Patent Application
20240369929
As consumer devices have gotten smaller and smaller in response to consumer demand, the individual components of these devices have necessarily decreased in size as well. Semiconductor devices, which make up a major component of devices such as mobile phones, computer tablets, and the like, have been pressured to become smaller and smaller, with a corresponding pressure on the individual devices (e.g., transistors, resistors, capacitors, etc.) within the semiconductor devices to also be reduced in size.
One enabling technology that is used in the manufacturing processes of semiconductor devices is the use of photolithographic materials. Such materials are applied to a surface of a layer to be patterned and then exposed to an energy that has itself been patterned. Such an exposure modifies the chemical and physical properties of the exposed regions of the photosensitive material. This modification, along with the lack of modification in regions of the photosensitive material that was not exposed, can be exploited to remove one region without removing the other.
However, as the size of individual devices has decreased, process windows for photolithographic processing has become tighter and tighter. As such, advances in the field of photolithographic processing are preferred to maintain the ability to scale down the devices.
Aspects of the present disclosure are best understood from the following detailed description when read with the accompanying figures. It is noted that, in accordance with the standard practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or reduced for clarity of discussion.
The following disclosure provides many different embodiments, or examples, for implementing different features of the provided subject matter. Specific examples of components and arrangements are described below to simplify the present disclosure. These are, of course, merely examples and are not intended to be limiting. For example, the formation of a first feature over or on a second feature in the description that follows may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features may be formed between the first and second features, such that the first and second features may not be in direct contact. In addition, the present disclosure may repeat reference numerals and/or letters in the various examples. This repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed.
The advanced lithography process, method, and materials described in the current disclosure can be used in many applications, including fin-type field effect transistors (FinFETs). For example, the fins may be patterned to produce a relatively close spacing between features, for which the above disclosure is well suited. In addition, spacers used in forming fins of FinFETs can be processed according to the above disclosure.
The formation of integrated circuits may include multiple etching processes, in which etching masks are used to define the patterns of etching. An etching mask may be a bi-layer mask, which includes a bottom layer (e.g., anti-reflective coating (BARC)) and a photoresist layer over the bottom layer, or a tri-layer mask, which includes a bottom layer, a middle layer over the bottom layer, and a photoresist layer over the middle layer.
An etching mask may be used for patterning a metal-containing layer. For example, in order to reduce gate leakage and enhance device performance, the formation of a metal gate includes removing a dummy polysilicon gate, depositing a work function metal layer, forming an etching mask over the work function metal layer, and patterning the work function metal layer by, for example, wet etching. The work function metal layer may substantially conformally cover a substrate having a plurality of protrusions (e.g., fin) and a plurality of gaps. When forming an etching mask over the work function metal layer, a bottom layer (e.g., BARC) of the etching mask should fill into the gaps to protect the work function metal layer. However, the gap-filling ability of the bottom layer is decreasing in small gaps (with gap widths less than or equal to 10 nm). If the bottom layer does not have high gap-filling ability, high wet etch resistance, and good adhesion ability to the metal layer, a portion of the work function metal layer may not be protected by the bottom layer, thereby resulting in damage or defect of the work function metal layer during the wet etching. The bottom layer is formed by crosslinking polymers. The gap-filling ability and the wet etch resistance are influenced by the molecular weight of the polymers. For a gap having a gap width less than or equal to about 10 nm, if the polymers have a low molecular weight (e.g., 100-4000), the bottom layer can have high gap-filling ability but low wet etch resistance because of the bottom layer includes small grains formed by the polymers. In contrast, if the polymers have a high molecular weight (e.g., >4000), the bottom layer can have high wet etch resistance but low gap-filling ability because of the bottom layer includes large grains formed by the polymers. Therefore, the design of the polymers used for forming the bottom layer should overcome these problems and should be proper for the bottom layer.
The present disclosure provides a composition for forming a protective layer that can be used as a bottom layer (e.g., BARC) of an etching mask and a method of manufacturing a semiconductor device by using the protective layer. The protective layer has high gap-filling ability, high wet etch resistance, and good adhesion ability to a metal-containing layer, such as a work function metal layer.
The composition of the present disclosure includes one or more cross-linkable polymers.
It is noted that the end unit EU1 has the end group EG1, the end group EG2 has the end group EG2, and each of the repeating units RU2 has a functional group FG1. The end groups EG1, EG2 and the functional group FG1 respectively include a cross-linkable group, such as an alkenyl or an alkynyl, which can enhance the degree of cross-linking between polymers. The structures of the end groups EG1, EG2 and the functional group FG1 will be further described later. In some embodiments, the polymers P1, P2, P3, and P4 respectively include the repeating units RU1 having different structures. In some embodiments, the polymers P3 and P4 respectively include the repeating units RU2 having different structures.
In some embodiments, the polymer backbones of the polymers P1, P2, P3, and P4 independently formed by polymerizing a monomer composition including monomers independently have an aryl (e.g., benzene ring) substituted with 1, 2, 3, 4, or 5 hydroxyl groups. In some embodiments, the monomers independently have a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, or a penta-hydroxyphenyl. In some embodiments, the monomers independently have a cross-linkable group, such as an alkenyl. In some embodiments, the polymers P1, P2, P3, and P4 are independently a novolac polymer, a substituted poly(hydroxystyrene) (PHS), an unsubstituted poly(hydroxystyrene), an acrylate polymer, or a substituted polyethylene, and the substituted poly(hydroxystyrene) and the substituted polyethylene are respectively substituted with one or more functional groups, such as a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, a penta-hydroxyphenyl, or combinations thereof. For example, the functional groups include
or combinations thereof.
In some embodiments, the repeating units RU1 are formed by monomers used for forming a novolac polymer, a substituted poly(hydroxystyrene), an unsubstituted poly(hydroxystyrene), an acrylate polymer, a substituted polyethylene, or combinations thereof. The substituted poly(hydroxystyrene) and the substituted polyethylene are respectively substituted with a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, a penta-hydroxyphenyl, or combinations thereof. In some embodiments, the monomers used for forming the repeating units RU1 includes, but not limited to,
benzene-1,2-diol, benzene-1,3-diol, benzene-1,4-diol, benzene-1,2,3-triol, benzene-1,2,4-triol, benzene-1,3,5-triol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene,
or combinations thereof. R1 and R2 are independently a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, or a penta-hydroxyphenyl. In some embodiments, a novolac polymer can be prepared by the condensation of formaldehyde and the above monomers used for forming the novolac polymer, such as phenol, m-cresol, or p-cresol. In some embodiments, the polymer backbone of polymers P1, P2, P3, or P4 has the repeating units RU1 including
or combinations thereof. R1 and R2 are independently a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, or a penta-hydroxyphenyl. In the present disclosure, * represent a bonding position.
Still referring to
The end groups EG1 and EG2 or the functional groups FG1 include
or combinations thereof. A is a substituted or unsubstituted hydrocarbon group, and B is a hydroxyl group, an alkyl group, or a fluoroalkyl group. In some embodiments, the end groups EG1 and EG2 and the functional group FG1 are the same or different from each other. In some embodiments, the polymer P3 or the polymer P4 includes different functional groups FG1. The end group EG1, the end group EG2, and the functional group FG1 respectively include an alkenyl or an alkynyl, which can enhance the degree of cross-linking between polymers. The alkynyl may have reactivity greater than that of the alkenyl. In some embodiments, A is the substituted hydrocarbon group substituted with a hydroxyl group, an ester group, a halogen group, or combinations thereof. In some embodiments, A is a branched or unbranched, cyclic or non-cyclic, or saturated or unsaturated hydrocarbon group. In some embodiments, A is a saturated hydrocarbon group, an aromatic hydrocarbon group (e.g., benzene ring), or an aromatic hydrocarbon group (e.g., benzene ring) substituted with 1, 2, 3, or 4 hydroxyl groups. In some embodiments, A has a carbon number between 1-6, such as 1, 2, 3, 4, 5, or 6. In some embodiments, the saturated hydrocarbon group has a carbon number between 1-6, such as 1, 2, 3, 4, 5, or 6. Furthermore, when A includes an aromatic hydrocarbon group (e.g., benzene ring), the reactivity of the alkenyl and the alkynyl can be enhanced. In some embodiments, B is an alkyl group having a carbon number between 1-6, such as 1, 2, 3, 4, 5, or 6. In some embodiments, B is a fluoroalkyl group having a structure of —(CH2)nCFx, n is 1-4, and x is 1-2.
In some embodiments, the end unit EU1 or the end unit EU2 is formed by a monomer having an aryl substituted with 1, 2, 3, 4, or 5 hydroxyl groups, and the monomer is substituted with the end group EG1 or the end group EG2. In some embodiments, the monomer is used for forming a novolac polymer, a substituted poly(hydroxystyrene), an unsubstituted poly(hydroxystyrene), an acrylate polymer, a substituted polyethylene, or combinations thereof, and the monomer is substituted with the end group EG1 or the end group EG2. In some embodiments, the repeating units RU2 is formed by monomers independently having an aryl substituted with 1, 2, 3, 4, or 5 hydroxyl groups, and the monomers respectively substituted with the functional group FG1. In some embodiments, the monomers are used for forming a novolac polymer, a substituted poly(hydroxystyrene), an unsubstituted poly(hydroxystyrene), an acrylate polymer, a substituted polyethylene, or combinations thereof, and the monomers are respectively substituted with the functional group FG1.
In some embodiments, the monomers used for forming the end unit EU1, the end unit EU2, and the repeating units RU2 respectively includes, but not limited to,
benzene-1,2-diol, benzene-1,3-diol, benzene-1,4-diol, benzene-1,2,3-triol, benzene-1,2,4-triol, benzene-1,3,5-triol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene,
or combinations thereof, and the monomers are substituted with one or more functional groups, such as the end group EG1, the end group EG2, or the functional group FG1. R1 and R2 are independently a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, or a penta-hydroxyphenyl. In some embodiments, the end unit EU1, the end unit EU2, and the repeating units RU2 respectively include
or combinations thereof. R1 and R2 are independently a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, or a penta-hydroxyphenyl, and the end unit EU1, the end unit EU2, and the repeating units RU2 are substituted with one or more functional groups, such as the end group EG1, the end group EG2, or the functional group FG1.
In some embodiments,
and n is 1-2.
In some embodiments.
such as
In some embodiments,
and n is 1-2.
In some embodiments.
such as
In some embodiments.
In some embodiments.
and n is 1-2.
In some embodiments,
Still referring to
In some embodiments, a composition used for forming a protective layer includes a polymer has a polymer backbone and end units, in which the polymer backbone and the end units are independently unsubstituted or substituted with one or more functional groups including
or combinations thereof. A is a substituted or unsubstituted hydrocarbon group. B is a hydroxyl group, an alkyl group, or a fluoroalkyl group. The polymer backbone, the end units, or a combination thereof is substituted. If the polymer backbone is substituted, the polymer is the polymer P3. If the end units are substituted, the polymer is the polymer P2. If the polymer backbone and the end units are substituted, the polymer is the polymer P4.
In some embodiments, the composition includes one or more polymers used for forming a protective layer, a cross-linker, and a solvent. In some other embodiments, the composition includes one or more polymers used for forming a protective layer and a solvent, and the composition is free of a cross-linker because of the polymer has cross-linkable groups, such as the end group EG1, the end group EG2, the functional group FG1, or combinations thereof. In some embodiments, the composition further includes an initiator. In some embodiments, a bake process can be performed to induce the cross-linking reaction and enhance the degree of cross-linking of the components in the composition. In other words, the bake process can promote the crosslinking reactions shown in
In some embodiments, the cross-linker has one or more epoxy group. In some embodiments, the cross-linker can be formed by monomers used for forming a novolac polymer, a substituted poly(hydroxystyrene), an unsubstituted poly(hydroxystyrene), an acrylate polymer, a substituted polyethylene, or combinations thereof, and the cross-linker is substituted with one or more epoxy group, which can react with the hydroxyl groups in the polymer. Please refer to the embodiments of the polymer P1 for the structure and the forming method of the cross-linker. The difference between the cross-linker and the polymer P1 is that the cross-linker is substituted with one or more epoxy group. In some embodiments, the cross-linker has a weight-average molecular weight between 100 daltons and 10000 daltons, such as 100, 500, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, or 10000 daltons.
In some embodiments, the solvent includes propylene glycol methyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), 1-ethoxy-2-propanol (PGEE), γ-butyrolactone (GBL), cyclohexanone (CHN), ethyl lactate (EL), methanol, ethanol, propanol, n-butanol, 4-methyl-2-pentanol, acetone, methyl ethyl ketone, dimethylformamide (DMF), isopropanol (IPA), tetrahydrofuran (THF), methyl isobutyl carbinol (MIBC), n-butyl acetate (nBA), 2-heptanone (MAK), dioxane, or combinations thereof. In some embodiments, the initiator is a thermal radical initiator, a photo radical initiator, or a combination thereof. In some embodiments, the thermal radical initiator is one or more selected from the group consisting of azobisisobutyronitrile (AIBN), 2,2′-azodi (2-methylbutyronitrile) (AMBN), 2,2′-azobis(2,4-dimethyl) valeronitrile (ADVN), 4,4′-azobis(4-cyanopentanoic acid) (ACVA), dimethyl 2,2′-azobis(2-methylpropionate), 2,2′-azobis(2-amidinopropane) dihydrochloride (AAPH), 2,2′-azobis [2-(2-imidazolin-2-yl)-propane] dihydrochloride, tert-butyl-hydroperoxide (TBHP), cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, benzoyl peroxide (BPO), dicyandiamide, cyclohexyl tosylate, diphenyl(methyl) sulfonium tetrafluoroborate, benzyl (4-hydroxyphenyl)-methylsulfonium hexafluoroantimonate, and (4-hydroxyphenyl) methyl-(2-methylbenzyl) sulfonium hexafluoroantimonate. In some embodiments, the photo radical initiator is one or more selected from the group consisting of camphorquinone, acetophenone, 3-acetophenol, 4-acetophenol, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone. 3-hydroxybenzophenone, 3,4-dimethylbenzophenone, 4-hydroxybenzophenone, 4-benzoylbenzoic acid, 2-benzoylbenzoic acid, methyl 2-benzoylbenzoate, 4,4′-dihydroxybenzophenone, 4-(dimethylamino)-benzophenone, 4,4′-bis(dimethylamino)-benzophenone, 4,4′-bis(diethylamino)-benzophenone, 4,4′-dichlorobenzophenone, 4-(p-tolylthio) benzophenone, 4-phenylbenzophenone, 1,4-dibenzoylbenzene, benzil, 4,4′-dimethylbenzil, p-anisil, 2-benzoyl-2-propanol, 2-hydroxy-4′-(2-hydroxyethoxy)-2-methylpropiophenone, 1-benzoylcyclohexanol, benzoin, and anisoin.
Please refer to
In some embodiments, the composition used for forming the protective layer further includes an oligomer to enhance the gap-filling ability of the composition. The oligomer is easier to flow into small gaps due to the smaller volume. Subsequently, the oligomer can be crosslinked with the polymer. The oligomer has an oligomer backbone and end units and has a weight-average molecular weight between 500 daltons and 1000 daltons, such as 500, 600, 700, 800, 900, or 1000 daltons. Please refer to the embodiments of the polymers for the structure and the forming method of the oligomer. The difference between the oligomer and the polymer is the weight-average molecular weight. For example, the oligomer backbone and the end units are independently unsubstituted or substituted with one or more functional groups including
or combinations thereof. The oligomer backbone, the end units, or a combination thereof is substituted. Please refer to the previously mentioned embodiments for the embodiments of A and B, and detailed descriptions thereof will not be repeated here.
In some embodiments, the composition used for forming the protective layer further includes one or more additives to enhance the gap-filling ability of the composition. The additive is easier to flow into small gaps due to the smaller volume. Subsequently, the oligomer can be crosslinked with the polymer and/or the oligomer.
In some embodiments, the composition includes additives having different structures. In some embodiments, the composition include one or more additives including:
benzene-1,2-diol, benzene-1,3-diol, benzene-1,4-diol, benzene-1,2,3-triol, benzene-1,2,4-triol, benzene-1,3,5-triol, 1,2,3,4-tetrahydroxybenzene, 1,2,3,5-tetrahydroxybenzene, 1,2,4,5-tetrahydroxybenzene,
or combinations thereof, R1 and R2 are independently a hydroxyphenyl, a di-hydroxyphenyl, a tri-hydroxyphenyl, a tetra-hydroxyphenyl, or a penta-hydroxyphenyl, and the additives are respectively substituted with one or more functional groups including:
or combinations thereof. A is a substituted or unsubstituted hydrocarbon group, and B is a hydroxyl group, an alkyl group, or a fluoroalkyl group. Please refer to the previously mentioned embodiments for the embodiments of A and B, and detailed descriptions thereof will not be repeated here.
Next, the present disclosure provides a method of manufacturing a semiconductor device.
During fabrication of a fin field effect transistor (FinFET) device, a gate replacement process may be implemented to adjust threshold voltage (Vt) associated with the fabrication steps. For example, during a “gate-last” process, a dummy gate structure is first formed over a substrate as a placeholder before forming other components, e.g., source/drain features. Once the other components have been formed, the dummy gate structure is removed, and a metal gate structure is formed in its place. Multiple patterning processes may be implemented to form various material layers within the metal gate structure to provide certain device capabilities such as multiple threshold voltages. Multi-threshold voltage (Vt) devices enable flexible and diverse applications of field effect transistors (FETs).
Multiple threshold voltages of the FinFET device have been accomplished by stacking multiple work function metal (WFM) layers in the metal gate structure. In one example, a thicker WFM stack leads to a higher work function and a higher threshold voltage (Vt). However, as device feature sizes decrease, many challenges arise when stacking WFM layers. For example, because of decreased fin-to-fin pitches, when forming an etching mask over the work function metal layer, the etching mask may not easily fill into the gaps between fins to protect the work function metal layer.
As shown in
The semiconductor device 200 is provided and includes a substrate 202 having a first region 203 and a second region 205, isolation structures 208 formed over the substrate 202 separating various components of the semiconductor device 200, gate spacers 212 as well as an interlayer dielectric (ILD) layer 218 formed on the isolation structures 208. In some embodiments, the first region 203 includes two fins, a fin 207a and a fin 207b, and the second region 205 also includes two fins, a fin 207c and a fin 207d. The fins 207a-207d may include FET features, such as channel regions 230a, 230b, 230c, and 230d, respectively. As shown in
Still referring to
In some embodiments, the gate trench 220 is formed by removing a dummy gate structure on the fins 207a-207d, thereby exposing the channel regions 230a-230d of the fins 207a-207d. The dummy gate structure may include one or more material layers, such as an oxide layer (i.e., a dummy gate dielectric layer), a poly-silicon layer (i.e., a dummy gate electrode), a hard mask layer, a capping layer, and/or other suitable layers. In some embodiments, forming the gate trench 220 includes performing an etch process that selectively removes the dummy gate structure using a dry etch process, a wet etch process, other suitable methods, or combinations thereof. A dry etch process may use chlorine-containing gases, fluorine-containing gases, and/or other etching gases. The wet etching solutions may include ammonium hydroxide (NH4OH), hydrofluoric acid (HF) or diluted HF, deionized water, tetramethylammonium hydroxide (TMAH), and/or other suitable wet etching solutions.
As shown in
In some embodiments, the substrate 202 includes FETs, various doped regions, such as source/drain regions, formed in or on the substrate 202. The doped regions may be doped with p-type dopants, such as phosphorus or arsenic, and/or n-type dopants, such as boron or BF2, depending on design specifications. The doped regions may be formed directly on the substrate 202, in a p-well structure, in an n-well structure, in a dual-well structure, or using a raised structure. Doped regions may be formed by implantation of dopant atoms, in-situ doped epitaxial growth, and/or other suitable techniques.
The first region 203 may be suitable for forming one or more n-type FinFETs, and the second region 205 may be suitable for forming one or more p-type FinFETs. Therefore, the channel regions 230a and 230b located on the fins 207a and 207b are n-type channels, and the channel regions 230c and 230d located on the fins 207c and 207d are p-type channels. In alternative embodiments, the first region 203 and the second region 205 may be suitable for forming FinFETs of a similar type, i.e., both n-type or both p-type, with different threshold voltage (Vt) design specifications. This configuration in
Other methods for forming the fins 207a-207d may be suitable. For example, the fins 207a-207d may be patterned using double-patterning or multi-patterning processes. Generally, double-patterning or multi-patterning processes combine photolithography and self-aligned processes, allowing patterns to be created that have, for example, pitches smaller than what is otherwise obtainable using a single, direct photolithography process. For example, in some embodiments, a sacrificial layer is formed over a substrate and patterned using a photolithography process. Spacers are formed alongside the patterned sacrificial layer using a self-aligned process. The sacrificial layer is then removed, and the remaining spacers, or mandrels, may then be used to pattern the fins.
The isolation structures 208 may include silicon oxide, silicon nitride, silicon oxynitride, fluoride-doped silicate glass (FSG), a low-k dielectric material, and/or other suitable materials. The isolation structures 208 may include shallow trench isolation (STI) features. In some embodiments, the isolation structures 208 are formed by etching trenches in the substrate 202 during the formation of the fins 207a-207c. The trenches may then be filled with an isolating material described above, followed by a chemical mechanical planarization (CMP) process. Other isolation structures such as field oxide, local oxidation of silicon (LOCOS), and/or other suitable structures may also be implemented as the isolation structures 208. Alternatively, the isolation structures 208 may include a multi-layer structure, for example, having one or more thermal oxide liner layers.
The gate spacers 212 form sidewalls of the gate trench 220. The gate spacers 212 may include a dielectric material, such as silicon oxide, silicon nitride, silicon carbide, silicon oxynitride, and/or other suitable dielectric materials. The gate spacers 212 may be a single layered structure or a multi-layered structure. In some embodiments, the ILD layer 218 includes a dielectric material, such as tetraethylorthosilicate (TEOS), un-doped silicate glass, or doped silicon oxide such as borophosphosilicate glass (BPSG), fused silica glass (FSG), phosphosilicate glass (PSG), boron doped silicon glass (BSG), and/or other suitable dielectric materials. The ILD layer 218 may include a multi-layer structure having multiple dielectric materials.
Please refer to
Please refer to
Following the formation of the gate dielectric layer 305, a work function metal (WFM) layer is formed thereon to provide work functions to adjust threshold voltages for the subsequent transistors. Each fin may be used to implement a FinFET with a source, a drain, a channel, and a gate, and a threshold voltage of the fin refers to a minimum gate-to-source voltage to create a conducting path in the channel between the source and the drain. Source/drain region(s) may refer to a source or a drain, individually or collectively dependent upon the context. The threshold voltage is impacted by various parameters including the work function of the gate. As device feature sizes decrease, implementing thick WFM structures during lithography and patterning processes poses many challenges.
Please refer to
Please refer to
In some embodiments, the protective layer 402 is formed by the composition of any one of embodiments mentioned previously. For example, the composition includes the polymer P2, the polymer P3, the polymer P4, or combinations thereof. In some embodiments, any one of the polymers used for forming the protective layer and any one of the compositions in the previously mentioned embodiments can be used for forming the protective layer 402. Since the protective layer 402 or the composition used for forming the protective layer 402 has high gap-filling ability, the gaps G can be filled with the protective layer 402 without voids. In some embodiments, the optional middle layer 403 includes an inorganic material, such as a nitride (such as silicon nitride), an oxynitride (such as silicon oxynitride), an oxide (such as silicon oxide), or combinations thereof. In some embodiments, the photoresist layer 404 includes an organic material, such as diazonaphthoquinone, novolac resins, bisphenol A novolac epoxy, off-stoichiometry thiol-enes (OSTE) polymer, or combinations thereof. In some embodiments, the protective layer 402 is formed by a spin-on process. In some embodiments, the optional middle layer 403 and the photoresist layer 404 are blanket deposited by using, for example, spin-on process, CVD, ALD, PVD, or combinations thereof.
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Based on the above discussions, it can be seen that the present disclosure offers the composition used for forming the protective layer (e.g., BARC) and the method of manufacturing the semiconductor device by using the protective layer. Since the compositions have high gap-filling ability, high wet etch resistance, and good adhesion ability to the metal layer (e.g., p-type WFM layer, n-type WFM layer), in the semiconductor device, the metal layer covering the substrate having the protrusions and gaps can be protected by the protective layer without being damaged during the etching process. Therefore, the semiconductor device can have good electrical performance.
In some embodiments, a method of manufacturing a semiconductor device includes the following operations. A protective layer is formed over a substrate, in which the protective layer is formed by a composition including a polymer having a polymer backbone and end groups. The polymer backbone is formed by polymerizing a monomer composition including first monomers, and each of the first monomer independently has an aryl substituted with 1, 2, 3, 4, or 5 hydroxyl groups. The end groups include:
or combinations thereof. A is a substituted or unsubstituted hydrocarbon group. B is a hydroxyl group, an alkyl group, or a fluoroalkyl group. A photoresist layer is formed over the protective layer. The photoresist layer is patterned.
In some embodiments, a method of manufacturing a semiconductor device includes the following operations. A bottom anti-reflective coating is formed over a substrate, in which the bottom anti-reflective coating is formed by a composition including a first polymer having a first polymer backbone. The first polymer backbone is substituted with one or more functional groups including:
or combinations thereof. A is a substituted or unsubstituted hydrocarbon group. B is a hydroxyl group, an alkyl group, or a fluoroalkyl group. A photoresist layer is formed over the bottom anti-reflective coating. The photoresist layer is patterned.
In some embodiments, a composition includes a polymer, a cross-linker, and a solvent. The polymer has a polymer backbone and first end units, in which the polymer backbone and the first end units are independently unsubstituted or substituted with one or more functional groups including
or combinations thereof. A is a substituted or unsubstituted hydrocarbon group. B is a hydroxyl group, an alkyl group, or a fluoroalkyl group. The polymer backbone, the first end units, or a combination thereof is substituted.
The foregoing outlines features of several embodiments so that those skilled in the art may better understand the aspects of the present disclosure. Those skilled in the art should appreciate that they may readily use the present disclosure as a basis for designing or modifying other processes and structures for carrying out the same purposes and/or achieving the same advantages of the embodiments introduced herein. Those skilled in the art should also realize that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that they may make various changes, substitutions, and alterations herein without departing from the spirit and scope of the present disclosure.
