TWI743720B - Method for forming semiconductor structure - Google Patents

Abstract

A method for forming a semiconductor device structure is provided. The method includes forming a material layer over a substrate and forming a resist layer over the material layer. The resist layer includes an inorganic material and an auxiliary. The inorganic material includes a plurality of metallic cores and a plurality of first linkers bonded to the metallic cores. The method includes exposing a portion of the resist layer. The resist layer includes an exposed region and an unexposed region. In the exposed region, the auxiliary reacts with the first linkers. The method also includes removing the unexposed region of the resist layer by using a developer to form a patterned resist layer. The developer includes a ketone-based solvent having a formula (a) or the ester-based solvent having a formula (b).

Description

Method for forming semiconductor structure

The present invention relates to a memory device, and particularly relates to a non-volatile memory device and a manufacturing method thereof.

Semiconductor devices are used in various electronic applications, such as personal computers, mobile phones, digital cameras, and other electronic devices. Semiconductor devices are usually manufactured by the following methods, including sequentially depositing material layers such as insulating or dielectric layers, conductive layers, and semiconductor layers on a semiconductor substrate, and patterning the above-mentioned material layers using a lithography process, thereby forming the semiconductor substrate Form circuit components and components. Usually, many integrated circuits are manufactured on a single semiconductor wafer, and each die is singulated by cutting between the integrated circuits along the cutting line. The above-mentioned dies are usually packaged separately in, for example, a multi-chip module or other types of packages.

However, these advances have increased the processing and manufacturing complexity of integrated circuits. As part sizes continue to shrink, manufacturing processes continue to become more difficult. Therefore, it has become a challenge to form reliable semiconductor devices in smaller and smaller sizes.

An embodiment of the present invention discloses a method for forming a semiconductor structure, including: forming a material layer on a substrate; forming a photoresist layer on the material layer, wherein the photoresist layer includes an inorganic material and an auxiliary agent, and the inorganic material includes A plurality of metal cores and a plurality of first linking groups, wherein the first linking group is bonded to the metal core; exposing a part of the photoresist layer, wherein the photoresist layer includes an exposed area and an unexposed area, and is in the exposed area , The auxiliary agent reacts with the first linking group; and a developer is used to remove the unexposed area of the photoresist layer to form a patterned photoresist layer, wherein the developer includes a ketone-based solvent, an ester-based solvent or The combination of the above, wherein the ketone-based solvent has a substituted or unsubstituted C ₆ -C ₇ cyclic ketone, and the ester-based solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy.

An embodiment of the present invention discloses a method for forming a semiconductor structure, including: forming a material layer on a substrate; forming a bottom layer on the material layer; forming an intermediate layer on the bottom layer; and forming a photoresist layer on the intermediate layer , Wherein the photoresist layer includes an inorganic material, and the inorganic material has a plurality of metal cores and a plurality of first linking groups, wherein the first linking group is bonded to the metal core; forming a modified layer under or above the photoresist layer, wherein The modification layer includes an auxiliary agent; an exposure process is performed to expose a part of the photoresist layer, wherein during the exposure process, the auxiliary agent reacts with the first linking group; and a ketone-based solvent or an ester-based solvent is used for the photoresist layer Development is performed to form a patterned photoresist layer, wherein the ketone-based solvent has a substituted or unsubstituted C ₆ -C ₇ cyclic ketone, and the ester-based solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy.

An embodiment of the present invention discloses a method for forming a semiconductor structure, including: forming a material layer on a substrate; forming a bottom layer on the material layer; forming an intermediate layer on the bottom layer; and forming a photoresist layer on the intermediate layer , Wherein the photoresist layer includes an inorganic material and an auxiliary agent, wherein the inorganic material includes a plurality of first linking groups bonded to a plurality of metal cores, and the auxiliary agent includes a plurality of second linking groups; an exposure process is performed to expose the photoresist layer During the exposure process, the second linking group reacts with the first linking group; an ester-based solvent is used to remove a portion of the photoresist layer to form a patterned photoresist layer, wherein the ester-based The solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Base, or linear or branched C ₃ -C ₆ alkoxy; use a patterned photoresist layer as a part of the mask to remove the intermediate layer to form a patterned intermediate layer; and use a patterned The middle layer is used as a part of the mask to remove the bottom layer to form a patterned bottom layer.

10: hood

12: Inorganic materials

14: adjuvant

16: Compound

102: substrate

104: Material layer

104a: Patterned material layer

105: doped area

106: bottom layer

106a: Patterned bottom layer

108: middle layer

108a: Patterned middle layer

109: Modification layer

109a: Patterned modification layer

110: photoresist layer

110a: Patterned photoresist layer

120: Three-layer photoresist layer

122: Metal Core

124: first linking group

172: Exposure Process

174: Ion implantation process

180: Development process

181: The second developing process

182: Cleaning process

L ₁ : the first linking group

L ₂ : second linking group

L ₃ : the third linking group

P1: first pitch

T ₁ : first thickness

T ₂ : second thickness

Complete the disclosure based on the following detailed description in conjunction with the attached drawings. It should be noted that, according to the general operations of this industry, the illustrations are not necessarily drawn to scale. In fact, it is possible to arbitrarily enlarge or reduce the size of the component to make a clear description.

1A to 1D are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

2A to 2C are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

FIG. 3A is a schematic diagram of the chemical structure of the photoresist layer before the exposure process according to some embodiments.

FIG. 3B is a schematic diagram of the chemical structure of the photoresist layer after the exposure process according to some embodiments.

4A to 4D are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

5A to 5E are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

6A to 6G are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

7A to 7F are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

8A to 8D are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention.

The following disclosure provides many different embodiments or examples to implement different features of the case. The following disclosure describes specific examples of each component and its arrangement to simplify the description. Of course, these specific examples are not meant to be limiting. For example, if this specification describes that a first component is formed on or above a second component, it means that it may include an embodiment in which the first component is in direct contact with the second component, or it may include additional The component is formed between the first component and the second component, and the first component and the second component may not be in direct contact with each other. In addition, the different examples disclosed below may reuse the same reference symbols and/or marks. These repetitions are for the purpose of simplification and clarity, and are not used to limit the specific relationship between the different embodiments and/or structures discussed.

Various changes of the embodiment are described below. Through the various views and the illustrated embodiments, similar element numbers are used to identify similar elements. It should be understood that additional operating steps may be provided before, during, or after performing the method, and in other embodiments of the method, some of the steps may be replaced or omitted.

The advanced lithography processes, methods, and materials described in the embodiments of the present invention can be used in a variety of applications, including fin-type field effect transistors (FinFET). For example, after the fins are patterned by the method described in the embodiments, there can be a relatively close spacing between the components, and the above-mentioned method in this article can be well applied to this. In addition, the spacers used to form the fins of the fin-type field effect transistors can also be processed by the process described in the embodiments.

The following provides embodiments of the semiconductor structure and its forming method. 1A to 1D are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. This method can be used in many applications, such as FinFET device structures.

Please refer to Figure 1A to provide a substrate 102. The substrate 102 may be made of silicon or other semiconductor materials. In some embodiments, the substrate 102 is a wafer. Alternatively or additionally, the substrate 102 may include other elemental semiconductor materials, for example, germanium (Ge). In some embodiments, the substrate 102 is made of a compound semiconductor or alloy semiconductor, for example, silicon carbide, gallium arsenide, indium arsenide, or indium phosphide, silicon germanium, silicon germanium, silicon germanium, phosphorous gallium arsenide, or phosphorous. Gallium indium. In some embodiments, the substrate 102 includes an epitaxial layer. For example, the substrate 102 has an epitaxial layer on a bulk semiconductor.

Some device components can be formed on the substrate 102. Such device components include transistors (for example, metal oxide semiconductor field effect transistors (MOSFETs), complementary metal oxide semiconductor (CMOS) transistors, and bipolar junction transistors. transistor (BJT), high-voltage transistor (high-voltage transistor), high-frequency transistor (high-frequency transistor), p-channel and/or n-channel field effect transistors (PFETs/NFETs, etc.), diodes Body and other suitable components. Various processes can be performed to form device components, such as deposition, etching, implantation, photolithography, annealing, and/or other suitable processes.

The substrate 102 may include various doped regions, for example, p-type wells or n-type wells. The doped regions may be doped with p-type dopants (for example, boron or boron difluoride (BF ₂ )) and/or n-type dopants (for example, phosphorus or arsenic). In some other embodiments, these doped regions may be directly formed on the substrate 102.

The substrate 102 also includes an isolation structure (not shown in the figure). The isolation structure is used to define and electrically isolate various devices formed in and/or on the substrate 102. In some embodiments, the isolation structure includes a shallow trench isolation (STI) structure, a local oxidation of silicon (LOCOS) structure, or other suitable isolation structures. In some embodiments, the isolation structure includes silicon oxide, silicon nitride, silicon oxynitride, fluoride-doped silicate glass (FSG), or other suitable materials.

Then, according to some embodiments of the present invention, a material layer 104 is formed on the substrate 102, and a photoresist layer 110 is formed on the material layer 104. In some embodiments, the photoresist layer 110 includes an inorganic material 12, an auxiliary 14 and a solvent. The inorganic material 12 and the auxiliary agent 14 are uniformly distributed in the solvent. The structure of the inorganic material 12 and the auxiliary agent 14 will be described in detail below. In some embodiments, the material layer 104 or the photoresist layer 110 is independently formed by a deposition process. The deposition process may include, for example, a spin-on coating process, chemical vapor deposition (chemical vapor deposition) CVD) process, physical vapor deposition (PVD) process and/or other suitable deposition processes.

Next, as shown in FIG. 1B, according to some embodiments of the present invention, a mask 10 is formed on the photoresist layer 110, and an exposure process 172 is performed on the photoresist layer 110 to form exposed areas and unexposed areas .

The radiation energy of the exposure process 172 can include a 248nm beam generated by a krypton fluoride (KrF) excimer laser, and a 193nm beam generated by an argon fluoride (ArF) excimer laser. , 157nm light beam generated by fluoride (F ₂ ) excimer laser, or extreme ultra-violet (EUV) light, for example, extreme ultraviolet light with a wavelength of about 13.5nm.

After the exposure process 172, a post-exposure-baking (PEB) process is performed. In some embodiments, the post-exposure baking process includes a microwave or infrared lamp heating process. In some embodiments, the post-exposure baking process is performed at a temperature ranging from about 70°C to about 250°C. In some other embodiments, the duration of the post-exposure baking process is in the range of about 20 seconds to about 240 seconds. It should be noted that, since the microwave or infrared lamp heating process can provide heat evenly, the photoresist layer 110 can be evenly baked at a specific temperature by using the microwave or infrared lamp heating process. By uniformly supplying heat, the chemical reaction in the photoresist layer 110 can react quickly. So one In the future, the heating time of the baking process can be reduced to less than 30 seconds.

FIG. 3A is a schematic diagram of the chemical structure of the photoresist layer before performing the exposure process 172 according to some embodiments.

In some embodiments, the photoresist layer 110 includes an inorganic material 12, an auxiliary agent 14, and a solvent. The inorganic material 12 and the auxiliary agent 14 are uniformly distributed in the solvent. The inorganic material 12 includes a plurality of metal cores 122 and a plurality of first linking groups (L ₁ ) 124, wherein the first linking group (L ₁ ) 124 is bonded to the metal core 122. In some embodiments, the first linking group (L ₁ ) 124 is chemically bonded to the metal core 122. The chemical bond of the chemical bond can be a single bond or a conjugated bond. The auxiliary agent 14 may include a photo acid generator (PAG), a quencher (Q), a cross-linking agent, a photo base generator (PBG), or a combination thereof. In some embodiments, the weight ratio of the auxiliary agent 14 to the solvent is in the range of about 0.1 wt% to about 10 wt%. If the weight ratio of the auxiliary agent 14 to the solvent is less than 0.1% by weight, the reaction rate of the crosslinking reaction between the inorganic material 12 and the auxiliary agent 14 may not be increased. If the weight ratio of the auxiliary agent 14 to the solvent is greater than 10 wt%, other undesired chemical reactions may occur. For example, if the amount of the auxiliary agent 14 is too large, the melting point of the inorganic material 12 may decrease. Once the melting point of the inorganic material 12 decreases, the heat resistance of the inorganic material 12 to the baking temperature will decrease, and the performance of the photoresist layer 110 will deteriorate.

In some embodiments, the metal core 122 is formed of metal, for example, tin (Sn), indium (In), antimony (Sb) or other suitable materials. In some embodiments, the first linking group 124 includes an aliphatic or aromatic group, unbranched or branched, cyclic or acyclic, saturated with hydrogen or oxygen or halogen and has 1-9 One carbon (C ₁ -C ₉ ) unit (for example, alkyl, alkene, benzene). In some embodiments, the first linking group 124 is used to provide radiation sensitivity. In some embodiments, the first linking group 124 has a hydroxyl group (-OH), the second linking group L ₂ has a hydroxyl group (-OH), and the two hydroxyl groups react with each other to perform a hydrolysis reaction. . In some other embodiments, the first linking group (L ₁ ) 124 has a carbon-carbon double bond (alkene) or carbon-carbon triple bond (alkynes), and the second linking group L _{2 is} connected to the first link The group (L ₁ ) 124 reacts to undergo an addition reaction. In some other embodiments, the first linking group (L ₁ ) 124 has a carbonyl group (C=O) or an imino group (C=N), and the second linking group L2 and the first linking group (L ₁ ) 124 reaction to proceed an addition reaction.

In some embodiments, the auxiliary agent 14 includes a second linking group L ₂ and a third linking group L ₃ , wherein the second linking group L ₂ and the third linking group L ₃ can interact with the second linking group L 2 and the third linking group L 3 on the metal core 122. A linking group 124 reacts. With the assistance of the auxiliary agent 14, one of the metal cores 122 is bonded to the other metal core 122 to form the compound 16, and the size of the compound 16 is larger than the size of each metal core 122.

In some specific embodiments, the solvent includes propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (1 -ethoxy-2-propanol, PGEE), gamma-butyrolactone (gamma-butyrolactone, GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, normal Butanol, acetone, dimethylformamide (DMF), isopropyl alcohol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-acetic acid N-butyl acetate (nBA), 2-heptanone (MAK) or a combination of the above.

In some embodiments, the photoacid generator (PAG) includes cations and anions. In some embodiments, the cation includes formula (I) or (II). In some embodiments, the anion includes formula (III), (IV), (V), (VI), (VII), (VIII), (IX), (X), (XI), or (XII).

In some embodiments, the quencher (Q) includes formula (XIII), (XIV), (XV), (XVI), (XVII), (XVIII), (XIX), (XX), or (XXI).

In some embodiments, the crosslinking agent includes formula (XXII), (XXIII), (XXIV), (XXV), (XXVI), (XXVII), (XXVIII), (XXIX), or (XXX).

In some embodiments, the photobase generator (PBG) includes formula (XXXI), (XXXII), (XXXIII), (XXXIV), (XXXV), (XXXVI), (XXXVII), (XXXVIII), or (XXXIX ), (XL), (XLI) or (XLII).

FIG. 3B is a schematic diagram of the chemical structure of the photoresist layer after the exposure process 172 according to some embodiments. It should be noted that after the exposure process 172, the auxiliary agent 14 is used to assist the cross-linking reaction between adjacent metal cores 122. More specifically, the second linking group L ₂ and the third linking group L _{3 of the} auxiliary agent 14 react with the first linking group 124 on the metal core 122 to form a gap between the inorganic material 12 and the auxiliary agent 14 Chemical bond. The chemical bond of the chemical bond can be a single bond or a conjugated bond. More specifically, the chemical bond is formed between the second linking group L _{2 of the} auxiliary agent 14 and the first linking group (L ₁ ) 124, and is formed between the third linking group L _{3 of the} auxiliary agent 14 and the first linking group (L 1) 124. A linking group (L ₁ ) between 124.

During the exposure process 172, the adjacent first linking groups L ₁ bonded to different metal cores 122 can react with each other through cross-linking reactions. The inorganic material 12 with the metal core 122 and the first linking group (L ₁ ) 124 is used to improve the radiation absorption of the exposure process 172. For example, In based (In based) or Sn based (Sn based) inorganic materials have good absorption of extreme ultraviolet light with a wavelength of 193 nm and extreme ultraviolet light with a wavelength of 13.5 nm. Before the exposure process 172 is performed, there is a distance between _{adjacent first linking groups L 1.} In order to increase the reaction rate of the cross-linking reaction, the auxiliary agent 14 is added to the photoresist layer 110. The auxiliary agent 14 can shorten the distance between adjacent metal cores 122. Therefore, with the assistance of the second linking group L ₂ and the third linking group L ₃ of the auxiliary agent 14, it is located on the first metal core 122 wherein (L ₁₎ 124 capable of reacting with a first coupling located in the second group wherein a first linking group (L ₁₎ 124 on the metal core 122. It should be noted that the crosslinking reaction between adjacent metal cores 122 is improved due to the addition of the auxiliary agent 14.

In a comparative example, the photoresist layer 110 includes an inorganic material 12 and a solvent, but does not include the auxiliary agent 14 described above. In this comparative example, the crosslinking reaction between adjacent metal cores 122 has a first reaction rate. In some embodiments, the photoresist layer 110 includes the above-mentioned inorganic material 12 and auxiliary agent 14 and the above-mentioned solvent. The crosslinking reaction between adjacent metal cores 122 has a second reaction rate. By adding the auxiliary agent 14, one of the metal cores 122 is bonded to the other metal core 122. With the assistance of the auxiliary agent 14, the reaction rate of the cross-linking reaction between adjacent metal cores 122 can be increased. Due to the assistance of the auxiliary agent 14, the second reaction rate is greater than the first reaction rate.

Next, as shown in FIG. 1C, according to some embodiments of the present invention, the photoresist layer 110 is developed by performing a development process 180 to form a patterned photoresist layer 110a. Compound 16 is formed in the photoresist layer 110. The compound 16 is formed by reacting the inorganic material 12 with the auxiliary agent 14. A part of the metal core 122 reacts with the auxiliary agent 14, but the other part of the metal core 122 still remains in the photoresist layer 110. In other words, the compound 16 is formed by the inorganic material 12 and the auxiliary agent 14 _{through the first linking group L 1} , the second linking group L ₂ and the third linking group L _3.

There are two types of development processes: a positive tone development (PTD) process and a negative tone development (NTD) process. The positive development process uses a positive tone developer. The positive tone developer generally refers to a developer that selectively dissolves and removes the exposed part of the photoresist layer. The negative tone developer is used in the negative tone developer. The negative tone developer generally refers to a developer that selectively dissolves and removes the unexposed part of the photoresist layer 110. In some embodiments, the positive development (PTD) developer is an aqueous base developer (aqueous base developer), for example, tetraalkylammonium hydroxide (TMAH).

The development process 180 is performed by using a developer. The developer has high hydrophobicity and low dipole momentum. In some embodiments, the dipole momentum of the developer used in the development process 180 is in the range of about 0.8 Debye to about 4 Debye. If the dipole momentum is less than 0.8 Debye, the solubility of the unexposed part of the photoresist layer 110 may be too low, and it may not be possible to completely remove the unwanted photoresist residue in the unexposed part (the unexposed part should be completely removed ). If the dipole momentum is greater than 4 Debye, the solubility of the exposed part of the photoresist layer 110 may be too high, and the exposed part of the photoresist layer 110 may be over-developed (the exposed part should be left), and the shape of the exposed part may be broken Or neck down.

In some embodiments, the negative tone development (NTD) process developer includes a ketone-based solvent, an ester-based solvent, or a combination thereof. In some embodiments, the negative-tone development process developer includes a ketone-based solvent, and the total number of carbon atoms in the ketone-based solvent is in the range of 5-15. In some embodiments, the ketone-based solvent has formula (a):

Wherein R ₁ is a linear or branched C ₁ -C ₅ alkyl group, and R ₂ is a linear or branched C ₃ -C ₉ alkyl group.

In some embodiments, the ketone-based solvent does not include 2-heptanone. In some embodiments, the ketone-based solvent is not 2-heptanone.

According to some embodiments of the present invention, Tables 1 to 9 show some examples of ketone-based developers. As shown in Table 1, the ketone-based solvent has the formula (a), wherein R ₁ is CH ₃ and R ₂ is a linear or branched C ₄ -C ₉ alkyl group. In some embodiments, the ketone-based solvent has formula (a), wherein R ₁ is CH ₃ and R ₂ is a branched C ₅ alkyl group. For example, the ketone-based solvent is 5-methyl-2-hexanone. In some embodiments, the ketone-based solvent has formula (a), wherein R ₁ is CH ₃ and R ₂ is a linear C ₆ alkyl group. For example, the ketone-based solvent is 2-octanone.

As shown in Table 2, the ketone-based solvent has the formula (a), wherein R ₁ is C ₂ H ₅ , and R ₂ is a linear or branched C ₄ -C ₈ alkyl group. In some embodiments, the ketone-based solvent has formula (a), wherein R ₁ is C ₂ H ₅ and R ₂ is a linear C ₄ alkyl group. For example, the ketone-based solvent is 3-heptanone.

As shown in Table 3, the ketone-based solvent has the formula (a), wherein R ₁ is a linear C ₃ H ₇ , and R ₂ is a linear or branched C ₃ -C ₇ alkyl group.

As shown in Table 4, the ketone-based solvent has the formula (a), wherein R ₁ is a branched C ₃ H ₇ , and R ₂ is a linear C ₄ -C ₆ alkyl group.

As shown in Table 5, the ketone-based solvent has the formula (a), wherein R ₁ is a branched C ₄ H ₉ and R ₂ is a branched C ₄ -C ₆ alkyl group.

table 5

As shown in Table 6, the ketone-based solvent has the formula (a), wherein R ₁ is a branched C ₅ H ₁₁ and R ₂ is a linear C ₄ -C ₅ alkyl group.

As shown in Table 7, the ketone-based solvent has the formula (a), wherein R ₁ is branched C ₃ H ₇ and R ₂ is C ₃ H ₇ .

As shown in Table 8, the ketone-based solvent has the formula (a), wherein R ₁ is CH ₃ or C ₃ H ₇ , and R ₂ is a linear or branched C ₃ -C ₅ alkyl group.

In some embodiments, the ketone-based solvent is a substituted or unsubstituted C ₆ -C ₇ cyclic ketones, wherein the substituent is hydrogen, an alkyl group. More specifically, as shown in Table 9, in some embodiments, the cyclic ketone has at least one hydrogen atom substituted with a C ₁ -C ₃ alkyl group, such as methyl (-CH ₃ ), ethyl (-C _2H5 ), isopropyl (-C ₃ H ₇ ) or n-propyl (-C ₃ H ₇ ).

In some embodiments, the developer includes an ester-based solvent, and the total number of carbon atoms the ester-based solvent has is in the range of 5-14. In some embodiments, the ester-based solvent has formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy.

According to some embodiments of the present invention, Tables 10 to 15 show some examples of ester-based solvents. As shown in Table 10, the ester-based solvent has the formula (b), wherein R ₃ is CH ₃ and R ₄ is a linear or branched C ₂ -C ₆ alkyl group, or a linear or branched C ₂ -C ₆ alkoxy.

As shown in Table 11, the ester-based solvent has the formula (b), wherein R ₃ is C ₂ H ₅ , and R ₄ is a linear or branched C ₄ alkyl group.

As shown in Table 12, the ester-based solvent has the formula (b), wherein R ₃ is C ₃ H ₇ , and R ₄ is a linear or branched C ₃ -C ₄ alkyl group.

As shown in Table 13, the ester-based solvent has the formula (b), wherein R ₃ is C ₄ H ₉ and R ₄ is a linear or branched C ₂ -C ₄ alkyl group.

As shown in Table 14, the ester-based solvent has the formula (b), wherein R ₃ is C ₅ H ₁₀ and R ₄ is a linear C ₂ alkyl group.

As shown in Table 15, the ester-based solvent has the formula (b), wherein R ₃ is C ₂ H ₅ O, and R ₄ is a linear or branched C ₂ -C ₃ alkyl group.

As shown in FIG. 1C, in some embodiments, a negative-tone development process is performed to preserve the exposed area of the photoresist layer 110, and the unexposed area of the photoresist layer 110 is removed by a ketone-based solvent. After the exposure process 172 is performed, the exposed area of the photoresist layer 110 becomes more hydrophilic. Therefore, a ketone-based solvent is used to remove the unexposed area of the photoresist layer 110. Furthermore, compared with inorganic materials, compound 16 has a larger average molecular weight. Therefore, compound 16 cannot be easily dissolved in organic solvents. Therefore, when the unexposed area of the photoresist layer 110 is removed, the exposed area of the photoresist layer 110 can still be retained.

The critical dimension (CD) of the patterned photoresist layer 110a is determined by the radiation energy of the exposure process and the developer of the development process. The radiation dose is used to induce the cross-linking reaction between the inorganic material 12 and the auxiliary agent 14. High radiation dose will cause a high degree of cross-linking reaction. Therefore, the radiation dose should be increased to obtain a larger critical size of the patterned photoresist layer 110a. However, higher radiation doses may result in higher costs. In order to reduce the cost of the exposure process, the unexposed area of the photoresist layer 110 in the embodiment of the present invention is removed by using a relatively hydrophobic ketone-based solvent. The compound 16 in the exposed area becomes hydrophilic and cannot be easily removed by the hydrophobic ketone-based solvent. Therefore, by using a hydrophobic ketone-based solvent, the critical size of the exposure area of the photoresist layer 110 can be increased. Inch.

In a comparative example, the ketone solvent is 2-heptanone. Compared with the 2-heptanone of this comparative example, the ketone-based solvents described in Table 1 to Table 9 of the present invention have higher hydrophobicity. Therefore, the exposed area of the photoresist layer 110 will not be removed due to the use of a hydrophobic ketone-based solvent. The embodiment of the present invention provides a simple method to obtain a larger critical size of the patterned photoresist layer 110a without increasing the radiation dose of the exposure process. In some embodiments, the radiation dose is reduced by about 5% to about 10%.

In some embodiments, the developer further includes water, and the ratio of water to the developer is in the range of about 0.01 wt% to about 3 wt%. During the cross-linking reaction between the inorganic material 12 and the auxiliary agent 14, water is used as a catalyst. If the cross-linking reaction is not completed during the exposure process, the water added to the developer during the development process can help the cross-linking reaction. It should be noted that the amount of water is not too much, so the polarity of the developer is not significantly affected by water.

In some embodiments, the developer further includes a surfactant. The surfactant is used to increase the solubility and reduce the surface tension on the material layer 104. In some embodiments, the ratio of the surfactant to the developer is in the range of about 0.01 wt% to about 1 wt%. In some embodiments, the surfactant includes the following formula (b), formula (c), formula (d), formula (e), formula (f), or formula (g), where n represents an integer. In formula (b), formula (c), formula (d), and formula (e), R is hydrogen or a linear C ₁ -C ₂₀ alkyl group. In formulas (f) and (g), R ₁ is hydrogen or a linear C ₁ -C ₂₀ alkyl group, R ₂ is hydrogen or a linear C ₁ -C ₂₀ alkyl group, and PO represents -CH ₂ -CH ₂ -O-, EO means -CH ₃ -CH-CH ₂ -O-.

In some embodiments, the step of using a ketone-based developer to remove the non-exposed areas of the photoresist layer is operated in a temperature range of about 10°C to about 80°C. The advantage of the temperature of the developer within the above range is that the solubility of the photoresist layer is reduced, so that more exposed areas of the photoresist layer can remain.

The exposed area of the photoresist layer 110 has a plurality of protruding structures. In some embodiments, there is a first pitch P1, which is the distance between the left side wall surface of the first protruding structure and the left side wall surface of the second protruding structure. In some embodiments, the first pitch P1 is about 10 nm to about 40 nm.

Thereafter, as shown in FIG. 1D, a part of the material layer 104 is removed by performing an etching process and using the patterned photoresist layer 110a as a mask. In this way, a patterned material layer 104a is formed.

The etching process includes many etching operations. The etching process may be a dry etching process or a wet etching process. After that, the patterned photoresist layer 110a is removed. In some embodiments, the patterned photoresist layer 110a is removed by a wet etching process including an alkaline solution, and the alkaline solution is tetraalkylammonium hydroxide. In some other embodiments, the patterned photoresist layer 110a is removed by a wet etching process including a hydrogen fluoride (HF) solution.

The auxiliary agent 14 in the photoresist layer 110 is used to increase the absorption energy of the photoresist layer 110 during the exposure process 172. With the assistance of the auxiliary agent 14, the radiation energy of the exposure process 172 can be reduced to about 3 millijoules (mJ) to about 20 millijoules (mJ). Furthermore, the line width roughness (LWR) of the photoresist layer 110 is improved by about 3% to about 40%. In addition, the critical dimension uniformity (CDU) is also improved by about 3% to about 40%. Therefore, the development resolution is improved.

Furthermore, by using a hydrophobic ketone-based solvent, the unexposed area of the photoresist layer 110 is removed, but the exposed area of the photoresist layer 110 is not removed. Because of the use of ketone-based solvents, the dose of extreme ultraviolet radiation is reduced. In this way, a larger critical size of the patterned photoresist layer 110a can be obtained without increasing the radiation dose of the exposure process. Therefore, the productivity of forming the semiconductor device structure is improved.

2A to 2C are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. The method described in the embodiment of the present invention can be used in a variety of applications, for example, a fin-type field-effect transistor device structure. Some of the processes and materials used to form the semiconductor device structure depicted in FIGS. 2A to 2C may be the same or similar to those used to form the semiconductor device structure depicted in FIGS. 1A to 1D. The materials will not be repeated here.

As shown in FIG. 2A, a development process 180 is performed to form a patterned photoresist layer 110a. However, some residues generated by the unreacted inorganic material 12 or the auxiliary agent 14 are not removed by the development process 180. Therefore, the patterned photoresist layer 110a has a protruding bottom. This protruding bottom may affect the subsequent patterning process.

As shown in FIG. 2B, in order to remove unwanted residues, a cleaning process 182 may be performed on the patterned photoresist layer 110a as needed. The cleaning process 182 is configured to remove residues that have not been completely removed by the development process 180. In some embodiments, the operating time of the development process 180 is in the range of about 15 seconds to about 150 seconds. In some embodiments, the operation time of the cleaning process 182 is about 15 seconds To about 150 seconds.

The cleaning process 182 includes the use of flushing solvents. In some embodiments, the processing solvent includes a developer and additives, where the developer includes, for example, the ketone-based solvent shown in Tables 1 to 9 or the ester-based solvent shown in Tables 10 to 15. In some other embodiments, the rinsing solvent is mainly made of the developer used in the development process 180, and the difference between the rinsing solvent and the developer is the additive. In some embodiments, the rinsing solvent is different from the developer used in the development process 180, and the rinsing solvent includes amide, alcohol, ether, or diol (diol) solvents.

The additives used in the rinse solvent in the cleaning process 182 include acid, and the acid has a pka in the range of -4 to 8. The concentration of the additive in the rinse solvent in the cleaning process 182 is in the range of about 100 ppm to about 50,000 ppm.

In some embodiments, the additives used in the cleaning process 182 include formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, butyric acid, valeric acid, oxalic acid, maleic acid, acrylic acid, hydrogen Chloric acid, nitric acid, boric acid, sulfuric acid, carbonic acid, phosphoric acid, hydrofluoric acid, hypochlorous acid, trifluoroacetic acid, hydrogen peroxide (H ₂ O ₂ ), tetra-n-butylammonium fluoride, TBAF) or a combination of the above.

In some embodiments, the additive used in the cleaning process 182 is tetra-n-butylammonium fluoride. In some embodiments, the additive used in the cleaning process 182 is acetic acid. In some other embodiments, the additive used in the cleaning process 182 is oxalic acid.

4A to 4D are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. The method described in the embodiment of the present invention can be used in a variety of applications, for example, a fin-type field-effect transistor device structure. Some of the processes and materials used to form the semiconductor device structure shown in FIG. 4A to FIG. 4D may be the same or similar to those used in forming the semiconductor device structure shown in FIG. 1A to FIG. 1D Some manufacturing processes and materials used in the structure of the semiconductor device will not be repeated here.

As shown in FIG. 4A, a modification layer 109 is formed on the material layer 104, and a photoresist layer 110 is formed on the modification layer 109. The modification layer 109 includes an auxiliary agent 14. The auxiliary agent 14 may include a photoacid generator (PAG), a matting agent (Q), a crosslinking agent, or a photobase generator (PBG). The material of the auxiliary agent 14 has been described in detail above, and the description will not be repeated here for the sake of brevity. The photoresist layer 110 includes an inorganic material 12 and a solvent. The inorganic material 12 is uniformly distributed in the solvent. The inorganic material 12 includes a plurality of metal cores 122 and a plurality of first linking groups (L ₁ ) 124, and the first linking group (L ₁ ) 124 is bonded to the metal core 122.

The photoresist layer 110 has a first thickness T ₁ , and the modification layer 109 has a second thickness T ₂ . In some embodiments, the first thickness T _{1 is} greater than the second thickness T ₂ . In some embodiments, _{the ratio of the first thickness T 1} to the second thickness T ₂ is in the range of about 5% to about 20%.

Thereafter, as shown in FIG. 4B, according to some embodiments of the present invention, a mask 10 is formed on the photoresist layer 110, and an exposure process 172 is performed on the photoresist layer 110 to form exposed areas and unexposed areas .

After the exposure process 172, the second linking group L ₂ and the third linking group L _{3 of the} auxiliary agent 14 react with the first linking group (L ₁ ) 124 on the metal core 122 to interact with the auxiliary material 12 Multiple chemical bonds are formed between the agents 14. With the assistance of the auxiliary agent 14, the chemical reaction between adjacent metal cores 122 can be accelerated. The compound 16 is formed in the photoresist layer 110, wherein the size of the compound 16 is larger than the size of one of the metal cores 122. More specifically, compared to the metal core 122 having the first linking group (L ₁ ) 124, the compound 16 has a larger average molecular weight.

Then, as shown in FIG. 4C, according to some embodiments of the present invention, the photoresist layer 110 and the modification layer 109 are developed by performing a development process 180 to form a patterned photoresist layer 110a and a patterned photoresist layer 110a.的装饰层109a. In some embodiments, the photoresist layer 110 and the modified layer 109 are performed at the same time 的Developer. In some embodiments, the photoresist layer 110 is patterned first, and then the modification layer 109 is patterned. In some embodiments, the compound 16 is closer to the interface between the modification layer 109 and the photoresist layer 110 than the inorganic material 12.

In some embodiments, a negative-tone development process is performed, the exposed area of the photoresist layer 110 is reserved, and the unexposed area of the photoresist layer 110 is removed by a developer. After the exposure process 172 is performed, the exposed area of the photoresist layer 110 becomes more hydrophilic. Therefore, an organic solvent is used to remove the unexposed area of the photoresist layer 110.

In some embodiments, the negative tone development (NTD) process developer includes a ketone-based solvent, an ester-based solvent, or a combination thereof. The total number of carbon atoms the ketone-based solvent has is in the range of 5-15. In some embodiments, the ketone-based solvent has formula (a):

Wherein R ₁ is a linear or branched C ₁ -C ₅ alkyl group, and R ₂ is a linear or branched C ₃ -C ₉ alkyl group. Detailed examples of ketone-based solvents are described in Tables 1 to 9. In some embodiments, the imaging agent includes 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination of the foregoing .

In some embodiments, the negative tone development (NTD) process developer includes an ester-based solvent, and the total number of carbon atoms in the ester-based solvent is in the range of 5-14. In some embodiments, the ester-based solvent has formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy. Detailed examples of ester-based solvents are described in Table 10 to Table 15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent, including 30 wt% to about 75 wt% of butyl acetate and 25 wt% to about 70 wt% of 1- Methoxy-2-propanol acetate.

In some embodiments, in order to remove unwanted residues, the patterned photoresist layer 110a may be subjected to a cleaning process 182 as needed. The cleaning process 182 includes the use of flushing solvents. In some embodiments, the processing solvent includes a developer and additives, where the developer includes, for example, a ketone-based solvent or an ester-based solvent.

Afterwards, as shown in FIG. 4D, a part of the material layer 104 is removed by performing an etching process and using the patterned photoresist layer 110a and the patterned modification layer 109a as a mask. In this way, a patterned material layer 104a is formed. After that, the patterned photoresist layer 110a is removed.

5A to 5E are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. The method described in the embodiment of the present invention can be used in a variety of applications, for example, a fin-type field-effect transistor device structure. Some of the processes and materials used to form the semiconductor device structure depicted in FIG. 5A to FIG. 5E may be the same or similar to those used to form the semiconductor device structure depicted in FIG. 1A to FIG. 1D. The materials will not be repeated here.

As shown in FIG. 5A, a modification layer 109 is formed on the photoresist layer 110. The modification layer 109 includes an auxiliary agent 14. The auxiliary agent 14 may include a photoacid generator, a quencher, a crosslinking agent, or a photobase generator. The material of the auxiliary agent 14 has been described in detail above, and it is omitted here for concise description. The photoresist layer 110 includes an inorganic material 12 and a solvent. The inorganic material 12 is uniformly distributed in the solvent. The inorganic material 12 includes a plurality of metal cores 122 and a plurality of first linking groups (L ₁ ) 124, wherein the first linking group (L ₁ ) 124 is bonded to the metal core 122.

After that, as shown in FIG. 5B, according to some embodiments of the present invention, a mask 10 is formed on the modification layer 109, and an exposure process 172 is performed on the modification layer 109 and the photoresist layer 110.

After the exposure process 172, the second linking group L ₂ and the third linking group L ₃ of the auxiliary agent 14 in the modification layer 109 and the first linking group 124 on the metal core 122 in the photoresist layer 110 Through the reaction, a plurality of chemical bonds are formed between the inorganic material 12 and the auxiliary agent 14.

Thereafter, as shown in FIG. 5C, according to some embodiments of the present invention, the modification layer 109 is developed by performing the first development process 180 to form a patterned modification layer 109a. In addition, a part of the photoresist layer 110 is also removed. In some embodiments, a negative-tone development process is performed to retain the exposed area of the modified layer 109, and the unexposed area of the modified layer 109 is removed by a ketone-based solvent, an ester-based solvent, or a combination thereof. Detailed examples of ketone-based solvents are described in Tables 1 to 9. In some embodiments, the imaging agent includes 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination of the foregoing . Detailed examples of ester-based solvents are described in Table 10 to Table 15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent, including 30 wt% to about 75 wt% of butyl acetate and 25 wt% to about 70 wt% of 1-methoxy-2 -Propanol acetate.

Next, as shown in FIG. 5D, according to some embodiments of the present invention, the photoresist layer 110 is developed by performing a second development process 181 to form a patterned photoresist layer 110a. The compound 16 is closer to the interface between the modification layer 109 and the photoresist layer 110 than the metal core 122.

Then, as shown in FIG. 5E, a part of the material layer 104 is removed by performing an etching process and using the patterned photoresist layer 110a and the patterned modification layer 109a as a mask. In this way, a patterned material layer 104a is formed. After that, the patterned photoresist layer 110a and the patterned modification layer 109a are removed.

6A to 6G are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. The method described in the embodiment of the present invention can be used in a variety of applications, for example, a fin-type field-effect transistor device structure. Some of the processes and materials used to form the semiconductor device structure depicted in FIGS. 6A to 6G may be the same or similar to those used to form the semiconductor device structure depicted in FIGS. 1A to 1D. The materials will not be repeated here.

As shown in FIG. 6A, a tri-layer photoresist layer 120 is formed on the material layer 104 on the substrate 102. The three-layer photoresist layer 120 includes a bottom layer 106, an intermediate layer 108, and a photoresist layer 110. The three-layer photoresist layer 120 is used to pattern the material layer 104 underneath and to be removed later.

A bottom layer 106 is formed on the material layer 104. The bottom layer 106 may be the first layer of a three-layer photoresist layer 120 (also referred to as a three-layer photoresist). The bottom layer 106 may include a material that is patternable and/or has anti-reflection properties. In some embodiments, the bottom layer 106 is a bottom anti-reflective coating (BARC) layer. In some embodiments, the bottom layer 106 includes a carbon backbone polymer. In some embodiments, the bottom layer 106 is formed of silicon free material. In some other embodiments, the bottom layer 106 includes a novolac resin, for example, a chemical structure having a plurality of phenol units bonded together. In some embodiments, the bottom layer 106 is formed by a spin coating process, a chemical vapor deposition process, a physical vapor deposition process, and/or other suitable deposition processes.

After that, an intermediate layer 108 is formed on the bottom layer 106, and a photoresist layer 110 is formed on the intermediate layer 108. In some embodiments, the bottom layer 106, the middle layer 108, and the photoresist layer (or top layer) 110 are referred to as a three-layer photoresist layer 120. The intermediate layer 108 may have a composition that can provide anti-reflection properties and/or hard mask properties for the lithography process. In addition, the intermediate layer 108 is designed to provide etching selectivity relative to the bottom layer 106 and the photoresist layer 110. In some embodiments, the intermediate layer 108 is formed of silicon nitride, silicon oxynitride, or silicon oxide. In some embodiments, the intermediate layer 108 includes a silicon-containing inorganic polymer. In some embodiments, the photoresist layer 110 includes a chemical structure as shown in FIG. 3A.

Next, as shown in FIG. 6B, according to some embodiments of the present invention, an exposure process (not shown) is performed on the photoresist layer 110 to form exposed areas and unexposed areas. Afterwards, the photoresist layer 110 is developed by a developer to form a patterned photoresist layer 110a. In some embodiments, the developer is a ketone-based solvent. Detailed examples of ketone-based solvents are described in Tables 1 to 9. In some embodiments, the imaging agent includes 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination of the foregoing . In some embodiments, the developer is an ester-based solvent. Detailed examples of ester-based solvents are described in Table 10 to Table 15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent, including 30 wt% to about 75 wt% of butyl acetate and 25 wt% to about 70 wt% of 1-methoxy-2 -Propanol acetate. After the exposure process, compound 16 is formed in the photoresist layer 110.

In some embodiments, in order to remove unwanted residues, a cleaning process may be performed on the patterned photoresist layer 110a as needed. The cleaning process includes the use of flushing solvents. In some embodiments, the processing solvent includes a developer and additives, where the developer includes, for example, a ketone-based solvent or an ester-based solvent.

Afterwards, as shown in FIG. 6C, according to some embodiments of the present invention, by using the patterned photoresist layer 110a as a mask, a part of the intermediate layer 108 is removed to form a patterned photoresist layer. The middle layer 108a. In this way, the pattern of the patterned photoresist layer 110a is transferred to the intermediate layer 108.

A part of the intermediate layer 108 is removed by a dry etching process, a wet etching process, or a combination of the above. In some embodiments, the etching process includes a plasma etching process, and the plasma etching process uses a fluorine-containing etchant, for example, CF ₂ , CF ₃ , CF ₄ , C ₂ F ₂ , C ₂ F ₃ , C ₃ F ₄ , C ₄ F ₄ , C ₄ F ₆ , C ₅ F ₆ , C ₆ F ₆ , C ₆ F ₈ or a combination of the above.

Thereafter, as shown in FIG. 6D, according to some embodiments of the present invention, the patterned photoresist layer 110a is removed. In some embodiments, the patterned photoresist layer 110a is removed by a wet etching process or a dry etching process. In some embodiments, the patterned photoresist layer 110a is removed by a wet etching process including an alkaline solution, wherein the alkaline solution is tetraalkylammonium hydroxide.

Next, as shown in FIG. 6E, according to some embodiments of the present invention, a portion of the bottom layer 106 is removed by using the patterned intermediate layer 108a as a mask to form a patterned bottom layer 106a. In this way, the pattern of the patterned middle layer 108a is transferred to the bottom layer 106.

Afterwards, as shown in FIG. 6F, according to some embodiments of the present invention, by performing an ion implantation process 174 and using the patterned intermediate layer 108a and the patterned bottom layer 106a as a mask, the material layer Part of 104 is doped. In this way, the doped region 105 is formed in the material layer 104. The doped region 105 may be doped with p-type dopants (for example, boron or boron difluoride (BF ₂ )) and/or n-type dopants (for example, phosphorus or arsenic). After that, the patterned intermediate layer 108a and the patterned bottom layer 106a are removed.

7A to 7F are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. The methods described in these embodiments can be used in a variety of applications, such as fin-type field-effect transistor device structures. Form the semiconductor device structure depicted in FIG. 7A to FIG. 7F Some of the processes and materials used may be the same or similar to those used to form the semiconductor device structure shown in FIG. 6A to FIG. 6G, and the description will not be repeated here.

As shown in FIG. 7A, a three-layer photoresist layer 120 is formed on the material layer 104. The intermediate layer 108 includes the auxiliary agent 14, and the auxiliary agent 14 is distributed in the solvent of the intermediate layer 108. The auxiliary agent 14 may include a photoacid generator, a quencher, a crosslinking agent, or a photobase generator. The photoresist layer 110 includes an inorganic material 12 and a solvent. The inorganic material 12 includes a first linking group (L ₁ ) 124, and the first linking group (L ₁ ) 124 is bonded to the metal core 122.

Thereafter, as shown in FIG. 7B, according to some embodiments of the present invention, a mask 10 is formed on the photoresist layer 110, and an exposure process 172 is performed on the intermediate layer 108 and the photoresist layer 110.

After the exposure process 172, the second linking group L ₂ and the third linking group L ₃ of the auxiliary agent 14 in the intermediate layer 108 and the first linking group 124 on the metal core 122 in the photoresist layer 110 Through the reaction, a plurality of chemical bonds are formed between the inorganic material 12 and the auxiliary agent 14. With the assistance of the auxiliary agent 14, the reaction rate of the chemical reaction between adjacent metal cores 122 can be increased.

Thereafter, as shown in FIG. 7C, according to some embodiments of the present invention, the photoresist layer 110 is developed by performing a development process to form a patterned photoresist layer 110a. The compound 16 is formed in the photoresist layer 110. The compound 16 is formed by reacting the inorganic material 12 with the auxiliary agent 14. In some embodiments, the developer is a ketone-based solvent, an ester-based solvent, or a combination of the foregoing. Detailed examples of ketone-based solvents are described in Tables 1 to 9. In some embodiments, the imaging agent includes 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination of the foregoing . Detailed examples of ester-based solvents are described in Table 10 to Table 15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent, including 30 wt% to about 75 wt% of butyl acetate and 25 wt% to about 70 wt% of 1-methoxy-2 -Propanol acetate.

Afterwards, as shown in FIG. 7D, according to some embodiments of the present invention, by using the patterned photoresist layer 110a as a mask, a part of the intermediate layer 108 is removed to form a patterned intermediate layer 108a. In this way, the pattern of the patterned photoresist layer 110a is transferred to the intermediate layer 108. After that, the process steps similar to those shown in FIG. 6D to FIG. 6G are continued to be performed on the substrate 102. In this way, as shown in FIG. 7F, a doped region 105 is formed in the material layer 104.

8A to 8D are schematic cross-sectional views of various stages of forming a semiconductor structure according to some embodiments of the present invention. The methods described in these embodiments can be used in a variety of applications, such as fin-type field-effect transistor device structures. Some of the processes and materials used to form the semiconductor device structure depicted in FIG. 8A to FIG. 8D may be the same or similar to those used to form the semiconductor device structure depicted in FIG. 6A to FIG. 6G. Materials, the description will not be repeated here.

As shown in FIG. 8A, according to some embodiments of the present invention, a modification layer 109 is formed on the three-layer photoresist layer 120.

Then, as shown in FIG. 8B, according to some embodiments of the present invention, an exposure process (not shown) is performed on the modification layer 109 and the photoresist layer 110. After that, the modified layer 109 and the photoresist layer 110 are developed sequentially by two kinds of developers to form the patterned modified layer 109a and the patterned photoresist layer 110a.

Then, as shown in FIG. 8C, according to some embodiments of the present invention, a part of the intermediate layer 108 is removed by using the patterned photoresist layer 110a and the patterned modification layer 109a as a mask. The patterned intermediate layer 108a is formed. In this way, the pattern of the patterned photoresist layer 110a is transferred to the intermediate layer 108. After that, the process steps similar to those shown in FIG. 6D to FIG. 6G are continued to be performed on the substrate 102. In this way, as shown in FIG. 8D, a doped region 105 is formed in the material layer 104.

Provided herein are some embodiments for forming semiconductor device structures. A material layer is formed on the substrate, and a photoresist layer is formed on the material layer. The photoresist layer includes an inorganic material and an auxiliary agent, and the inorganic material includes a plurality of metal cores and a plurality of first linking groups, wherein the first linking group is bonded to the metal core. The aforementioned auxiliary agent includes a plurality of second linking groups L ₂ and a plurality of third linking groups L ₃ . After the exposure process is performed on the photoresist layer, the second linking group L ₂ and the third linking group L _{3 of} the auxiliary agent react with the first linking group L _{1 of} the inorganic material to form a A compound, wherein the size of the compound is larger than the respective size of each metal core. The aforementioned auxiliary agent can accelerate the crosslinking reaction among the _{first linking group L 1} , the second linking group L ₂ and the third linking group L _3. In addition, a ketone-based solvent, an ester-based solvent, or a combination thereof is used to remove the unexposed area of the photoresist layer. Due to the addition of auxiliary agents and the use of hydrophobic ketone-based solvents in the photoresist layer, the radiation energy of the exposure process can be reduced. Furthermore, the line width roughness (LWR) of the photoresist layer is improved. Therefore, the line critical dimension uniformity (LCDU) is improved.

In some embodiments, a method of forming a semiconductor structure is provided. The method includes forming a material layer on the substrate, and forming a photoresist layer on the material layer. The photoresist layer includes an inorganic material and an auxiliary agent, and the inorganic material includes a plurality of metal cores and a plurality of first linking groups, wherein the first linking group is bonded to the metal core. This method includes exposing a part of the photoresist layer, and the photoresist layer includes an exposed area and an unexposed area, and in the exposed area, the auxiliary agent reacts with the first linking group. The method also includes using a developer to remove the unexposed regions of the photoresist layer to form a patterned photoresist layer. The above-mentioned developer includes a ketone-based solvent, an ester-based solvent, or a combination thereof, wherein the above-mentioned ketone-based solvent has a substituted or unsubstituted C ₆ -C ₇ cyclic ketone, and the above-mentioned ester-based solvent has the formula (b) :

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy.

In some embodiments, R ₃ is CH ₃ , and R ₄ is a linear or branched C ₂ -C ₆ alkyl group, or a linear or branched C ₂ -C ₆ alkoxy group.

In some embodiments, R ₃ is C ₂ H ₅ , and R ₄ is a linear or branched C ₄ alkyl group.

In some embodiments, R ₃ is C ₃ H ₇ , and R ₄ is a linear or branched C ₃ -C ₄ alkyl group.

In some embodiments, R ₃ is C ₄ H ₉ and R ₄ is a linear or branched C ₂ -C ₄ alkyl group.

In some embodiments, R3 is C ₅ H ₁₀ and R4 is a linear C ₂ alkyl group.

In some embodiments, R3 is C ₂ H ₅ O, and R ₄ is a linear or branched C ₂ -C ₃ alkyl group.

In some embodiments, the auxiliary agent includes a plurality of second linking groups, and during the exposure process, the second linking group reacts with the first linking group, so that the auxiliary agent and the inorganic material can react with each other. Multiple chemical bonds are formed between them.

In some embodiments, the step of using a developer to remove the unexposed area of the photoresist layer is operated at a temperature ranging from about 10°C to about 80°C.

In some embodiments, the method further includes: after using the developer, performing a rinsing process on the photoresist layer with a rinsing solvent.

In some embodiments, the above-mentioned processing solvent includes the above-mentioned developer and an additive, and the above-mentioned additive includes an acid.

In some embodiments, the above-mentioned acids include formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, butyric acid, valeric acid, oxalic acid, maleic acid, acrylic acid, hydrochloric acid, nitric acid, boric acid , Sulfuric acid, carbonic acid, phosphoric acid, hydrofluoric acid, hypochlorous acid, trifluoroacetic acid or a combination of the above.

In some embodiments, a method of forming a semiconductor structure is provided. The method includes forming a material layer on the substrate, and forming a bottom layer on the material layer. The method also includes forming an intermediate layer on the bottom layer, and forming a photoresist layer on the intermediate layer. The photoresist layer includes an inorganic material, and the inorganic material has a plurality of metal cores and a plurality of first linking groups, wherein the first linking group is bonded to the metal core. The method further includes forming a modified layer below or above the photoresist layer, and the modified layer includes an auxiliary agent. The method further includes performing an exposure process to expose a part of the photoresist layer, and during the exposure process, the auxiliary agent reacts with the first linking group. This method includes developing the photoresist layer using a ketone-based solvent or an ester-based solvent to form a patterned photoresist layer, wherein the ketone-based solvent has a substituted or unsubstituted C ₆ -C ₇ ring Like ketones, the above-mentioned ester-based solvents have the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy.

In some embodiments, the method further includes: developing the above-mentioned modification layer to form a patterned modification layer; and using the above-mentioned patterned photoresist layer as a mask to pattern the above-mentioned intermediate layer to form a patterned Intermediate layer; remove the patterned photoresist layer and the above pattern A patterned modification layer; and using the patterned intermediate layer as a mask to pattern the bottom layer to form a patterned bottom layer.

In some embodiments, the method further includes: after using the ketone-based solvent or the ester-based solvent, performing a rinsing process on the photoresist layer, wherein the rinsing process includes a rinsing solvent.

In some embodiments, the aforementioned rinse solvent includes additives, and the aforementioned additives include formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, butyric acid, valeric acid, oxalic acid, maleic acid, acrylic acid, Hydrochloric acid, nitric acid, boric acid, sulfuric acid, carbonic acid, phosphoric acid, hydrofluoric acid, hypochlorous acid, trifluoroacetic acid or a combination of the above.

In some embodiments, the method further includes: after exposing the above-mentioned part of the above-mentioned photoresist layer, forming a compound in the exposed region of the above-mentioned photoresist layer, wherein the above-mentioned compound is composed of the above-mentioned metal core, the above-mentioned second linking group and The above-mentioned first linking group is made, and the above-mentioned compound is not removed by the above-mentioned ketone-based solvent.

In some embodiments, a method of forming a semiconductor structure is provided. The method includes forming a material layer on the substrate, and forming a bottom layer on the material layer. The method includes forming an intermediate layer on the bottom layer, and forming a photoresist layer on the intermediate layer. The photoresist layer includes an inorganic material and an auxiliary agent. The inorganic material includes a plurality of first linking groups bonded to a plurality of metal cores, and the auxiliary agent includes a plurality of second linking groups. This method also includes performing an exposure process to expose a part of the photoresist layer, and during the exposure process, the second linking group reacts with the first linking group. This method includes using an ester-based solvent to remove a portion of the above-mentioned photoresist layer to form a patterned photoresist layer, wherein the above-mentioned ester-based solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy.

This method includes using the patterned photoresist layer as a mask to remove a part of the intermediate layer to form a patterned intermediate layer, and using the patterned intermediate layer as a mask to remove a part of the bottom layer , To form a patterned bottom layer.

In some embodiments, the method further includes: after exposing the above-mentioned part of the above-mentioned photoresist layer, forming a compound in the exposed region of the above-mentioned photoresist layer, wherein the above-mentioned compound is composed of the above-mentioned metal core, the above-mentioned second linking group and The above-mentioned first linking group is made, and the above-mentioned compound is not removed by the above-mentioned ketone-based solvent.

In some embodiments, the method further includes: performing a rinsing process on the photoresist layer after using the ester-based solvent, wherein the rinsing process includes a rinsing solvent, and the rinsing solvent includes the ester-based solvent and additives.

The foregoing text summarizes the components of many embodiments, so that those skilled in the art can better understand the embodiments of the present invention from various aspects. Those skilled in the art should understand, and can easily design or modify other processes and structures based on the embodiments of the present invention, so as to achieve the same purpose and/or achieve the same purpose as the embodiments described herein. The same advantages. Those skilled in the art should also understand that these equivalent structures do not depart from the spirit and scope of the present invention. Without departing from the spirit and scope of the present invention, various changes can be made to the present invention, Replace or modify.

Although the present invention has been disclosed in several preferred embodiments as above, it is not intended to limit the present invention. Anyone with ordinary knowledge in the art can make any changes without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be subject to the scope of the attached patent application.

12: Inorganic materials

14: adjuvant

16: Compound

122: Metal Core

124: first linking group

L ₁ : the first linking group

L ₂ : second linking group

L ₃ : the third linking group

Claims (9)

A method for forming a semiconductor structure includes: forming a material layer on a substrate; forming a photoresist layer on the material layer, wherein the photoresist layer includes an inorganic material and an auxiliary agent, wherein the inorganic material includes A plurality of metal cores and a plurality of first linking groups, and wherein the first linking groups are bonded to the metal cores; an exposure process is performed to expose a part of the photoresist layer, wherein the photoresist layer includes An exposed area and an unexposed area, and in the exposed area, the auxiliary agent reacts with the first linking groups, wherein the auxiliary agent includes a plurality of second linking groups, and during the exposure process, The second linking groups react with the first linking groups to form a plurality of chemical bonds between the auxiliary agent and the inorganic material; and using a developer to remove the unexposed area of the photoresist layer , To form a patterned photoresist layer, wherein the developer includes a ketone-based solvent, an ester-based solvent or a combination of the above, wherein the ketone-based solvent has a substituted or unsubstituted C ₆ -C ₇ cyclic ketones, this ester-based solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy. The method for forming a semiconductor structure according to claim 1, wherein a developer is used to move The step of removing the unexposed area of the photoresist layer is operated in a temperature range of about 10°C to about 80°C. The method for forming a semiconductor structure according to claim 1, further comprising: after using the developer, performing a rinsing process on the photoresist layer using a rinsing solvent, wherein the rinsing solvent includes the developer and an additive, and The additive includes an acid, and wherein the acid includes formic acid, acetic acid, propionic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, butyric acid, valeric acid, oxalic acid, maleic acid, acrylic acid, hydrochloric acid, nitric acid , Boric acid, sulfuric acid, carbonic acid, phosphoric acid, hydrofluoric acid, hypochlorous acid, trifluoroacetic acid or a combination of the above. A method for forming a semiconductor structure includes: forming a material layer on a substrate; forming a bottom layer on the material layer; forming an intermediate layer on the bottom layer; and forming a photoresist layer on the intermediate layer , Wherein the photoresist layer includes an inorganic material, and the inorganic material has a plurality of metal cores and a plurality of first linking groups, wherein the first linking groups are bonded to the metal cores; forming a modified layer on Below or above the photoresist layer, wherein the modification layer includes an auxiliary agent; an exposure process is performed to expose a part of the photoresist layer, wherein during the exposure process, the auxiliary agent and the first linking groups are performed Reaction; and using a ketone-based solvent or an ester-based solvent to develop the photoresist layer to form a patterned photoresist layer, wherein the ketone-based solvent has substituted or unsubstituted C _6- C ₇ cyclic ketone, the ester-based solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Group, or linear or branched C ₃ -C ₆ alkoxy. The method for forming a semiconductor structure according to claim 4, further comprising: developing the modification layer to form a patterned modification layer; and using the patterned photoresist layer as a mask to pattern the intermediate layer , To form a patterned intermediate layer; remove the patterned photoresist layer and the patterned modification layer; and use the patterned intermediate layer as a mask to pattern the bottom layer to A patterned bottom layer is formed. The method for forming a semiconductor structure according to claim 4, further comprising: after using the ketone-based solvent or the ester-based solvent, performing a rinsing process on the photoresist layer, wherein the rinsing process includes a rinsing solvent. A method for forming a semiconductor structure includes: forming a material layer on a substrate; forming a bottom layer on the material layer; forming an intermediate layer on the bottom layer; and forming a photoresist layer on the intermediate layer , Wherein the photoresist layer includes an inorganic material and an auxiliary agent, wherein the inorganic material includes a plurality of first linking groups bonded to a plurality of metal cores, and the auxiliary agent includes a plurality of second linking groups; performing an exposure process , To expose a part of the photoresist layer, wherein during the exposure process, the second linking groups react with the first linking groups; an ester-based solvent is used to remove a part of the photoresist layer, To form a patterned photoresist layer, wherein the ester-based solvent has the formula (b):

Wherein R ₃ is a linear or branched C ₁ -C ₅ alkyl group, or a linear or branched C ₂ alkoxy group, and R ₄ is a linear or branched C ₂ -C ₆ alkane Base, or linear or branched C ₃ -C ₆ alkoxy; use the patterned photoresist layer as a mask to remove a part of the intermediate layer to form a patterned intermediate layer; And using the patterned intermediate layer as a mask to remove a part of the bottom layer to form a patterned bottom layer. The method for forming a semiconductor structure according to claim 7, further comprising: after exposing the part of the photoresist layer, forming a compound in an exposed area of the photoresist layer, wherein the compound is composed of the metal cores , The second linking group and the first linking group are made, and the compound is not removed by the ketone-based solvent. The method for forming a semiconductor structure according to claim 7, further comprising: after using the ester-based solvent, performing a rinsing process on the photoresist layer, wherein the rinsing process includes a rinsing solvent, and the rinsing solvent includes the Ester-based solvent and an additive.

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