Patterned composition as well as preparation method and application thereof

Abstract

The invention provides a patterning composition as well as a preparation method and application thereof. The patterning composition comprises the following components in percentage by mass: 90-99.9% of an organic solvent; 0.05%-7% of a photosensitive resin; 0.01%-3% of an ionic liquid; in the ionic liquid, the ionic liquid containing vinyl accounts for 10% or less of the total mass of the ionic liquid. According to the application, the patterning composition is prepared by selecting the appropriate ionic liquid to improve the conductivity of the patterning composition, so that the antistatic capability of the patterning film prepared from the patterning composition can be further improved when the patterning film is exposed by electron beams or ion beams; the prepared patterned film is ensured to have excellent exposure performance and stability, the problems of electron beam or ion beam offset and pattern deformation caused by charge accumulation in the electron beam or ion beam exposure process are reduced, and the precision of the prepared pattern is improved.

Description

Technical Field

[0001] The embodiments of the present application relate to the field of semiconductor manufacturing technology, and specifically to a patterned composition, a preparation method, and an application thereof. Background Art

[0002] With the advancement of semiconductor technology, the industry's requirements for the precision of micro-patterns in semiconductor devices are becoming increasingly stringent. Micro-patterning exposure for semiconductor devices typically utilizes light or other energy sources. Electron beam or ion beam exposure technologies, due to their maskless pattern generation capabilities and theoretically extremely high resolution, are considered promising technologies in semiconductor manufacturing. However, the electron beam or ion beam exposure process can cause charge accumulation on the coating surface, causing the electron beam or ion beam to deflect. This can lead to pattern misalignment and overlay errors in the patterned film, compromising the performance of the resulting semiconductor device. Summary of the Invention

[0003] In view of this, embodiments of the present application provide a patterned composition, a preparation method thereof, and an application thereof. By selecting a suitable ionic liquid to prepare the patterned composition, the present application improves the conductivity of the patterned composition, thereby further improving the antistatic ability of the patterned film prepared from the patterned composition when exposed to an electron beam or ion beam. While ensuring that the patterned film has excellent exposure performance and stability, the problem of electron beam or ion beam deviation and pattern deformation caused by charge accumulation during the electron beam or ion beam exposure process is reduced, thereby improving the accuracy of the resulting pattern.

[0004] In a first aspect, the present application provides a patterned composition, comprising the following components in percentage by weight:

[0005] Organic solvents: 90%-99.9%;

[0006] Photosensitive resin: 0.05%-7%;

[0007] Ionic liquids: 0.01%-3%;

[0008] In the ionic liquid, the ionic liquid containing vinyl groups accounts for less than 10% of the total mass of the ionic liquid.

[0009] The patterned composition provided by the present application adds a suitable ionic liquid and controls its content within the above-mentioned range. On the one hand, these ionic liquids can provide electrical conductivity for the patterned composition, thereby improving the antistatic ability of the patterned film obtained by the patterned composition when exposed to an electron beam or ion beam, greatly reducing the accumulated charge on the surface of the patterned film during the electron beam or ion beam exposure process, reducing the offset of the electron beam or ion beam, and improving the precision of the obtained patterned film. On the other hand, it can also ensure that the obtained patterned film has excellent exposure performance and stability, thereby improving the overall performance of the semiconductor device. Moreover, the present application prepares semiconductor devices by using the patterned film obtained by the patterned composition, which can reduce the difficulty of preparation and shorten the process flow while ensuring the production of high-quality and high-precision micro-patterns, thereby improving the preparation efficiency of semiconductor devices and effectively reducing their production costs.

[0010] In some embodiments of the present application, in the patterned composition, the mass percentage of the ionic liquid is 0.01%-0.8%.

[0011] In some embodiments of the present application, the mass of the ionic liquid accounts for 5%-50% of the total mass of the ionic liquid and the photosensitive resin.

[0012] In some embodiments of the present application, the ionic liquid includes cations and anions, and the cations include one or more cations represented by formula (I) to formula (VI):

[0013]

[0014] Among them, R1-R 15 are independently selected from hydrogen, substituted or unsubstituted alkyl, cycloalkyl, alkoxy, heterocyclic, aryl, aralkyl or aryloxy groups; the substituent group in the substituted alkyl group is selected from one or more of hydroxyl, hydroxyl, cyano, alkoxy, -COOR1, carboxyl, amino, sulfonic acid and -Si(OR2)3, wherein R1 is an alkyl group and R2 is an alkyl group;

[0015] The anions include halide ions, tetrafluoroborate anions, bis(trifluoromethanesulfonyl imide) anions, trifluoromethanesulfonate anions, trifluoroacetic acid anions, acetate ions, dihydrogen phosphate anions, hydrogen sulfate ions, formate ions, p-toluenesulfonic acid anions, hexafluorophosphate anions, nitrate ions, N(CF3SO2)2 - 、N(CN)2 - 、N(CN)3 - 、CH3OSO3 - 、(C2H5)2PO4 - 、N(C2F5SO2)2 -、N(CF3CO)2 - 、(CF3SO2)(CF3CO) - 、N(FSO2)2 - One or more of .

[0016] In some embodiments of the present application, the organic solvent includes one or more of carboxylic acid ester solvents, ether solvents, alcohol solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, organic acid solvents and ketone solvents.

[0017] In some embodiments of the present application, the photosensitive resin includes one or more of acrylates and their derivatives, phenolic resins and their derivatives, epoxy resins and their derivatives, and polyimide resins and their derivatives.

[0018] A second aspect of the present application provides a patterned film, formed using the patterned composition provided in the first aspect. The patterned film provided herein is formed using a patterned composition containing an ionic liquid, and has excellent electrical conductivity, effectively improving its antistatic properties during electron beam exposure, thereby reducing electron beam offset and improving the precision of the resulting patterned film. Furthermore, the patterned film has excellent stability and exposure performance, thereby improving the overall performance and yield of semiconductor devices.

[0019] In some embodiments of the present application, the conductivity of the patterned film is greater than or equal to 1×10 -7 S / cm.

[0020] In a third aspect, the present application provides a patterned substrate, which is obtained by coating the patterned composition provided in the first aspect onto a substrate, followed by exposure and development. The patterned film provided herein has both good electrical conductivity and exposure properties, and the patterned substrate produced therefrom exhibits minimal pattern deviation and high precision.

[0021] The fourth aspect of the present application further provides a semiconductor device, which is made using the patterned composition provided in the first aspect, or the patterned film provided in the second aspect. The semiconductor device provided in the present application has good overall performance and high yield.

[0022] A fifth aspect of the present application further provides a method for preparing a semiconductor device, comprising:

[0023] coating the patterning composition provided in the first aspect on a substrate to form a film layer on the substrate;

[0024] The film layer is exposed and developed to form a patterned film on the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 Target patterns obtained by electron beam exposure are preset for the embodiments and comparative examples;

[0026] Figure 2 : is the electron beam offset of the patterned compositions of Example 1 and Comparative Example 1 under different exposure surface doses. DETAILED DESCRIPTION

[0027] The present application is further described in detail below in conjunction with preferred embodiments, but the protection scope of the present application is not limited to the following specific embodiments.

[0028] In this application, all professional terms have the same meanings as those generally understood by those skilled in the art. The professional terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of this application.

[0029] Micropatterning of semiconductor devices refers to the transfer of micropatterns onto substrates using a coating of a patterned composition, activated by light or other energy sources such as electron beams. For example, in the fabrication of semiconductor devices, the process involves first applying a patterned composition onto the substrate to form a film. Then, through processes such as exposure and development, the pre-defined pattern is transferred to the substrate, resulting in a micro-geometric pattern corresponding to the mask.

[0030] With the development of semiconductor technology, the industry's requirements for the precision of micro-patterns in semiconductor devices are becoming increasingly higher. Electron beam or ion beam exposure technology is considered to be a technology with great development potential in the field of semiconductor manufacturing processes due to its mask-free pattern generation capability and theoretically extremely high resolution. However, during the electron beam or ion beam exposure process, charge accumulation will occur on the surface of the coating, causing the electron beam or ion beam to deviate, which in turn leads to problems such as pattern misalignment and overlay error of the patterned film, affecting the performance of the final semiconductor device. In order to solve the problem of electron beam or ion beam deviation, some methods currently introduce a charge dissipation layer on the patterned film to achieve charge dissipation, balance the surface charge, and thus reduce the deviation of the electron beam or ion beam. The charge dissipation layer is typically made of metal or conductive polymer. However, metal electron dissipation layers are difficult to remove and require additional deposition and removal steps in the semiconductor device fabrication process, which prolongs the process and increases production time and costs. Furthermore, metal elements typically have large atomic masses, which can cause forward scattering that reduces the resolution of the patterned film, narrows the process window, and thus affects the precision of the micro-patterns. The thickness of the electron dissipation layer of conductive polymers is typically large, resulting in severe forward scattering, affecting the sidewall morphology of the patterned film, leading to problems such as chamfers and increased critical dimensions of the pattern. Therefore, there is an urgent need to provide a method that effectively addresses the problem of electron or ion beam offset without compromising the precision and quality of micro-patterning.

[0031] In order to solve the above problems, the present application provides a patterned composition, which improves the conductivity of the patterned composition by adding a suitable ionic liquid and controlling its content within a suitable range, thereby improving the antistatic ability of the patterned film made from the patterned composition when exposed to an electron beam or ion beam. While ensuring that the patterned film has excellent exposure performance and stability, the problem of electron beam or ion beam deviation and pattern deformation caused by charge accumulation during electron beam or ion beam exposure is reduced, thereby improving the accuracy of the pattern obtained.

[0032] The present application provides a patterned composition, which includes the following components in percentage by weight:

[0033] Organic solvents: 90%-99.9%;

[0034] Photosensitive resin: 0.05%-7%;

[0035] Ionic liquids: 0.01%-3%;

[0036] In the ionic liquid, the ionic liquid containing vinyl groups accounts for less than 10% of the total mass of the ionic liquid.

[0037] The patterned composition provided by the present application is by adding suitable ionic liquid and controlling its content within the above range. On the one hand, these ionic liquids can provide electrical conductivity for the patterned composition, and its structure and physicochemical properties will not change during the exposure process, thereby improving the antistatic ability of the patterned film obtained by the patterned composition when it is exposed to electron beams, greatly reducing the accumulated charge on the surface of the patterned film during the electron beam exposure process, reducing the electron beam offset, and improving the performance of semiconductor devices. On the other hand, these ionic liquids also have good stability, are not prone to reactions such as cross-linking during the exposure process, causing the structure to change, thereby ensuring the stability and exposure performance of the patterned film obtained by the patterned composition. In addition, the patterned composition provided by the present application is by selecting a suitable component formula and controlling the content of each component within a suitable range, so that the patterned composition also has good stability and has good solubility resistance for organic solvents. The present application uses a patterned film prepared from the patterned composition to prepare semiconductor devices, which can ensure the production of high-quality, high-precision micro-patterns without adding the corresponding deposition and removal processes of the metal charge dissipation layer, thereby reducing the preparation difficulty, shortening the process flow, and thereby improving the preparation efficiency of semiconductor devices and effectively reducing their production costs.

[0038] In some embodiments of the present application, the ionic liquid includes cations and anions. In some embodiments of the present application, the cations in the ionic liquid can be organic cations, and the organic cations include quaternary ammonium cations as shown in formula (I), quaternary phosphine cations as shown in formula (II), phosphorus-containing ring skeleton cations, imidazole cations as shown in formula (III), pyridinium cations as shown in formula (IV), pyrrolidine cations as shown in formula (V), and piperidinium cations as shown in formula (VI). The above formulas (I) to (VI) are as follows:

[0039]

[0040] Among them, R1-R 15 They are independently selected from hydrogen atom, substituted or unsubstituted alkyl, cycloalkyl, alkoxy, heterocyclic group, aryl, aralkyl or aryloxy; the substituent group in the substituted alkyl is selected from one or more of hydroxyl, cyano, alkoxy, -COOR1, carboxyl, amino, sulfonic acid and -Si(OR2)3, wherein R1 is an alkyl group and R2 is an alkyl group.

[0041] In some embodiments of the present application, the alkyl group may be a straight-chain alkyl group or a branched-chain alkyl group. In some specific embodiments, the alkyl group may include, but is not limited to, at least one of a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 4-methylbutyl group, a 2,2-dimethylpropyl group, an n-hexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 4-methylpentyl group, a 5-methylpentyl group, a 2-ethylbutyl group, a 3-ethylbutyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. In some specific embodiments of the present application, the cycloalkyl group may include, but is not limited to, at least one of a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

[0042] In some embodiments of the present application, R1-R 15 It can be a substituted alkyl group, in which case the substituent group is selected from one or more of a hydroxyl group (-OH), a cyano group (-CN), an alkoxy group, -COOR1, a carboxyl group (-COOH), an amino group (-NH2), a sulfonic group (-HSO3) and -Si(OR2)3, wherein R1 is an alkyl group and R2 is an alkyl group. In some specific embodiments, R1 can be, but is not limited to, a methyl group, an ethyl group, a n-propyl group or an isopropyl group, and R2 can be, but is not limited to, a methyl group, an ethyl group, a n-propyl group or an isopropyl group. In some specific embodiments, the substituent group can be, for example, one or more of a hydroxyl group, a cyano group, a methoxy group, an ethoxy group, -COOCH3, -COOCH2CH3, a carboxyl group, an amino group, a sulfonic group and -Si(OCH3)3.

[0043] In the embodiments of the present application, an alkoxy group refers to a group consisting of an alkyl group and an oxygen atom, typically represented by -OR3, where R3 is an alkyl group. In some specific embodiments, the alkoxy group can be, for example, a methoxy group (-OCH3), an ethoxy group (-OCH2CH3), or a propoxy group (-OCH2CH2CH3).

[0044] In the embodiments of the present application, a heterocyclic group refers to a group containing a heterocyclic structure, wherein the atoms constituting the ring in the heterocyclic structure include carbon atoms and at least one heteroatom. In the embodiments of the present application, the heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. In the embodiments of the present application, the heteroatom in the heterocyclic group may include, but is not limited to, at least one of a nitrogen atom, a sulfur atom, and an oxygen atom.

[0045] In the embodiments of the present application, an aryl group refers to a functional group or substituent derived from a benzene ring. In some specific embodiments, an aryl group may be, for example, a phenyl group or a naphthyl group. In the embodiments of the present application, an aralkyl group refers to a group in which an aromatic ring is connected to an alkyl group. In some specific embodiments, an aralkyl group may be, for example, a benzyl group. In the embodiments of the present application, an aryloxy group refers to a group consisting of an aryl group and an oxygen atom, generally represented by -OAr, where Ar is an aryl group. In some specific embodiments, an aryloxy group includes, but is not limited to, a phenoxy group or a naphthyloxy group.

[0046] By selecting cations of suitable structure, and the above-mentioned cationic substituent groups do not contain vinyl groups, the ionic liquid can have good stability and is not prone to cross-linking and other reactions during the exposure process that lead to structural changes, thereby ensuring the stability and exposure performance of the patterned film prepared by the patterned composition.

[0047] In the embodiment of the present application, when the ionic liquid includes two or more cations as shown in formula (I) to formula (VI), when the cation types are the same, the corresponding R1-R 15 For example, when the ionic liquid comprises two or more quaternary ammonium cations as shown in formula (I), the groups R1-R4 of the different cations may be the same or different.

[0048] In the embodiment of the present application, the anions in the ionic liquid include halide ions, tetrafluoroborate anions (BF4 - ), bis(trifluoromethanesulfonyl)imide anion, trifluoromethanesulfonic acid anion, trifluoroacetic acid anion (CF3COO - ), acetate ion (CH3COO - ), dihydrogen phosphate anion (H2PO4 - ), hydrogen sulfate ion (HSO4 - ), formate ion (HCOO -), p-toluenesulfonic acid anion, hexafluorophosphate anion (PF6 - ), nitrate ions (NO3 - )、N(CF3SO2)2 - 、N(CN)2 - 、N(CN)3 - 、CH3OSO3 - 、(C2H5)2PO4 - 、N(C2F5SO2)2 - 、N(CF3CO)2 - 、(CF3SO2)(CF3CO) - 、N(FSO2)2 - In the embodiment of the present application, halide ions include but are not limited to fluoride ions (F - ), chloride ion (Cl - ), bromide ion (Br - ) and iodide ion (I - ) at least one of. The present application selects an ionic liquid containing suitable types of anions and cations for matching, which can make the ionic liquid more compatible with other components such as the photosensitive resin and organic solvent in the patterned composition system, and can further improve the stability and conductivity of the patterned composition, thereby further improving the stability and conductivity of the obtained patterned film. In the embodiment of the present application, the ionic liquid in the patterned composition includes but is not limited to characterization by infrared spectroscopy, nuclear magnetic resonance, etc. Specifically, for example, the characteristic chemical bonds of specific ions in the ionic liquid can be characterized by using an infrared spectrometer, or, for example, the position and area of ​​the characteristic peaks of specific ions in the ionic liquid can be characterized by using a nuclear magnetic resonance spectrometer.

[0049] In an embodiment of the present application, the mass percentage of the ionic liquid in the patterned composition is 0.01%-3%. In some specific embodiments, the mass percentage of the ionic liquid in the patterned composition can be, for example, 0.01%, 0.02%, 0.03%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, or 3%. In an embodiment of the present application, the ionic liquid can also be referred to as a low-temperature molten salt, which refers to a salt that is liquid at a relatively low temperature (generally below 100°C) and is composed entirely of anions and cations. Ionic liquids are generally ionic compounds composed of organic cations and inorganic or organic anions. Compared to water and common organic solvents, ionic liquids can better achieve charge transfer. The present application controls the content of the ionic liquid in the patterned composition within a suitable range. On the one hand, the patterned composition can have a more excellent ionic conductivity, further reducing the electron beam offset. On the other hand, it can further avoid the possibility of the photosensitive resin in the non-exposed part developing during exposure, thereby further improving the contrast of the pattern obtained after exposure and effectively reducing the roughness of the patterned film, further improving the exposure performance of the patterned film. In some embodiments of the present application, the mass percentage of the ionic liquid in the patterned composition can be 0.01%-0.8%. The present application further controls the content of the ionic liquid in the patterned composition within the above range, which can further improve the accuracy and contrast of the pattern obtained after exposure. In the embodiment of the present application, the content of the ionic liquid in the patterned composition includes but is not limited to characterization by high performance liquid chromatography.

[0050] In an embodiment of the present application, the photosensitive resin includes one or more of acrylates and their derivatives, phenolic resins and their derivatives, epoxy resins and their derivatives, and polyimide resins and their derivatives. In some specific implementations, the photosensitive resin may be, for example, a polymethyl methacrylate (PMMA)-based resin or a styrene methacrylate (ZEP)-based resin. The patterned composition can be divided into a positive patterned composition and a negative patterned composition based on whether the cross-linking reaction or the chemical bond cleavage reaction dominates after the patterned composition is exposed to energy. Among them, after the patterned film formed by the patterned composition is exposed to energy, the chemical bond cleavage reaction in the exposed area dominates, which is a positive patterned composition. The positive patterned composition is easily soluble in the developer after exposure, and the exposed area is washed away to form a positive pattern; after the patterned composition is exposed to energy, the cross-linking reaction in the exposed area dominates, which is a negative patterned composition. The small molecules in the negative patterned composition are cross-linked and polymerized to form macromolecules after exposure, which are difficult to dissolve in the developer, and the exposed area is not washed away to form a negative pattern. In the embodiments of the present application, the patterned composition can be a positive patterned composition or a negative patterned composition. Since the ionic liquid provided in the present application has good stability, its application scenarios are broadened, that is, it can be applied in positive patterned composition systems or negative patterned composition systems. In the embodiments of the present application, the photosensitive resin in the patterned composition includes, but is not limited to, characterization by infrared spectroscopy, nuclear magnetic resonance, and the like.

[0051] In an embodiment of the present application, the mass percentage of the photosensitive resin in the patterned composition is 0.05%-7%. In some specific embodiments, the mass percentage of the photosensitive resin in the patterned composition can be, for example, 0.05%, 0.08%, 0.1%, 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, or 7%. By controlling the content of the photosensitive resin in the patterned composition within the above range, the present application can ensure good film-forming properties, excellent exposure properties, and suitable coating viscosity of the patterned composition on the one hand, and effectively control the production cost of the patterned composition on the other hand. In some embodiments of the present application, the patterned composition can be first subjected to rotary evaporation or freeze-drying, and then the obtained solid can be tested by nuclear magnetic resonance to calculate the mass percentage of the photosensitive resin in the patterned composition.

[0052] In an embodiment of the present application, the mass of the ionic liquid in the patterned composition accounts for 5%-50% of the total mass of the ionic liquid and the photosensitive resin. In some specific embodiments, the mass of the ionic liquid in the patterned composition can, for example, account for 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, or 50% of the total mass of the ionic liquid and the photosensitive resin. By controlling the ratio of the ionic liquid and the photosensitive resin in the patterned composition within an appropriate range, the present application can further improve the stability of the patterned composition and the solvent resistance of the patterned film, further extend the storage period of the patterned composition and the quality of the spin coating film, thereby further improving the success rate of micro-patterning in the semiconductor device preparation process and the quality of the obtained micro-pattern, thereby improving the overall performance of the semiconductor device.

[0053] In the embodiments of the present application, the patterned composition may further include other additives, such as leveling agents, surfactants, and the like. The addition of leveling agents and surfactants can further enhance the coating performance and coating uniformity of the patterned composition. Those skilled in the art can determine the amount of the above-mentioned additives in the patterned composition based on specific production requirements. For example, the amount of the leveling agent can be adjusted based on the desired coating thickness.

[0054] In the embodiment of the present application, the organic solvent in the patterned composition can be any organic solvent known in the art that can dissolve and disperse the aforementioned ionic liquid, photosensitive resin and other components, including but not limited to one or more of carboxylic acid ester solvents, ether solvents, alcohol solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, organic acid solvents and ketone solvents. In some specific embodiments of the present application, the organic solvent includes one or more of anisole, chlorobenzene and p-dichlorobenzene. By selecting a suitable organic solvent, the present application can make the photosensitive resin and the ionic liquid more evenly dispersed in the patterned composition, improve the component uniformity and stability of the patterned composition, and thus ensure the stability and solvent resistance of the patterned film prepared by the patterned composition. And the above-mentioned organic solvent will completely evaporate during the pre-baking pretreatment process before the coating is exposed, so as not to affect the subsequent formation of the patterned film and the quality of the patterned film.

[0055] In some embodiments of the present application, a method for preparing a patterned composition comprises mixing a photosensitive resin, an ionic liquid, and an organic solvent to obtain a patterned composition. The method for preparing the patterned composition provided herein is simple, has low production costs, utilizes readily available raw materials, and exhibits excellent electrical conductivity and stability. In some specific embodiments of the present application, the mixing process further comprises the addition of other additives.

[0056] In some embodiments of the present application, the application process of the patterned composition may also involve the preparation of a patterned composition coating, which may be specifically: providing a substrate, coating the patterned composition provided above on the surface of the substrate, and forming a patterned composition coating after drying. In some embodiments of the present application, the substrate also includes spin-coating a lower layer material on the substrate. In some specific embodiments, the lower layer material can be, for example, carbon. The organic solvent in the patterned composition can be removed by drying (pre-baking pretreatment).

[0057] The present application also provides a patterned film, which is formed using the patterned composition provided above in the present application. The patterned film can be used to make a high-precision mask in an integrated circuit patterning process, and the pattern of the patterned film can be transferred to a substrate such as a silicon wafer by electronic exposure to form a preset pattern on the substrate. Since the patterned composition provided in the embodiment of the present application contains an ionic liquid and has good electrical conductivity, the patterned composition coating obtained therefrom has high electrical conductivity and good exposure performance, strong antistatic ability when exposed to an electron beam, small electron beam offset, and good accuracy of the obtained pattern.

[0058] In some embodiments of the present application, a method for preparing a patterned film includes: coating a patterned composition on a substrate to form a patterned composition coating; exposing and developing the patterned composition coating to form a patterned film on the substrate surface.

[0059] In the embodiment of the present application, the conductivity of the patterned film is greater than or equal to 1×10 -7 S / cm. In some embodiments, the conductivity of the patterned film can be, for example, 1×10 -7 S / cm, 2×10 -7 S / cm, 3×10 -7 S / cm, 5×10 -7 S / cm, 6×10 -7 S / cm, 8×10 -7 S / cm, 1×10 -6 S / cm, 2×10 -6 S / cm, 3×10 -6 S / cm, 5×10 -6 S / cm, 6×10 -6 S / cm, 8×10 -6 S / cm, 1×10 -5 S / cm, 2×10 -5 S / cm, 5×10 -5 The patterned film provided in the present application has good electrical conductivity, strong antistatic ability when exposed by electron beam, small electron beam offset, and the obtained pattern has high imaging quality and precision.

[0060] The present application also provides a patterned substrate, which is obtained by coating the patterned composition described above on a substrate, exposing it to light, and developing it. In the embodiments of the present application, the substrate can be selected according to actual needs. Specifically, the substrate can be, but is not limited to, a silicon wafer or a silicon wafer covered with a coating. Exemplarily, the coating can be an anti-reflective coating, an anti-etching coating, an epitaxial layer, a metal layer, a dielectric layer, a finishing layer, or a supporting layer.

[0061] The present application also provides a semiconductor device, which is prepared using the patterned composition or patterned film described in any of the above embodiments. The semiconductor device provided in the present application has high precision, which is beneficial to improving the comprehensive performance of the semiconductor device. In some embodiments of the present application, the semiconductor device includes a structure to be patterned (such as a substrate to be patterned) coated with the above-mentioned patterned composition to form a film, and then exposed and developed to form a film layer (i.e., a patterned film) that is etched. In the present application, there is no restriction on the specific type of semiconductor device. In some specific embodiments of the present application, the semiconductor device may be an integrated circuit device including a chip. During the preparation of the chip, other functional layers may be prepared after completing the aforementioned patterning process.

[0062] The present application also provides a method for preparing a patterned film, comprising:

[0063] S101, coating the patterned composition described in any one of the above embodiments on a substrate to form a film layer on the substrate;

[0064] S102, coating the patterned composition, or exposing the film layer to an exposure light source, by electron beam or ion beam direct writing;

[0065] S103 , developing the exposed patterned composition coating, or film layer, with a developer to form a patterned film on the substrate.

[0066] The preparation method provided in this application is simple, and the semiconductor device produced has excellent comprehensive performance, which is conducive to its commercial application.

[0067] In step S101, the substrate can be selected according to actual needs. Specifically, the substrate can be, but is not limited to, a silicon wafer or a silicon wafer covered with a coating. For example, the coating can be an anti-reflective coating, an anti-etching coating, an epitaxial layer, a metal layer, a dielectric layer, a modified layer, or a supporting layer. Usually, other coatings can be obtained by pre-treating the substrate. The pre-treatment method can be: subjecting the silicon wafer substrate to O2 plasma surface hydrophilic activation; or cleaning in Piranha solution (H2O: 30% ammonia water: 30% H2O2 = 5:1:1) for 15min-20min, and then washing with deionized water and isopropyl alcohol to complete the hydrophilic treatment; or using evaporation or spin coating to cover the substrate with hexamethyldisilazane (Hexamethyldisilazane, HMDS) to perform surface hydrophobic treatment on the substrate; the hydrophobic treatment can be after the hydrophilic treatment; or adding a bottom antireflection coating (BARC), a bottom carbon-containing coating (SOC), or a bottom silicon-containing coating (SOG).

[0068] In embodiments of the present application, an appropriate volume of the patterning composition is applied to the substrate via spin coating, depending on the substrate size, to form a patterning composition coating having a thickness of 5 nm to 1000 nm. The surface roughness Rq of the patterning composition coating may be less than 1 nm. For example, a 4-inch substrate may be spin-coated with 1 mL to 5 mL of the patterning composition.

[0069] In some embodiments of the present application, the substrate may be cleaned before coating to remove impurities and dust from the substrate surface. Specifically, the cleaning method may include, but is not limited to, using a solvent, acid, ultrasonic or spray cleaning. In some embodiments of the present application, the cleaning method may be ultrasonic cleaning.

[0070] In step S102, the light source for exposure may be, but is not limited to, ultraviolet light, X-rays, electron beams, ion beams, etc. In some specific embodiments of the present application, the light source for exposure may be an electron beam or an ion beam.

[0071] In some embodiments of the present application, a baking treatment may be performed after coating and before exposure to remove excess organic solvent in the film layer and improve the stability and structural reliability of the patterned composition; a baking treatment may also be performed after exposure and before development to promote chemical reactions in the coating. In some specific embodiments, the baking temperature is 60°C-250°C, and the baking time is 20s-300s. Specifically, the baking temperature may be, for example, 60°C, 80°C, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, 220°C, 240°C, 250°C, etc., and the baking time may be, for example, 20s, 40s, 60s, 80s, 100s, 120s, 150s, 160s, 180s, 200s, 220s, 240s, 250s, 280s, 300s, etc. In some embodiments of the present application, the baking temperature may be 60°C-150°C, and the baking time may be 20s-80s. In some specific embodiments of the present application, the baking temperature may be 100°C-200°C, and the baking time may be 70s-120s.

[0072] In step S103, a developing solution is used for development. Since the chemical properties and solubility of the exposed area in the film layer change, the exposed film layer needs to be cleaned with a developing solution to obtain a patterned film. In the embodiment of the present application, the cleaning time is 10s-300s, and the cleaning can be divided into single-step cleaning and multi-step cleaning. In the cleaned film layer, if the exposed area is washed away, it is a positive development, forming a positive pattern, and the patterned composition is a positive patterned composition; if the exposed area is not washed away, it is a negative development, forming a negative pattern, and the patterned composition is a negative patterned composition.

[0073] In some embodiments of the present application, the developing solution includes a developer. The developer can be selected according to the properties of the patterned composition and used in combination to improve the etching effect. The development time is 10s-120s. In the embodiments of the present application, the developer can include but is not limited to organic solutions, inorganic solutions, pure solvents, mixed solvents, solvents containing other additives, etc. Specifically, in some embodiments of the present application, the developer can be a tetramethylammonium hydroxide (TMAH) aqueous solution with a concentration of 0.5%-5%, or it can be an organic solvent such as ketones, alcohols, ethers, esters, lactones, high-boiling point alcohols, etc., among which ketones can be, for example, cyclohexanone and methyl-2-n-pentyl ketone; alcohols can be, for example, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol and diacetone alcohol; ethers can be, for example, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether , propylene glycol dimethyl ether, diethylene glycol dimethyl ether; esters can be, for example, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, 3-ethoxymethyl propionate, 3-ethoxyethyl propionate, tert-butyl acetate, tert-butyl propionate and propylene glycol monotert-butyl ether acetate; lactones can be, for example, γ-butyrolactone; high-boiling point alcohol solvents can be, for example, diethylene glycol, propylene glycol, glycerol, 1,4-butanediol, 1,3-butanediol. In an embodiment of the present application, the developer can be a mixture of any one or more of the above solutions. In some embodiments, after development, rinsing and baking are further included to remove impurities on the surface of the patterned film, improve the structural reliability of the patterned film, and thereby improve the quality of the obtained pattern.

[0074] In some embodiments of the present application, a patterned substrate can be obtained by coating a substrate to be patterned with the patterning composition, exposing and developing the formed film layer (ie, patterned film), and etching the film layer.

[0075] The present invention also provides a semiconductor device, which is made using the patterned film provided in the present invention or includes the above-mentioned patterned substrate. Due to the use of the patterned film provided in the present invention, the semiconductor device provided in the present invention has high precision.

[0076] In the embodiments of the present application, there is no particular limitation on the structure of the semiconductor device, and those skilled in the art can design it based on actual application needs and prepare it based on the patterned composition provided in the embodiments of the present application.

[0077] In the embodiments of the present application, there is no limitation on the specific type of semiconductor device. In some embodiments of the present application, the semiconductor device may be an integrated circuit device including a chip. During the chip preparation process, the preparation of other functional layers may be performed after the aforementioned patterning process is completed.

[0078] The present application also provides a method for preparing a semiconductor device, comprising:

[0079] S201, coating the aforementioned patterned composition provided in an embodiment of the present application on a substrate to form a film layer on the substrate;

[0080] S202 , exposing and developing the film layer to form a patterned film on the substrate.

[0081] The process parameters involved in the above process can be found in the relevant description of the preparation method of the patterned film in the previous article, and will not be repeated here.

[0082] In some embodiments of the present application, after forming a patterned film on a substrate, the method for preparing the semiconductor device further comprises:

[0083] S203 , etching or electron injection is performed on the substrate to be patterned to form a patterned substrate, thereby obtaining a semiconductor device.

[0084] The technical solution of this application is described in detail below with multiple embodiments.

[0085] Example 1

[0086] A patterning composition comprises anisole (an organic solvent), polymethyl methacrylate (PMMA) (a photosensitive resin), and tributylmethylammonium bis(trifluoromethanesulfonyl)imide (an ionic liquid). The composition comprises, based on the total mass of the patterning composition, 97% by mass of the organic solvent, 0.15% by mass of the ionic liquid, and 2.85% by mass of the photosensitive resin.

[0087] Example 2

[0088] The difference from Example 1 is that the mass percentage of the ionic liquid is 0.3%, and the mass percentage of the photosensitive resin is 2.7%.

[0089] Example 3

[0090] The difference from Example 1 is that the mass percentage of the ionic liquid is 0.45%, and the mass percentage of the photosensitive resin is 2.55%.

[0091] Example 4

[0092] The difference from Example 1 is that the mass percentage of the ionic liquid is 0.6%, and the mass percentage of the photosensitive resin is 2.4%.

[0093] Example 5

[0094] The difference from Example 1 is that the mass percentage of the ionic liquid is 0.75%, and the mass percentage of the photosensitive resin is 2.25%.

[0095] Example 6

[0096] The difference from Example 1 is that the mass percentage of the ionic liquid is 0.9%, and the mass percentage of the photosensitive resin is 2.1%.

[0097] Example 7

[0098] The difference from Example 1 is that the mass percentage of the ionic liquid is 1.05%, and the mass percentage of the photosensitive resin is 1.95%.

[0099] Example 8

[0100] The difference from Example 1 is that the mass percentage of the ionic liquid is 1.2%, and the mass percentage of the photosensitive resin is 1.8%.

[0101] Example 9

[0102] The difference from Example 1 is that the mass percentage of the organic solvent is 99.9%, the mass percentage of the ionic liquid is 0.01%, and the mass percentage of the photosensitive resin is 0.09%.

[0103] Example 10

[0104] The difference from Example 1 is that the mass percentage of the organic solvent is 94%, the mass percentage of the ionic liquid is 3%, and the mass percentage of the photosensitive resin is 3%.

[0105] Example 11

[0106] The difference from Example 1 is that the mass percentage of the organic solvent is 99.4%, the mass percentage of the ionic liquid is 0.03%, and the mass percentage of the photosensitive resin is 0.57%.

[0107] Example 12

[0108] The difference from Example 1 is that the organic solvent is cyclohexanone.

[0109] Example 13

[0110] The difference from Example 1 is that the ionic liquid is 1-ethyl-3-methylimidazole dicyandiamide salt.

[0111] In order to highlight the beneficial effects of the embodiments of the present application, the following comparative examples are provided.

[0112] Comparative Example 1

[0113] The difference from Example 1 is that no ionic liquid is added, and the mass percentage of the photosensitive resin is 3%.

[0114] Comparative Example 2

[0115] The difference from Example 1 is that the mass percentage of the organic solvent is 92%, the mass percentage of the ionic liquid is 5%, and the mass percentage of the photosensitive resin is 3%.

[0116] Comparative Example 3

[0117] The difference from Example 1 is that the ionic liquid is 1-vinyl-3-butylimidazole bis(trifluoromethanesulfonyl)imide salt.

[0118] Comparative Example 4

[0119] The difference from Example 1 is that the ionic liquid is replaced by graphene.

[0120] Performance Testing

[0121] Composition stability:

[0122] The patterned compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were allowed to stand at 25° C. for 30 days. The texture of the patterned compositions (i.e., whether there was delamination, solid precipitation, etc.) was observed. The stability of the patterned compositions was classified into three categories based on the different texture states:

[0123] ○ indicates no stratification and no solid precipitation, indicating good stability;

[0124] △ indicates that there is stratification but no solid precipitation, and the stability is average;

[0125] × indicates that there is stratification and solid precipitation, indicating poor stability;

[0126] The observed results are shown in Table 1.

[0127] Physical properties:

[0128] The patterned compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were spin-coated on a silicon substrate at a spin coating speed of 4000 rpm, a spin coating acceleration of 2000 rpm / s, and a total spin coating time of 60 s. The samples were then heated on a hot plate at 120° C. for 120 s to obtain corresponding film layers. The thickness h0, roughness Rq, and electrical conductivity of the film layers were measured, respectively. The results are shown in Table 1, where NA indicates that the value is too low to be measured.

[0129] Film solvent resistance:

[0130] The patterned compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were spin-coated on a silicon substrate (spin-coating parameters), and then heated on a hot plate at 120° C. for 120 seconds to obtain the corresponding film layer, which was then immersed in an isopropyl alcohol solvent for 1 minute. After air-drying, the thickness h of the film layer was measured using an ellipsometer. The definition is: film loss rate = (h0-h0) / h0*100%. The solvent resistance of the film layer is divided into three categories according to different film loss rate ranges:

[0131] ○ indicates that the film loss rate is less than 1%;

[0132] △ indicates the film loss rate is 1%-10%;

[0133] × indicates that the film loss rate is greater than 10%;

[0134] The calculated results are shown in Table 1.

[0135] Residual adhesive ratio after exposure and development:

[0136] The patterned compositions of Examples 1 to 13 and Comparative Examples 1 to 3 were spin-coated on a SOC (System on Chip) substrate, and then heated on a hot plate at 120° C. for 120 s to obtain the corresponding film layers. Electron beam exposure of a square pattern with a side length of 2 μm*2 μm was performed at a dose of 400 μC / cm 2 After exposure, the patterned composition film layer was developed with isopropyl alcohol for 120 seconds, and the film thickness at the exposure position was measured using an AFM (Atomic Force Microscopy):

[0137] ○ indicates that the film thickness at the exposure position is less than 1% of the total thickness of the patterned composition film before exposure;

[0138] △ indicates that the film thickness at the exposure position is 1-3% of the total thickness of the patterned composition film before exposure;

[0139] X indicates that the thickness of the film layer at the exposure position is greater than 3% of the total thickness of the patterned composition film layer before exposure.

[0140] The calculated results are shown in Table 1.

[0141] Table 1

[0142]

[0143] As can be seen from Table 1, compared to Comparative Example 1 in which no ionic liquid is added, the embodiment of the present application can significantly improve the conductivity of the film layer by adding an ionic liquid to the patterned composition, thereby improving the antistatic ability of the film layer when exposed to an electron beam, and reducing the deviation of the electron beam. And from the data of Examples 1-8, it can be seen that when the total content of the ionic liquid and the photosensitive resin remains unchanged, increasing the content of the ionic liquid (increasing the ratio of the ionic liquid to the photosensitive resin) can improve the conductivity of the film layer but reduce the solvent resistance of the film layer. Therefore, controlling the ratio of the ionic liquid to the photosensitive resin within a suitable range can further improve the solvent resistance of the film layer while ensuring that the film layer has good conductivity. Comparing Comparative Example 2 and Example 1, it can be seen that the addition of an excessive amount of ionic liquid will not only seriously affect the solvent resistance of the film layer, but also affect the stability of the composition. It can be seen from the data of Comparative Example 3 and Example 1 that Comparative Example 3 uses an ionic liquid containing a vinyl group, which results in a large amount of residual adhesive in the patterned composition film layer after exposure and development, affecting its exposure and development effect. Example 1 uses an ionic liquid that does not contain a vinyl group, which can effectively reduce the proportion of residual adhesive in the patterned composition film layer after exposure and development, has better exposure performance, and thus improves the performance of the semiconductor device.

[0144] Offset

[0145] The target pattern obtained by electron beam exposure is preset as Figure 1 As shown, from left to right are five line segments numbered ①-⑤, and a square with a side length of 30μm and a line segment numbered ⑥ as one side. Among them, the distance between any two adjacent line segments in the five line segments numbered ①-⑤ is 1μm, that is, D0; the exposure sequence is ①-②-③-④-⑥ (square)-⑤. The patterned composition film layer of Example 1 and Comparative Example 1 was exposed to electron beam light source, exposure line dose of 1000pC / cm, developer solution of isopropyl alcohol, and development time of 120s, with base surface doses of 0, 100μC / cm 2 , 200μC / cm 2 、300μC / cm 2 , 400μC / cm 2 , 500μC / cm 2 、600μC / cm 2 , 700μC / cm 2 、800μC / cm 2 Exposure is performed, and in the actual pattern obtained, the distance between the line segment marked ③ and the line segment marked ⑤ is d 35 , the distance between the line segment labeled ② and the line segment labeled ④ is d 24 , let the offset d = d 35 -d 24, the results are as follows Figure 2 As shown. Figure 2 It can be seen that compared with the comparative example 1 in which no ionic liquid is added, the deviation of the electron beam can be significantly reduced in Example 1 of the present application by adding the ionic liquid to the patterning composition.

[0146] Exposure performance

[0147] The patterned compositions of Examples 1 to 13 and Comparative Examples 1 to 4 were spin-coated on a SOC substrate, and then heated at 120° C. for 120 s using a hot plate to obtain the corresponding film layers for electron beam exposure of dense hole patterns. The hole diameters ranged from 18 nm to 50 nm, specifically including 18 nm, 20 nm, 22 nm, 24 nm, 26 nm, 28 nm, 30 nm, 35 nm, 40 nm, and 50 nm, and the exposure dose range was 100 μC / cm 2 -1000μC / cm 2 The exposure system was a Hitachi electron beam microscope equipped with a Raith pattern generator. After exposure, the film was developed using isopropyl alcohol for 120 seconds. The pattern of the patterned composite film was characterized using an electron beam microscope. SMILE software was used to identify and calculate the achievable resolution and LCDU (Local Critical Dimension Uniformity) of the pattern. The results are shown in Table 2, where NA indicates a poor value that could not be measured.

[0148] Table 2

[0149]

[0150] The data in Table 2 demonstrate that the addition of a suitable amount of a specific type of ionic liquid in the examples of this application effectively improves the exposure performance of the patterned composition. Furthermore, the data from Comparative Example 4 and Examples 1-13 demonstrate that simply adding graphene, which enhances film conductivity, does not improve the exposure performance of the patterned composition. This is likely due to the poor solubility and dispersibility of graphene, which affects the uniformity of the film and, consequently, the exposure performance. By selecting and adding a suitable ionic liquid to the patterned composition, the present application achieves a film with excellent conductivity, stability, and exposure performance.

[0151] It should be understood that the first, second and various numerical numbers involved in this document are only distinguished for the convenience of description and are not intended to limit the scope of this application.

[0152] In this application, "at least one" means one or more, and "plurality" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b or c", or "at least one of a, b and c" can all mean: a, b, c, ab (i.e., a and b), ac, bc or abc, where a, b, c can be single or multiple.

[0153] In this application, “-” represents a range value, including the endpoint values ​​at both ends. For example, the value of a can be 0.5-15, which means that the value of a can be between 0.5 and 15, and includes the endpoint values ​​0.5 and 15.

[0154] It should be understood that in the various embodiments of the present application, the size of the serial numbers of the above-mentioned processes does not mean the order of execution. Some or all of the steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of the present application.

Claims

1. A patterned composition, characterized in that The agglomerated composition includes the following components in percentage by mass: Organic solvents: 90%-99.9%; Photosensitive resin: 0.05%-7%; Ionic liquids: 0.01%-3%; In the ionic liquid, the ionic liquid containing vinyl groups accounts for less than 10% of the total mass of the ionic liquid.

2. The patterned composition according to claim 1, wherein In the patterned composition, the mass percentage of the ionic liquid is 0.01%-0.8%.

3. The patterned composition according to claim 1, wherein The mass of the ionic liquid accounts for 5% to 50% of the total mass of the ionic liquid and the photosensitive resin.

4. The patterned composition according to claim 1, wherein The ionic liquid includes cations and anions, and the cations include one or more cations having structures shown in formula (I) to formula (VI): Among them, R1-R 15 are independently selected from hydrogen, substituted or unsubstituted alkyl, cycloalkyl, alkoxy, heterocyclic, aryl, aralkyl or aryloxy groups; the substituent in the substituted alkyl group is selected from one or more of hydroxyl, cyano, alkoxy, -COOR1, carboxyl, amino, sulfonic acid and -Si(OR2)3, wherein R1 is an alkyl group and R2 is an alkyl group; The anions include halide ions, tetrafluoroborate anions, bis(trifluoromethanesulfonyl imide) anions, trifluoromethanesulfonate anions, trifluoroacetic acid anions, acetate ions, dihydrogen phosphate anions, hydrogen sulfate ions, formate ions, p-toluenesulfonic acid anions, hexafluorophosphate anions, nitrate ions, N(CF3SO2)2 - 、N(CN)2 - 、N(CN)3 - 、CH3OSO3 - 、(C2H5)2PO4 - 、N(C2F5SO2)2 - 、N(CF3CO)2 - 、(CF3SO2)(CF3CO) - 、N(FSO2)2 - One or more of .

5. The patterned composition according to claim 1, wherein The photosensitive resin includes one or more of acrylate and its derivatives, phenolic resin and its derivatives, epoxy resin and its derivatives, and polyimide resin and its derivatives.

6. A patterned film, characterized in that The patterned film is formed using the patterned composition according to any one of claims 1 to 5.

7. The patterned film according to claim 6, wherein The conductivity of the patterned film is greater than or equal to 1×10 -7 S / cm.

8. A patterned substrate, characterized in that The patterned substrate is obtained by coating the patterned composition according to any one of claims 1 to 5 on a substrate, and then exposing and developing the substrate.

9. A semiconductor device, characterized in that: The semiconductor device is made using the patterned composition according to any one of claims 1 to 5, or is made using the patterned film according to claim 6 or 7.

10. A method for preparing a semiconductor device, characterized in that: include: applying the patterning composition according to any one of claims 1 to 5 on a substrate to form a film layer on the substrate; The film layer is exposed and developed to form a patterned film on the substrate.

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