8 alkyl, or C3-C8 cycloalkyl.

[0026] In one possible implementation, R1 is independently selected from fluorine, iodine, C1-C6 alkyl, or C3-C6 cycloalkyl.

[0027] In one possible implementation, R1 is independently selected from C1-C4 alkyl groups.

[0028] In one possible implementation, x is selected from 0, 1, 2, or 3.

[0029] In one possible implementation, x is 0.

[0030] The alkyl side chain on the benzene ring in the photo-alkali-producing agent slightly disrupts the π electron distribution. Without the alkyl group, the conjugation of the molecule shown in Formula I is more complete, thereby further improving the resolution of the patterned composition containing the photo-alkali-producing agent and improving the line width roughness.

[0031] In one possible implementation, "optionally substituted" means unsubstituted or substituted by one or more substituents independently selected from: halogen, hydroxyl, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C 15 carbonyl group, C2-C 15 Heterocyclic group, C6-C 20 Aryl or C2-C 20 Mixed aromatic compounds.

[0032] In one possible implementation, "optionally substituted" means unsubstituted or substituted by one or more substituents selected independently from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, or C1-C6 alkoxy.

[0033] In one possible implementation, "optionally substituted" means unsubstituted or substituted with one or more C1-C6 alkyl groups.

[0034] In one possible implementation, "optionally substituted" means unsubstituted or substituted with one or more methyl, ethyl, or isopropyl groups.

[0035] In one possible embodiment, the compound has the structure shown in Formula II, Formula III, Formula IV, or Formula V:

[0036] Formula II,

[0037] Formula III,

[0038] Formula IV,

[0039] Formula V, Wherein, R1, R0 and x are as defined in Formula I above; R2' and R3' are each independently selected from halogens, optionally substituted alkyl groups, or optionally substituted cycloalkyl groups; in Formula II, m and n are each independently selected from integers from 0 to 3; in Formula III, m and n are each independently selected from integers from 0 to 5; in Formulas IV and V, m and n are each independently selected from integers from 0 to 7.

[0040] The compound has the structure shown in Formula II, Formula III, Formula IV or Formula V, which extends its conjugated system, expands the π electron delocalization range, increases molecular rigidity, redshifts the ultraviolet-visible light absorption, and significantly enhances fluorescence and photoelectric response performance, thereby improving the resolution of patterned compositions including the photo-induced alkalizing agent and improving line width roughness.

[0041] In one possible implementation, R2' and R3' are each independently selected from halogens, optionally substituted C1-C8 alkyl groups, or optionally substituted C3-C8 cycloalkyl groups.

[0042] In one possible implementation, R2' and R3' are each independently selected from iodine, C1-C6 alkyl, or C3-C8 cycloalkyl.

[0043] In one possible implementation, R2' and R3' are each independently selected from iodine, C1-C4 alkyl, or C3-C6 cycloalkyl.

[0044] In one possible implementation, R2' and R3' are each independently selected from C1-C4 alkyl groups.

[0045] In one possible implementation, in Equation II, m and n are each independently selected from 0 or 1; in Equation III, m and n are each independently selected from integers from 0 to 3; and in Equations IV and V, m and n are each independently selected from integers from 0 to 4.

[0046] In one possible implementation, in Formulas II, III, IV and V, m and n are each independently selected from 0 or 1.

[0047] In one possible implementation, m and n are both 0 in Equations II, III, IV and V.

[0048] In one possible implementation, the compound is: , , , , , , , , , , , , ,or .

[0049] In a second aspect, this application provides a patterned composition, which is a chemically amplified patterned composition; the patterned composition comprises at least one of the photo-alkali-generating agent, acid-sensitive polymer, photoacid generator, and solvent according to any one of the first aspects above; or, the patterned composition comprises the photo-alkali-generating agent, acid-sensitive polymer, photoacid generator, and solvent according to any one of the first aspects above.

[0050] In one possible implementation, the mass ratio of the photoacid generator to the compound in the patterned composition is 10:1 to 4:1.

[0051] In one possible implementation, the mass ratio of the photoacid generator to the compound in the patterned composition is 5:1 to 4:1.

[0052] In one possible implementation, the acid-sensitive polymer is an acid-sensitive polymer containing two acid-instable groups.

[0053] When the acid-sensitive polymer contains two acid-instable groups, the low activation energy groups will be preferentially removed during the acid amplification and deprotection process. This process may not necessarily cause a significant change in the dissolution rate of the exposed area before and after exposure. At this time, only a small amount of high activation energy groups need to be removed to cause a great change in the dissolution rate of the exposed area, thereby improving the contrast between the exposed and unexposed areas and resulting in better patterning performance.

[0054] In one possible implementation, the acid-sensitive polymer is selected from at least one of the following compounds: , , ,or .

[0055] In one possible implementation, the patterned composition comprises 1-15 parts by weight of the acid-sensitive polymer, based on 100 parts by weight of the patterned composition.

[0056] In one possible implementation, the patterned composition comprises 1-10 parts by weight of the acid-sensitive polymer, based on 100 parts by weight of the patterned composition.

[0057] In one possible implementation, the polydispersity index (PDI) of the acid-sensitive polymer is 1.51-1.57, and the weight-average molecular weight (Mw) of the acid-sensitive polymer is 7.9k-8.7k.

[0058] In one possible implementation, the photoacid generator is an ionic photoacid generator.

[0059] In one possible implementation, the photoacid generator is an ionic photoacid generator comprising a cation of diaryliodonium ion or triarylsulfonium ion and an anion of aromatic fluorosulfonate ion.

[0060] In one possible implementation, the photoacid generator is selected from at least one of the following compounds: , ,or .

[0061] In one possible implementation, the patterned composition comprises 0.01-0.20 parts by weight of the photoacid generator, based on 100 parts by weight of the patterned composition.

[0062] In one possible implementation, the patterned composition comprises 0.01-0.10 parts by weight of the photoacid generator, based on 100 parts by weight of the patterned composition.

[0063] In one possible implementation, the content of the compound is from 0.001 wt% to 0.020 wt% based on the total weight of the patterned composition.

[0064] In one possible implementation, the content of the compound is from 0.001 wt% to 0.010 wt% based on the total weight of the patterned composition.

[0065] In one possible implementation, the solid content of the patterned composition is from 0.5 wt% to 3.0 wt% based on the total weight of the patterned composition.

[0066] In one possible implementation, the solid content of the patterned composition is from 1.0 wt% to 2.5 wt% based on the total weight of the patterned composition.

[0067] Thirdly, this application provides a patterning method, the patterning method comprising: patterning a coating formed using the patterning composition described in this disclosure.

[0068] When a coating formed using the patterning composition described in this disclosure is patterned, the triphenylmethane conjugated structural framework of the photo-inducing alkali-producing agent included in the patterning composition of this disclosure is photoresponsive and releases OH under high-energy excitation. - Furthermore, by changing the pH value to achieve alkalinity and neutralize some of the acid, the acid concentration in local areas of the patterned material can be precisely controlled, thereby improving the resolution of the pattern prepared by the method described in this disclosure and improving the line width roughness.

[0069] Fourthly, this application provides a method for fabricating a semiconductor device, the method comprising the patterning method described in this disclosure.

[0070] Fifthly, this application provides a patterned film formed by the patterning method described in this disclosure.

[0071] The patterned film described in this disclosure has improved resolution and reduced line width roughness.

[0072] In one possible implementation, the linewidth roughness of the patterned film is less than 4.7 nm.

[0073] In one possible implementation, the linewidth roughness of the patterned film is below 4.5 nm.

[0074] In one possible implementation, the linewidth roughness of the patterned film is below 3.1 nm.

[0075] In one possible implementation, the critical dimension of the patterned film is below 30 nm.

[0076] In a sixth aspect, this application provides a semiconductor device comprising a substrate and functional layers formed on the substrate, wherein at least one of the functional layers comprises a pattern formed by the patterned composition described in this disclosure, or comprises a patterned film described in this disclosure.

[0077] In one possible implementation, the functional layer includes one or more of a semiconductor layer, a conductive layer, and a dielectric layer.

[0078] In a seventh aspect, this application provides an electronic device, the electronic device including the semiconductor device described in the sixth aspect of this disclosure; and one or more of a packaging substrate, bonding wire, molding compound and pins.

[0079] Eighthly, this application provides an electronic device comprising: a circuit board and the electronic device described in the seventh aspect of this disclosure, wherein the electronic device is electrically connected to the circuit board.

[0080] Compared with the prior art, the inventions in this disclosure have one or more of the following beneficial effects: The patterned compositions described in this disclosure can exhibit excellent overall exposure performance when used for charged particle beam exposure, for example, achieving linewidth roughness (LWR) of less than 4.7 nm (e.g., below 4.5 nm, below 3.7 nm, below 3.6 nm, below 3.5 nm, below 3.4 nm, and even below 3.1 nm).

[0081] The patterned compositions described in this disclosure can exhibit high resolution when used for charged particle beam exposure, for example, achieving optimal critical dimensions (CD) below 30 nm or even below 25 nm. Attached Figure Description

[0082] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0083] Figure 1 The ultraviolet-visible absorption spectra of the photo-induced alkali-producing agent PBG 344 described in Examples 1-5 of this application are shown. Figure 2 A scanning electron microscope (SEM) image of a resist pattern formed by the patterning process of the patterned composition of Example 1 of this application; Figure 3 This is a SEM image of the resist pattern formed by the patterning process of the patterned composition of Example 2 of this application; Figure 4 This is a SEM image of the resist pattern formed by the patterning process of the patterned composition of Example 3 of this application; Figure 5 This is a SEM image of the resist pattern formed by the patterning process of the patterned composition of Example 4 of this application; Figure 6 This is a SEM image of the resist pattern formed by the patterning process of the patterned composition of Example 5 of this application; Figure 7 SEM image of the resist pattern formed by the patterning process of the patterned composition of Comparative Example 1 of this application; Figure 8 SEM image of the resist pattern formed by the patterning process of the patterned composition of Comparative Example 2 of this application; Figure 9 This is a SEM image of the resist pattern formed by the patterning process of the patterned composition of Comparative Example 3 of this application. Detailed Implementation

[0084] definition The terms “comprising” or “including” as used herein should be interpreted as having a non-exhaustive meaning and allowing for the addition or reference to further elements, such as adding features or method steps or members or components to anything that includes the listed elements. “Comprising” may be replaced by “including” if the practice of a given language variant requires it, or may be limited to “consistently consisting of” if other elements besides those listed are not essential to the practice of this disclosure, or may be limited to “consisting of” in the absence of any other elements.

[0085] The term "aromatic fluorosulfonate ionic photoacid generator" as used in this article refers to an ionic photoacid generator (PAG) formed by the ionic bonding of aromatic fluorosulfonate anions and onium salt cations (such as triarylsulfonium, diaryliodonium, etc.). Its anions have fluorine-substituted aromatic rings and sulfonate structures, and the cations can absorb energy and undergo photolysis reactions, forming strong aromatic fluorosulfonic acids from the anions, which then catalyze the deprotection reaction of acid-sensitive polymers in chemically amplified patterned compositions.

[0086] As used in this article, "semiconductor device" refers to an electronic device whose conductivity is between that of a good conductor and an insulator, and which utilizes the special electrical properties of semiconductor materials to perform a specific function.

[0087] As used herein, the term "patterning" refers to photolithography, a crucial step in electronic device manufacturing. This step involves etching a patterned structure onto a material to be patterned (i.e., a patterning composition) through exposure and development processes. The pattern on the photomask is then transferred to a substrate using an etching process. This substrate can include not only silicon wafers but also other metal layers, dielectric layers, and the aforementioned substrates with surface modifications or added supporting layers.

[0088] As used herein, the term "patterned composition" refers to an etching-resistant material whose solubility in a developer changes after exposure to light or radiation such as ultraviolet light, deep ultraviolet light, X-rays, or charged particle beams (e.g., electron beams or ion beams). For example, the patterned composition is obtained by exposure with charged particle beams, where the charged particles may include electron beams and ion beams.

[0089] As used herein, the term "developer" refers to a pure or mixed solvent that dissolves soluble areas of a patterned composition after exposure has caused a change in solubility.

[0090] As used in this paper, the term "mask" refers to a mask that serves as an optical element in the optical path during the patterning process. The mask carries the design pattern, and light selectively transmits the design pattern onto the patterning material film (the layer to be patterned) through its transmission or reflection.

[0091] As used herein, "acid-instable group" refers to a group that can be hydrolyzed or cleaved under acidic conditions. Examples of "acid-instable groups" include, but are not limited to, ester groups, acetals, ketals, and acid anhydrides.

[0092] The term "ester group" refers to a -C=(O)OR or -OC=(O)R group, where R can be a saturated or unsaturated hydrocarbon group, such as an alkyl group as defined below.

[0093] In this article, “PDI” refers to the polydispersity index, which is a chemical parameter characterizing the molecular weight distribution of polymers and is defined as the ratio of weight-average molecular weight (Mw) to number-average molecular weight (Mn).

[0094] The terms “optional” or “optionally” mean that the event or condition described below may or may not occur, including both the occurrence and non-occurrence of the event or condition. For example, the ethyl group “optionally” being halogenated means that the ethyl group can be unsubstituted (CH2CH3), monosubstituted (e.g., CH2CH2F, CH2CH2Cl, etc.), polysubstituted (e.g., CHFCH2F, CH2CHF2, CHFCH2Cl, CH2CHCl2, etc.), or fully substituted (CF2CF3, CF2CCl3, CCl2CCl3, etc.). Those skilled in the art will understand that for any group containing one or more substituents, no substitution or substitution pattern that is spatially impossible and / or cannot be synthesized is introduced.

[0095] The term "substituted" refers to the substitution of one or more (e.g., 1, 2, 3, 4, 5, 6) hydrogen atoms on a particular atom by a substituent, provided that the valence state of the particular atom is normal and the substituted compound is stable. When the substituent is oxo (i.e., =O), it means that two hydrogen atoms are substituted; oxo substitution does not occur on aromatic groups.

[0096] When any variable (e.g., R) a R b When a group appears more than once in the composition or structure of a compound, its definition is independent in each case. For example, if a group is surrounded by two R... b Replaced, then each R b Each has its own independent options.

[0097] The term "ester group" refers to a -C=(O)OR or -OC=(O)R group, where R can be a saturated or unsaturated hydrocarbon group, such as alkyl groups as defined below.

[0098] The numerical range representing the number of carbon atoms in this article refers to the integers within a given range, for example, "C1-C1". 20 "or "C 1-20 "" means that the group can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

[0099] The terms “halogen,” “halogenated,” or “halogen” themselves or as part of another substituent represent fluorine (F), chlorine (Cl), bromine (Br), or iodine (I) atoms.

[0100] The term "alkyl" refers to a straight-chain or branched saturated hydrocarbon group. Examples of alkyl groups include, but are not limited to, C1-C1 alkyl groups. 20 Alkyl, C1-C 10 Alkyl, C1-C6 alkyl, C1-C4 alkyl, C4-C 12 Alkyl, C6-C 12 Alkyl groups, such as methyl (Me), ethyl (Et), propyl (e.g., n-propyl and isopropyl), butyl (e.g., n-butyl, isobutyl, s-butyl, tert-butyl), pentyl (e.g., n-pentyl, isopentyl, neopentyl), etc.; for example, the term "C 1-6 "Alkyl" refers to an alkyl group containing 1 to 6 (e.g., 1, 2, 3, 4, 5, 6) carbon atoms (e.g., methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, hexyl, 2-methylpentyl, etc.).

[0101] The term "alkoxy" refers to -O-alkyl, where "alkyl" is defined as above, and examples of "alkoxy" include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, and isopentoxy. "Optionally substituted alkoxy" means that the alkyl group in the group is substituted or unsubstituted.

[0102] As used herein, the term "aryl" refers to a monocyclic or fused polycyclic system consisting solely of carbon atoms as cyclic atoms, and having at least one aromatic ring or all of its rings being aromatic rings. The term "C6-C" is also used. 14 "Aryl" or "aromatic ring" refers to an aryl or aromatic ring as defined above, having 6 to 14 carbon atoms (e.g., 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms). The term "C"... 10 -C 30 "Aryl" or "aromatic ring" refers to an aryl group or aromatic ring as defined above having 10 to 30 carbon atoms (e.g., 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbon atoms). The aryl group includes a ring system formed by the fusion of aromatic rings with other aromatic rings, or by the fusion of an aromatic ring with a non-aromatic carbon ring (e.g., cycloalkanes, cycloalkenes, or cycloalkynes). Furthermore, in the aforementioned fused aryl group, the connection site between the aryl group and the remaining portion of the molecule can be on the aromatic ring or on other rings fused with the aromatic ring. Non-limiting examples of aryl groups include, but are not limited to, phenyl, naphthyl, anthracene, 1,2,3,4-tetrahydronaphthyl, indanyl, etc.

[0103] As used herein, the term "fused ring (or fused cyclic group)" refers to an organic compound structure in which two or more rings (e.g., carbocyclic rings) are coupled together by sharing two adjacent carbon atoms and a covalent bond. For example, a fused ring can refer to a group formed by the fusion of multiple benzene rings, such as naphthalene, anthracene, or phenanthrene. It can also refer to a macrocyclic system formed by the fusion of multiple heterocyclic rings, such as porphyrin rings. It should be noted that the carbocyclic and heterocyclic rings are non-aromatic.

[0104] As used herein, the term "heteroaryl" refers to a monocyclic or fused polycyclic system containing at least one (e.g., 1 to 5, such as 1, 2, 3, 4, or 5) heteroatom (selected from at least one of N, O, S, Si, or an oxo group) as a ring atom, with the remaining ring atoms being carbon, and having at least one aromatic ring or all rings in a heteroaryl group being aromatic rings. The cyclic carbon atom and heteroatom may be substituted with an oxo or thio group. The term "C1-C" is also used. 30 "Heteroaryl" refers to a heteroaryl group as defined above that has 1 to 30 carbon atoms (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30). The term "8- to 30-membered heteroaryl" means a heteroaryl group with 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 ring atoms, and whose ring atoms contain 1 to 5 independently selected heteroatoms as described above. The heteroaryl group comprises a ring system formed by the fusion of a heteroaryl ring with an aromatic carbon ring, a heteroaryl ring with another heteroaryl ring, or a heteroaryl ring with a non-aromatic carbon ring (e.g., cycloalkanes, cycloalkenes, or cycloalkynes) or a heterocycle (e.g., heterocyclic alkanes, heterocyclic alkenes, or heterocyclic alkynes), and in the aforementioned fused heteroaryl group, the connection site between the heteroaryl group and the remaining portion of the molecule can be on the heteroaryl ring or on other rings fused with the heteroaryl ring. Non-limiting examples of heteroaryl groups include, but are not limited to, pyrroleyl, furanyl, thiopheneyl, imidazolyl, oxazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyrazinyl, quinolinyl, isoquinolinyl, tetrazolyl, triazolyl, triazinyl, benzofuranyl, benzothiopheneyl, indoleyl, isoindoleyl, etc. , , , and wait.

[0105] As used herein, the term "optionally substituted" means unsubstituted or substituted independently by one or more substituents selected from: halogen, hydroxyl, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C 15 carbonyl group, C2-C 15 Heterocyclic group, C6-C 20 Aryl or C2-C 20 Heteroaryl. As an example, “optionally substituted” may mean substituted by one or more substituents independently selected from: halogen, C1-C6 alkyl or C1-C6 alkoxy, for example, substituted by one or more C1-C6 alkyl groups (e.g., substituted by one or more groups independently selected from methyl, ethyl or isopropyl).

[0106] In this paper, when a substituent is cross-bonded to two atoms on a ring, this substituent can bond to any atom on that ring. As an example, structural units... This indicates that R2 can be substituted at any position on the naphthalene ring.

[0107] Chemically amplified patterning materials (CARs) are mainly composed of acid-sensitive polymers, photoacid generators (PAGs), additives, and solvents. PAGs decompose upon exposure to produce acid (H+). + These acids act as catalysts during post-exposure baking (PEB), causing unstable acid groups suspended on the resin to detach, thereby altering the polymer's polarity and allowing the patterned material to dissolve in the developer. However, if the acid diffusion suppression of the photoacid generator is insufficient, deprotection reactions can occur in unexposed areas, leading to reduced resolution, increased linewidth roughness (LWR), and poorer critical dimension uniformity (CDU). PAG involves a trade-off between acid strength and diffusion. Weak acids diffuse slowly but have low catalytic efficiency, potentially requiring higher concentrations and introducing uniformity issues. Low-temperature PEB suppresses diffusion but may result in incomplete reactions, causing "T-top" defects in the pattern. In addition to photoacid generators, chemically amplified resists often require the addition of alkaline neutralizers (Quenchers) to control acid diffusion. This is mainly because alkaline neutralizers can neutralize some of the acid generated during exposure of the photoacid generator, offsetting the effect of scattered light on the pattern.

[0108] When small molecule alkaline compounds, as acid diffusion inhibitors, have poor compatibility with the matrix resin, they are difficult to disperse uniformly in the film to be patterned, resulting in reduced resolution and increased roughness. This fails to solve the problem of roughened edges of the patterned material caused by photo-acid diffusion.

[0109] This disclosure provides a photo-based alkali generator, a patterning composition, a patterning method, a patterned film, and their applications, wherein OH groups are released through exposure using a fluorene alcohol derivative photo-based alkali generator (PBG). - This method specifically neutralizes "excess acid on the surface" and "diffusion of excess acid in non-exposed areas," aiming to reduce the problems of low resolution and excessive LWR caused by uneven acid distribution in existing patterning materials.

[0110] In some embodiments, this application provides a photo-induced alkali-generating agent for patterning, wherein the photo-induced alkali-generating agent is selected from at least one compound represented by Formula I:

[0111] Formula I, Wherein, A and B are each independently selected from aromatic rings or heteroaromatic rings; R1 is each independently selected from halogens, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, or optionally substituted aryl groups; R2 and R3 are each independently selected from halogens, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen, optionally substituted alkyl groups, or optionally substituted aryl groups; m and n are each independently selected from integers from 0 to 8; at least one of m and n is not 0; x is selected from integers from 0 to 5.

[0112] As an example, m and n can each be independently selected from 0, 1, 2, 3, 4, 5, 6, 7, or 8; x can be 0, 1, 2, 3, 4, or 5.

[0113] In one possible implementation, A and B are each independently selected from C6-C. 14 Aromatic rings or C2-C 14 Mixed fragrance ring.

[0114] In one possible implementation, A and B are each independently selected from benzene rings, naphthalene rings, anthracene rings, or phenanthrene rings.

[0115] In one possible implementation, A and B are each independently selected from benzene rings, naphthalene rings, or anthracene rings.

[0116] In one possible implementation, both A and B are benzene rings.

[0117] In one possible implementation, R2 and R3 are each independently selected from halogens, optionally substituted C1-C8 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, or -N(RO)2, provided that at least one of R2 and R3 is -N(RO)2, wherein R0 is each independently selected from hydrogen, optionally substituted C1-C6 alkyl groups, or optionally substituted C6-C... 14 Aryl.

[0118] In one possible implementation, R2 and R3 are each independently selected from iodine, C1-C6 alkyl, C3-C8 cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C6 alkyl.

[0119] In one possible implementation, R2 and R3 are each independently selected from iodine, C1-C4 alkyl, C3-C6 cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C4 alkyl.

[0120] In one possible implementation, R2 and R3 are each independently selected from C1-C4 alkyl or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C4 alkyl.

[0121] In one possible implementation, at least two of R2 and R3 are -N(R0)2; wherein each R0 is independently selected from hydrogen or C1-C6 alkyl.

[0122] In one possible implementation, at least one R2 and at least one R3 are -N(R0)2; wherein each R0 is independently selected from hydrogen or C1-C6 alkyl.

[0123] In one possible implementation, R2 and R3 each have one of the following components: -N(R0)2; wherein each of R0 is independently selected from hydrogen or C1-C6 alkyl groups.

[0124] In one possible implementation, m and n are each independently selected from integers from 1 to 6.

[0125] In one possible implementation, m and n are each independently selected from integers from 1 to 4.

[0126] In one possible implementation, m and n are each independently selected from 1 or 2.

[0127] In one possible implementation, both m and n are 1.

[0128] In one possible implementation, -N(RO)2 is -N(CH3)2.

[0129] In one possible implementation, R1 is independently selected from halogens, optionally substituted C1-C8 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, or optionally substituted C6-C4 alkyl groups. 14 Aryl.

[0130] In one possible implementation, R1 is independently selected from fluorine, iodine, C1-C8 alkyl, or C3-C8 cycloalkyl.

[0131] In one possible implementation, R1 is independently selected from fluorine, iodine, C1-C6 alkyl, or C3-C6 cycloalkyl.

[0132] In one possible implementation, R1 is independently selected from C1-C4 alkyl groups.

[0133] In one possible implementation, x is selected from 0, 1, 2, or 3.

[0134] In one possible implementation, x is 0.

[0135] In one possible implementation, "optionally substituted" means unsubstituted or substituted by one or more substituents independently selected from: halogen, hydroxyl, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C 15 carbonyl group, C2-C 15 Heterocyclic group, C6-C 20 Aryl or C2-C 20 Mixed aromatic compounds.

[0136] In one possible implementation, "optionally substituted" means unsubstituted or substituted by one or more substituents selected independently from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl, or C1-C6 alkoxy.

[0137] In one possible implementation, "optionally substituted" means unsubstituted or substituted independently by one or more C1-C6 alkyl groups.

[0138] In one possible implementation, "optionally substituted" means unsubstituted or substituted independently by one or more methyl, ethyl, or isopropyl groups.

[0139] In one possible embodiment, the compound has the structure shown in Formula II, Formula III, Formula IV, or Formula V:

[0140] Formula II,

[0141] Formula III,

[0142] Formula IV,

[0143] Formula V, Wherein, R1, R0 and x are as defined in Formula I above; R2' and R3' are each independently selected from halogens, optionally substituted alkyl groups, or optionally substituted cycloalkyl groups; in Formula II, m and n are each independently selected from integers from 0 to 3; in Formula III, m and n are each independently selected from integers from 0 to 5; in Formulas IV and V, m and n are each independently selected from integers from 0 to 7.

[0144] As an example, in Equation II, m and n can each be 0, 1, 2, or 3 independently; in Equation III, m and n can each be 0, 1, 2, 3, 4, or 5 independently; and in Equations IV and V, m and n can each be 0, 1, 2, 3, 4, 5, 6, or 7 independently.

[0145] In one possible implementation, R2' and R3' are each independently selected from halogens, optionally substituted C1-C8 alkyl groups, or optionally substituted C3-C8 cycloalkyl groups.

[0146] In one possible implementation, R2' and R3' are each independently selected from iodine, C1-C6 alkyl, or C3-C8 cycloalkyl.

[0147] In one possible implementation, R2' and R3' are each independently selected from iodine, C1-C4 alkyl, or C3-C6 cycloalkyl.

[0148] In one possible implementation, R2' and R3' are each independently selected from C1-C4 alkyl groups.

[0149] In one possible implementation, in Equation II, m and n are each independently selected from 0 or 1; in Equation III, m and n are each independently selected from integers from 0 to 3; and in Equations IV and V, m and n are each independently selected from integers from 0 to 4.

[0150] In one possible implementation, in Formulas II, III, IV and V, m and n are each independently selected from 0 or 1.

[0151] In one possible implementation, m and n are both 0 in Equations II, III, IV and V.

[0152] In one possible implementation, the compound is: , , , , , , , , , , , , ,or .

[0153] In some embodiments, this application provides a patterned composition, which is a chemically amplified patterned composition; the patterned composition contains at least one of the photo-induced alkali-generating agent, acid-sensitive polymer, photoacid generator, and solvent described in one or more embodiments of this disclosure; or, the patterned composition contains the photo-induced alkali-generating agent, acid-sensitive polymer, photoacid generator, and solvent described in one or more embodiments of this disclosure.

[0154] In one possible implementation, the mass ratio of the photoacid generator to the compound in the patterned composition is 10:1 to 4:1, for example 10:1, 19:2, 9:1, 17:2, 8:1, 15:2, 7:1, 13:2, 6:1, 11:2, 5:1, 9:2, or 4:1, or any value between the above two.

[0155] In one possible implementation, the mass ratio of the photoacid generator to the compound in the patterned composition is 5:1 to 4:1.

[0156] In one possible implementation, the mass ratio of the photoacid generator to the compound in the patterned composition is 4:1.

[0157] In one possible implementation, the acid-sensitive polymer is an acid-sensitive polymer containing two acid-instable groups.

[0158] In one possible implementation, the acid-sensitive polymer is selected from at least one of the following compounds: , , ,or .

[0159] In one possible implementation, the patterned composition comprises 1-15 parts by weight of the acid-sensitive polymer, based on 100 parts by weight of the patterned composition.

[0160] In one possible implementation, the patterned composition comprises 1-10 parts by weight of the acid-sensitive polymer, based on 100 parts by weight of the patterned composition.

[0161] In one possible implementation, the PDI of the acid-sensitive polymer is 1.51-1.57, and the Mw of the acid-sensitive polymer is 7.9k-8.7k.

[0162] As an example, the PDI of the acid-sensitive polymer can be 1.51, 1.52, 1.53, 1.54, 1.55, 1.56, or 1.57, or any value between two of the above; the Mw of the acid-sensitive polymer can be 7.9k, 8.0k, 8.1k, 8.2k, 8.3k, 8.4k, 8.5k, 8.6k, or 8.7k, or any value between two of the above.

[0163] In one possible implementation, the photoacid generator is an ionic photoacid generator.

[0164] In one possible implementation, the photoacid generator is an ionic photoacid generator comprising a cation of diaryliodonium ion or triarylsulfonium ion and an anion of aromatic fluorosulfonate ion.

[0165] In one possible implementation, the photoacid generator is selected from at least one of the following compounds: , ,or .

[0166] In one possible implementation, the patterned composition comprises 0.01-0.20 parts by weight of the photoacid generator, based on 100 parts by weight of the patterned composition.

[0167] In one possible implementation, the patterned composition comprises 0.01-0.10 parts by weight of the photoacid generator, based on 100 parts by weight of the patterned composition.

[0168] In one possible implementation, the content of the compound is from 0.001 wt% to 0.020 wt% based on the total weight of the patterned composition.

[0169] In one possible implementation, the content of the compound is from 0.001 wt% to 0.010 wt% based on the total weight of the patterned composition.

[0170] In one possible implementation, the solid content of the patterned composition is from 0.5 wt% to 3.0 wt% based on the total weight of the patterned composition, for example, 0.5 wt%, 0.6 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.5 wt%, 1.6 wt%, 1.8 wt%, 2.0 wt%, 2.2 wt%, 2.4 wt%, 2.5 wt%, 2.6 wt%, 2.8 wt%, 3.0 wt%, or any value between the above values.

[0171] In one possible implementation, the solid content of the patterned composition is from 1.0 wt% to 2.5 wt% based on the total weight of the patterned composition.

[0172] In some embodiments, this application provides a patterning method comprising: patterning a coating formed using a patterning composition described in one or more embodiments of this disclosure; and one or more of cleaning, dehydration baking, thin film deposition, exposure, development, and ion implantation.

[0173] In one possible implementation, the exposure is performed using a charged particle beam.

[0174] In one possible implementation, the charged particles include an electron beam and an ion beam.

[0175] In some embodiments, this application provides a method for fabricating a semiconductor device, the method including the patterning method described in one or more embodiments of this disclosure.

[0176] In some embodiments, this application provides a patterned film formed by the patterning method described in one or more embodiments of this disclosure.

[0177] In one possible implementation, the linewidth roughness of the patterned film is less than 4.7 nm, for example less than 4.6 nm, less than 4.5 nm, less than 4.4 nm, less than 4.2 nm, less than 4 nm, less than 3.8 nm, less than 3.6 nm, less than 3.5 nm, less than 3.4 nm, less than 3.2 nm, or less than 3.1 nm.

[0178] In one possible implementation, the linewidth roughness of the patterned film is below 4.5 nm.

[0179] In one possible implementation, the linewidth roughness of the patterned film is below 3.1 nm.

[0180] In one possible implementation, the critical dimensions of the patterned film are below 30 nm, for example below 28 nm, below 26 nm, below 25 nm, below 24 nm, below 22 nm, below 20 nm, below 18 nm, below 16 nm, below 15 nm, below 14 nm, below 12 nm, below 10 nm, below 8 nm, below 7 nm, below 6 nm, below 5 nm, below 4 nm, or below 3 nm.

[0181] In some embodiments, this application provides a semiconductor device including a substrate and a functional layer formed on the substrate, wherein at least one of the functional layers comprises a pattern formed by a patterned composition according to one or more embodiments of this disclosure, or comprises a patterned film according to one or more embodiments of this disclosure.

[0182] It can be understood that the substrate serves as the base for supporting the device; the functional layer is a layer structure on the substrate that has a specific function (such as electrical, optical or chemical).

[0183] In one possible implementation, the functional layer may include one or more of a semiconductor layer, a conductive layer, and a dielectric layer. Specifically: the semiconductor layer is primarily used to form active transistor cells, typically including active regions, polysilicon, and semiconductor epitaxial layers; the conductive layer is used to form various conductive paths and electrode structures, typically including silicides, contact plugs, vias, metal gates, metal lines, pads, and metal barrier layers; the dielectric layer primarily serves to provide electrical isolation, dielectric support, and device protection, typically including shallow trench isolation dielectrics, gate dielectrics, gate sidewall dielectrics, contact layer dielectrics, inter-metal dielectrics, and top passivation dielectrics. The aforementioned semiconductor layer, conductive layer, and dielectric layer may be independent of each other or may be arranged in an alternating manner.

[0184] It is understood that the semiconductor device may be a wafer, an unpackaged or packaged chip, etc.

[0185] In some embodiments, this application provides an electronic device including a semiconductor device as described in one or more embodiments of this disclosure; and one or more of a packaging substrate, bonding wires, molding compound, and pins.

[0186] In some embodiments, this application provides an electronic device, which includes a circuit board and electronic components described in one or more embodiments of this disclosure, wherein the electronic components are electrically connected to the circuit board.

[0187] In one possible implementation, the electronic device is selected from: consumer electronic devices, home electronic appliances, vehicle electronic devices, communication and network equipment, industrial control equipment, medical electronic devices, security and Internet of Things equipment, office and financial equipment, agricultural electronic devices, educational and scientific research electronic devices, new energy and energy storage system equipment, robotics and automated execution equipment, rail transit and intelligent transportation system equipment, and environmental protection and environmental monitoring equipment.

[0188] To make the embodiments of this disclosure easier to understand, the present disclosure will be described in detail below with reference to the embodiments. These embodiments are for illustrative purposes only and are not limited to the application scope of this disclosure.

[0189] Example Preparation Example A photo-induced alkali-generating agent (A) derived from fluorene alcohol is used. Its triphenylmethane conjugated framework is photoresponsive and can release alkali through photoexcitation to neutralize part of the acid. This allows for precise control of the acid concentration in local areas of the patterned material, thereby changing the solubility of the patterned material and achieving precise control over pattern formation.

[0190] 1. A patterned composition comprising a fluorenol derivative photoalkalizing agent (A), an acid-sensitive polymer (B) copolymerizing two acid-instable groups, a photoacid generator (C), and a solvent, wherein the proportions are 100 parts of the acid-sensitive polymer (B), 15 parts of the photoacid generator, 3 parts of the photoalkalizing agent or 3 parts of the amine quencher, and the total solid content is 1.43 wt%.

[0191] The solvent is a mixed solution of propylene glycol methyl ether acetate and γ-butyrolactone (PGMEA:GBL) in a ratio of 6:1. The structure of the photo-induced alkali-generating agent (A) PBG 344 (CAS: 59135-64-7) in the examples is shown below. It has strong absorption in the wavelength ranges of 300-580 nm and 700-1000 nm in common solvents such as PGME and GBL, and has maximum absorption at 350 nm and 570 nm. The acid-sensitive polymer (B) used in the examples or comparative examples is shown in Table 1. The structural formula of the photoacid generator (C) in the examples and comparative examples is shown in Table 2. The structural formulas of the photodegrading alkali PBG 346 and the amine quencher (Q) in the comparative examples are shown in Table 3.

[0192]

[0193] Formula (A) (Photo-induced alkali production agent PBG 344) Table 1

[0194] Table 2

[0195] Table 3

[0196] 2. Preparation method of patterned composition: Add acid-sensitive polymer solution, photoacid generator, photoacid inhibitor (e.g., photo-induced alkali production agent, amine quencher), and solvent to a glass bottle. At room temperature, shake the mixture in the glass bottle for 1 hour to ensure complete dissolution, and then filter it through a 0.22-micron PTFE filter to obtain the patterned material solution.

[0197] Table 4. Patterned compositions (by mass) used in the examples and comparative examples

[0198] Example 1 Add 1.0 g of acid-sensitive polymer P1, 0.015 g of photoacid generator PAG 603, 0.003 g of PBG 344, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22-micron filter to obtain a patterned material solution, designated as PR-1.

[0199] Example 2 Add 1.0 g of acid-sensitive polymer P1, 0.015 g of photoacid generator PAG 572, 0.003 g of PBG 344, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22-micron filter to obtain a patterned material solution, designated as PR-2.

[0200] Example 3 Add 1.0 g of acid-sensitive polymer P2, 0.015 g of photoacid generator PAG 603, 0.003 g of PBG 344, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22-micron filter to obtain a patterned material solution, designated as PR-3.

[0201] Example 4 Add 1.0 g of acid-sensitive polymer P3, 0.015 g of photoacid generator PAG 603, 0.003 g of PBG 344, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22-micron filter to obtain a patterned material solution, designated as PR-4.

[0202] Example 5 Add 1.0 g of acid-sensitive polymer P4, 0.015 g of photoacid generator PAG 562, 0.003 g of PBG 344, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22-micron filter to obtain a patterned material solution, designated as PR-5.

[0203] Comparative Example 1 Add 1.0 g of acid-sensitive polymer P1, 0.015 g of photoacid generator PAG 603, 0.003 g of photodegrading base PBG 346, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22 micron filter to obtain a patterned material solution, designated as PR-D1.

[0204] Comparative Example 2 Add 1.0 g of acid-sensitive polymer P1, 0.015 g of photoacid generator PAG 603, 0.003 g of amine quencher B 113, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22 micron filter to obtain a patterned material solution, designated as PR-D2.

[0205] Comparative Example 3 Add 1.0 g of acid-sensitive polymer P1, 0.015 g of photoacid generator PAG 603, 0.003 g of amine quencher B 323, 60 g of PGMEA, and 10 g of GBL to a 100 mL amber glass bottle. Shake the mixture in the glass bottle for 1 hour at room temperature to ensure complete dissolution. Then filter the solution through a 0.22-micron filter to obtain a patterned material solution, designated PR-D3.

[0206] Test case Patterning methods (1) Silicon wafer pretreatment: The silicon wafer is baked at 150°C for 60 s to remove the adsorbed water on the surface of the silicon wafer. Then the surface of the silicon wafer is treated with a coating of hexamethyldisilazane (HMDS) or an organic hydrocarbon (e.g., spin-on carbon (SOC)) as the bottom layer of the patterning material. (2) Coating: The patterned composition is coated onto the treated silicon wafer using a spin coater at a spin speed of 1500-3000 rpm; (3) Pre-baking: The temperature is 80-130℃ and the time is 30-120 s; (4) Exposure: Exposure is performed on a 5 kV electron beam exposure system; (5) Post-baking: The temperature is 90℃ and the time is 60 s; (6) Development: 2.38% tetramethylammonium hydroxide (TMAH) developer is used for 60 s; (7) Rinsing: Deionized water is used for 30 s.

[0207] Patterning performance evaluation The patterning results of the developed silicon wafers were examined using a scanning electron microscope. The critical dimensions and line width roughness were measured using software that measures critical dimensions and line width roughness. The minimum equidistant line width that can be clearly distinguished was used as the limiting resolution to evaluate the performance of the patterned material composition. The results are shown in Table 5.

[0208] Table 5

[0209] Examples 1-5 demonstrate that the patterned compositions of the present disclosure have excellent performance in terms of critical dimensions and / or line width roughness, and the patterned compositions obtained by electroparticle beam exposure of the present disclosure can even achieve critical dimensions below 25 nm.

[0210] Example 1 and Comparative Example 1 show that the LWR of the composition containing the fluorene alcohol derivative PBG 344 is significantly lower than that of the composition containing PBG346.

[0211] Examples 1 and Comparative Examples 2 and 3 show that the linewidth roughness of the composition formed by the photoacid inhibitor with the structure of small molecule amine quencher is significantly higher than that of the patterned composition formed by the fluorene alcohol derivative PBG 344, and the overall exposure performance of Comparative Examples 2 and 3 is significantly lower than that of Example 1.

[0212] The disclosed method uses a patterning composition containing a photo-induced alkali-generating agent, different acid-sensitive polymers, a photoacid generator, and a solvent, resulting in a pattern with superior resolution and line width roughness, and a clearer pattern.

[0213] The above embodiments have further illustrated the purpose, technical solution, and advantages of this application. It should be understood that the above descriptions are merely embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A photo-induced alkali-generating agent, characterized in that, The photo-induced alkali-generating agent is used for patterning, and the photo-induced alkali-generating agent is selected from at least one of the compounds shown in Formula I: Formula I, Among them, A and B are each independently selected from aromatic rings or heteroaromatic rings; R1 is independently selected from halogens, optionally substituted alkyl groups, optionally substituted cycloalkyl groups, or optionally substituted aryl groups; R2 and R3 are each independently selected from halogen, optionally substituted alkyl, optionally substituted cycloalkyl, or -N(RO)2, provided that at least one of R2 and R3 is -N(RO)2, wherein R0 is each independently selected from hydrogen, optionally substituted alkyl, or optionally substituted aryl. m and n are each independently selected from integers from 0 to 8; at least one of m and n is not 0; x is an integer selected from 0 to 5.

2. The photo-induced alkali-producing agent according to claim 1, characterized in that, A and B are each independently selected from C6-C 14 Aromatic rings or C2-C 14 Mixed fragrance ring; Alternatively, A and B can be independently selected from benzene rings, naphthalene rings, anthracene rings, or phenanthrene rings; Alternatively, A and B can be independently selected from benzene rings, naphthalene rings, or anthracene rings; Alternatively, both A and B are benzene rings.

3. The photo-induced alkali-producing agent according to claim 1 or 2, characterized in that, R2 and R3 are each independently selected from halogens, optionally substituted C1-C8 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, or -N(RO)2, provided that at least one of R2 and R3 is -N(RO)2, wherein R0 is each independently selected from hydrogen, optionally substituted C1-C6 alkyl groups, or optionally substituted C6-C4 cycloalkyl groups. 14 Aryl; Alternatively, R2 and R3 are each independently selected from iodine, C1-C6 alkyl, C3-C8 cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C6 alkyl. Alternatively, R2 and R3 are each independently selected from iodine, C1-C4 alkyl, C3-C6 cycloalkyl, or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C4 alkyl. Alternatively, R2 and R3 are each independently selected from C1-C4 alkyl or -N(R0)2, provided that at least one of R2 and R3 is -N(R0)2, wherein R0 is each independently selected from hydrogen or C1-C4 alkyl; And / or, at least two of R2 and R3 are -N(R0)2; wherein each R0 is independently selected from hydrogen or C1-C6 alkyl; Alternatively, at least one R2 and at least one R3 are -N(R0)2; wherein each R0 is independently selected from hydrogen or C1-C6 alkyl; Alternatively, one of R2 and R3 may be -N(R0)2; wherein each of R0 is independently selected from hydrogen or C1-C6 alkyl; And / or, m and n are each independently selected from integers from 1 to 6; Alternatively, m and n can be independently selected from integers 1 to 4; Alternatively, m and n can be independently selected from 1 or 2; Alternatively, both m and n are 1; Alternatively, -N(R0)2 can be -N(CH3)2.

4. The photo-induced alkali-producing agent according to claim 1 or 2, characterized in that, R1 is independently selected from halogens, optionally substituted C1-C8 alkyl groups, optionally substituted C3-C8 cycloalkyl groups, or optionally substituted C6-C... 14 Aryl; Alternatively, R1 can be independently selected from fluorine, iodine, C1-C8 alkyl, or C3-C8 cycloalkyl; Alternatively, R1 can be independently selected from fluorine, iodine, C1-C6 alkyl, or C3-C6 cycloalkyl; Alternatively, each R1 is independently selected from C1-C4 alkyl groups; And / or, x is selected from 0, 1, 2 or 3; Alternatively, x is 0.

5. The photo-induced alkali-producing agent according to claim 1 or 2, characterized in that, The term "optionally substituted" refers to unsubstituted or substituted with one or more substituents independently selected from: halogen, hydroxyl, amino, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C3-C 15 carbonyl group, C2-C 15 Heterocyclic group, C6-C 20 Aryl or C2-C 20 Mixed aromatics; Alternatively, "optionally substituted" means unsubstituted or substituted by one or more substituents selected independently from the following: halogen, C1-C6 alkyl, C1-C6 haloalkyl or C1-C6 alkoxy; Alternatively, "optionally substituted" means unsubstituted or substituted independently by one or more C1-C6 alkyl groups; Alternatively, "optionally substituted" means unsubstituted or substituted independently by one or more methyl, ethyl, or isopropyl groups.

6. The photo-induced alkali-producing agent according to claim 1 or 2, characterized in that, The compound has the structure shown in Formula II, Formula III, Formula IV or Formula V: Formula II, Formula III, Formula IV, Formula V, in, R1, R0, and x are defined as in Formula I of claim 1; R2' and R3' are each independently selected from halogens, optionally substituted alkyl groups, or optionally substituted cycloalkyl groups; In Equation II, m and n are each independently selected from integers from 0 to 3; in Equation III, m and n are each independently selected from integers from 0 to 5; in Equations IV and V, m and n are each independently selected from integers from 0 to 7.

7. The photo-induced alkali-producing agent according to claim 6, characterized in that, R2' and R3' are each independently selected from halogens, optionally substituted C1-C8 alkyl groups, or optionally substituted C3-C8 cycloalkyl groups; Alternatively, R2' and R3' may be independently selected from iodine, C1-C6 alkyl, or C3-C8 cycloalkyl; Alternatively, R2' and R3' may be independently selected from iodine, C1-C4 alkyl, or C3-C6 cycloalkyl; Alternatively, R2' and R3' may be independently selected from C1-C4 alkyl groups; And / or, in Equation II, m and n are each independently selected from 0 or 1; in Equation III, m and n are each independently selected from integers from 0 to 3; in Equations IV and V, m and n are each independently selected from integers from 0 to 4. Alternatively, in Equations II, III, IV and V, m and n are each independently selected from 0 or 1; Alternatively, in Equations II, III, IV, and V, both m and n are 0.

8. The photo-induced alkali-producing agent according to claim 1 or 2, characterized in that, The compound is: , , , , , , , , , , , , ,or .

9. A patterned composition, characterized in that, The patterning composition is a chemically amplified patterning composition; The patterned composition comprises at least one of the photo-alkali-generating agent, acid-sensitive polymer, photoacid generator, and solvent according to any one of claims 1-8; Alternatively, the patterned composition comprises a photoalkali-generating agent, an acid-sensitive polymer, a photoacid generator, and a solvent according to any one of claims 1-8.

10. The patterned composition according to claim 9, characterized in that, The mass ratio of the photoacid generator to the compound in the patterned composition is 10:1 to 4:

1. Alternatively, the mass ratio of the photoacid generator to the compound in the patterned composition is 5:1 to 4:

1.

11. The patterned composition according to claim 9, characterized in that, The acid-sensitive polymer is an acid-sensitive polymer containing two acid-instable groups; Alternatively, the acid-sensitive polymer is selected from at least one of the following compounds: 、 、 ,or ; Alternatively, based on 100 parts by weight of the patterned composition, the patterned composition comprises 1-15 parts by weight of the acid-sensitive polymer; Alternatively, based on 100 parts by weight of the patterned composition, the patterned composition comprises 1-10 parts by weight of the acid-sensitive polymer; And / or, the polydispersity index (PDI) of the acid-sensitive polymer is 1.51-1.57, and the weight-average molecular weight (Mw) of the acid-sensitive polymer is 7.9k-8.7k.

12. The patterned composition according to claim 9, characterized in that, The photoacid generator is an ionic photoacid generator; Alternatively, the photoacid generator may be an ionic photoacid generator comprising a cation of diaryliodonium ion or triarylsulfonium ion and an anion of aromatic fluorosulfonate ion. Alternatively, the photoacid generator is selected from at least one of the following compounds: , ,or ; And / or, based on 100 parts by weight of the patterned composition, the patterned composition contains 0.01-0.20 parts by weight of the photoacid generator; Alternatively, based on 100 parts by weight of the patterned composition, the patterned composition contains 0.01-0.10 parts by weight of the photoacid generator.

13. The patterned composition according to claim 9, characterized in that, The content of the compound is from 0.001 wt% to 0.020 wt% based on the total weight of the patterned composition. Alternatively, the content of the compound is from 0.001 wt% to 0.010 wt% based on the total weight of the patterned composition; And / or, based on the total weight of the patterned composition, the solid content of the patterned composition is from 0.5 wt% to 3.0 wt%; Alternatively, the solid content of the patterned composition is from 1.0 wt% to 2.5 wt% based on the total weight of the patterned composition.

14. A patterning method, characterized in that, The patterning method includes: Patterning is performed on a coating formed using the patterning composition according to any one of claims 9-13.

15. A method for fabricating a semiconductor device, characterized in that, The method includes the patterning method according to claim 14.

16. A patterned film, characterized in that, The patterned film is formed by the patterning method described in claim 14.

17. The patterned film according to claim 16, characterized in that, The linewidth roughness of the patterned film is less than 4.7 nm; Alternatively, the linewidth roughness of the patterned film is below 4.5 nm; Alternatively, the linewidth roughness of the patterned film is below 3.1 nm; And / or, the critical dimensions of the patterned film are below 30 nm.

18. A semiconductor device, characterized in that, The semiconductor device includes a substrate and a functional layer formed on the substrate, at least one of the functional layers comprising a pattern formed by a patterned composition according to any one of claims 9-13, or comprising a patterned film according to claim 16 or 17.

19. The semiconductor device according to claim 18, characterized in that, The functional layer includes one or more of a semiconductor layer, a conductive layer, and a dielectric layer.

20. An electronic device, characterized in that, The electronic device includes a semiconductor device according to claim 18 or 19; and one or more of a packaging substrate, bonding wire, molding compound, and pins.

21. An electronic device, characterized in that, The electronic device includes a circuit board and an electronic device according to claim 20, wherein the electronic device is electrically connected to the circuit board.

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