CN111752093A - Method of forming a semiconductor structure - Google Patents

Abstract

A method for forming a semiconductor device structure is provided herein. The method includes forming a material layer on a substrate, and forming a photoresist layer on the material layer. The photoresist layer includes an inorganic material and an auxiliary agent. The inorganic material includes a plurality of metal cores and a plurality of first linking groups, and the first linking group is bonded to the metal core. The method includes exposing a portion of the photoresist layer. The photoresist layer includes an exposed area and an unexposed area. In the exposed area, the auxiliary agent reacts with the first linking group. The method includes removing the unexposed area of the photoresist layer using a developer to form a patterned photoresist layer. The developer includes a ketone-based solvent having formula (a) or an ester-based solvent having formula (b).

Description

Method of forming a semiconductor structure

technical field

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

Background technique

Semiconductor devices are used in various electronic applications, such as personal computers, mobile phones, digital cameras, and other electronic equipment. 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 photolithography process, thereby forming on the semiconductor substrate. Circuit components and components. Many integrated circuits are typically fabricated on a single semiconductor wafer, and individual dies are singulated by dicing between the integrated circuits along dicing lines. The individual dies described above are typically packaged separately, eg, in a multi-chip module, or in other types of packages.

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

SUMMARY OF THE INVENTION

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 inorganic materials and auxiliary materials 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; exposing a portion of the photoresist layer, wherein the photoresist layer includes an exposed area and an unexposed area, and in the exposed area, the adjuvant reacts with the first linking group; and using a developer to remove the unexposed area of the photoresist layer to form a patterned photoresist An etch layer, wherein the developer comprises a ketone-based solvent, an ester-based solvent, or a combination thereof, wherein the ketone-based solvent has a substituted or unsubstituted _{C6 -} C7 cyclic ketone, and the ester-based solvent has the formula ( b):

wherein R ₃ is linear or branched C ₁ -C ₅ alkyl, or linear or branched C ₂ alkoxy, and R ₄ is 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; forming a photoresist layer on the intermediate layer above the 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 the photoresist under or over the resist layer, wherein the trim layer includes an adjuvant; performing an exposure process to expose a portion of the photoresist layer, wherein during the exposure process, the adjuvant reacts with the first linking group; A ketone-based solvent or an ester-based solvent develops the photoresist layer to form a patterned photoresist layer, wherein the ketone-based solvent has a substituted or unsubstituted _{C6 -} C7 ring The ketone, ester-based solvent has formula (b):

wherein R ₃ is linear or branched C ₁ -C ₅ alkyl, or linear or branched C ₂ alkoxy, and R ₄ is 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; forming a photoresist layer on the intermediate layer above the 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 portion of the photoresist layer, wherein during the exposure process, the second linking group reacts with the first linking group; using an ester-based solvent to remove a portion of the photoresist layer to form A patterned photoresist layer wherein the ester-based solvent has the formula (b):

wherein R ₃ is linear or branched C ₁ -C ₅ alkyl, or linear or branched C ₂ alkoxy, and R ₄ is linear or branched C ₂ -C ₆ alkane radical, or linear or branched C3 _{- C6} alkoxy; using the patterned photoresist layer as a mask to remove part of the interlayer to form a patterned interlayer; and using The patterned interlayer acts as a mask to remove a portion of the base layer to form a patterned base layer.

Description of drawings

The full disclosure is made in accordance with the following detailed description in conjunction with the accompanying drawings. It should be noted that, in accordance with common practice in the industry, the illustrations are not necessarily drawn to scale. In fact, the dimensions of elements may be arbitrarily enlarged or reduced for clarity.

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

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

3A is a schematic diagram of a chemical structure of a photoresist layer prior to an exposure process in accordance with some embodiments.

3B is a schematic diagram of a chemical structure of a photoresist layer after an exposure process in accordance with some embodiments.

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

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

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

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

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

Among them, the reference numerals are described as follows:

10: Mask

12: Inorganic Materials

14: Auxiliary

16: Compounds

102: Substrate

104: Material Layer

104a: Patterned Material Layer

105: Doping region

106: Ground Floor

106a: Patterned bottom layer

108: middle layer

108a: Patterned Intermediate Layer

109: Retouch layer

109a: Patterned Finishing Layer

110: Photoresist layer

110a - patterned photoresist layer

120: Three-layer photoresist layer

122: Metal Core

124: The first linking group

172: Exposure Process

174: Ion implantation process

180: Development process

182: Cleaning Process

L ₁ : the first linking group

L ₂ : the second linking group

L ₃ : the third linking group

P1: first pitch

T ₁ : first thickness

T ₂ : Second thickness

Detailed ways

The following disclosure provides many different embodiments or examples for implementing different features of the present invention. The following disclosure describes specific examples of various components and their arrangements to simplify the description. Of course, these specific examples are not intended to be limiting. For example, if the specification describes that a first part is formed on or over a second part, it means that it may include embodiments in which the first part and the second part are in direct contact, and may also include additional An embodiment in which a part is formed between the first part and the second part, so that the first part and the second part may not be in direct contact. Additionally, the different examples disclosed below may reuse the same reference signs and/or labels. These repetitions are for the purpose of simplicity and clarity and are not intended to limit the particular relationship between the various embodiments and/or structures discussed.

Various variations of the embodiments are described below. Similar element numbers are used to designate similar elements throughout the various views and depicted embodiments. It should be understood that additional operational steps may be provided before, between, or after performing the described methods, and in other embodiments of the described methods, some of the described 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 (FinFETs). For example, fins can have tighter spacing between components after being patterned by the methods described in the embodiments, and the methods described above are well suited for this. In addition, the spacers used to form the fins of the fin field effect transistors can also be processed by the processes described in the embodiments.

Embodiments of semiconductor structures and methods of forming the same are provided below. 1A-1D are schematic cross-sectional views of various stages of forming a semiconductor structure in accordance with some embodiments of the present invention. This method can be used in many applications, eg, Fin Field Effect Transistor (FinFET) device structures.

Referring to FIG. 1A , a substrate 102 is provided. The substrate 102 may be made of silicon or other semiconductor material. In some embodiments, the substrate 102 is a wafer. Alternatively or additionally, the substrate 102 may include other elemental semiconductor materials, such as germanium (Ge). In some embodiments, the substrate 102 is made of a compound semiconductor or alloy semiconductor, eg, silicon carbide, gallium arsenide, indium arsenide, or indium phosphide, silicon germanium, silicon germanium carbide, gallium arsenide phosphorous, 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 may be formed on the substrate 102 . Such device components include transistors (eg, metal oxide field effect transistors (MOSFETs), complementary metal oxide semiconductor (CMOS) transistors, bipolar junction transistors (BJTs), high-voltage transistors, high-frequency transistors, p-channel and/or n-channel field effect transistors (PFETs/NFETs, etc.), diodes, and other suitable components. Various processes may be performed to form device components, eg, deposition, etching, implantation, photolithography, annealing, and/or other suitable processes.

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

The substrate 102 also includes isolation structures (not shown). The isolation structures are used to define and electrically isolate various devices formed in and/or on the substrate 102 . In some embodiments, the isolation structures include shallow trench isolation (STI) structures, local oxidation of silicon (LOCOS) structures, 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.

Thereafter, 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 structures 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 are each independently formed through a deposition process, which may include, for example, a spin-on coating process, chemical vapor deposition (chemical vapor deposition) 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 an exposure areas and unexposed areas.

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

After the exposure process 172, a post-exposure-baking (PEB) process is performed. In some embodiments, the post-exposure bake process includes a heating process using microwaves or infrared lamps. In some embodiments, the post-exposure bake process is performed at a temperature ranging from about 70°C to about 250°C. In some other embodiments, the post-exposure bake process is performed for a duration 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 uniformly, the photoresist layer 110 can be uniformly 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 be made to react rapidly. In this way, 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 prior to the exposure process 172 in accordance with some embodiments.

In some embodiments, the photoresist layer 110 includes an inorganic material 12, an adjuvant 14, and a solvent. The inorganic material 12 and the adjuvant 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 groups (L ₁ ) 124 are bonded to the metal cores 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 adjuvant 14 may include a photo acid generator (PAG), a quencher (Q), a crosslinking agent, a photobase generator (PBG), or a combination thereof. In some embodiments, the weight ratio of the adjuvant 14 to the solvent is in the range of about 0.1 wt % to about 10 wt %. If the weight ratio of the adjuvant 14 to the solvent is less than 0.1 wt %, the reaction rate of the crosslinking reaction between the inorganic material 12 and the adjuvant 14 may not be increased. If the weight ratio of the adjuvant 14 to the solvent is greater than 10 wt %, other undesired chemical reactions may occur. For example, if the amount of the adjuvant 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 112 is formed of a metal, eg, tin (Sn), indium (In), antimony (Sb), or other suitable materials. In some embodiments, the first linking group 124 includes aliphatic or aromatic groups, unbranched or branched, cyclic or acyclic saturated with hydrogen or oxygen or halogen and with 1-9 A carbon (C ₁ -C ₉ ) unit (eg, 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 one hydroxyl group (-OH), the second linking group L ₂ has one hydroxyl group (-OH), and the two hydroxyl groups react with each other to undergo a hydrolysis reaction. . In some other embodiments, the first linking group (L ₁ ) 124 has one carbon-carbon double bond (alkene) or carbon-carbon triple bond (alkyne), and the second linking group L ₂ is linked to the first The group (L ₁ ) 124 reacts to perform 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 is associated with the first linking group (L _{1 )} . ) 124 reaction to carry out the addition reaction.

In some embodiments, the adjuvant 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 first linking group L 2 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 compound 16 has a size larger than that of each metal core 122 .

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

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

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

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

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

3B is a schematic diagram of the chemical structure of the photoresist layer after exposure process 172 is performed, in accordance with some embodiments. It should be noted that after the exposure process 172 , the adjuvant 14 is used to assist the cross-linking reaction between the 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 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 . A linking group (L ₁ ) between 124.

During the exposure process 172, adjacent first linking groups L ₁ bonded to different metal cores 122 may react with each other by performing a cross-linking reaction. The inorganic material 12 having the metal core 122 and the first linking group (L ₁ ) 124 is used to enhance the radiation absorption of the exposure process 172 . For example, In-based or Sn-based inorganic materials have good absorption properties for 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, a distance exists between adjacent first linking agents L1. In order to increase the reaction rate of the cross-linking reaction, the adjuvant 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 One of the first linking groups (L ₁ ) 124 of the can react with one of the first linking groups (L ₁ ) 124 located on the second metal core 122 . Note that the cross-linking reaction between adjacent metal cores 122 is improved due to the addition of the adjuvant 14 .

In a comparative example, the photoresist layer 110 includes the inorganic material 12 and the solvent, but does not include the adjuvant 14 described above. In this comparative example, the cross-linking reaction between adjacent metal cores 122 has the first reaction rate. In some embodiments, the photoresist layer 110 includes the above-mentioned inorganic material 12 and the auxiliary agent 14 and the above-mentioned solvent. The cross-linking reaction between adjacent metal cores 122 has a second reaction rate. One of the metal cores 122 is bonded to the other metal core 122 by adding the auxiliary agent 14 . With the assistance of the auxiliary agent 14, the reaction rate of the cross-linking reaction between adjacent metal cores 122 is improved. Due to the assistance of the adjuvant 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 photoresist layer 110 . Compound 16 is formed by reacting inorganic material 12 with adjuvant 14 . A portion of the metal core 122 reacts with the auxiliary agent 14 , but another portion of the metal core 122 remains in the photoresist layer 110 . In other words, the compound 16 is formed from 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: positive tone development (PTD) process and negative tone development (NTD) process. The positive tone development process uses a positive tone developer, which generally refers to a developer that selectively dissolves and removes exposed portions of a photoresist layer. The negative tone development process uses a negative tone developer, which generally refers to a developer that selectively dissolves and removes unexposed portions of the photoresist layer 110 . In some embodiments, the positive tone developing (PTD) developer is an aqueous base developer, eg, tetraalkylammonium hydroxide (TMAH).

The developing 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 developing 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 portions of the photoresist layer 110 may be too low and the undesired photoresist residues in the unexposed portions may not be completely removed (should be Remove unexposed parts completely). If the dipole momentum is greater than 4 Debye, the solubility of the exposed portion of the photoresist layer 110 may be too high, and the exposed portion of the photoresist layer 110 may be overdeveloped (the exposed portion should remain), and the exposure Parts may be cracked or necked in shape.

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 ketone-based solvent has a total number of carbon atoms in the range of 5 to 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.

Tables 1-9 show some examples of ketone-based developers in accordance with some embodiments of the present invention. As shown in Table 1, the ketone-based solvent has formula ( _a ), wherein R1 is _CH3 and R2 is linear or branched _{C4 - C9} alkyl. In some embodiments, the ketone-based solvent is of formula (a), wherein R ₁ is CH ₃ and R ₂ is a branched C ₅ alkyl group. For example, a ketone-based solvent is 5-methyl-2-hexanone. In some embodiments, the ketone-based solvent is of formula (a), wherein R ₁ is CH ₃ and R ₂ is linear C ₆ alkyl. For example, a ketone-based solvent is 2-octanone.

Table 1

As shown in Table ₂ , the ketone-based solvent has _formula ( _a ), wherein R1 is _C2H5 and R2 is linear or branched _C4 - _C8 alkyl. In some embodiments, the ketone-based solvent is of formula (a), wherein R ₁ is C ₂ H ₅ and R ₂ is a linear C ₄ alkyl group. For example, a ketone-based solvent is 3-heptanone.

Table 2

As shown in Table ₃ , the ketone-based solvent has the _formula ( _a ), wherein R1 is linear _C3H7 and R2 is linear or branched C3 _{- C7} alkyl.

table 3

As shown in Table 4, the ketone-based solvent has _formula ( _a ), wherein R1 is branched _C3H7 and R2 is linear _{C4 - C6} alkyl.

Table 4

As shown in Table ₅ , the ketone-based solvent has formula ( _a ), wherein R1 is branched _C4H9 and R2 is branched _{C4 - C6} alkyl.

table 5

As shown in Table ₆ , the ketone-based solvent has formula ( _a ), wherein R1 is branched _C5H11 and R2 is linear _{C4 - C5} alkyl.

Table 6

As shown in Table ₇ , the ketone _- based solvent has _formula ( _a ), wherein R1 is branched _C3H7 and R2 is _C3H7 .

Table 7

As shown in Table ₈ , the ketone-based solvent has _formula ( _a ), wherein R1 is _CH3 or _C3H7 , and R2 is linear or branched C3 _{- C5} alkyl.

Table 8

In some embodiments, the ketone-based solvent is a substituted or unsubstituted _{C6 -} C7 cyclic ketone, wherein the substituents are hydrogen, alkyl. More specifically, as shown in Table 9, in some embodiments, cyclic ketones have at least one hydrogen atom substituted with a _{C1 -} C3 alkyl group, eg, methyl ( _-CH3 ), ethyl (-C _2H5 ), isopropyl ( _-C3H7 ) or n _{- propyl} ( _-C3H7 ).

Table 9

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

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

Tables 10-15 show some examples of ester-based solvents in accordance with some embodiments of the present invention. As shown in Table 10, the ester-based solvent has formula (b), wherein _R3 is _CH3 and R4 is linear or branched _{C2 - C6} alkyl, or linear or branched C ₂ -C ₆ alkoxy.

Table 10

As shown in Table 11, the ester-based solvent has the _formula (b), wherein _R3 is _C2H5 and R4 is a linear or branched _C4 alkyl group _.

Table 11

As shown in Table 12, the ester-based solvent has the formula ( _b ), wherein _R3 is _C3H7 and R4 is a linear or branched C3 _{- C4} alkyl group _.

Table 12

As shown in Table ₁₃ , the ester-based solvent has the formula (b), wherein _R3 is _C4H9 and R4 is a linear or branched C2 _{- C4} alkyl group _.

Table 13

As shown in Table ₁₄ , the ester-based solvent has the _formula (b), wherein _R3 is _C5H10 and R4 is a linear _C2 alkyl group.

Table 14

As shown in Table 15, the ester-based solvent has the _formula (b), wherein _R3 is _C2H5O and R4 is a linear or branched _{C2 - C3} alkyl group.

Table 15

As shown in FIG. 1C, in some embodiments, a negative tone development process is performed, leaving exposed areas of photoresist layer 110, and removing unexposed areas of photoresist layer 110 by a ketone-based solvent . After the exposure process 172 is performed, the exposed areas of the photoresist layer 110 become more hydrophilic, and thus, the unexposed areas of the photoresist layer 110 are removed using a ketone-based solvent. Furthermore, compared with inorganic materials, compound 16 has a larger average molecular weight, so compound 16 cannot be easily dissolved in organic solvents. Therefore, when the unexposed areas of the photoresist layer 110 are removed, the exposed areas of the photoresist layer 110 may still remain.

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 a cross-linking reaction between the inorganic material 12 and the auxiliary agent 14 . High radiation doses will result in a high degree of crosslinking. Therefore, the radiation dose should be increased to obtain a larger critical dimension 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 areas of the photoresist layer 110 of the embodiments of the present invention are removed by using a relatively hydrophobic ketone-based solvent. Compound 16 in the exposed regions becomes hydrophilic and not easily removed by hydrophobic ketone-based solvents. Therefore, the critical dimension of the exposed area of the photoresist layer 110 can be increased by using a hydrophobic ketone-based solvent.

In a comparative example, the ketone solvent is 2-heptanone. Compared to the 2-heptanone of this comparative example, the ketone-based solvents described in Tables 1 to 9 of the present invention are more hydrophobic. Therefore, the exposed areas of the photoresist layer 110 are not removed by using the hydrophobic ketone-based solvent. Embodiments of the present invention provide a simple method to obtain a larger critical dimension 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 developer is in the range of about 0.01 wt % to about 3 wt %. During the crosslinking reaction between the inorganic material 12 and the adjuvant 14, water is used as a catalyst. If the crosslinking reaction does not go to completion during the exposure process, water added to the developer during the development process can aid the crosslinking reaction. Note that the amount of water is not too much, so the polarity of the developer is not significantly affected by the water.

In some embodiments, the developer further includes a surfactant. Surfactants are used to increase solubility and reduce surface tension on material layer 104 . In some embodiments, the ratio of surfactant to developer is in the range of about 0.01 wt % to about 1 wt %. In some embodiments, the surfactant comprises 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 linear C ₁ -C ₂₀ alkyl. In formulas (f) and (g), R ₁ is hydrogen or straight-chain C ₁ -C ₂₀ alkyl, R ₂ is hydrogen or straight-chain C ₁ -C ₂₀ alkyl, and PO represents -CH ₂ -CH ₂ -O-, EO represents _-CH3 -CH- _CH2 -O-.

In some embodiments, the step of removing the non-exposed areas of the photoresist layer using a ketone-based developer is performed at a temperature ranging from about 10°C to about 80°C. The advantage of having the temperature of the developer within the above range is to reduce the solubility of the photoresist layer so that more exposed areas of the photoresist layer can survive.

The exposed regions of the photoresist layer 110 have 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.

After that, as shown in FIG. 1D , a portion of the material layer 104 is removed by performing an etching process and using the patterned photoresist layer 110 a as a mask. In this way, the 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 etch process including a hydrogen fluoride (HF) solution.

The adjuvant 14 in the photoresist layer 110 is used to enhance the energy absorption of the photoresist layer 110 during the exposure process 172 . With the assistance of adjuvant 14, the radiation energy of 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, critical dimension uniformity (CDU) is also improved by about 3% to about 40%. Therefore, the development resolution is improved.

Again, by using a hydrophobic ketone-based solvent, the unexposed areas of the photoresist layer 110 are removed, but the exposed areas of the photoresist layer 110 are not removed. Because of the use of ketone-based solvents, the dose of EUV radiation is reduced. In this way, a larger critical dimension of the patterned photoresist layer 110a can be obtained without increasing the radiation dose of the exposure process. Thus, the throughput of forming semiconductor device structures is improved.

2A-2C are schematic cross-sectional views of various stages of forming a semiconductor structure in accordance with some embodiments of the present invention. The methods described in the embodiments of the present invention can be used in a variety of applications, eg, fin field effect transistor device structures. Some of the processes and materials used to form the semiconductor device structures shown in FIGS. 2A-2C may be the same or similar to some of the processes and materials used to form the semiconductor device structures shown in FIGS. 1A-1D , here The description will not be repeated.

As shown in FIG. 2A , a patterned photoresist layer 110 a is formed by performing a developing process 180 . However, some residues from unreacted inorganic material 12 or adjuvant 14 are not removed by developing process 180 . The patterned photoresist layer 110a thus has a protruding bottom. This protruding bottom may affect subsequent patterning processes.

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

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

The additives used in the rinse solvent in the cleaning process 182 include acid, and this 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, additives used in 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 cleaning process 182 is tetra-n-butylammonium fluoride. In some embodiments, the additive used in cleaning process 182 is acetic acid. In some other embodiments, the additive used in cleaning process 182 is oxalic acid.

4A-4D are schematic cross-sectional views of various stages of forming a semiconductor structure in accordance with some embodiments of the present invention. The methods described in the embodiments of the present invention can be used in a variety of applications, eg, fin field effect transistor device structures. Some of the processes and materials used to form the semiconductor device structures shown in FIGS. 4A-4D may be the same or similar to some of the processes and materials used to form the semiconductor device structures shown in FIGS. 1A-1D , here The description will not be repeated.

As shown in FIG. 4A , a trim layer 109 is formed on the material layer 104 , and a photoresist layer 110 is formed on the trim layer 109 . The modification layer 109 includes the adjuvant 14 . The adjuvant 14 may include a photoacid generator (PAG), a matting agent (Q), a crosslinking agent, or a photobase generator (PBG). The materials of the adjuvant 14 have been described in detail above, and the repeated description is omitted here for brevity. The photoresist layer 110 includes the 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 groups (L ₁ ) 124 are bonded to the metal cores 122 .

The photoresist layer 110 has a first thickness T ₁ and the trim 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%.

Then, 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 an exposure 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 react with the auxiliary agent 12 on the inorganic 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 is accelerated. 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, the compound 16 has a larger average molecular weight than the metal core 122 having the first linking group (L ₁ ) 124 .

Next, 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 developing process 180 to form a patterned photoresist layer 110 a and the patterned modification layer 109a. In some embodiments, the photoresist layer 110 and the modification layer 109 are developed simultaneously. In some embodiments, the photoresist layer 110 is patterned first, and then the trim layer 109 is patterned. In some embodiments, compound 16 is closer to the interface between trim layer 109 and photoresist layer 110 than inorganic material 12 is.

In some embodiments, a negative tone development process is performed, leaving exposed areas of the photoresist layer 110 and removing unexposed areas of the photoresist layer 110 by a developer. After the exposure process 172 is performed, the exposed areas of the photoresist layer 110 become more hydrophilic, and thus, the unexposed areas of the photoresist layer 110 are removed using an organic solvent.

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 possessed by the ketone-based solvent is in the range of 5 to 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 1-9. In some embodiments, the developer comprises 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination thereof .

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

wherein R ₃ is linear or branched C ₁ -C ₅ alkyl, or linear or branched C ₂ alkoxy, and R ₄ is 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 Tables 10-15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent comprising 30 wt % to about 75 wt % butyl acetate and 25 wt % to about 70 wt % 1- Methoxy-2-propanol acetate.

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

After that, 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 110 a and the patterned trim layer 109 a as masks. In this way, the patterned material layer 104a is formed. After that, the patterned photoresist layer 110a is removed.

5A-5E are schematic cross-sectional views of various stages of forming a semiconductor structure in accordance with some embodiments of the present invention. The methods described in the embodiments of the present invention can be used in a variety of applications, eg, fin field effect transistor device structures. Some of the processes and materials used to form the semiconductor device structures shown in FIGS. 5A-5E may be the same or similar to some of the processes and materials used to form the semiconductor device structures shown in FIGS. 1A-1D , here The description will not be repeated.

As shown in FIG. 5A , a modification layer 109 is formed on the photoresist layer 110 . The modification layer 109 includes the adjuvant 14 . The adjuvant 14 may include a photoacid generator, a quencher, a crosslinking agent, or a photobase generator. The materials of the adjuvant 14 have been described in detail above, and are omitted here for the sake of brevity. The photoresist layer 110 includes the 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 groups (L ₁ ) 124 are bonded to the metal cores 122 .

Then, 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 adjuvant 14 in the modification layer 109 are linked to the first link on the metal core 122 in the photoresist layer 110 The groups 124 react, thereby forming a plurality of chemical bonds between the inorganic material 12 and the auxiliary agent 14 .

Then, as shown in FIG. 5C , according to some embodiments of the present invention, the modification layer 109 is developed by performing the first developing process 180 to form a patterned modification layer 109 a. Additionally, a portion of the photoresist layer 110 is also removed. In some embodiments, a negative tone development process is performed, leaving the exposed areas of the modification layer 109, and the unexposed areas of the modification layer 109 are removed by a ketone-based solvent, an ester-based solvent, or a combination thereof. Detailed examples of ketone-based solvents are described in Tables 1-9. In some embodiments, the developer comprises 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination thereof . Detailed examples of ester-based solvents are described in Tables 10-15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent comprising 30 wt % to about 75 wt % butyl acetate and 25 wt % to about 70 wt % 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 developing process 181 to form a patterned photoresist layer 110 a. Compound 16 is closer to the interface between trim layer 109 and photoresist layer 110 than metal core 122 is.

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

6A-6G are schematic cross-sectional views of various stages of forming a semiconductor structure in accordance with some embodiments of the present invention. The methods described in the embodiments of the present invention can be used in a variety of applications, eg, fin field effect transistor device structures. Some of the processes and materials used to form the semiconductor device structures shown in FIGS. 6A to 6G may be the same or similar to some of the processes and materials used to form the semiconductor device structures shown in FIGS. This will not be repeated.

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 underlying material layer 104 and is subsequently removed.

A bottom layer 106 is formed over the material layer 104 . The bottom layer 106 may be the first layer of a tri-layer photoresist layer 120 (also referred to as a tri-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 a silicon free material. In some other embodiments, the bottom layer 106 includes a novolac resin, eg, a chemical structure having multiple 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, bottom layer 106 , intermediate layer 108 , and photoresist layer (or top layer) 110 are referred to as tri-layer photoresist layer 120 . The intermediate layer 108 may have a composition that provides anti-reflection properties and/or hard mask properties for use in photolithographic processes. Additionally, the intermediate layer 108 is designed to provide etch 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 depicted 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 an exposed area and an unexposed area. After that, 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 1-9. In some embodiments, the developer comprises 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination thereof . In some embodiments, the developer is an ester-based solvent. Detailed examples of ester-based solvents are described in Tables 10-15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent comprising 30 wt % to about 75 wt % butyl acetate and 25 wt % to about 70 wt % 1-methoxy-2 -Propanol acetate. After the exposure process, compound 16 is formed in the photoresist layer 110 .

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

Thereafter, as shown in FIG. 6C, according to some embodiments of the present invention, a patterned interlayer is formed by removing a portion of the interlayer 108 by using the patterned photoresist layer 110a as a mask layer 108a. As such, the pattern of the patterned photoresist layer 110a is transferred to the intermediate layer 108 .

A portion of the intermediate layer 108 is removed by a dry etching process, a wet etching process, or a combination thereof. _In some embodiments, the etching process includes a plasma etching process, and the plasma etching process uses a fluorine _- containing etchant, eg, _CF2 , _CF3 , _CF4 , _C2F2 , _C2F3 , _C3 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, the patterned photoresist layer 110a is removed in accordance with some embodiments of the present invention. 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 etch 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 patterned bottom layer 106a is formed by removing a portion of the bottom layer 106 by using the patterned intermediate layer 108a as a mask. As such, the pattern of the patterned intermediate layer 108a is transferred to the bottom layer 106 .

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

7A-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, eg, fin field effect transistor device structures. Some of the processes and materials used to form the semiconductor device structures shown in FIGS. 7A to 7F may be the same or similar to some of the processes and materials used to form the semiconductor device structures shown in FIGS. 6A to 6G , here The description will not be repeated.

As shown in FIG. 7A , a three-layer photoresist layer 120 is formed on the material layer 104 . The intermediate layer 108 includes the adjuvant 14 , and the adjuvant 14 is distributed in the solvent of the intermediate layer 108 . The adjuvant 14 may include a photoacid generator, a quencher, a crosslinking agent, or a photobase generator. The photoresist layer 110 includes the 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 .

Then, 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 adjuvant 14 in the intermediate layer 108 are linked to the first link on the metal core 122 in the photoresist layer 110 The groups 124 react, thereby forming a plurality of chemical bonds 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 the adjacent metal cores 122 is increased.

Then, 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 110 a. Compound 16 is formed in photoresist layer 110 . Compound 16 is formed by reacting inorganic material 12 with adjuvant 14 . In some embodiments, the developer is a ketone-based solvent, an ester-based solvent, or a combination thereof. Detailed examples of ketone-based solvents are described in Tables 1-9. In some embodiments, the developer comprises 3-heptanone, 4-heptanone, 2-octanone, 5-methyl-2-hexanone, 2,4-dimethyl-3-pentanone, or a combination thereof . Detailed examples of ester-based solvents are described in Tables 10-15. In some embodiments, the developer is an ester-based solvent, and the ester-based solvent is a co-solvent comprising 30 wt % to about 75 wt % butyl acetate and 25 wt % to about 70 wt % 1-methoxy-2 -Propanol acetate.

Thereafter, as shown in FIG. 7D, according to some embodiments of the present invention, a patterned interlayer is formed by removing a portion of the interlayer 108 by using the patterned photoresist layer 110a as a mask layer 108a. As such, 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-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, eg, fin field effect transistor device structures. Some of the processes and materials used to form the semiconductor device structures shown in FIGS. 8A to 8D may be the same or similar to some of the processes and materials used to form the semiconductor device structures shown in FIGS. 6A to 6G , here The description will not be repeated.

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

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

Thereafter, as shown in FIG. 8C , according to some embodiments of the present invention, a portion of the interlayer 108 is removed by using the patterned photoresist layer 110a and the patterned trim layer 109a as masks , and the patterned intermediate layer 108a is formed. As such, 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 .

Some embodiments for forming semiconductor device structures are provided herein. 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 groups are bonded to the metal cores. The above-mentioned 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 L2 and the _third linking group L3 of the auxiliary agent react with the _first linking group L1 of the inorganic material, to form a compound wherein the size of the compound is larger than the respective size of each metal core. The above-mentioned auxiliary agent can accelerate the cross-linking reaction between 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 of the above is used to remove the unexposed areas of the photoresist layer described above. Due to the addition of an adjuvant and the use of a hydrophobic ketone-based solvent in the above-mentioned 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, an improvement in line critical dimension uniformity (LCDU) is achieved.

In some embodiments, methods of forming semiconductor structures are 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 groups are bonded to the metal cores. The method includes exposing a portion of the photoresist layer, and the photoresist layer includes an exposed area and an unexposed area, and in the exposed area, the adjuvant reacts with the first linking group. The method also includes removing the unexposed areas of the photoresist layer using a developer to form a patterned photoresist layer. The above developer includes a ketone-based solvent, an ester-based solvent, or a combination of the above, wherein the above-mentioned ketone-based solvent has a substituted or unsubstituted _{C6 -} C7 cyclic ketone, and the above-mentioned ester-based solvent has formula (b) :

wherein R ₃ is linear or branched C ₁ -C ₅ alkyl, or linear or branched C ₂ alkoxy, and R ₄ is 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 linear or branched C ₂ -C ₆ alkyl, or linear or branched C ₂ -C ₆ alkoxy.

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

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

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

_In some embodiments, R3 is _C5H10 and R4 is straight chain _C2 alkyl.

_In some embodiments, _R3 is _C2H5O and R4 is linear or branched _{C2 -} C3 alkyl.

In some embodiments, the adjuvant 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 adjuvant and the inorganic material are reacted with each other. multiple chemical bonds are formed between them.

In some embodiments, the step of removing the unexposed regions of the photoresist layer using a developer is performed 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 rinse solvent includes the developer and an additive, and the additive includes an acid.

In some embodiments, such 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, methods of forming semiconductor structures are 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 over the bottom layer, and forming a photoresist layer over 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 groups are bonded to the metal cores. The method also includes forming a trim layer under or over the photoresist layer, and the trim layer includes an adjuvant. The method further includes performing an exposure process to expose a portion of the photoresist layer, and during the exposure process, the adjuvant reacts with the first linking group. The method includes developing the above-mentioned photoresist layer with a ketone-based solvent or an ester-based solvent, wherein the above-mentioned ketone-based solvent has a substituted or unsubstituted, to form a patterned photoresist layer The _{C6 -} C7 cyclic ketone, the above-mentioned ester-based solvent has the formula (b):

wherein R ₃ is linear or branched C ₁ -C ₅ alkyl, or linear or branched C ₂ alkoxy, and R ₄ is 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 modification layer to form a patterned modification layer; patterning the intermediate layer using the patterned photoresist layer as a mask to form a modified layer patterned interlayer; removing the patterned photoresist layer and the patterned trim layer; and patterning the bottom layer using the patterned interlayer as a mask to form a patterned bottom layer.

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

In some embodiments, the rinse solvent includes an additive, and the additive 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 combinations thereof.

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

In some embodiments, methods of forming semiconductor structures are provided. The method includes forming a material layer on a substrate, and forming a bottom layer on the material layer. The method includes forming an intermediate layer over the bottom layer, and forming a photoresist layer over 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. The method also includes performing an exposure process to expose a portion of the photoresist layer, and during the exposure process, the second linking group reacts with the first linking group. The method includes removing a portion of the photoresist layer using an ester-based solvent having formula (b) to form a patterned photoresist layer:

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

The method includes removing a portion of the interlayer using the patterned photoresist layer as a mask to form a patterned interlayer, and removing the interlayer using the patterned interlayer as a mask part of the bottom layer to form a patterned bottom layer.

In some embodiments, the method further includes: after exposing the portion of the photoresist layer, forming a compound in the exposed region of the photoresist layer, wherein the compound is composed of the metal core, the The second linking group and the first linking group described above are 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 rinse process on the photoresist layer after using the ester-based solvent, wherein the rinse process includes a rinse solvent, and the rinse solvent includes the ester-based solvent and additives.

The foregoing context has outlined components of many embodiments so that those of ordinary skill in the art may better understand various aspects of embodiments of the invention. Those of ordinary skill 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 as the embodiments introduced herein, etc. advantage. Those of ordinary skill in the art should also realize that such equivalent structures do not depart from the spirit and scope of the invention. Various changes, substitutions or modifications can be made in the present invention without departing from the spirit and scope of the invention.

Although the present invention has been disclosed above with several preferred embodiments, it is not intended to limit the present invention. Any person of ordinary skill in the art can make any changes and modifications without departing from the spirit and scope of the present invention. Therefore, the protection scope of the present invention should be determined by the appended claims.

Claims (10)

1. A method of forming a semiconductor structure, comprising:

forming a material layer on a substrate;

forming a photoresist layer over the material layer, wherein the photoresist layer comprises an inorganic material and an adjuvant, wherein the inorganic material comprises a plurality of metal cores and a plurality of first linking groups, and wherein the plurality of first linking groups are bonded to the plurality of metal cores;

exposing a portion of the photoresist layer, wherein the photoresist layer includes an exposed region and an unexposed region, and in the exposed region, the auxiliary reacts with the plurality of first linking groups; and

removing the unexposed region of the photoresist layer using a developer to form a patterned photoresist layer, wherein the developer comprises a ketone-based solvent, an ester-based solvent, or a combination thereof, wherein the ketone-based solvent has a substituted or unsubstituted C₆-C₇A cyclic ketone, the ester-based solvent having formula (b):

wherein R is₃Is straight-chain or branched C₁-C₅Alkyl, or straight or branched C₂Alkoxy radical, and R₄Is straight-chain or branched C₂-C₆Alkyl, or straight or branched C₃-C₆An alkoxy group.

2. The method according to claim 1, wherein the auxiliary agent comprises a plurality of second linking groups, and the plurality of second linking groups react with the plurality of first linking groups during the exposure process to form a plurality of chemical bonds between the auxiliary agent and the inorganic material.

3. The method according to claim 1, wherein the step of removing the unexposed regions of the photoresist layer using a developer is performed at a temperature in a range from about 10 ℃ to about 80 ℃.

4. The method of forming a semiconductor structure of claim 1, further comprising:

after the developer is used, a rinsing process is performed on the photoresist layer using a rinsing solvent.

5. A method of forming a semiconductor structure, comprising:

forming a material layer on a substrate;

forming a bottom layer on the material layer;

forming a middle layer on the bottom layer;

forming a photoresist layer on the intermediate layer, wherein the photoresist layer comprises an inorganic material having a plurality of metal cores and a plurality of first connecting groups, wherein the plurality of first connecting groups are bonded to the plurality of metal cores;

forming a modifying layer below or above the photoresist layer, wherein the modifying layer comprises an auxiliary agent;

performing an exposure process to expose a portion of the photoresist layer, wherein the adjuvant reacts with the plurality of first linking groups during the exposure process; and

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 C₆-C₇A cyclic ketone, the ester-based solvent having formula (b):

wherein R is₃Is straight-chain or branched C₁-C₅Alkyl, or straight or branched C₂Alkoxy radical, and R₄Is straight-chain or branched C₂-C₆Alkyl, or straight or branched C₃-C₆An alkoxy group.

6. The method of forming a semiconductor structure of claim 5, further comprising:

developing the modified layer to form a patterned modified layer;

patterning the intermediate layer using the patterned photoresist layer as a mask to form a patterned intermediate layer;

removing the patterned photoresist layer and the patterned modifying layer; and

the bottom layer is patterned using the patterned middle layer as a mask to form a patterned bottom layer.

7. The method of forming a semiconductor structure of claim 5, further comprising:

after using the ketone-based solvent or the ester-based solvent, a rinsing process is performed on the photoresist layer, wherein the rinsing process includes a rinsing solvent.

8. A method of forming a semiconductor structure, comprising:

forming a material layer on a substrate;

forming a bottom layer on the material layer;

forming a middle layer on the bottom layer;

forming a photoresist layer on the intermediate layer, wherein the photoresist layer comprises an inorganic material and an adjuvant, wherein the inorganic material comprises a plurality of first connecting groups bonded to a plurality of metal cores, and the adjuvant comprises a plurality of second connecting groups;

performing an exposure process to expose a portion of the photoresist layer, wherein the second linking groups react with the first linking groups during the exposure process;

removing a portion of the photoresist layer using an ester-based solvent to form a patterned photoresist layer, wherein the ester-based solvent has formula (b):

wherein R is₃Is straight-chain or branched C₁-C₅Alkyl, or straight or branched C₂Alkoxy radical, and R₄Is straight-chain or branched C₂-C₆Alkyl, or straight or branched C₃-C₆An alkoxy group;

removing a portion of the intermediate layer using the patterned photoresist layer as a mask to form a patterned intermediate layer; and

a portion of the bottom layer is removed using the patterned middle layer as a mask to form a patterned bottom layer.

9. The method of forming a semiconductor structure of claim 8, further comprising:

after exposing the portion of the photoresist layer, forming a compound in an exposed region of the photoresist layer, wherein the compound is made up of the plurality of metal cores, the plurality of second linking groups, and the plurality of first linking groups, and the compound is not removed by the ketone-based solvent.

10. The method of forming a semiconductor structure of claim 8, further comprising:

after the ester-based solvent is used, a rinsing process is performed 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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