Method of manufacturing semiconductor device and composition comprising floating additive

Abstract

The invention relates to a method of manufacturing a semiconductor device and a composition comprising a floating additive. Specifically, a method of manufacturing a semiconductor device includes forming a photoresist layer including a photoresist composition over a substrate, and forming a floating additive layer including a floating additive polymer. The floating additive polymer includes a draping fluorine substituted organic group, and one or more of a draping acid generating group, a draping base group, a draping acid labile group, a draping chromophore group, a draping developer solubility promoter group, and a draping acid diffusion control group. The photoresist layer is selectively exposed to actinic radiation to form a potential pattern. The potential pattern is developed to form a pattern in the photoresist layer.

Description

[0001] Cross - Reference to Related Applications

[0002] This application claims priority to U.S. Provisional Application No. 63 / 553,517, filed on February 14, 2024, the entire disclosure of which is incorporated herein by reference. Technical Field

[0003] This application relates to a method of manufacturing a semiconductor device and a composition comprising a floating additive. Background Art

[0004] As consumer devices become smaller in response to consumer demands, the size of the individual components of these devices must necessarily decrease. Semiconductor devices, which are the main components of devices such as mobile phones, tablet computers, etc., have faced increasing pressure to become smaller, and the size of individual devices within the semiconductor device (e.g., transistors, resistors, capacitors, etc.) has also faced corresponding shrinking pressure.

[0005] One enabling technology used in the semiconductor device manufacturing process is the use of photoresist materials. Such materials are applied to the surface of the layer to be patterned and then exposed to energy that is itself already patterned. This exposure changes the chemical and physical properties of the exposed area of the photosensitive material. This modification, as well as the lack of modification in the unexposed area of the photosensitive material, can be utilized to remove one area without removing the other, or vice versa.

[0006] However, as the size of individual devices has decreased, the process window for lithographic processing has become increasingly stringent. Therefore, advancements in the field of lithographic processing have helped to maintain the ability to scale down devices.

[0007] As the semiconductor industry has progressed to nanotechnology process nodes that pursue higher device density, higher performance, and lower cost, shrinking semiconductor feature sizes has faced challenges. Summary of the Invention

[0008] Some embodiments of the present invention relate to a method of manufacturing a semiconductor device, the method comprising: forming a photoresist layer comprising a photoresist composition over a substrate; forming a floating additive layer comprising a floating additive polymer, wherein the floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of pendant acid-generating groups, pendant base groups, pendant acid-labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid diffusion control groups; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and developing the selectively exposed photoresist layer to form a pattern in the photoresist layer.

[0009] Some embodiments of the present invention relate to a method of manufacturing a semiconductor device, the method comprising: forming a photoresist layer comprising a photoresist composition over a substrate, wherein the photoresist composition comprises: a first polymer; a photoactive compound; and a second polymer, the second polymer comprising pendant fluorine-substituted organic groups, and one or more of a pendant acid generating group, a pendant base group, a pendant acid labile group, a pendant chromophore group, a pendant developer solubility promoter group, and a pendant acid diffusion control group; floating the second polymer over the first polymer and the photoactive compound to form a floating layer over the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the floating layer to form a latent pattern in the photoresist layer; and developing the latent pattern to form a pattern in the photoresist layer.

[0010] Some embodiments of the present invention relate to a stacked structure, the stacked structure comprising: a photoresist layer disposed over a substrate; and a floating additive layer disposed over the photoresist layer, wherein the photoresist layer comprises a photoresist polymer and a photoactive compound; and the floating additive layer comprises a floating additive polymer, wherein the floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of a pendant acid generating group, a pendant base group, a pendant acid labile group, a pendant chromophore group, a pendant developer solubility promoter group, and a pendant acid diffusion control group, wherein the floating additive polymer and the photoresist polymer are different polymers. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The present disclosure will be best understood from the following detailed description when read in conjunction with the accompanying drawings. It is to be emphasized that, in accordance with standard practice in the industry, various features are not drawn to scale and are for illustrative purposes only. In fact, for the sake of clarity of discussion, the dimensions of various features may be arbitrarily increased or decreased.

[0012] Figure 1 A process flow for manufacturing a semiconductor device according to an embodiment of the present disclosure is shown.

[0013] Figure 2 Process stages of sequential operations according to an embodiment of the present disclosure are shown.

[0014] Figure 3A and Figure 3B Process stages of sequential operations according to an embodiment of the present disclosure are shown.

[0015] Figure 4A and Figure 4BShows the process stages of sequential operations according to an embodiment of the present disclosure.

[0016] Figure 5A and Figure 5B Shows the process stages of sequential operations according to an embodiment of the present disclosure.

[0017] Figure 6 Shows the process stages of sequential operations according to an embodiment of the present disclosure.

[0018] Figure 7 Shows the process stages of sequential operations according to an embodiment of the present disclosure.

[0019] Figure 8 Shows the process stages of sequential operations according to an embodiment of the present disclosure.

[0020] Figure 9A 、 Figure 9B and Figure 9C Shows the process stages of sequential operations according to an embodiment of the present disclosure.

[0021] Figure 10A 、 Figure 10B and Figure 10C Shows the process stages of sequential operations according to an embodiment of the present disclosure, and Figure 10D Shows an example of a polymer according to an embodiment of the present disclosure.

[0022] Figure 11A 、 Figure 11B 、 Figure 11C 、and Figure 11D Shows the process stages of sequential operations according to an embodiment of the present disclosure.

[0023] Figure 12A and Figure 12B Shows an example of a polymer according to an embodiment of the present disclosure.

[0024] Figure 13A and Figure 13B Shows examples of polymers and pendant groups according to an embodiment of the present disclosure.

[0025] Figure 14A 、 Figure 14B 、 Figure 14C 、 Figure 14D 、 Figure 14E 、 Figure 14F 、 Figure 14G 、and Figure 14H Shows examples of polymers and pendant groups according to an embodiment of the present disclosure.

[0026] Figure 15 Shows examples of polymer pendant groups according to an embodiment of the present disclosure.

[0027] Figure 16A shows an open-loop reaction, and Figure 16B 、 Figure 16C 、and Figure 16D show examples of polymer pendant groups according to embodiments of the present disclosure.

[0028] Figure 17A 、 Figure 17B 、 Figure 17C 、and Figure 17D show examples of polymers according to embodiments of the present disclosure.

[0029] Figure 18A show an organometallic precursor according to embodiments of the present disclosure. Figure 18B and Figure 18C show examples of organometallic precursors according to embodiments of the present disclosure.

[0030] Figure 19 show a deposition apparatus according to embodiments of the present disclosure.

[0031] Figure 20A and Figure 20B are diagrams of a controller according to some embodiments of the present disclosure.

[0032] Figure 21 show process stages of sequential operations according to embodiments of the present disclosure.

[0033] Figure 22A and Figure 22B show process stages of sequential operations according to embodiments of the present disclosure.

[0034] Figure 23A and Figure 23B show process stages of sequential operations according to embodiments of the present disclosure.

[0035] Figure 24A and Figure 24B show process stages of sequential operations according to embodiments of the present disclosure.

[0036] Figure 25 show process stages of sequential operations according to an embodiment of the present disclosure.

[0037] Figure 26 show process stages of sequential operations according to an embodiment of the present disclosure.

[0038] Figure 27 show process stages of sequential operations according to an embodiment of the present disclosure. Detailed Description

[0039] It should be understood that the following disclosure provides many different embodiments or examples for implementing different features of the present disclosure. Specific embodiments or examples of components and arrangements are described below to simplify the present disclosure. Of course, these are merely examples and are not intended to be limiting. For example, the dimensions of an element are not limited to the disclosed ranges or values, but may depend on the process conditions of the device and / or the desired properties. In addition, forming a first feature above or on top of a second feature in the following description may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed between the first and second features such that the first and second features are not in direct contact. For simplicity and clarity, various features may be drawn at different scales arbitrarily.

[0040] Further, for ease of description, spatially relative terms such as "below", "beneath", "lower", "above", "upper", etc. may be used herein to describe the relationship of one element or feature shown in the figures to another element or feature or features. In addition to the orientation depicted in the figures, the spatially relative terms are also intended to cover different orientations of the device during use or operation. The device may be oriented in other ways (rotated 90 degrees or in other orientations) and the spatially relative descriptors used herein may be interpreted accordingly. In addition, the term "made of" may mean "comprising" or "consisting of". In the present disclosure, unless otherwise specified, the phrase "one of A, B, and C" means "A, B, and / or C" (A, B, C, A and B, A and C, B and C, or A, B, and C), rather than meaning one element from A, one element from B, and one element from C. In the present disclosure, the source and drain may be used interchangeably and may be referred to as source / drain. The source / drain region may refer to the source or the drain individually or generically depending on the context.

[0041] In the field of lithographic processing, it is desirable to improve line width roughness (LWR), improve local critical dimension uniformity (LCDU), and reduce exposure dose (EOP) to continue to scale down devices and effectively increase the yield of semiconductor devices. Deep ultraviolet (DUV), electron beam (e-beam), and extreme ultraviolet (EUV) lithography have been developed to reduce critical dimensions and increase device yield. EUV lithography has been developed for nanotechnology process nodes, such as those below the 40 nm process node. In some embodiments, an organic polymer-based photoresist is used in lithography. However, the C, N, and O atoms in the polymer of the organic photoresist are weak in EUV photon absorption. It has been found that certain metals have a higher EUV photon absorption rate. To utilize the higher EUV photon absorption rate of metals, metal photoresists have been developed. The lithographic performance is further improved by treating the photoresist layer with an additive composition that floats above the photoresist layer during actinic radiation exposure and increases the solubility of the photoresist during the development operation. The additive composition can be applied to the photoresist layer at various times during the lithographic patterning process.

[0042] Figure 1 Process flow 100 is shown, and Figures 2 to 10D shows the various stages of manufacturing a semiconductor device according to an embodiment of the present disclosure. In some embodiments, in the photoresist underlayer formation operation S110 as Figure 1 shown, as Figure 2As shown, a photoresist bottom layer 20 is formed above the substrate 10. In some embodiments, before forming the bottom layer 20 above the substrate 10, a floating additive is mixed with the photoresist bottom layer material in operation S115. Then, in some embodiments, the bottom layer material containing the floating additive is applied to the substrate in operation S130a. In some embodiments, the bottom layer material is applied by a spin coating technique. During spin coating, phase separation occurs between the bottom layer material and the floating additive, and the floating additive rises and covers or floats above the bottom layer material layer. In some embodiments, during the material dispensing operation, the substrate rotates at a spin rate of about 100 rpm to about 3000 rpm. In other embodiments, the substrate rotates at a spin rate of about 200 rpm to 1500 rpm. When the spin rate is below the disclosed range, phase separation may be insufficient. When the spin rate is above the disclosed range, the bottom layer may be formed too thin. In some embodiments, after the formation of the photoresist bottom layer or the completion of the bottom layer material dispensing, the rotation of the substrate continues for a period of time.

[0043] In some embodiments, the photoresist bottom layer 20 is formed, and then a floating additive layer 22 is formed above the bottom layer 20 in operation S130b. In some embodiments, the photoresist bottom layer 20 is a bottom anti-reflective coating (BARC) layer. Any suitable BARC material can be used.

[0044] Then, in Figure 1 operation S125, as Figure 3A shown, a photoresist layer 15 is formed above the photoresist bottom layer 20. In some embodiments, before forming the photoresist layer above the bottom layer 20, a baking operation is performed on the bottom layer 20 to drive off the solvent in the base composition. In some embodiments, as Figure 3B shown, the photoresist layer 15 is formed above the substrate 10 in operation S125. Then, as Figure 4A and Figure 4B shown, in the floating additive layer application operation S130d, a floating additive layer 22 is formed above the photoresist layer 15. Figure 4A An embodiment of the stacked structure is shown, where a first floating additive layer 20 is formed below the photoresist layer 15, and a second floating additive layer is formed above the photoresist layer 15. Figure 4BAn embodiment of the stacked structure is shown, where the floating additive layer 22 is formed only above the upper surface of the photoresist layer. In some embodiments, before forming the photoresist layer, the floating additive composition is mixed with the photoresist material composition in operation S120. Then, in operation S130c, the floating additive / photoresist material composition is applied to the substrate 10 or the photoresist bottom layer 20 by a spin coating operation to separate the floating additive from the photoresist material, thereby forming the floating additive layer 22 above the photoresist layer 15. In some embodiments, the spin coating operation is performed at a spin rate of about 100 rpm to about 3000 rpm during the photoresist / floating additive composition dispensing operation, and similar to the bottom layer forming operation, is performed at a spin rate of about 200 rpm to 1500 rpm.

[0045] In other embodiments, the floating additive layer is formed by chemical vapor deposition (CVD), physical vapor deposition (PVD), or atomic layer deposition (ALD). In other embodiments, the additive layer is formed by a spray technique or by gas, liquid, or solid chemical treatment.

[0046] In some embodiments, the floating additive layers 20, 22 are formed in a chamber 335 (e.g., a vacuum chamber as shown in Figure 2 , Figure 4A and Figure 4B ). In some embodiments, the vacuum chamber 335 is used for CVD, PVD, or ALD operations. In some embodiments, as shown in Figure 3A and Figure 3B , the chamber 335 is the same as the chamber for forming the photoresist layer 15. In other embodiments, the chamber 335 for forming the floating additive layer is a different chamber from the chamber for forming the photoresist layer.

[0047] In some embodiments, a gas purge of the chamber 335 is performed before or after forming the floating additive layers 20, 22 or the photoresist layer 15. In some embodiments, the chamber is purged with one or more of carbon dioxide, nitrogen, helium, neon, argon, or dry air, where the dew point of the dry air is about -40 °C or lower. In other embodiments, the humidity of the purge air varies between about 0 and about 100% relative humidity depending on the process requirements.

[0048] In some embodiments, a pre-exposure baking operation S140 is performed to drive off the solvent in the photoresist layer 15 or to cure the photoresist layer 15. In some embodiments, the baking operation is performed in a chamber 335 (e.g., a vacuum chamber). In some embodiments, the photoresist layer 15 is heated at a temperature in the range of about 40°C to about 300°C for about 10 seconds to about 10 minutes. After the pre-exposure baking operation S140, the substrate 10 coated with the photoresist layer 15 is cooled in a cooling operation. In some embodiments, as Figure 3A and Figure 4A shown, heating and cooling are performed using a heater / cooler 330. In some embodiments, the heater / cooler 330 is a hot plate including an internal coolant flow channel. In some embodiments, heating or cooling is controlled by a controller 260 (see Figure 20A , Figure 20B ). Similarly, the heating and cooling operations can be performed after forming the lower or first floating additive layer 20 (see Figure 2 ) and after forming the upper or second floating additive layer 22 (see Figure 4A and Figure 4B ).

[0049] In some embodiments, the floating additive layer 22 is formed after the baking and cooling operation S140. In some embodiments, after the pre-exposure baking / cooling operation S140 and before selectively exposing the photoresist layer 15 to actinic radiation S150, a floating additive layer material is applied to the photoresist layer 15 in a floating additive layer application operation S130e.

[0050] After the pre-exposure baking / cooling operation S140 of the photoresist layer 15, the photoresist layer 15 is selectively exposed to actinic radiation 45 / 97 in an operation S150 (see Figure 5A and Figure 5B ). In some embodiments, the photoresist layer 15 is selectively exposed to ultraviolet radiation. In some embodiments, the radiation is electromagnetic radiation, such as g-line (wavelength of about 436 nm), i-line (wavelength of about 365 nm), ultraviolet radiation, deep ultraviolet radiation, extreme ultraviolet, electron beam, etc. In some embodiments, the radiation source is selected from the group consisting of: a mercury vapor lamp, a xenon lamp, a carbon arc lamp, a KrF excimer laser (wavelength of 248 nm), an ArF excimer laser (wavelength of 193 nm), an F2 excimer laser (wavelength of 157 nm), or a CO2 laser-excited Sn plasma (extreme ultraviolet, wavelength of 13.5 nm).

[0051] As Figure 5AAs shown, in some embodiments, the exposure radiation 45 passes through the photomask 30 before irradiating the photoresist layer 15. In some embodiments, the photomask 30 has a pattern to be replicated in the photoresist layer 15. In some embodiments, the pattern is formed by the opaque pattern 35 on the photomask substrate 40. The opaque pattern 35 can be formed of a material opaque to ultraviolet radiation (such as chromium), while the photomask substrate 40 is formed of a material transparent to ultraviolet radiation (such as fused silica).

[0052] In some embodiments, extreme ultraviolet lithography is used to perform selective exposure of the photoresist layer 15 to form an exposed region 50 and an unexposed region 52. In some embodiments of the extreme ultraviolet lithography operation, a reflective photomask 65 is used to form patterned exposure light in some embodiments, as Figure 5B shown. The reflective photomask 65 includes a low thermal expansion glass substrate 70, on which a reflective multilayer 75 of Si and Mo is formed. A capping layer 80 and an absorber layer 85 are formed on the reflective multilayer 75. A back conductive layer 90 is formed on the back surface of the low thermal expansion glass substrate 70. In some embodiments of extreme ultraviolet lithography, the extreme ultraviolet radiation 95 is directed towards the reflective photomask 65 at an incident angle of about 6°. A portion 97 of the extreme ultraviolet radiation is reflected by the Si / Mo multilayer 75 towards the substrate 10 coated with photoresist, while a portion of the extreme ultraviolet radiation incident on the absorber layer 85 is absorbed by the photomask. In some embodiments, additional optical devices including mirrors are located between the reflective photomask 65 and the substrate coated with photoresist.

[0053] The region 50 of the photoresist layer exposed to radiation undergoes a chemical reaction, thereby changing its solubility in a subsequently applied developer relative to the unexposed region 52 of the photoresist layer. In some embodiments, the exposed portion 50 of the photoresist layer becomes more soluble in the developer.

[0054] The selectively exposed photoresist layer 15 then undergoes a post exposure baking (PEB) or cooling operation S160. In some embodiments, during the post exposure baking or cooling operation S160, the photoresist layer 15 is heated or cooled to a temperature in the range of about -30°C to about 300°C. In some embodiments, a heater / cooler 330 and a controller 260 are used to control the temperature. In other embodiments, the photoresist layer 15 is heated to a temperature in the range of about 40°C to about 160°C for about 20 s to about 120 s. Post exposure baking can be used to assist in the generation, distribution, and reaction of acids / bases / free radicals generated from radiation 45 / 97 impinging on the photoresist layer 15 during exposure. Such assistance helps to create or enhance a chemical reaction that creates a chemical difference between the exposed regions 50 and the unexposed regions 52 within the photoresist layer.

[0055] Subsequently, the selectively exposed photoresist layer is developed by applying a developer to the selectively exposed photoresist layer in operation S170. As Figure 6 shown, the developer 57 is supplied from a dispenser 62 to the photoresist layer 15. In some embodiments, the exposed regions 50 of the photoresist layer, the exposed regions of the lower or first floating additive layer 20, and the upper or second floating additive layer 22 are removed by the developer 57, thereby forming a pattern of openings 55 in the photoresist layer 15 to expose the substrate 10, as Figure 7 shown.

[0056] In some embodiments, the pattern of openings 55 in the patterned photoresist layer 15 is extended into the substrate 10 to create a pattern of openings 55' in the substrate 10, thereby transferring the pattern in the photoresist layer 15 into the substrate 10, as Figure 8 shown. The pattern is extended into the substrate by etching using one or more suitable etchants. In some embodiments, the etching operation removes the remaining portion of the lower floating additive layer 20. In some embodiments, the photoresist layer pattern 55 is at least partially removed during the etching operation. In other embodiments, after etching the substrate 10, the photoresist layer pattern 55 and any remaining portion of the floating additive layer 20 below the photoresist layer pattern 55 are removed by using a suitable photoresist stripping solvent or by a photoresist ashing operation.

[0057] The lithographic patterning operations will be discussed with reference to various embodiments of the present disclosure. Figures 9A to 9C A lithographic patterning operation is shown in which a BARC layer 12 is formed over the substrate and floating additive layers 20, 22 are formed on two major surfaces of the photoresist layer 15, as Figure 9AAs shown. In some embodiments, the thickness of the floating additive layers 20, 22 is each about 1 nm to about 10 nm, and in other embodiments is about 2 nm to about 7 nm. In some embodiments, the thickness of the floating additive layers 20, 22 is about 5 nm.

[0058] In this embodiment, the floating additive material comprises a polymer having pendant acid-labile groups (ALGs) and pendant acid-generating groups (e.g., photoacid generator (PAG) groups) and pendant fluorine-substituted organic groups (e.g., fluoroalcohols). The pendant fluorine-substituted organic groups allow the polymer to phase separate during the spin coating operation and float above the photoresist layer.

[0059] In Figure 9B , the photoresist layer 15 is exposed to actinic radiation 45 through a photomask 30. The actinic radiation causes the PAG in the floating additive layer to release an acid (H+), which diffuses into the photoresist layer 15 and replenishes the acid (H+) generated in the exposed regions of the photoresist layer. As Figure 9C shown, the acid released by the PAG also cleaves the ALG to form hydrophilic carboxylic acid groups, thereby increasing the solubility of the floating additive layer in the photoresist developer solution. In some embodiments, the floating additive material composition comprises a base, such as a quencher, or a base generator.

[0060] As Figure 9C shown, the floating additive layer improves the post-development inspection (ADI), local critical dimension uniformity (LCDU), and line width roughness (LWR) of the resulting pattern 55. Since the floating additive has PAG groups, it can increase the PAG loading at the top and bottom in the photoresist layer to improve the PAG uniformity of the photoresist. The floating additive according to the present disclosure has a low surface energy of less than about 35 mJ / m 2 , absorbs EUV radiation, and generates secondary electrons.

[0061] Figures 10A to 10C Shows an embodiment similar to the Figures 9A to 9C embodiment. In Figures 10A to 10C , the floating additive layer 22 is formed only on the upper surface of the photoresist layer 15. The floating additive material is blended into the photoresist solution. After the photoresist spin coating operation S125, the floating additive phase separates in the upper portion of the photoresist layer due to the pendant fluorine-substituted organic groups.

[0062] Figure 10DShows an example of a floating additive polymer according to an embodiment of the present disclosure. The polymer includes a pendant acid-labile group attached to the polymer backbone via a linkage R1, a pendant photoacid generator attached to the polymer backbone via a linkage R2, and a pendant fluorine-substituted organic group attached to the polymer backbone via a linkage R3, where x and y represent the number of carbon atoms and fluorine atoms, respectively. In some embodiments, 1 ≤ x ≤ 9 and 1 ≤ y ≤ 19. In some embodiments, the polymer backbone is polystyrene or poly(meth)acrylate.

[0063] In some embodiments, the floating additive polymer includes a pendant photoacid generator in an amount of about 0 wt% to about 50 wt% based on the total weight of the floating additive polymer, a pendant fluorine-substituted organic group in an amount of about 1 wt% to about 90 wt%, and a pendant ALG in an amount of about 0 wt% to about 90 wt%. In some embodiments, the contents of PAG, ALG, and the fluorine-substituted organic group are all greater than 0 wt%.

[0064] Embodiments of the R1, R2, and R3 linkage units independently include non-branched, C3-C9 branched, C3-C9 cyclic or acyclic, saturated or unsaturated, aromatic or non-aromatic, unsubstituted or halogen-substituted groups of 1-9 carbons (C1-C9); or -S-; -P-; -P(O2)-; -C(=O)S-; -C(=O)O-; -O-; -N-; -C(=O)N-; -SO2O-; -SO2S-; -SO-; -SO2-; a carboxylic acid group, an ether group, a ketone group, or an ester group. In some embodiments, the R1, R2, and R3 linkage units include an iodine substituent.

[0065] The concentration range of the floating additive polymer in the photoresist material or the photoresist underlayer composition can be from about 0.1 wt% to about 50 wt% based on the total weight of the floating additive polymer and the photoresist composition or the photoresist underlayer composition. The range of the weight-average molecular weight of the floating additive polymer is about 100 to about 50,000 in some embodiments, about 400 to about 20,000 in other embodiments, about 1,000 to about 15,000 in other embodiments, and about 5,000 to about 10,000 in other embodiments.

[0066] In some embodiments, the floating additive polymer and the floating additive polymer and the photoresist material composition or the underlying material composition are dissolved in a casting solvent. The casting solvent can be propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), gamma-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), or one or more of any other suitable solvents.

[0067] Figures 11A to 11D Illustrates a photolithographic patterning operation in accordance with an embodiment of the present disclosure. In Figure 11A , the floating additive polymer 19 is mixed with the casting solvent 17 in the photoresist material, and the resulting composition is disposed on the substrate 10 according to any of the techniques disclosed herein. The coated substrate is rotated by a spin coating operation, or rotated as disclosed herein after depositing the floating additive polymer / photoresist mixture on the substrate, to phase separate the mixture, thereby forming the floating additive layer 22. During or after spinning the substrate, the photoresist layer 15 and the floating additive layer 22 are baked using a heater 330 (such as a hot plate as disclosed herein) to drive off (evaporate) the casting solvent 17 (see Figure 11B ). Subsequently, the floating additive layer 22 and the photoresist layer 15 are Figure 11C exposed to actinic radiation 45 and Figure 11D developed in Figure 11D to form the patterned photoresist layer 55. As Figure 11D shown, the floating additive layer 22 is a sacrificial layer that is removed during the development operation.

[0068] Figure 12A and Figure 12BAnother floating additive polymer according to an embodiment of the present disclosure is shown. In some embodiments, the backbone of the additive is a styrene polymer containing one or more iodine atom substituents. The iodine atoms can enhance the sensitivity of the photoresist by generating more secondary electrons. The styrene polymer increases the glass transition (Tg) value and reduces the etching rate.

[0069] Due to the presence of fluorine atoms, the fluorine-substituted organic group Rf helps the floating additive float on top of the photoresist during spin coating / drying or post-coating baking. Rf can also have a developer solubility improvement function, which helps remove the additive during the development process.

[0070] R5 is a pendant chromophore group. The pendant chromophore group absorbs out-of-band (OOB) radiation to improve LWR and LCDU.

[0071] R4 is a bulky group with a high Tg group, and the high Tg group can help control the diffusion of the photoacid generator at the top of the photoresist, which improves the resist profile in some embodiments. In other embodiments, R4 is an acid generating group, a base or quencher group, or a base generating group.

[0072] In some embodiments, R6 is a developer solubility promoter. The R6 developer solubility promoter undergoes a ring-opening reaction in a liquid with a pH > about 10 and is converted into a carboxylic acid that will dissolve in an aqueous developer (such as a tetramethylammonium hydroxide (TMAH) developer). In other embodiments, R6 is an acid-labile group (ALG). The R6 group increases the solubility of the floating additive layer, such that the floating additive layer is removed during development, which may reduce the aspect ratio to improve the etch window.

[0073] The floating additive polymer according to the present disclosure has two to six different monomer units selected from the following: 1) a fluorine-substituted organic group, 2) an acid generating group or a base group, 3) a high Tg acid diffusion control group, 4) a developer solubility promoter group, 5) a chromophore group (OOB control group), and 6) an acid-labile group.

[0074] In Figure 12AIn the polymers shown in the embodiments, Xa, Xb, Xc, and Xd are independently H; a fluorine atom; a C1-C20 alkyl group; a C3-C20 cycloalkyl group, a C1-C20 hydroxyalkyl group; a C1-C20 alkoxy group; a C2-C20 alkoxyalkyl group; a C2-C20 acetyl group; a C3-C20 acetylalkyl group; a C1-C20 carboxyl group; a C2-C20 alkylcarboxyl group; a C4-C20 cycloalkylcarboxyl group; a C3-C20 saturated or unsaturated hydrocarbon ring; or a C2-C20 heterocyclic group, which may be a 2-D ring or a 3-D structure; or a C6-C20 aromatic group. A1, A2, A3, and A4 are independently PhCOO-, PhO-, a C1-C20 alkyl group, a C3-C20 cycloalkyl group, a C1-C20 hydroxyalkyl group, a C1-C20 alkoxy group, a C1-C20 alkoxyalkyl group, a C1-C20 acetyl group, a C3-C20 acetylalkyl group, or a C6-C20 aromatic group. Any one of A1, A2, A3, and A4 may be unsubstituted or substituted by a halogen. In some embodiments, A1, A2, A3, and A4 absorb radiation in the wavelength range from about 10 nm to about 500 nm. In some embodiments, the PhCOO- group and the PhO- group are substituted by at least one I atom. In some embodiments, A1, A2, A3, and A4 are independently a direct bond between Rf, R4, R5, and R6 and the polymer chain, where no more than two of A1, A2, A3, and A4 are direct bonds. Ra, Rb, Rc, and Rd are independently a direct bond, an oxygen atom, a C1-C7 alkyl group, a C1-C7 carboxyl group, a C3-C7 cycloalkyl group, a C1-C7 hydroxyalkyl group, a C1-C7 alkoxy group, a C2-C7 alkoxyalkyl group, a C2-C7 acetyl group, a C3-C7 acetylalkyl group. In some embodiments, the combination of A1, A2, A3, A4, Rf, R4, R5, and R6 contains from about one to about ten aromatic rings to achieve OOB absorption and contains from about one to about ten iodine atoms to achieve EUV sensitivity. In Figure 12A In the polymers of

[0075] Due to the floating fluorine atoms, the floating additive polymer can float on top of the photoresist layer. The fluorine atoms reduce the surface energy, allowing the polymer to float more easily in some embodiments. In some embodiments, Rf is a fluoroalcohol group, which helps to make the floating additive more soluble in aqueous developers such as TMAH. In some embodiments, Rf is a C1-C9 fluorinated organic group, a C1-C9 fluoroalcohol group, a C1-C9 fluorocarbon group, a C1-C9 fluoroalkoxy group, a C1-C9 fluoroester group, a C1-C9 hydroxyfluoroester group, or a C1-C9 fluoroether group. In some embodiments, there are two or more Rf groups bonded to A1. In some embodiments, A1 is a direct bond. Some examples of monomer units containing fluorine-substituted organic groups include, but are not limited to Figure 13A and Figure 13B as shown in the embodiments. In Figure 13A , x and y represent the number of carbon atoms and fluorine atoms, respectively. In some embodiments, 1 ≤ x ≤ 9 and 1 ≤ y ≤ 19.

[0076] The pendant acid-generating and base groups can be any suitable acid-generating group, such as a photoacid generator (PAG) or a thermal acid generator (TAG); a base or quencher group; or a base-generating group, such as a thermal base generator (TBG) group or a photobase generator (PBG) group.

[0077] In some embodiments, the pendant base group is monoethanolamine, monoisopropanolamine, 2-amino-2-methyl-1-propanol, H-benzotriazole, 1,2,4-triazole, 1,8-diazabicycloundec-7-ene, -NR2, -NHR, -NR2, -C3H4O2NH2, -CH2O2NH2, -NHCH2NH2, -NHC2H4NH2, -(NH) x R x 、-(NH) x O2R x 、and -(NH) x OR x , where x = 1-8 and R is a hydrocarbon having 1 to 15 carbons.

[0078] Some examples of pendant acid-generating groups include, but are not limited to Figure 14A and Figure 14B as shown in the embodiments. Some examples of pendant base groups or pendant quencher groups include, but are not limited to Figure 14D and Figure 14E as shown in the embodiments. Some examples of monomer units containing pendant base groups include, but are not limited to Figure 14FThe embodiments shown in. Some examples of pendant TBG groups include, but are not limited to Figure 14G The embodiments shown in. Some examples of pendant PBG groups include, but are not limited to Figure 14H The embodiments shown in. In some embodiments, Figure 12A A2 or A3 in is a direct bond.

[0079] In some embodiments, Figure 12A R4 in the pendant group of is bulky or has a high Tg, which helps to control the resist profile. In some embodiments, the R4 pendant group includes 2D and 3D C6-C20 rings and fused ring structures. In some embodiments, the R4 pendant group includes an adamantyl or norbornyl group.

[0080] In some embodiments, Figure 12A R5 in the pendant group of is a chromophore that absorbs radiation in the wavelength range of about 100 nm to about 400 nm. In some embodiments, the R5 pendant group absorbs out-of-band (OOB) radiation, which can reduce lithography performance. In some embodiments, the R5 pendant group improves the LWR and LCDU of the photoresist pattern in some embodiments. In some embodiments, R5 includes phenyl, naphthyl, anthracenyl, phenanthryl, and pentacenquinonyl groups. Some examples of monomer units containing pendant chromophore groups include, but are not limited to Figure 15 The embodiments shown in.

[0081] In some embodiments, Figure 12A The R6 pendant group in is a developer solubility promoter or an acid-labile group. In some embodiments, the developer solubility promoter contains a heterocyclic structure that opens upon exposure to a liquid with a pH greater than about 10 to form a carboxylic acid that is more soluble in an aqueous alkaline developer (such as a TMAH developer), as shown in Figure 16A In some embodiments, Figure 12A The R6 pendant group in includes, but is not limited to Figure 16B The lactones shown in. In some embodiments, the R6 pendant group is an alkyl- or hydroxyalkyl-substituted lactone. In some embodiments, the lactone includes a five- or six-membered heterocycle. Some examples of monomer units including pendant developer solubility promoters include, but are not limited to Figure 16C The embodiments shown in.

[0082] In some embodiments, Figure 12A The R6 pendant group in is an acid-labile group. Some examples of the acid-labile group include, but are not limited to Figure 16D The embodiments shown in.

[0083] In some embodiments, the floating additive polymer has the following structure:

[0084]

[0085] Wherein: A is the polymer backbone, B is a pendant fluorinated organic group, C is a pendant acid - generating group, and D is a pendant base, quencher, or base - generating group.

[0086] In some embodiments, the polymer backbone is polystyrene, polyacrylate, polymethacrylate, polyethylene, polypropylene, polyvinyl chloride, polytetrafluoroethylene, polyamide, polyurethane, polyamic acid, polyimide, polyacrylonitrile, polyester, polysiloxane, polyphosphazene, and polymetallic polymer. The polymetallic polymer may comprise one or more of Ag, Cd, In, Sn, Sb, Te, Cs, Au, Hg, Tl, Pb, Bi, Po, and At. In some embodiments, the degree of polymerization is p, and p can be about 3 ≤ p ≤ about 1000.

[0087] B is a pendant fluorinated organic group, and it can be any pendant fluorinated group disclosed herein. The number of fluorinated organic groups in the floating additive polymer is q, and q can be about 2 ≤ q ≤ about 5000.

[0088] C is a pendant acid - generating group, and it can be any of the pendant acid - generating groups disclosed herein. The number of acid - generating groups in the additive is r, and r is about 2 ≤ r ≤ about 5000.

[0089] D is a pendant base, quencher, or base - generating group, and it can be any of the bases, quenchers, or base - generating groups disclosed herein. The number of bases, quenchers, or base - generating groups is s, and s can be about 2 ≤ s ≤ about 5000.

[0090] Some examples of the floating additive polymers according to the present disclosure include, but are not limited to Figure 17A , Figure 17B , Figure 17C , and Figure 17D the embodiments disclosed in

[0091] In some embodiments, the solvent is selected based on the dissolution rate of the base. Solvents suitable for the base composition include one or more selected from the group consisting of: acetonitrile, acetic acid, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), 5-15 carbon alkyl chain solvents including n-pentane, cyclohexane, 2,2-dimethylpentane, 2,4-dimethylpentane, etc.

[0092] In Figures 2 to 11D it, in some embodiments, substrate 10 includes a single crystal semiconductor layer on at least its surface portion. Substrate 10 may comprise a single crystal semiconductor material such as, but not limited to, Si, Ge, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, and InP. In some embodiments, substrate 10 is the silicon layer of a SOI (silicon-on-insulator) substrate. In certain embodiments, substrate 10 is made of crystalline Si.

[0093] Substrate 10 may include one or more buffer layers (not shown) in its surface region. The buffer layer may be used to gradually change the lattice constant from that of the substrate to that of the subsequently formed source / drain regions. The buffer layer may be formed of epitaxially grown single crystal semiconductor material such as, but not limited to, Si, Ge, GeSn, SiGe, GaAs, InSb, GaP, GaSb, InAlAs, InGaAs, GaSbP, GaAsSb, GaN, GaP, and InP. In one embodiment, a silicon germanium (SiGe) buffer layer is epitaxially grown on silicon substrate 10. The germanium concentration of the SiGe buffer layer may increase from 30 atomic % in the bottommost buffer layer to 70 atomic % in the topmost buffer layer.

[0094] In some embodiments, substrate 10 includes one or more layers of at least one metal, metal alloy, and metal nitride / sulfide / oxide / silicide having the formula MXa, where M is a metal and X is N, S, Se, O, Si, and a is from about 0.4 to about 2.5. In some embodiments, substrate 10 includes titanium, aluminum, cobalt, ruthenium, titanium nitride, tungsten nitride, tantalum nitride, and combinations thereof.

[0095] In some embodiments, substrate 10 includes having the formula MX bAt least one dielectric of silicon or metal oxide or nitride, where M is a metal or Si, X is N or O, and b ranges from about 0.4 to about 2.5. In some embodiments, substrate 10 includes silicon dioxide, silicon nitride, aluminum oxide, hafnium oxide, lanthanum oxide, and combinations thereof.

[0096] Photoresist layer 15 is a photosensitive layer that is patterned by exposure to actinic radiation. Generally, the chemical properties of the photoresist regions affected by the incident radiation vary depending on the type of photoresist used. Photoresist layer 15 can be a positive resist or a negative resist. A positive resist refers to a photoresist material that becomes soluble in a developer when exposed to actinic radiation (e.g., UV light or e-beam), while the unexposed (or less exposed) regions of the photoresist are insoluble in the developer. On the other hand, a negative resist refers to a photoresist material that becomes insoluble in a developer when exposed to actinic radiation, while the unexposed (or less exposed) regions of the photoresist are soluble in the developer. The regions of the negative resist that become insoluble upon exposure to radiation may become insoluble due to a crosslinking reaction caused by exposure to radiation. In some embodiments, the resist is a negative tone developed (NTD) resist. In an NTD resist, the portions of the photoresist layer exposed to actinic radiation do not crosslink. However, the developer is selected to selectively dissolve the unexposed portions of the photoresist layer such that the exposed portions remain on the substrate. In some embodiments, the NTD developer is an organic developer such as n-butyl acetate.

[0097] The photoresist composition used in some embodiments according to the present disclosure includes a polymer in a solvent and one or more photoactive compounds (PACs). In some embodiments, the polymer includes a hydrocarbon structure (e.g., an alicyclic hydrocarbon structure) that contains one or more groups that will decompose (e.g., acid-labile groups) or otherwise react when mixed with an acid, base, or radical generated by the PAC (as further described below). In some embodiments, the hydrocarbon structure includes repeating units that form the backbone of the polymer. This repeating unit can include acrylate, methacrylate, crotonate, vinyl ester, maleic diester, fumaric diester, itaconic diester, (meth)acrylonitrile, (meth)acrylamide, styrene, vinyl ether, combinations thereof, etc.

[0098] In some embodiments, the photoresist includes a polymer having acid-labile groups. The acid-labile groups can be Figure 16D one or more of the groups shown in

[0099] In some embodiments, the specific structures of the repeating units for the hydrocarbon structures include one or more of the following: methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, acetyloxyethyl acrylate, phenyl acrylate, 2-hydroxyethyl acrylate, 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, cyclohexyl acrylate, benzyl acrylate, 2-alkyl-2-adamantyl (meth)acrylate or dialkyl(1-adamantyl)methyl (meth)acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, n-hexyl methacrylate, 2-ethylhexyl methacrylate, acetyloxyethyl methacrylate, phenyl methacrylate, 2-hydroxyethyl methacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-(2-methoxyethoxy)ethyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-acetyloxy-2-hydroxypropyl methacrylate, 3-chloroacetyloxy-2-hydroxypropyl methacrylate, butyl crotonate, hexyl crotonate, etc. Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, dimethyl maleate, diethyl maleate, dibutyl maleate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, acrylamide, methylacrylamide, ethylacrylamide, propylacrylamide (methyl acrylamide), n-butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, 2-methoxyethylacrylamide, dimethylacrylamide, diethylacrylamide, phenylacrylamide, benzylacrylamide, methacrylamide (methacrylamide), methylmethacrylamide, ethylmethacrylamide, propylmethacrylamide, n-butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, 2-methoxyethylmethacrylamide, dimethylmethacrylamide, diethylmethacrylamide, phenylmethacrylamide, benzylmethacrylamide, methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, methoxystyrene, butoxystyrene, acetyloxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, vinyl benzoate methyl ester, α-methylstyrene, maleimide, vinyl pyridine, vinyl pyrrolidone, vinyl carbazole, combinations of these, etc.

[0100] In some embodiments, the repeating unit of the hydrocarbon structure further has a monocyclic or polycyclic hydrocarbon structure substituted therein, or the monocyclic or polycyclic hydrocarbon structure is the repeating unit to form an alicyclic hydrocarbon structure. In some embodiments, specific examples of the monocyclic structure include bicycloalkanes, tricycloalkanes, tetracycloalkanes, cyclopentane, cyclohexane, etc. In some embodiments, specific examples of the polycyclic structure include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0101] A group that will decompose is attached to the hydrocarbon structure such that the group will react with the acid / base / free radical generated by the PAC during exposure. A group that reacts with an acid is called an acid-labile group. In some embodiments, the group to be decomposed is a carboxylic acid group, a fluorinated alcohol group, a phenolic alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, a tris(alkylsulfonyl)methylene group, a combination thereof, etc. Specific groups for the fluorinated alcohol group include fluorinated hydroxyalkyl groups, such as hexafluoroisopropanol groups in some embodiments. Specific groups for the carboxylic acid group include acrylic acid groups, methacrylic acid groups, etc.

[0102] In some embodiments, the acid-labile group (ALG) decomposes under the action of the acid generated by the photoacid generator, leaving a carboxylic acid group hanging on the polymer resin chain, as shown in the ALG deprotection reaction:

[0103]

[0104] In some embodiments, the polymer further comprises other groups attached to the hydrocarbon structure, and the groups help to improve various properties of the polymerizable resin. For example, incorporating a lactone group into the hydrocarbon structure helps to reduce the amount of line edge roughness after the photoresist has been developed, thereby helping to reduce the number of defects that occur during development. In some embodiments, the lactone group includes a ring having five to seven members, but any suitable lactone structure can alternatively be used for the lactone group.

[0105] The individual components of the photoresist are placed in a solvent to aid in mixing and dispensing the photoresist. To aid in the mixing and dispensing of the photoresist, the solvent is selected at least in part based on the materials chosen for the polymer resin and the PAC. In some embodiments, the solvent is selected such that the polymer resin and the PAC can be uniformly dissolved in the solvent and dispensed onto the layer to be patterned.

[0106] In some embodiments, the polymer comprises groups that can help increase the adhesion of the photoresist layer 15 to the underlying structure (e.g., the substrate 10). Polar groups can be used to assist in increasing adhesion. Suitable polar groups include hydroxyl groups, cyano groups, etc., but any suitable polar group can alternatively be used.

[0107] Optionally, in some embodiments, the polymer comprises one or more alicyclic hydrocarbon structures that also do not contain groups that will decompose in some embodiments. In some embodiments, hydrocarbon structures that do not contain groups that will decompose include, for example, structures such as 1 - adamantyl (meth)acrylate, tricyclodecyl (meth)acrylate, cyclohexyl (meth)acrylate, combinations thereof, and the like. In some embodiments, the photoresist composition comprises one or more photoactive compounds (PACs).

[0108] In some embodiments, the PACs include photoacid generators, photobase generators, photo - decomposable bases, radical generators, etc. In some embodiments where the PAC is a photoacid generator, the PAC includes halo - triazines, onium salts, diazonium salts, aromatic diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonates, oxime sulfonates, diazo - disulfones, disulfones, o - nitrobenzyl sulfonates, sulfonated esters, halo - sulfonyloxy dicarboximides, diazo - disulfones, α - cyano - oxime sulfonates, imide sulfonates, ketone diazo - sulfones, sulfonyl diazo - esters, 1,2 - bis(arylsulfonyl)hydrazines, nitrobenzyl esters, and s - triazine derivatives, combinations thereof, and so on.

[0109] Specific examples of photoacid generators include α - (trifluoromethylsulfonyloxy) - bicyclo[2.2.1]hept - 5 - ene - 2,3 - dicarboximide (MDT), N - hydroxy - naphthalimide (DDSN), benzoin tosylate, tert - butylphenyl - α - (p - toluenesulfonyloxy) - acetate, and tert - butyl - α - (p - toluenesulfonyloxy) - acetate, triaryl sulfonium and diaryl iodonium hexafluoroantimonates, hexafluoroarsenates, trifluoromethanesulfonates, iodonium perfluorooctanesulfonates, N - camphorsulfonyloxy naphthalimide, N - pentafluorophenylsulfonyloxy naphthalimide, ionic iodonium sulfonates (such as diaryl iodonium (alkyl or aryl) sulfonates and bis(di - tert - butylphenyl)iodonium camphenyl sulfonate, etc.), perfluoroalkane sulfonates (such as perfluoropentane sulfonate, perfluorooctane sulfonate, perfluoromethane sulfonate), aryl (such as phenyl or benzyl) trifluoromethanesulfonates (such as triphenylsulfonium trifluoromethanesulfonate or bis(tert - butylphenyl)iodonium trifluoromethanesulfonate); pyrogallol derivatives (such as trimethanesulfonate of pyrogallol), trifluoromethanesulfonate of hydroxyimide, α,α' - bis - sulfonyl diazomethane, sulfonates of nitro - substituted benzyl alcohols, naphthoquinone - 4 - diazides, alkyl disulfones, etc.

[0110] In some embodiments where the PAC is a free radical generator, the PAC includes n-phenylglycine; aromatic ketones, including benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone, N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 3,3'-dimethyl-4-methoxybenzophenone, p,p'-bis(dimethylamino)benzophenone, p,p'-bis(diethylamino)benzophenone; anthraquinones, 2-ethylanthraquinone; naphthoquinones; and phenanthraquinones; benzoins, including benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin phenyl ether, methyl benzoin and ethyl benzoin; benzyl derivatives, including dibenzyl, benzyl diphenyl disulfide and benzyl dimethyl ketal; acridine derivatives, including 9-phenylacridine and 1,7-bis(9-acridinyl)heptane; thioxanthones, including 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone and 2-isopropylthioxanthone; acetophenones, including 1,1-dichloroacetophenone, p-tert-butyl dichloroacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and 2,2-dichloro-4-phenoxyacetophenone; 2,4,5-triaryl imidazole dimers, including 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4-bis(p-methoxyphenyl)-5-phenylimidazole dimer, 2-(2,4-dimethoxyphenyl)-4,5-diphenylimidazole dimer and 2-(p-methylthiophenyl)-4,5-diphenylimidazole dimer; combinations thereof, and the like.

[0111] In some embodiments, the solvent is an organic solvent and includes one or more any suitable solvents, such as ketones, alcohols, polyols, ethers, glycol ethers, cyclic ethers, aromatic hydrocarbons, esters, propionates / esters, lactates, lactic esters, alkylene glycol monoalkyl ethers, alkyl lactates, alkoxy propionate alkyl esters, cyclic lactones, monoketone compounds containing a ring, alkylene carbonates, alkoxy acetic acid alkyl esters, pyruvic acid alkyl esters, lactate esters, ethylene glycol alkyl ether acetates, diethylene glycol, propylene glycol alkyl ether acetates, alkylene glycol alkyl ether esters, alkylene glycol monoalkyl esters, and the like.

[0112] The photoresist composition may also include a variety of other additives that assist the photoresist in achieving high resolution. For example, some embodiments of the photoresist also include a surfactant to help improve the ability of the photoresist to coat the surface to which it is applied. Other additives added to some embodiments of the photoresist are stabilizers that help prevent the undesired diffusion of the acid generated during the exposure of the photoresist; dissolution inhibitors that are used to help control the dissolution of the photoresist during development; plasticizers that are used to reduce delamination and cracking between the photoresist and the underlying layer (e.g., the layer to be patterned); and adhesion promoters.

[0113] In some embodiments, the photoresist layer 15 is made of a metal photoresist composition that includes a first compound or first precursor and a second compound or second precursor combined in a vapor state. As Figure 18A shown, the first precursor or first compound is an organometal having the following formula: M a R b X c , where M is at least one of Sn, Bi, Sb, In, Te, Ti, Zr, Hf, V, Co, Mo, W, Al, Ga, Si, Ge, P, As, Y, La, Ce, or Lu; and R is a substituted or unsubstituted alkyl, alkenyl, or carboxylic acid group. In some embodiments, M is selected from the group consisting of Sn, Bi, Sb, In, Te, and combinations thereof. In some embodiments, R is a C3-C6 alkyl, alkenyl, or carboxylic acid. In some embodiments, R is selected from the group consisting of propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, tert-pentyl, hexyl, isohexyl, sec-hexyl, tert-hexyl, and combinations thereof. X is a ligand, ion, or other moiety that is reactive with the second compound or second precursor; and in some embodiments, 1 ≤ a ≤ 2, b ≥ 1, c ≥ 1, and b + c ≤ 5. In some embodiments, the alkyl, alkenyl, or carboxylic acid group is substituted with one or more fluorine groups. In some embodiments, as Figure 18A shown, the organometal precursor is a dimer, where each monomer unit is linked by an amine group and has the following formula: M a R b X c , as defined above.

[0114] In some embodiments, R is an alkyl, such as C n H 2n+1 , where n ≥ 3. In some embodiments, R is fluorinated, such as having the formula C n F x H((2n+1)-x) 。In some embodiments, R has at least one β-hydrogen or β-fluorine. In some embodiments, R is selected from the group consisting of isopropyl, n-propyl, tert-butyl, isobutyl, n-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, and sec-pentyl, and combinations thereof.

[0115] In some embodiments, X is any moiety that is readily replaceable by a second compound or second precursor to form an M-OH moiety, such as a moiety selected from the group consisting of amines, including dialkylamino and monoalkylamino; alkoxy; carboxylic acid, halogen, and sulfonic acid. In some embodiments, the sulfonic acid group is substituted with one or more amine groups. In some embodiments, the halide ion is one or more selected from the group consisting of F, Cl, Br, and I. In some embodiments, the sulfonic acid group includes a substituted or unsubstituted C1-C3 group.

[0116] In some embodiments, the first organometallic compound or first organometallic precursor comprises a metal core M + and a ligand L attached to the metal core M + as Figure 18B shown. In some embodiments, the metal core M + is a metal oxide. In some embodiments, the ligand L comprises a C3-C12 aliphatic or aromatic group. The aliphatic or aromatic group may be straight-chain or branched-chain, having a cyclic or acyclic saturated pendant group containing 1-9 carbons, including alkyl groups, alkenyl groups, and phenyl groups. The branched-chain group may be further substituted with oxygen or halogen. In some embodiments, the C3-C12 aliphatic or aromatic group includes a heterocyclic group. In some embodiments, the C3-C12 aliphatic or aromatic group is attached to the metal via an ether bond or an ester linkage. In some embodiments, the C3-C12 aliphatic or aromatic group includes nitrile and sulfonic acid substituents.

[0117] In some embodiments, the organometallic precursor or organometallic compound includes sec - hexyltris(dimethylamino)tin, tert - hexyltris(dimethylamino)tin, iso - hexyltris(dimethylamino)tin, n - hexyltris(dimethylamino)tin, sec - pentyltris(dimethylamino)tin, tert - pentyltris(dimethylamino)tin, iso - pentyltris(dimethylamino)tin, n - pentyltris(dimethylamino)tin, sec - butyltris(dimethylamino)tin, tert - butyltris(dimethylamino)tin, iso - butyltris(dimethylamino)tin, n - butyltris(dimethylamino)tin, isopropyltris(dimethylamino)tin, n - propyltris(diethylamino)tin, and similar alkyl(tris)(tert - butoxy)tin compounds, including sec - hexyltris(tert - butoxy)tin, tert - hexyltris(tert - butoxy)tin, iso - hexyltris(tert - butoxy)tin, n - hexyltris(tert - butoxy)tin, sec - pentyltris(tert - butoxy)tin, tert - pentyltris(tert - butoxy)tin, iso - pentyltris(tert - butoxy)tin, n - pentyltris(tert - butoxy)tin, tert - butyltris(tert - butoxy)tin, iso - butyltris(butoxy)tin, n - butyltris(butoxy)tin, sec - butyltris(butoxy)tin, isopropyltris(dimethylamino)tin, or n - propyltris(butoxy)tin. In some embodiments, the organometallic precursor or organometallic compound is fluorinated. In some embodiments, the boiling point of the organometallic precursor or compound is below about 200 °C.

[0118] In some embodiments, the first compound or first precursor includes one or more unsaturated bonds that can coordinate with functional groups (such as hydroxyl groups) on the surface of the intermediate bottom layer or substrate to improve the adhesion of the photoresist layer to the substrate or bottom layer.

[0119] In some embodiments, the second precursor or second compound is at least one of an amine, a borane, a phosphine, or water. In some embodiments, the amine has the formula N p H n X m , where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 when p is 1, and n + m = 4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br, and I. In some embodiments, the borane has the formula B p H n X m , where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 when p is 1, and n + m = 4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br, and I. In some embodiments, the phosphine has the formula P p H n X m , where 0 ≤ n ≤ 3, 0 ≤ m ≤ 3, n + m = 3 when p is 1, or n + m = 4 when p is 2, and each X is independently a halogen selected from the group consisting of F, Cl, Br, and I.

[0120] Figure 18C Examples of organometallic precursors according to embodiments of the present disclosure are shown. In Figure 18C wherein Bz is a phenyl group.

[0121] In some embodiments, the operation S125 of forming the photoresist layer is performed by a vapor deposition operation. In some embodiments, the vapor deposition operation includes atomic layer deposition (ALD) and chemical vapor deposition (CVD). In some embodiments, the ALD includes plasma-enhanced atomic layer deposition (PE-ALD); the CVD includes plasma-enhanced chemical vapor deposition (PE-CVD), metal-organic chemical vapor deposition (MO-CVD), atmospheric pressure chemical vapor deposition (AP-CVD), and low pressure chemical vapor deposition (LP-CVD).

[0122] Figure 19 A resist layer deposition apparatus 200 according to some embodiments of the present disclosure is shown. In some embodiments, the deposition apparatus 200 is an ALD or CVD apparatus. The deposition apparatus 200 includes a vacuum chamber 205. A substrate support table 210 in the vacuum chamber 205 supports a substrate 10, such as a silicon wafer. In some embodiments, the substrate support table 210 includes a heater or a chiller. In some embodiments, a first precursor or compound gas supply 220 and a carrier gas / purge gas supply 225 are connected to an inlet 230 in the chamber via a gas line 235, and a second precursor or compound gas supply 240 and the carrier gas / purge gas supply 225 are connected to another inlet 230' in the chamber via another gas line 235'. The chamber is evacuated, and excess reactants and reaction by-products are removed through a vacuum pump 245 via an outlet 250 and an exhaust line 255. In some embodiments, the flow rate or pulse of the precursor gas and the carrier gas / purge gas, the evacuation of the excess reactants and reaction by-products, the pressure inside the vacuum chamber 205, and the temperature of the vacuum chamber 205 or the wafer support table 210 are controlled by a controller 260 configured to control each of these parameters.

[0123] In some embodiments, depositing a photoresist layer includes combining a first compound or first precursor with a second compound or second precursor in a vapor state to form a photoresist composition. In some embodiments, the first compound or first precursor and the second compound or second precursor of the photoresist composition are introduced into the deposition chamber 205 (CVD chamber) via inlets 230, 230' approximately simultaneously. In some embodiments, the first compound or first precursor and the second compound or second precursor are introduced into the deposition chamber 205 (ALD chamber) in an alternating manner via inlets 230, 230', i.e., first one compound or precursor is introduced, then the other compound or precursor is introduced, and then the introduction of one compound or precursor and the other compound or precursor is repeated alternately subsequently.

[0124] In some embodiments, the temperature of the deposition chamber 205 during the deposition operation ranges from about 30°C to about 400°C, and in other embodiments, the temperature of the deposition chamber 205 ranges from about 50°C to about 250°C. In some embodiments, the pressure in the deposition chamber 205 during the deposition operation ranges from about 5 mTorr to about 100 mTorr, and in other embodiments, the pressure in the deposition chamber 205 ranges from about 100 mTorr to about 10 mTorr. In some embodiments, the plasma power is less than about 1000 W. In some embodiments, the plasma power ranges from about 100 W to about 900 W. In some embodiments, the flow rate of the first compound or precursor and the second compound or precursor ranges from about 100 sccm to about 1000 sccm. In some embodiments, the flow rate ratio of the organometallic compound precursor to the second compound or precursor ranges from about 1:1 to about 1:5. In some embodiments, when the operating parameters exceed the above ranges, an unsatisfactory photoresist layer is produced. In some embodiments, the formation of the photoresist layer occurs in a single chamber (one-pot layer formation).

[0125] In a CVD process according to some embodiments of the present disclosure, two or more gaseous streams of an organometallic precursor and a second precursor are introduced into a deposition chamber 205 of a CVD apparatus in separate inlet paths 230, 235 and 230', 235', where they mix in the gas phase and react to form a reaction product. In some embodiments, the streams are introduced using separate injection inlets 230, 230' or a dual-plenum showerhead. The deposition apparatus is configured such that the streams of the organometallic precursor and the second precursor mix in the chamber, allowing the organometallic precursor and the second precursor to react to form a reaction product. Without limiting the mechanism, function, or utility of the present disclosure, it is believed that the molecular weight of the product from the gas-phase reaction becomes heavier and then condenses or otherwise deposits onto the substrate 10.

[0126] In some embodiments, an ALD process is used to deposit a photoresist layer. During ALD, a layer is grown on the substrate 10 by exposing the surface of the substrate to alternating gaseous compounds (or precursors). Different from CVD, the precursors are introduced as a series of consecutive, non-overlapping pulses. In each of these pulses, the precursor molecules react with the surface in a self-limiting manner, so the reaction terminates once all the reaction sites on the surface are consumed. Thus, the maximum amount of material deposited on the surface after a single exposure to all the precursors (a so-called ALD cycle) is determined by the nature of the precursor-surface interaction.

[0127] In one embodiment of the ALD process, in the first half-reaction, an organometallic precursor is pulsed to deliver a metal-containing precursor to the surface of the substrate 10. In some embodiments, the organometallic precursor reacts with a suitable underlying species (such as OH or NH functional groups on the surface of the substrate) to form a new self-saturated surface. In some embodiments, excess unused reactants and reaction by-products are removed by evacuation using a vacuum pump 245 and / or by flowing an inert purge gas. Then, in some embodiments, a second precursor (such as ammonia (NH3)) is pulsed into the deposition chamber. NH3 reacts with the organometallic precursor on the substrate to obtain a reaction product photoresist on the substrate surface. The second precursor also forms self-saturated bonds with the underlying reactive species to provide another self-limiting and saturated second half-reaction. In some embodiments, a second purge is performed to remove unused reactants and reaction by-products. The pulses of the first precursor and the second precursor are alternated with intervening purge operations until the desired thickness of the photoresist layer is reached.

[0128] In some embodiments, a carrier gas is used to transport a first compound and a second compound or precursor into deposition chamber 205. The carrier gas, purge gas, deposition gas, or other process gas may include nitrogen, hydrogen, argon, neon, helium, or a combination thereof.

[0129] In some embodiments, the photoresist layer 15 is formed to a thickness of about 5 nm to about 50 nm, and in other embodiments to a thickness of about 10 nm to about 30 nm. Those of ordinary skill in the art will recognize that additional thickness ranges within the above specified ranges are contemplated and within the present disclosure. The thickness can be evaluated using non-contact methods of x-ray reflectivity and / or ellipsometry based on the optical properties of the photoresist layer. In some embodiments, the thickness of each photoresist layer is relatively uniform to facilitate processing. In some embodiments, the variation in the thickness of the deposited photoresist layer from the average thickness is no greater than ±25%, and in other embodiments the thickness of each photoresist layer varies from the average photoresist layer thickness by no greater than ±10%. In some embodiments, such as for high uniformity deposition on a larger substrate, the photoresist layer uniformity can be evaluated, excluding a 1 cm edge, i.e., the layer uniformity of portions of the coating within 1 cm of the edge is not evaluated. Those of ordinary skill in the art will recognize that additional ranges within the above specified ranges are contemplated and within the present disclosure.

[0130] In some embodiments, the organometallic compound includes tin (Sn), antimony (Sb), bismuth (Bi), indium (In), and / or tellurium (Te) as metal components; however, the present disclosure is not limited to these metals. In other embodiments, additional suitable metals include titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), cobalt (Co), molybdenum (Mo), tungsten (W), aluminum (Al), gallium (Ga), silicon (Si), germanium (Ge), phosphorus (P), arsenic (As), yttrium (Y), lanthanum (La), cerium (Ce), lutetium (Lu), or a combination thereof. The additional metals can be used as an alternative or supplement to Sn, Sb, Bi, In, and / or Te.

[0131] The particular metal used can significantly affect the absorption of radiation. Thus, the metal component can be selected based on the desired radiation and absorption cross-section. Tin, antimony, bismuth, tellurium, and indium provide strong absorption of extreme ultraviolet light at 13.5 nm. Hafnium provides good absorption of electron beams and extreme UV radiation. Metal compositions containing titanium, vanadium, molybdenum, or tungsten have strong absorption at longer wavelengths to provide sensitivity, for example, to ultraviolet light at a wavelength of 248 nm.

[0132] In some embodiments, the resist layer 15 is formed by mixing an organometallic compound in a solvent to form a resist composition and dispensing the resist composition onto the substrate 10. To facilitate the mixing and dispensing of the photoresist, the solvent is selected at least in part based on the materials selected for the metal resist. In some embodiments, the solvent is selected such that the organometallic dissolves uniformly into the solvent and is dispensed onto the layer to be patterned.

[0133] In some embodiments, the resist solvent is an organic solvent and includes any suitable solvent, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), formic acid, acetic acid, propionic acid, butyric acid, and the like.

[0134] Those of ordinary skill in the art will recognize that the materials listed and described above as examples of materials that can be used as solvent components for photoresists are merely illustrative and are not intended to limit the embodiments. Instead, any suitable material that will dissolve the metal photoresist material can be used to assist in the mixing and application of the photoresist. All such materials are fully intended to be included within the scope of the embodiments.

[0135] In some embodiments, Figure 19The resist layer deposition apparatus 200 shown is also used to apply a floating additive composition to the substrate 10, the BARC layer 20, or the photoresist layer 15. The floating additive composition supply 260 and the carrier gas supply 265 are connected via a supply line 270 to an inlet 275 within the chamber. In some embodiments, the inlet 275 is configured to deliver the floating additive composition as a liquid spray or as an atomized vapor. In some embodiments, a purge gas supply 280 is connected via a gas supply line 285 to a purge gas inlet 290. In some embodiments, the chamber 205 is purged with the purge gas prior to introducing the floating additive composition into the chamber 205. In some embodiments, the floating additive composition is introduced into the chamber 205 prior to forming the photoresist layer 15, and in other embodiments, the floating additive composition is added after forming the photoresist layer 15. In other embodiments, the floating additive composition is introduced into the chamber 205 substantially simultaneously with the introduction of the photoresist components, and the floating additive composition is directly applied to the photoresist layer 15 while the photoresist layer 15 is being formed. In some embodiments, the flow rates of the floating additive composition, the carrier gas, or the purge gas are also controlled by the controller 260, which is configured to control each of these parameters, as well as the flow rates of the precursor gases and the carrier / purge gases, the evacuation of excess reactants and reaction by-products, the pressure within the vacuum chamber 205, and the temperature of the vacuum chamber 205 or the wafer support stage 210.

[0136] In some embodiments, the floating additive composition and the photoresist composition are applied to the substrate 10 to form a photoresist layer 15 treated with the base composition, as Figure 2 , Figure 3A , Figure 4A and Figure 4B shown. In some embodiments, processes such as spin coating, dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, lamination, extrusion coating, CVD, ALD, PVD, combinations thereof, etc. are used to apply the floating additive composition and the photoresist composition. In some embodiments, the thickness of the photoresist layer 15 ranges from about 10 nm to about 300 nm.

[0137] In some embodiments, after the photoresist layer 15 has been formed on the substrate 10, the pre-exposure bake and cool operations S140 are performed as described herein (see Figure 1 ), and as discussed herein and as Figure 1 , Figure 5A and Figure 5BAs shown, the photoresist layer 15 is selectively exposed to form an exposed area 50 and an unexposed area 52. In some embodiments, radiation exposure is performed by placing a substrate coated with photoresist in a lithography tool. In Figure 5A and Figure 5B the embodiments shown, the lithography tool includes a photomask 30, 65, optics, an exposure radiation source for providing radiation 45, 97 for exposure, and a movable stage for supporting and moving the substrate under the exposure radiation.

[0138] Subsequently, the selectively exposed photoresist layer 15 is post-exposure baked / cooled and then developed, as Figure 6 shown. In some embodiments of the present disclosure, the developer composition 57 contains an ammonium compound. In some embodiments, suitable bases include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide and combinations thereof; or inorganic bases selected from the group consisting of ammonium hydroxide, ammonium sulfamate, ammonium carbamate, NaOH, KOH, LiOH, Ca(OH)2, Ba(OH)2, Na2CO3, NH4OH, Mg(OH)2, RbOH, CsOH, Sr(OH)2, and combinations thereof, or inorganic bases selected from the group consisting of ammonia, ammonium hydroxide, ammonium sulfamate, ammonium carbamate, and combinations thereof. In some embodiments, the concentration of the base is about 1 ppm to about 30 wt% based on the total weight of the developer composition.

[0139] In some embodiments, the developer composition contains water or ethylene glycol at a concentration of about 0.001 wt% to about 30 wt% based on the total weight of the developer composition.

[0140] In some embodiments, the photoresist developer composition contains a surfactant in a concentration range of about 0.001 wt% to less than about 5 wt% based on the total weight of the developer composition to increase solubility and reduce surface tension on the substrate. In other embodiments, the concentration range of the surfactant is about 0.01 wt% to about 1 wt% based on the total weight of the developer composition.

[0141] When the concentration of the developer composition components exceeds the disclosed range, the performance and development efficiency of the developer composition may be reduced, resulting in an increase in photoresist residues and scum in the photoresist pattern, and an increase in line width roughness and line edge roughness.

[0142] In some embodiments, the developer 57 is applied to the photoresist layer 15 using a spin coating process. In the spin coating process, the developer 57 is applied to the photoresist layer 15 from above the photoresist layer while the substrate coated with photoresist is rotating, as Figure 7As shown. In some embodiments, while rotating the substrate 10 coated with photoresist at a speed between about 100 rpm and about 2000 rpm, the developer 57 is supplied at a rate between about 5 ml / min and about 800 ml / min. In some embodiments, the temperature of the developer during the developing operation is between about 20 °C and about 75 °C. In some embodiments, the developing operation lasts between about 10 seconds and about 10 minutes.

[0143] Although the spin coating operation is a suitable method for developing the photoresist layer 15 after exposure, it is intended to be illustrative and not intended to limit the embodiments. Instead, any suitable developing operation can be alternatively used, including dipping processes, immersion processes, and spraying methods. All such developing operations are included within the scope of the embodiments.

[0144] During the developing process, the developer composition 57 dissolves the exposed portions of the photoresist regions exposed to radiation, the upper floating additive layer 22, and the lower floating additive layer 20, thereby Figure 7 as shown, exposing the surface of the substrate 10 and leaving well-defined unexposed photoresist regions 52, having improved clarity when compared to conventional lithography techniques.

[0145] After the developing operation S170, the remaining developer is removed from the patterned photoresist-covered substrate. In some embodiments, a spin drying process is used to remove the remaining developer, but any suitable removal technique can be used. After the photoresist layer 15 is developed and the remaining developer is removed, additional processing is performed while the patterned photoresist layer 50 is in place. For example, in some embodiments, an etching operation using dry or wet etching is performed to transfer the pattern 50 of the photoresist layer to the underlying substrate 10, thereby forming Figure 8 as shown, a groove 55'. The substrate 10 has a different etching resistance than the photoresist layer 15. In some embodiments, the etchant has a higher selectivity for the substrate 10 than for the photoresist layer 15.

[0146] In some embodiments, the controller 260 is a computer system. Figure 20A and Figure 20B shows a computer system 260 for controlling the deposition apparatus 200 and its components according to various embodiments of the present disclosure. Figure 20AFIG. 0 is a schematic diagram of a computer system 260 that controls the deposition apparatus 200 and its components. In some embodiments, the computer system 260 is programmed to monitor and control the flow rates of precursor gases and carrier / purge gases, the evacuation of excess reactants and reaction by-products, the pressure within the vacuum chamber 205, the temperature of the vacuum chamber 205 or the wafer support stage 210, and the flow rate of the base composition.

[0147] As Figure 20A shown, in some embodiments, the computer system 260 is provided with a computer 1001 that includes an optical disc read-only memory (e.g., CD-ROM or DVD-ROM) drive 1005 and a disk drive 1006, a keyboard 1002, a mouse 1003 (or other similar input device), and a monitor 1004.

[0148] Figure 20B FIG. 9 is a diagram showing the internal configuration of the computer system 260. In Figure 20B addition to the optical disc drive 1005 and the disk drive 1006, the computer 1001 is further provided with one or more processors 1011, such as a micro-processor unit (MP) or a central processing unit (CPU); a read-only memory (ROM) 1012 in which programs, such as a bootstrap program, are stored; a random access memory (RAM) 1013 that is connected to the processor 1011 and temporarily stores commands of application programs therein and is provided with a temporary electronic storage area; a hard disk 1014 in which application programs, operating system programs, and data are stored; and a data communication bus 1015 that connects the processor 1011, the ROM 1012, etc. Note that the computer 1001 may include a network card (not shown) that is used to provide a connection to a computer network (e.g., a local area network (LAN), a wide area network (WAN), or any other useful computer network) to transmit data used by the computer system 260 and the deposition apparatus 200. In various embodiments, the controller 260 communicates with the deposition apparatus 200 and its components via a wireless or hardwired connection.

[0149] A program for causing a computer system 260 to execute a method for controlling a deposition apparatus 200 and its components is stored on an optical disc 1021 or a magnetic disk 1022, which is inserted into an optical disc drive 1005 or a magnetic disk drive 1006 and transferred to a hard disk 1014. Alternatively, the program is transmitted to the computer system 500 via a network (not shown) and stored in the hard disk 1014. When executed, the program is loaded into the RAM 1013. In various embodiments, the program is loaded from the optical disc 1021 or the magnetic disk 1022, or directly from the network.

[0150] The stored program does not necessarily have to include, for example, an operating system (OS) or a third-party program to cause the computer 1001 to execute the methods disclosed herein. In some embodiments, the program may only contain a command portion to call appropriate functions (modules) in a controlled manner and obtain desired results. In various embodiments described herein, the controller 260 communicates with the deposition apparatus 200 to control various functions of the deposition apparatus.

[0151] In various embodiments, the controller 260 is coupled to the deposition apparatus 200. The controller 260 is configured to provide control data to these system components and receive process and / or status data from these system components. For example, in some embodiments, the controller 260 includes a microprocessor, a memory (e.g., volatile or non-volatile memory), and digital I / O ports that are capable of generating inputs sufficient to transfer and activate a processing system, as well as monitoring control voltages from the deposition apparatus 200. In addition, the program stored in the memory is used to control the above components of the deposition apparatus 200 according to a process recipe. In addition, the controller 260 is configured to analyze the process and / or status data, compare the process and / or status data with target process and / or status data, and use the comparison to change the process and / or control system components. In addition, the controller 260 is configured to analyze the process and / or status data, compare the process and / or status data with historical process and / or status data, and use the comparison to predict, prevent, and / or declare a fault or an alarm.

[0152] As described above, the executed program causes the processor or computer 260 to measure the pressure in the coolant or cooling fluid line or conduit, determine the pressure difference between the inflow line and the outflow line of the coolant or cooling fluid, determine whether the pressure difference is greater than a threshold value, and when the pressure difference is greater than the stored threshold value, adjust the valve to change the flow rate of the coolant or cooling fluid to reduce the pressure difference. In some embodiments, the executed program causes the processor or computer 500 to measure the pressure in the coolant or cooling fluid line or conduit periodically (e.g., every second, every 10 seconds, every 20 seconds, or every 30 seconds).

[0153] In some embodiments, before forming the photoresist layer 15 or the floating additive layers 20, 22, a layer to be patterned (target layer) 60 is disposed above the substrate, as Figure 21 , Figure 22A , Figure 22B , Figure 23A , and Figure 23B shown. In some embodiments, a pre-exposure bake / cool operation S140 is performed to dry and cure the photoresist layer 15 discussed herein with reference Figure 1 to FIG. 4. In some embodiments, the target layer 60 is a metallization layer or a dielectric layer (e.g., a passivation layer) disposed above the metallization layer. In embodiments where the target layer 60 is a metallization layer, the target layer 60 is formed of a conductive material using metallization processes and metal deposition techniques, including chemical vapor deposition, atomic layer deposition, and physical vapor deposition (sputtering). Similarly, if the target layer 60 is a dielectric layer, the target layer 60 is formed by dielectric layer formation techniques, including thermal oxidation, CVD, ALD, and PVD.

[0154] Subsequently, in operation S150, the photoresist layer 15 is selectively exposed to actinic radiation 45, 97 to form exposed regions 50 and unexposed regions 52 in the photoresist layer, as Figure 24A and Figure 24B shown and described herein in connection with Figure 5A and Figure 5B .

[0155] As Figure 21 shown, a post-exposure bake / cool operation S160 is subsequently performed, as described herein.

[0156] As Figure 25 shown, subsequently, in operation S170, the selectively exposed photoresist layer 50, 52 is developed by dispensing developer 57 from dispenser 62 to form a pattern of photoresist openings 55, as Figure 26 shown. The developing operation is in connection with the present reference Figure 6 andFigure 7 The development operation explained is similar.

[0157] Then, as Figure 27 shown, the pattern 55 in the photoresist layer 15 is transferred to the target layer 60 using an etching operation, and the photoresist layer is removed as explained in the reference Figure 8 to form the pattern 55' in the target layer 60.

[0158] Other embodiments include other operations before, during, or after the above operations. In some embodiments, the disclosed method includes forming a fin field effect transistor (FinFET) structure. In some embodiments, a plurality of active fins are formed on a semiconductor substrate. Such embodiments further include etching the substrate through the openings of a patterned hard mask to form trenches in the substrate; filling the trenches with a dielectric material; performing a chemical mechanical polishing (CMP) process to form shallow trench isolation (STI) features; and epitaxially growing or recessing the STI features to form fin-shaped active regions. In some embodiments, one or more gate electrodes are formed on the substrate. Some embodiments include forming gate spacers, doped source / drain regions, contacts for gate / source / drain features, etc. In other embodiments, the target pattern is formed as a metal wire in a multi-level interconnect structure. For example, the metal wire can be formed in an inter-layer dielectric (ILD) layer of a substrate, and the ILD layer has been etched to form a plurality of trenches. The trenches can be filled with a conductive material, such as a metal; and a process such as chemical mechanical planarization (CMP) can be used to polish the conductive material to expose the patterned ILD layer, thereby forming the metal wire in the ILD layer. The above are non-limiting examples of devices / structures that can be fabricated and / or improved using the methods described herein.

[0159] In some embodiments, active components such as diodes, field-effect transistors (FETs), metal-oxide semiconductor field-effect transistors (MOSFETs), complementary metal-oxide semiconductor (CMOS) transistors, bipolar transistors, high-voltage transistors, high-frequency transistors, sheet FETs (such as nanosheet FETs), FinFETs, gate-all-around FETs (GAA FETs), other three-dimensional (3D) FETs, other memory cells, and combinations thereof are formed in accordance with embodiments of the present disclosure.

[0160] Compared with traditional methods, the novel floating additive layer application technology and semiconductor manufacturing method according to the present disclosure provide higher semiconductor device feature density and fewer defects in a more efficient process. The novel technology and method provide a floating additive layer that satisfies the following functions: (1) a thin phase separation layer about 5 nm thick, (2) improved out-of-band (OOB) radiation absorbance, (3) a high glass transition temperature (Tg), (4) high developer solubility, (5) high sensitivity to extreme ultraviolet (EUV) and e-beam radiation, (6) high etch resistance, and (7) high molecular weight.

[0161] The floating additive layer according to the present disclosure can be used in sub-28 nm technology. In ArF immersion technology, it can be used for water isolation shielding, dissolution control, and profile adjustment. In EUV technology, the floating additive layer acts as a sacrificial layer, providing improved post-develop inspection (ADI), local critical dimension uniformity (LCDU), and line width roughness (LWR). In some embodiments, the floating additive layer provides improved LWR / LCDU stability. In some embodiments, the LCDU is increased by more than about 3%. In some embodiments, the variations in LWR and LCDU are reduced to less than about 5%. The floating additive layer of the present disclosure can also allow the use of a lower exposure dose to achieve reduced LWR and LCDU variations, thus providing cost savings and increased device yield.

[0162] One embodiment of the present disclosure is a method of manufacturing a semiconductor device, the method comprising forming a photoresist layer comprising a photoresist composition over a substrate; and forming a floating additive layer comprising a floating additive polymer. The floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of pendant acid generating groups, pendant base groups, pendant acid labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid diffusion control groups. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern. The selectively exposed photoresist layer is developed to form a pattern in the photoresist layer. In one embodiment, the photoresist layer is formed in a vacuum chamber. In one embodiment, the floating additive polymer is added to the photoresist composition before forming the photoresist layer. In one embodiment, a floating additive layer comprising a floating additive polymer is formed over the photoresist layer before the photoresist layer is selectively exposed to actinic radiation. In one embodiment, the method comprises forming a photoresist underlayer comprising a floating additive polymer over the substrate before forming the photoresist layer. In one embodiment, the photoresist composition comprises a metal resist. In one embodiment, the method comprises heating the photoresist layer at a temperature ranging from 40 °C to 300 °C before the photoresist layer is selectively exposed to actinic radiation. In one embodiment, the pendant fluorine-substituted organic groups comprise fluoroalcohol groups. In one embodiment, the floating additive polymer comprises pendant acid generating groups and pendant acid labile groups. In one embodiment, the floating additive polymer comprises pendant chromophore groups. In one embodiment, the floating additive polymer comprises pendant developer solubility promoter groups.

[0163] Another embodiment of the present disclosure is a method of manufacturing a semiconductor device, the method comprising forming a photoresist layer comprising a photoresist composition over a substrate. The photoresist composition comprises a first polymer; a photoactive compound; and a second polymer, the second polymer comprising pendant fluorine-substituted organic groups, and one or more of pendant acid generating groups, pendant base groups, pendant acid labile groups, pendant chromophore groups, pendant developer solubility enhancing groups, and pendant acid diffusion control groups. The second polymer is floated over the first polymer and the photoactive compound to form a floating layer over the photoresist layer. The photoresist layer is selectively exposed to actinic radiation through the floating layer to form a latent pattern in the photoresist layer. The latent pattern is developed to form a pattern in the photoresist layer. In one embodiment, floating the second polymer comprises rotating the substrate while forming the photoresist layer or after forming the photoresist layer. In one embodiment, the method comprises heating the photoresist layer at a temperature in the range of 40 °C to 300 °C before selectively exposing the photoresist layer to actinic radiation. In one embodiment, the first polymer comprises pendant acid labile groups. In one embodiment, the floating layer is removed during development of the latent pattern. In one embodiment, the second polymer comprises pendant acid generating groups and pendant acid labile groups.

[0164] Another embodiment of the present disclosure is a photoresist composition, which comprises a photoresist polymer, a photoactive compound, and a floating additive polymer. The floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of a pendant acid-generating group, a pendant base group, a pendant acid-labile group, a pendant chromophore group, a pendant developer solubility promoter group, and a pendant acid diffusion control group. The floating additive polymer and the photoresist polymer are different polymers. In one embodiment, the photoresist polymer comprises a pendant acid-labile group. In one embodiment, the pendant fluorine-substituted organic group comprises a fluoroalcohol group. In one embodiment, the floating additive polymer comprises a pendant acid-labile group. In one embodiment, the floating additive polymer comprises a pendant chromophore group. In one embodiment, the floating additive polymer comprises a pendant developer solubility promoter group. In one embodiment, the floating additive polymer comprises a pendant acid diffusion control group. In one embodiment, the floating additive polymer comprises a polystyrene or poly(meth)acrylate backbone. In one embodiment, the floating additive polymer comprises a pendant acid-labile group, a pendant acid-generating group, and a pendant fluorine-substituted organic group, wherein the pendant fluorine-substituted organic group is a fluoroalcohol group. In one embodiment, the floating additive polymer comprises a pendant acid diffusion control group, a pendant chromophore group, a pendant developer solubility promoter group, and a pendant fluorine-substituted organic group, wherein the pendant fluorine-substituted organic group is a fluoroalcohol group.

[0165] Another embodiment of the present disclosure is a method of manufacturing a semiconductor device, the method comprising forming an underlying photoresist layer over a substrate, and forming a first floating layer over the underlying photoresist layer. The first floating layer comprises a first floating polymer having pendant fluorine-substituted organic groups, and one or more of a pendant acid generating group, a pendant base group, a pendant acid labile group, a pendant chromophore group, a pendant developer solubility enhancer group, and a pendant acid diffusion control group. A photoresist layer is formed over the first floating layer. A second floating layer is formed over the photoresist layer. The second floating layer comprises a second floating polymer having pendant fluorine-substituted organic groups, and one or more of a pendant acid generating group, a pendant base group, a pendant acid labile group, a pendant chromophore group, a pendant developer solubility enhancer group, and a pendant acid diffusion control group. The photoresist layer is selectively exposed to actinic radiation to form a latent pattern, and then the latent pattern is developed to form a pattern in the photoresist layer. In one embodiment, the second floating layer is removed during development of the latent pattern. In one embodiment, the photoresist layer comprises a photoresist polymer, and the photoresist polymer, the first floating polymer, and the second floating polymer are different polymers.

[0166] Another embodiment of the present disclosure is a composition comprising a polymer having pendant fluorine-substituted organic groups, and one or more of a pendant acid generating group, a pendant base group, a pendant acid labile group, a pendant developer solubility enhancer group, a pendant chromophore group, and a pendant acid diffusion control group; and a solvent. In one embodiment, the pendant fluorine-substituted organic groups include fluoroalcohol groups. In one embodiment, the polymer comprises a pendant acid generating group and a pendant acid labile group. In one embodiment, the polymer comprises a pendant chromophore group. In one embodiment, the polymer comprises a pendant developer solubility enhancer group. In one embodiment, the polymer comprises a polystyrene or poly(meth)acrylate backbone. In one embodiment, the polystyrene or poly(meth)acrylate backbone comprises iodine as a substituent.

[0167] Another embodiment of the present disclosure is a polymer comprising a polymer backbone comprising pendant fluorine-substituted organic groups, and one or more of pendant acid-generating groups, pendant base groups, pendant acid-labile groups, pendant chromophore groups, pendant acid-diffusion control groups, and pendant developer solubility promoter groups, wherein the polymer backbone comprises polystyrene or poly(meth)acrylate. In one embodiment, the polymer comprises pendant fluorine-substituted organic groups, pendant acid-generating groups, and pendant acid-labile groups, wherein the pendant fluorine-substituted organic group is a fluoroalcohol group. In one embodiment, the polymer comprises pendant fluorine-substituted organic groups, pendant acid-diffusion control groups, pendant chromophore groups, and pendant developer solubility promoter groups.

[0168] Another embodiment of the present disclosure is a stacked structure comprising a photoresist layer disposed over a substrate, and a floating additive layer disposed over the photoresist layer. The photoresist layer comprises a photoresist polymer and a photoactive compound. The floating additive layer comprises a floating additive polymer. The floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of pendant acid-generating groups, pendant base groups, pendant acid-labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid-diffusion control groups. The floating additive polymer and the photoresist polymer are different polymers. In one embodiment, the stacked structure comprises a bottom photoresist layer disposed between the substrate and the photoresist layer, and the bottom photoresist layer comprises a floating additive polymer. In one embodiment, the photoresist polymer comprises pendant acid-labile groups, and the pendant fluorine-substituted organic group comprises a fluoroalcohol group.

[0169] This application also includes the following exemplary embodiments:

[0170] Embodiment 1. A method of manufacturing a semiconductor device, the method comprising:

[0171] Forming a photoresist layer comprising a photoresist composition over a substrate;

[0172] Forming a floating additive layer comprising a floating additive polymer,

[0173] wherein the floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of pendant acid-generating groups, pendant base groups, pendant acid-labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid-diffusion control groups;

[0174] Selectively exposing the photoresist layer to actinic radiation to form a latent pattern; and

[0175] Develop the selectively exposed photoresist layer to form a pattern in the photoresist layer.

[0176] Embodiment 2. The method according to Embodiment 1, wherein the photoresist layer is formed in a vacuum chamber.

[0177] Embodiment 3. The method according to Embodiment 1, wherein the floating additive polymer is added to the photoresist composition before forming the photoresist layer.

[0178] Embodiment 4. The method according to Embodiment 1, wherein a floating additive layer containing the floating additive polymer is formed above the photoresist layer before selectively exposing the photoresist layer to actinic radiation.

[0179] Embodiment 5. The method according to Embodiment 1, the method further comprising forming a photoresist underlayer above the substrate before forming the photoresist layer, wherein the photoresist underlayer contains a floating additive polymer.

[0180] Embodiment 6. The method according to Embodiment 1, wherein the photoresist composition contains a metal resist.

[0181] Embodiment 7. The method according to Embodiment 1, the method further comprising heating the photoresist layer at a temperature ranging from 40 °C to 300 °C before selectively exposing the photoresist layer to actinic radiation.

[0182] Embodiment 8. The method according to Embodiment 1, wherein the pendant fluorine-substituted organic group includes a fluoroalcohol group.

[0183] Embodiment 9. The method according to Embodiment 1, wherein the floating additive polymer contains the pendant acid generating group and the pendant acid labile group.

[0184] Embodiment 10. The method according to Embodiment 1, wherein the floating additive polymer contains the pendant chromophore group.

[0185] Embodiment 11. The method according to Embodiment 1, wherein the floating additive polymer contains the pendant developer solubility promoter group.

[0186] Embodiment 12. A method of manufacturing a semiconductor device, the method comprising:

[0187] Forming a photoresist layer containing a photoresist composition above a substrate,

[0188] Wherein the photoresist composition comprises:

[0189] A first polymer;

[0190] A photoactive compound; and

[0191] A second polymer, the second polymer comprising pendant fluorine-substituted organic groups, and one or more of pendant acid-generating groups, pendant base groups, pendant acid-labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid diffusion control groups;

[0192] Floating the second polymer above the first polymer and the photoactive compound to form a floating layer above the photoresist layer;

[0193] Selectively exposing the photoresist layer to actinic radiation passing through the floating layer to form a latent pattern in the photoresist layer; and

[0194] Developing the latent pattern to form a pattern in the photoresist layer.

[0195] Embodiment 13. The method according to Embodiment 12, wherein floating the second polymer comprises rotating the substrate while forming the photoresist layer or after forming the photoresist layer.

[0196] Embodiment 14. The method according to Embodiment 12, the method further comprising heating the photoresist layer at a temperature in the range of 40 °C to 300 °C before selectively exposing the photoresist layer to actinic radiation.

[0197] Embodiment 15. The method according to Embodiment 12, wherein the first polymer comprises pendant acid-labile groups.

[0198] Embodiment 16. The method according to Embodiment 12, wherein the floating layer is removed during development of the latent pattern.

[0199] Embodiment 17. The method according to Embodiment 12, wherein the second polymer comprises the pendant acid-generating groups and the pendant acid-labile groups.

[0200] Embodiment 18. A stacked structure, the stacked structure comprising:

[0201] A photoresist layer disposed above a substrate; and

[0202] A floating additive layer disposed over the photoresist layer, wherein the photoresist layer comprises a photoresist polymer, and

[0203] a photoactive compound; and

[0204] the floating additive layer comprises a floating additive polymer,

[0205] wherein the floating additive polymer comprises pendant fluorine-substituted organic groups, and one or more of a pendant acid generating group, a pendant base group, a pendant acid labile group, a pendant chromophore group, a pendant developer solubility enhancing group, and a pendant acid diffusion control group,

[0206] wherein the floating additive polymer and the photoresist polymer are different polymers.

[0207] Embodiment 19. The stacked structure according to Embodiment 18, further comprising a bottom photoresist layer disposed between the substrate and the photoresist layer, wherein the bottom photoresist layer comprises the floating additive polymer.

[0208] Embodiment 20. The stacked structure according to Embodiment 18, wherein the photoresist polymer comprises pendant acid labile groups, and the pendant fluorine-substituted organic groups comprise fluoroalcohol groups.

[0209] The foregoing has outlined the features of several embodiments or examples so that those skilled in the art may better understand the aspects of the present disclosure. Those skilled in the art should appreciate that they can readily use the present disclosure as a basis for designing or modifying other methods and structures for carrying out the same purposes and / or achieving the same advantages as the embodiments introduced herein. Those skilled in the art should also recognize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they may make various changes, substitutions and alterations therein without departing from the spirit and scope of the present disclosure.

Claims

1. A method for manufacturing a semiconductor device, the method comprising: forming a photoresist layer comprising a photoresist composition over a substrate; forming a floating additive layer comprising a floating additive polymer, wherein the floating additive polymer comprises pendant fluorine-substituted organic groups and one or more of pendant acid generating groups, pendant base groups, pendant acid labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid diffusion control groups; selectively exposing the photoresist layer to actinic radiation to form a latent pattern; as well as The selectively exposed photoresist layer is developed to form a pattern in the photoresist layer. The method of claim 1 , wherein the photoresist layer is formed in a vacuum chamber. 3 . The method of claim 1 , wherein the floating additive polymer is added to the photoresist composition before forming the photoresist layer.

4. The method of claim 1, wherein a floating additive layer comprising the floating additive polymer is formed over the photoresist layer prior to selectively exposing the photoresist layer to actinic radiation. 5 . The method of claim 1 , further comprising forming a photoresist underlayer over the substrate before forming the photoresist layer, wherein the photoresist underlayer comprises a floating additive polymer.

6. The method of claim 1, wherein the photoresist composition comprises a metal resist.

7. The method of claim 1, further comprising heating the photoresist layer at a temperature ranging from 40°C to 300°C prior to selectively exposing the photoresist layer to actinic radiation.

8. The method of claim 1, wherein the pendant fluorine-substituted organic group comprises a fluoroalcohol group.

9. A method for manufacturing a semiconductor device, the method comprising: forming a photoresist layer comprising a photoresist composition over the substrate, The photoresist composition comprises: a first polymer; Photoactive compounds; as well as a second polymer comprising pendant fluorine-substituted organic groups and one or more of pendant acid generating groups, pendant base groups, pendant acid labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid diffusion control groups; floating the second polymer over the first polymer and the photoactive compound to form a floating layer over the photoresist layer; selectively exposing the photoresist layer to actinic radiation through the floating layer to form a latent pattern in the photoresist layer; as well as The latent pattern is developed to form a pattern in the photoresist layer.

10. A stacking structure, comprising: a photoresist layer disposed above the substrate; as well as a floating additive layer disposed above the photoresist layer, wherein the photoresist layer comprises a photoresist polymer, and a photoactive compound; and The floating additive layer comprises a floating additive polymer, wherein the floating additive polymer comprises pendant fluorine-substituted organic groups and one or more of pendant acid generating groups, pendant base groups, pendant acid labile groups, pendant chromophore groups, pendant developer solubility promoter groups, and pendant acid diffusion control groups, wherein the floating additive polymer and the photoresist polymer are different polymers.

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