Methods and compositions for forming trenches using advanced trajectory-based patterning processes

Abstract

A method for forming a semiconductor device can include: coating a reversible outer coating layer on first mandrels on a substrate; inducing a cross-linking reaction within the reversible outer coating layer, the cross-linking reaction rendering the reversible outer coating layer insoluble in a developer and forming a cross-linked outer coating layer; diffusing acid particles from the first mandrels into a first portion of the cross-linked outer coating layer; inducing a de-cross-linking reaction within the first portion of the cross-linked outer coating layer to form de-cross-linked regions, wherein unmodified regions of the cross-linked outer coating layer form second mandrels; and selectively removing the de-cross-linked regions with the developer, such that the first mandrels and the second mandrels form a mandrel pattern on the substrate, wherein the developer has a solubility distance in the range of zero to seven with respect to methyl isobutyl carbinol in Hansen solubility parameter space.

Description

Cross-references to related applications

[0001] This application claims priority and benefit to U.S. non-provisional application No. 18 / 908,557, filed October 7, 2024, and U.S. provisional application No. 63 / 555,246, filed February 19, 2024, which are incorporated herein by reference in their entirety. Technical Field

[0002] This disclosure relates generally to methods for manufacturing semiconductor devices, and more specifically to developer compositions for sub-resolution photolithographic patterning in methods for manufacturing semiconductor devices. Background Technology

[0003] In materials processing methods such as photolithography, creating a patterned layer typically involves applying a thin layer of radiation-sensitive material (such as a photoresist) to the upper surface of a substrate. This radiation-sensitive material can be transformed into a patterning mask that can be used to etch or transfer a pattern into a lower layer of the substrate. Patterning a radiation-sensitive material typically involves exposing it to a photolithographic exposure system, for example, by a radiation source through a mask (and associated optics). This exposure can create a latent pattern within the radiation-sensitive material, which can then be developed. "Developing" can refer to dissolving and removing a portion of the radiation-sensitive material to create an embossed pattern (morphological pattern). Depending on the photoresist hue (positive or negative) and / or the type of developing solvent used, the removed portion of the material can be either an irradiated or unirradiated area of ​​the radiation-sensitive material. The embossed pattern can then be used as a mask layer defining the pattern.

[0004] The application and development of various films used for patterning may include heat treatment or “baking.” Newly applied films may undergo post-application baking (PAB) to evaporate solvents and / or improve material properties, such as structural stiffness or etch resistance. Post-exposure baking (PEB) may be performed to set a given pattern and limit or prevent accidental removal of material. Manufacturing tools used for coating and developing substrates typically include one or more baking modules.

[0005] Some photolithography processes involve coating a substrate with a photoresist and then exposing it to a light pattern to create an embossed pattern that can be used as a mask or template for additional processing, such as transferring the pattern to an underlying layer. In related photolithography processes, a bottom antireflective coating (BARC) film can be applied to the substrate before coating it with the photoresist and then exposing it. These processes can be used as discrete operations in microchip manufacturing. Summary of the Invention

[0006] According to embodiments of this disclosure, for a developer configured to selectively remove a solubility switching region of a first material layer during a semiconductor manufacturing process to form a mandrel pattern in the layer on a substrate, the developer may have a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter (HSP) space in the range of zero to seven.

[0007] According to embodiments of this disclosure, a method for forming a semiconductor device may include: coating a reversible outer coating layer on a first mandrel on a substrate; inducing a crosslinking reaction within the reversible outer coating layer, the crosslinking reaction rendering the reversible outer coating layer insoluble in a developer and forming a crosslinked outer coating layer; diffusing acid particles from the first mandrel into a first portion of the crosslinked outer coating layer; inducing a decrosslinking reaction within the first portion of the crosslinked outer coating layer to form a decrosslinked region, wherein an unmodified region of the crosslinked outer coating layer forms a second mandrel; and selectively removing the decrosslinked region with a developer, such that the first and second mandrels form a mandrel pattern on the substrate, wherein the developer has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter space in the range of zero to seven.

[0008] According to embodiments of this disclosure, a method for formulating a developer for developing patterned materials having reversible solubility in a process for manufacturing semiconductor devices can be provided. The method includes: identifying a list of materials, wherein each individual material in the list has a dispersion component between 14 and 18, a polar component between 2 and 8, and a hydrogen bonding component between 7 and 16, according to a Hansen solubility parameter (HSP) component system; and selecting a combination of two or more materials from the list, and mixing the selected combination of the two or more materials in a certain ratio to formulate the developer such that the developer has a combined solubility distance relative to methyl isobutyl methanol (MIBC) in the HSP space in the range of zero to seven. Attached Figure Description

[0009] To gain a more complete understanding of this disclosure and its advantages, reference is now made to the following description taken in conjunction with the accompanying drawings, in which:

[0010] Figures 1A to 1I Cross-sectional views are shown of different stages of a method for forming a mandrel pattern according to embodiments of this disclosure;

[0011] Figure 2 A flowchart illustrating a method for forming a mandrel pattern according to an embodiment of this disclosure is provided;

[0012] Figure 3 It is a three-dimensional (3D) plot of the Hansen solubility parameter (HSP) space according to an embodiment of the present disclosure;

[0013] Figure 4 The image is a screenshot of a computer program according to an embodiment of the present disclosure, which provides a material list including HSP information for each of the listed materials.

[0014] Figure 5 This is a flowchart of a method for selecting a developer according to embodiments of this disclosure; and

[0015] Figure 6 The image is a screenshot of a computer program according to an embodiment of this disclosure, which provides an example combination of materials including HSP information for each of the listed materials. Detailed Implementation

[0016] Referring now to the accompanying drawings, illustrative exemplary embodiments are shown and described, in which the same reference numerals are used throughout the views to denote the same or similar elements. The drawings are not drawn to scale, and in some places, they are exaggerated or simplified for illustrative purposes. Those skilled in the art can understand many possible applications and variations of other embodiments based on the following illustrative exemplary embodiments provided in this disclosure.

[0017] In some embodiments of this disclosure, the developer can be configured to selectively remove decrosslinked regions of a reversible outer coating layer during a semiconductor manufacturing process to form a mandrel pattern on a substrate, wherein the developer has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter (HSP) space ranging from zero to seven. In some embodiments of this disclosure, a method for forming a semiconductor device may include: coating a reversible outer coating layer on a first mandrel on a substrate; inducing a crosslinking reaction within the reversible outer coating layer, the crosslinking reaction rendering the reversible outer coating layer insoluble in the developer and forming a crosslinked outer coating layer; diffusing acid particles from the first mandrel into a first portion of the crosslinked outer coating layer; inducing a decrosslinking reaction within the first portion of the crosslinked outer coating layer to form decrosslinked regions, wherein unmodified regions of the crosslinked outer coating layer form a second mandrel; and selectively removing the decrosslinked regions with the developer, such that the first and second mandrels form a mandrel pattern on the substrate, wherein the developer has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter space ranging from zero to seven. The following description, with reference to the accompanying drawings, details some exemplary embodiments of this disclosure, as well as some exemplary variations thereof. Other embodiments may also be understood in light of the entire specification and claims herein.

[0018] In this disclosure, terms such as “first” and “second” may be used to describe various components, but these components are not necessarily limited by such terms (e.g., regarding the order, sequence, importance, or number of such components in the embodiments). Such terms may be used only for the purpose of distinguishing one component from other components in a given embodiment or group of embodiments. For example, without departing from the scope of the claims under this disclosure, a first component may be referred to as a second component, and similarly, a second component may be referred to as a first component. Because semiconductor geometries and sizes can be so extremely small (e.g., on the order of 1 nm to 5 nm), the terms “film” and “layer” are used interchangeably herein.

[0019] Continuous miniaturization may require increased patterning resolution. One approach is spacer techniques that define sub-resolution line features through atomic layer deposition (ALD). However, a challenge is that using spacer techniques can involve a series of complex operations if contrasting tonal features are desired, including outcoating with another material (“outer coating”) using the spacer features as a core, chemical mechanical planarization (CMP), and reactive ion etching (RIE) that excavates the spacer material to leave narrow trenches; these can be expensive.

[0020] In such cases, spacer technology may involve a series of complex and expensive steps, including applying an external coating of another material (“external coating”) using the spacer feature as a core, chemical mechanical planarization (CMP) to expose the spacer feature, and reactive ion etching (RIE) to remove the spacer material, leaving narrow trenches.

[0021] Anti-spacer technology is an alternative self-aligned method that uses the diffusion length of the reactive material across the boundary between the outer coating and the adjacent layer to define the critical dimension (CD), thereby creating narrow trenches around features of this adjacent layer after the outer coating has developed. More refined features, such as narrow trench contacts, can be formed when the generation of the reactive material is spatially controlled via exposure through a mask. The CD itself can be tailored based on the physical and chemical properties of the reactive material (e.g., its molecular weight and affinity for interacting with the host material) and by varying the baking temperature and time in post-exposure baking (PEB). Therefore, anti-spacer technology enables the patterning of narrow trench contact features at dimensions exceeding the capabilities of advanced lithography.

[0022] Anti-spacer formation can achieve self-aligned dual patterning (SADP) via spin-coating, thereby increasing throughput and reducing overall cost. The limitations of conventional SADP processes, such as the ability to achieve only a single discrepancy (CD) across the entire substrate, can be overcome by anti-spacer processes. Because features can be formed through the physical generation of solubility-modified materials and subsequent diffusion across interfaces, the formation and mobility of the diffused material can be tuned across the substrate, enabling multiple feature widths to be achieved in a single process. However, within anti-spacer flows where the CD of a single mandrel is altered, the density of the final pattern can be limited, which may be particularly noticeable when the final target spacing approaches half the resolution limit of the photolithography exposure. To achieve 1:1 line-to-space (L / S) mandrel patterns (e.g., equidistant spacing between mandrels), the initial photolithography exposure can be biased to account for the addition of mandrels or anti-spacers and to achieve the target spacing.

[0023] When the target spacing approaches half the resolution limit of photolithography exposure, proper offset may no longer be achievable and may require additional post-exposure processes. The resolution limitations of the photolithography technique employed may prevent the desired offset of the incoming L / S pattern for symmetrical L / S patterning, potentially leading to asymmetrical L / S patterning after multiple patterning processes. In particular, some features may still be limited by the resolution of the photolithography process.

[0024] The example embodiments described in this disclosure can provide compositions and formulations of developers or solvents for use in reverse spacer patterning schemes to achieve matte lithographic mandrel patterns. This scheme can rely on a solubility-altering substance diffusing outward from the photoresist mandrel into a reversible outer coating to induce a reaction, thereby forming narrow trenches. The resulting process flow can overcome the spacing limitations of acid-advanced unidirectional diffusion processes using post-lithographic trimming of the photoresist mandrel to achieve the desired bias in line-space patterns, thereby achieving a final symmetrical mandrel pattern.

[0025] Figures 1A to 1I Demonstrates the use of forming Figure 2 The example method for mandrel patterning of the spacing division process shown includes cross-sectional views of different stages.

[0026] refer to Figure 1A A mandrel 106 can be formed on substrate 102. Figure 2(See box S1). The substrate 102 may be part of, or include a semiconductor device or semiconductor structure, and may be formed in any suitable manner, including any suitable combination of wet and / or dry deposition, photolithography, and etching techniques. For example, a semiconductor structure may include the substrate 102 in which various device regions are formed. In embodiments, the substrate 102 may include isolation regions (such as shallow trench isolation (STI) regions), diffusion regions, and other regions formed in the substrate.

[0027] Substrate 102 may include a semiconductor layer suitable for various microelectronic devices. In embodiments, substrate 102 may be, for example, a silicon wafer or a silicon-on-insulator (SOI) wafer. In embodiments, substrate 102 may include, for example, a silicon-germanium wafer, a silicon carbide wafer, a gallium arsenide wafer, a gallium nitride wafer, or other compound semiconductors. In embodiments, substrate 102 may include, for example, a heterolayer, such as silicon-germanium on silicon, gallium nitride on silicon, silicon-carbon on silicon, or a silicon or SOI substrate on silicon. In embodiments, substrate 102 may be patterned or embedded in other components of a semiconductor device or semiconductor structure.

[0028] Further reference Figure 1A In one embodiment, an intermediate layer 104 may be formed on the substrate 102, such that the mandrel 106 is formed on the intermediate layer 104. The intermediate layer 104 may be on the mandrel pattern 144 (see...). Figure 1I The intermediate layer 104 is the target for pattern transfer in subsequent processing after the formation of the intermediate layer 104 is completed. The intermediate layer 104 may include, for example, silicon, silicon oxynitride, organic materials, inorganic materials, amorphous carbon, etc. The intermediate layer 104 may be selected, for example, to have anti-reflective properties, such as by using a silicon-bottom anti-reflective coating (Si-BARC). The intermediate layer 104 may be a mask layer containing a hard mask. The intermediate layer 104 may be a stacked hard mask containing two or more layers of, for example, two or more different materials. For example, in an embodiment where the hard mask contains two layers, the first layer of the hard mask may contain a metal-based layer, such as titanium nitride, titanium, tantalum nitride, tantalum, a tungsten-based compound, a ruthenium-based compound, or an aluminum-based compound, and the second layer of the hard mask may include a dielectric layer, such as silicon dioxide, silicon nitride, silicon oxynitride, silicon carbide, amorphous silicon, or polycrystalline silicon. The intermediate layer 104 may be deposited using any suitable deposition process. For example, suitable deposition processes may include spin coating, chemical vapor deposition (CVD), atomic layer deposition (ALD), plasma deposition (e.g., plasma-enhanced CVD (PECVD) or plasma-enhanced ALD (PEALD)) and / or other layer deposition processes or combinations thereof.

[0029] In an embodiment, the mandrel 106 may be formed by forming a photoresist layer (not shown) on an intermediate layer 104 and patterning the photoresist layer using any suitable photolithography technique. For example, the photoresist layer may contain a positive-tone photoresist or a negative-tone photoresist. In the example embodiment shown, the photoresist layer may contain a positive-tone chemically amplified photoresist (CAR). The photoresist layer may be deposited on the substrate 102 in any suitable manner. For example, the photoresist layer may be deposited by spin coating, spraying, dip coating, or roll coating. As a specific example, the photoresist layer may be deposited on the substrate 102 using a spin coating deposition technique, which may also be referred to as spin coating. In an embodiment, the photoresist layer may contain a reagent-generating component that generates a solubility-changing reagent (e.g., an acid) in response to a suitable reagent activation trigger (e.g., heat and / or radiation). Example reagent generating components may include a thermal acid generator (TAG) configured to generate acid in response to heat or a photoacid generator (PAG) configured to generate acid in response to photochemical radiation.

[0030] By spin-coating deposition, a specific material (e.g., the material of a photoresist layer) can be deposited on a substrate 102 (e.g., on an intermediate layer 104 that may be formed on the substrate 102). The substrate 102 can then be rotated at a relatively high speed (or possibly a relatively low speed if it is not already rotated), causing centrifugal force to move the deposited material toward the edge of the substrate 102, thereby coating the substrate 102. Excess material is typically spin-off from the substrate 102. In embodiments, the spin-coating deposition technique may include dispensing liquid chemicals onto the substrate 102 (e.g., onto the top surface of the intermediate layer 104) using a coating module with a liquid delivery system that can dispense one or more types of liquid chemicals. The dispensing volume may be in the range of 0.2 mL to 10 mL, for example, in the range of 0.5 mL to 2 mL. The substrate 102 may be secured to a rotating chuck that supports the substrate 102. The rotational speed during liquid dispensing may be in the range of 50 rpm to 3000 rpm, for example, in the range of 1000 rpm to 2000 rpm. The system may also include an annealing module that can bake or apply light radiation to the substrate 102 after the chemicals have been applied. It is understood that this example spin-coating deposition technique and associated numerical values ​​are provided as examples only. In embodiments, CVD processes, plasma-enhanced CVD processes, ALD processes, or other suitable processes can be used to deposit the photoresist layer.

[0031] After the photoresist layer is formed, a mask (not shown) can be positioned on the photoresist layer. The mask can be used to adjust the dose (or intensity) of radiation (e.g., photochemical radiation) that can be used to expose the photoresist layer. The mask can include regions with different transparency to the radiation (e.g., opaque and transparent regions). The photoresist layer can then be subjected to an exposure step through the mask. The radiation can expose the exposed areas of the photoresist layer, while the unexposed (or unmodified) areas of the photoresist layer can be protected by the mask. The exposure step can be performed, for example, using photolithography techniques such as dry lithography (e.g., using 193 nm dry lithography), immersion lithography (e.g., using 193 nm immersion lithography), i-line lithography (e.g., exposure using 365 nm wavelength UV radiation), H-line lithography (e.g., exposure using 405 nm wavelength UV radiation), extreme UV (EUV) lithography, deep UV (DUV) lithography, or any suitable photolithography technique.

[0032] In this embodiment, radiation can generate acid in the exposed areas of the photoresist layer. The acid can be generated by PAG that may be present in the photoresist layer under the influence of radiation. The acid can react with the material of the photoresist layer and alter the solubility of the exposed areas of the photoresist layer. Subsequently, the exposed areas of the photoresist layer can be removed by performing a development process using a suitable developer. The development process can form multiple openings 108 in the photoresist layer that expose multiple portions of the intermediate layer 104. Unexposed areas of the photoresist layer can form a mandrel 106.

[0033] The mandrel 106 may have a first width W1, and the opening 108 may have a second width W2. In embodiments, the first width W1 and / or the second width W2 may have a minimum value achievable through photolithography. In the example embodiment shown, the ratio W1:W2 may, for example, be equal to 1:1.

[0034] refer to Figure 1B The outer coating layer 110 can be deposited on the substrate 102 in any suitable manner. For example, the outer coating layer 110 can be deposited by spin coating, spraying, dip coating, or roll coating. As a specific example, the outer coating layer 110 can be deposited on the substrate 102 using a spin coating deposition technique, which can also be referred to as spin coating. The spin coating deposition technique has been referenced above. Figure 1A The description will be provided and will not be repeated here. The outer coating layer 110 may also be referred to as a finishing layer. The outer coating layer 110 may fill the opening 108 (see example...). Figure 1A And covers the top surface of the mandrel 106 (see example). Figure 1B ).

[0035] The material used for the outer coating layer 110 can be selected such that the outer coating layer 110 can be removed during a subsequent development process, as described in more detail below. In embodiments, the outer coating layer 110 can be a multi-component material comprising a first component and a second component during deposition. The first component can be, for example, a polymer. The second component can be, for example, a solubility-modifying agent 112, such as an acid (e.g., a free acid). In the illustrated example embodiment, the solubility-modifying agent 112 can comprise a plurality of acid particles that, in Figure 1B The component is depicted as a solid four-pointed star. As another example, the second component can be a reagent-generating component that generates a solubility-changing reagent (e.g., an acid) in response to a suitable reagent activation trigger (e.g., heat or radiation). Example reagent-generating components may include a TAG configured to generate an acid in response to heat or a PAG configured to generate an acid in response to photochemical radiation.

[0036] For example, if the outer coating layer 110 includes a free acid, the solubility-changing reagent 112 can be a free acid, and subsequent baking of the substrate 102 can diffuse the free acid (e.g., Figure 1B (As indicated by arrow 114 in the diagram) into the peripheral portion of the mandrel 106, and can make the peripheral portion of the mandrel 106 soluble in developer.

[0037] As another example, if the outer coating layer 110 contains TAG as a reagent-generating component, subsequent baking of the substrate 102 can cause the TAG to generate a solubility-modifying reagent 112 (e.g., an acid) (this can be referred to as acid activation), which can cause the generated solubility-modifying reagent 112 to diffuse (e.g., ...). Figure 1B (As indicated by arrow 114 in the diagram) into the peripheral portion of the mandrel 106, and can make the peripheral portion of the mandrel 106 soluble in developer.

[0038] As another example, when the outer coating layer 110 includes PAG as a reagent-generating component, an exposure step can be performed, which includes exposing the outer coating layer 110 to radiation (e.g., photochemical radiation), followed by baking the substrate 102. The exposure step can cause the PAG to generate a solubility-changing reagent 112 (e.g., an acid), which can be referred to as acid activation. Baking the substrate 102 can cause the generated solubility-changing reagent 112 to diffuse (e.g., ...). Figure 1B (As indicated by arrow 114 in the diagram) into the peripheral portion of the mandrel 106, and can make the peripheral portion of the mandrel 106 soluble in developer.

[0039] refer to Figure 1CA baking process can be performed on substrate 102. In embodiments, the baking process can be a thermal process, which is performed by heating substrate 102 to a temperature of 50°C to 250°C (e.g., 60°C to 140°C in some embodiments) in a process chamber under vacuum or gas flow. In a particular example, substrate 102 can be baked for a duration ranging from 1 minute to 3 minutes. Baking conditions can be selected to promote the diffusion of solubility-modifying reagent 112 (and possibly the generation of solubility-modifying reagent 112 from reagent-generating components of outer coating layer 110, if applicable) and mandrel 106 (see Figure 1B The solubility of the surrounding area of ​​the target first depth D1 is altered. The first depth D1 can be adjusted by parameters of the baking process (e.g., baking temperature and baking duration) and material parameters (e.g., polymer composition of mandrel 106 and acid composition and acid concentration in outer coating layer 110).

[0040] refer to Figure 1C The solubility-modifying reagent 112 can chemically react with the material of the mandrel 106 to form modified regions 116 of the mandrel 106. This chemical reaction can alter the solubility of the modified regions 116 of the mandrel 106, allowing the modified regions 116 of the mandrel 106 to be removed during subsequent development. Each modified region 116 can be removed along the corresponding mandrel 106 (see...). Figure 1C The unmodified region 118 extends to the sidewalls and top surface.

[0041] refer to Figure 1D A suitable developer can be used to perform a development process on substrate 102. In an embodiment, the developer may include a metal ion-free (MIF) developer, such as an aqueous solution of tetramethylammonium hydroxide (TMAH). In an embodiment, the developer solution may include a metal ion-containing developer, such as an aqueous solution of sodium hydroxide (NaOH) or potassium hydroxide (KOH). In an embodiment, the development process may include immersing or soaking substrate 102 in the developer.

[0042] In this embodiment, the developer can remove the outer coating layer 110 (see [reference]). Figure 1C ) and modified region 116 (see Figure 1C ), and form an opening 120 that exposes the intermediate layer 104 (see example) Figure 1D The remaining unmodified region 118 of the mandrel 106 (see...) Figure 1C A trimmed mandrel 122 can be formed on the intermediate layer 104. (Using...) Figures 1B to 1D The described operations can be collectively described as a dressing process or the formation of a dressed mandrel ( Figure 2 (frame S2).

[0043] The modified mandrel 122 can have a third width W3, and the opening 120 can have a fourth width W4. The third width W3 of the mandrel 122 can be smaller than the first width W1 of the mandrel 106 (e.g., compared to...). Figure 1A In an embodiment, when the first width W3 is less than the minimum achievable through photolithography, the trimmed mandrel 122 can have a sub-photolithographic width. The fourth width W4 of the opening 120 is greater than the second width W2 of the opening 108 (e.g., compared to...). Figure 1A In the example embodiment shown, the ratio W3:W4 can be equal to 1:3. This pattern of the trimmed mandrel 122 can also be referred to as a 1:3 line-space (L / S) pattern. In the embodiment, the ratio W3:W4 can be in the range of 1:2 to 1:5.

[0044] refer to Figure 1E The outer coating layer 124 can be deposited on the substrate 102 in any suitable manner. Figure 2 (See box S3). For example, the outer coating layer 124 can be deposited by spin coating, spraying, dip coating, or roll coating. As a specific example, the outer coating layer 124 can be deposited on the substrate 102 using a spin coating deposition technique, which can also be referred to as spin coating. Spin coating deposition techniques have been referenced above. Figure 1A The description will be provided and will not be repeated here. The outer coating layer 124 may also be referred to as a reversible outer coating (ROC) layer. The outer coating layer 124 may fill the opening 120 (see...). Figure 1D And cover the top surface of the trimmed mandrel 122 (see) Figure 1E The outer coating layer 124 may have a thickness TH on the top surface of the trimmed mandrel 122.

[0045] The material of the outer coating layer 124 can be selected to be non-mixed with the material of the trimmed mandrel 122. The material of the outer coating layer 124 can, for example, contain various solutes in an application-specific organic solvent system.

[0046] In embodiments, the material of the outer coating layer 124 may comprise a first solute and a second solute in a solvent. The first solute may contain a portion capable of reacting with a portion of the second solute to form an acetal bond (or "crosslink"). In one solute, such a portion may contain an organic hydroxyl functional group or a carboxylic acid functional group, and in another solute, such a portion may be an enol ether functional group (e.g., a vinyl ether) or an N-methoxymethylamide functional group. In embodiments, the solute may have multiple functional groups capable of crosslinking. In embodiments, the composition may contain an additional solute, such as a third solute, which contains a weak acid ("catalyst") catalyzing the crosslinking reaction.

[0047] In embodiments, one solute may be a polymer, and the other may be a small molecule with a mass less than 1000 daltons. In such cases, the small molecule may be referred to as a "crosslinking agent" or "crosslinker." In embodiments, both solutes may be polymers, and the solute present in the composition at a lower abundance may be referred to as a crosslinking agent, while the solute present at a higher abundance may be simply referred to as a "polymer." In embodiments where the solutes are present in equal abundance, the solute comprising an enol ether or N-methoxymethylamide functional group may be referred to as a crosslinking agent, while the other solute may be simply referred to as a "polymer."

[0048] The crosslinking agent can have the function of reacting with the polymer to promote the curing of the composition of the outer coating layer 124. The crosslinking agent can further enable the formation of an insoluble network by forming acetal bonds between the crosslinking agent and the polymer.

[0049] The catalysts present in the examples can serve to lower the activation energy for initiating crosslinking (e.g., by lowering the baking temperature and / or reducing the baking time). The catalysts may include sulfonic acids, such as p-toluenesulfonic acid (pTSA), dodecylbenzenesulfonic acid, mixtures thereof, etc. In the examples, the catalyst may be omitted.

[0050] refer to Figure 1F After depositing the outer coating layer 124, a baking process can be performed on the substrate 102 to induce crosslinking within the outer coating layer 124, thereby making the crosslinked outer coating layer 126 insoluble in the subsequently used developer. Figure 2 (See box S4 in the original text). In an embodiment, the baking process can be a thermal process, which is performed by heating the substrate 102 to a temperature of 50°C to 300°C in a process chamber under vacuum or gas flow. In an embodiment, baking can be performed, for example, at a temperature of less than 150°C for less than 6 minutes.

[0051] refer to Figure 1G This can cause the reagent within the modified mandrel 122 to undergo component decomposition, resulting in a solubility-altering reagent 130 (e.g., free acid). Figure 2 (See box S5 in the example embodiment). In the illustrated embodiment, the solubility-changing reagent 130 may include acid particles that, in Figure 1G The core is depicted as a solid circle. In embodiments where the reagent-generating component includes PAG, the solubility-modifying reagent 130 (e.g., free acid) may be generated in response to exposing the core 122 to radiation 128 (e.g., photochemical radiation). In embodiments, the substrate 102 may be irradiated with radiation 128. In such embodiments, each core 122 may include substantially a similar amount of the solubility-modifying reagent 130 (e.g., free acid).

[0052] refer to Figure 1H A baking process can be performed on substrate 102. Figure 2 (See box S6 in the image). The baking process can alter the solubility of reagent 130 and cause diffusion (e.g., ...). Figure 1H (As indicated by arrow 132) the mandrel 122 extends outward, crosses the interface between the mandrel 122 and the crosslinked outer coating layer 126, and enters the crosslinked outer coating layer 126, thereby inducing a decrosslinking reaction within the crosslinked outer coating layer 126 to reach a target second depth D2, forming a decrosslinked region 134. The decrosslinked region 134 may also be referred to as an anti-spacer. In an embodiment, the baking process may be a thermal process performed by heating the substrate 102 to a temperature of 50°C to 300°C in a process chamber under vacuum or gas flow. In an embodiment, baking may be performed, for example, at a temperature of less than 150°C for less than 6 minutes.

[0053] The second depth D2 can be adjusted by parameters of the baking process (e.g., baking temperature and / or baking duration) and / or material parameters (e.g., polymer composition of the crosslinked outer coating layer 126, and acid composition and concentration in the mandrel 122). In an embodiment, the second depth D2 and the thickness TH of the outer coating layer 124 can be adjusted (see [reference]). Figure 1E This results in a second depth D2 greater than the thickness TH. In such cases, the solubility of reagent 130 is altered (see...). Figure 1G ) can diffuse from the top surface of the mandrel 122 (e.g. Figure 1H (As indicated by arrow 132 in the diagram) to the top surface of the crosslinked outer coating layer 126, such that the top surface of the decrosslinked region 134 is exposed and can be flush with the top surface of the crosslinked outer coating layer 126.

[0054] refer to Figure 1I A suitable developer can be used to perform a development process on substrate 102. Figure 2 (See box S7 in the image). A suitable developer may include one that removes the decrosslinked region 134 (see box S7 in the image). Figure 1HThe organic solvent is selective. In an embodiment, the solubility of the decrosslinked region 134 in a suitable developer may be greater than the solubility of the crosslinked outer coating layer 126 and the trimmed mandrel 122 in a suitable developer. The development process may selectively remove the decrosslinked region 134 to form a first opening 138 and a second opening 140 exposing the intermediate layer 104. The remaining region of the crosslinked outer coating layer 126 may form a sub-mandrel 136. The trimmed mandrel 122 and the sub-mandrel 136 may form a mandrel pattern 144 on the substrate 102. In an embodiment, the trimmed mandrel 122 may have a first height H1, and the sub-mandrel 136 may have a second height H2, wherein the second height H2 is greater than the first height H1. In an embodiment, the width of the sub-mandrel 136 may increase as the sub-mandrel 136 extends away from the substrate 102. In such embodiments, the sub-mandrel 136 may include an overhanging region 146 extending over the first opening 138 and the second opening 140.

[0055] In an embodiment, the mandrel pattern 144 may include a mandrel pattern 142. Each mandrel pattern 142 may include a first mandrel 122 and a second mandrel 136, a first opening 138 and a second opening 140, wherein the first opening 138 is inserted between the first mandrel 122 and the second mandrel 136, and the second mandrel 136 is inserted between the first opening 138 and the second opening 140. The first mandrel 122 may have a fifth width W5, the second mandrel 136 may have a seventh width W7, the first opening 138 may have a sixth width W6, and the second opening 140 may have a width W8. In the example embodiment shown, the ratio W5:W6:W7:W8 may be equal to 1:1:1:1. In such embodiments, the mandrel pattern 144 may also be referred to as a 1:1:1:1 L / S pattern. In other embodiments, the ratio W5:W6:W7:W8 can be equal to 1:X:(3-2X):X, where X is the second depth D2 measured in units of the fifth width W5, and X ranges from 0 to 3 / 2. In embodiments, the pattern of the mandrel pattern 144 can be adjusted by adjusting X (i.e., by adjusting the second depth D2). In the example where X=1 (i.e., D2=W5), the mandrel pattern 144 is a 1:1:1:1 L / S pattern.

[0056] In an embodiment, the pattern of the mandrel pattern 144 can be transferred into the intermediate layer 104. For example, the intermediate layer 104 can be etched using an anisotropic etching process (such as reactive ion etching (RIE)) while using the mandrel pattern 144 as an etching mask. In an embodiment, the transferred pattern can be used, for example, to form contact holes, vias, metal lines, gate lines, isolation regions, and other features useful in semiconductor manufacturing.

[0057] The reverse spacer process and reversible exterior coatings are disclosed in (1) U.S. Provisional Application No. 63 / 555,246, filed February 19, 2024; (2) U.S. Provisional Application No. 63 / 603,580, filed November 28, 2023; (3) U.S. Application No. 18 / 615,313, filed March 25, 2024; and (4) U.S. Application No. 18 / 617,951, filed March 27, 2024, each of which is incorporated herein by reference in its entirety.

[0058] For suitable reversible outer coating (ROC) layer materials, a suitable developer can be selected to selectively remove decrosslinked regions of the converted reversible outer coating layer while leaving the unconverted reversible outer coating layer and the unmodified regions of the patterned photoresist intact. In the embodiments of this disclosure, 4-methyl-2-pentanol or methyl isobutyl methanol (MIBC) (e.g., CAS #108-11-2) can be selected as suitable developers for many suitable reversible outer coating layer materials, such as ROC layers comprising a first material with phenolic functional groups and a second material with vinyl ether functional groups, or ROC layers comprising a first material with methacrylic acid functional groups and a second material with vinyl ether functional groups. However, the embodiments of this disclosure are not necessarily limited to these example ROC layer materials.

[0059] In embodiments of this disclosure, a suitable developer may be selected, for example, having solvent properties similar to MIBC, but which may be selected based on other advantageous properties of the material, such as non-flammability, non-toxicity, greater environmental friendliness (sustainability), providing good environmental, health, and safety specifications, providing shorter or longer chemical reaction times, providing greater selectivity for certain selected ROC layer materials, being available at a lower cost, being more available and / or less costly in certain plant locations, providing favorable temperature operating requirements, or providing a more precise or smoother surface after removing the developed material, or any combination thereof. In embodiments of this disclosure, a suitable developer may be a combination of two or more materials that, when combined, have solvent properties similar to MIBC, but which may be selected based on other advantageous properties of the materials (such as the example properties listed above).

[0060] To select a suitable developer, the Hansen solubility parameter can be considered and / or used to determine whether a given solvent, or a given combination of two or more materials, has solvent properties similar to those of MIBC for a given ROC layer material or group of ROC layer materials.

[0061] The Hansen solubility parameter (HSP) is a set of three parameters that can predict the solubility of materials (especially polymers) in different solvents. The principle behind HSP is based on the principle of "like dissolves like" (i.e., materials with similar solubility parameters are likely to dissolve in each other). The first parameter constituting the HSP is the dispersion force parameter (δD), which represents the van der Waals forces, or dispersion forces, present in all molecules. The second parameter constituting the HSP is the polar force parameter (δP), which represents the dipole-dipole interactions between polar molecules. The third parameter constituting the HSP is the hydrogen bond parameter (δH), which represents the hydrogen bond potential of the molecule.

[0062] These three parameters of HSP can be used to create a 3D space, which can be called Hansen space or HSP space, where solvents and solutes can be mapped. For example, software called HSPiP (or the practical application of the Hansen solubility parameter) can be used to determine how well a solvent or mixture matches a target.

[0063] Figure 3 This is a three-dimensional (3D) plot of the Hansen solubility parameter (HSP) space according to embodiments of this disclosure. More specifically, Figure 3 An example HSP space is shown in spheres for a set of potential solvent mappings associated with a given solute, with the center of the sphere at the HSP mapping point of MIBC. Figure 3 The radius of the sphere shown can represent the distance to a reference point in the HSP space of the MIBC. Therefore, a combination of solvents or materials having an HSP solvent value relative to a particular material or within a “distance” to the reference point of the MIBC on the HSP map (i.e., within a sphere on the 3D HSP map or within the radius of a sphere whose center point is at the MIBC, which serves as the reference point) can be considered sufficiently similar to replace the MIBC or as a suitable alternative to the MIBC for a given ROC layer material. In the context of the embodiments of this disclosure, the “distance” of the solvent’s solubility distance relative to the MIBC in HSP space, or the combined solubility distance of a combination of two or more materials relative to the MIBC in HSP space, is an absolute distance (a positive number) (i.e., independent of its position relative to the MIBC on the 3D map).

[0064] In embodiments, the solubility distance of the solvent in the HSP space relative to the MIBC in the range of 0 to 7 can be considered compatible and usable. In embodiments, the combined solubility distance of a combination of two or more materials in the HSP space relative to the MIBC in the range of 0 to 7 can be considered compatible and usable; however, combinations of solvents or materials with larger solubility distances (e.g., up to 10) may also be effective in some embodiments or applications. Alternatively, in embodiments, the solubility distance of the solvent in the HSP space relative to the MIBC in the upper limits of 0 to 3, 4, or 5 (e.g., 0-3, 0-4, or 0-5) can be considered compatible and usable. And alternatively, in embodiments, the combined solubility distance of a combination of two or more materials in the HSP space relative to the MIBC in the upper limits of 0 to 3, 4, or 5 (e.g., 0-3, 0-4, or 0-5) can be considered compatible and usable. Generally, a lower solubility distance or combined solubility distance in the HSP space relative to the MIBC may be a better choice for better compatibility and / or better performance compared to a higher solubility distance or combined solubility distance with a closer upper limit.

[0065] The concept of “distance” in this article also includes nonsolvents that provide a similar combined solubility parameter to MIBC when combined (e.g., a combined solubility distance of seven or less relative to MIBC). Figure 3 The 3D plot shows the solvent parameters (square plot points) of many other solvents graphically plotted relative to the MIBC plot point, and a sphere surrounding the MIBC plot point (i.e., the center of the sphere is the MIBC plot point). Simulations using HSPiP software have shown that two or more non-solvents can be combined, and the mathematical product and actual solubility of these combined materials can, in practice, simulate the mathematical product and actual solubility of a given solvent (such as MIBC) and / or can be sufficiently similar in solvent properties relative to MIBC (e.g., within seven or fewer distances relative to MIBC in HSP space).

[0066] Therefore, for embodiments of this disclosure, the HSP solubility space relative to the MIBC in the range of zero to seven can be defined, for example, as a set of individual solvents and / or combinations of materials / solvents that can provide the same or similar solvent properties as the MIBC. Figure 3As shown, when mapped in a 3D plot of HSP solubility values ​​relative to the MIBC, this can be visualized using a sphere with a given radius (e.g., radius = seven distance units), with the MIBC serving as a reference point at the center of the sphere. Therefore, for embodiments of this disclosure, solvents (which may include combinations of solvents and / or non-solvents) close to each other in HSP space may be able to dissolve similar solutes, and materials close to each other in Hansen space can be considered compatible with a given semiconductor process flow.

[0067] refer to Figure 3 The HSP value of the MIBC, taking the center point of the sphere (as a reference point), can be δD = 15.4, δP = 3.3, and δH = 12.3. Using the HSP, the solubility distance of the solvent (e.g., where the solvent can be a suitable developer) can be calculated using Equation 1: Equation 1 Where Dist represents the solubility distance of the solvent, i represents the solvent, t represents the target (e.g., MIBC), δDt and δDi represent the dispersion forces of the i-th chemical and the target, respectively, δPt and δPi represent the dipole-dipole interactions between the polar molecules of the i-th chemical and the target, respectively, and δHt and δHi represent the hydrogen bonding potentials of the molecules of the i-th chemical and the target, respectively.

[0068] The combined solubility distance in the HSP space relative to MIBC in the range of zero to seven can refer to a specific range of solubility compatibility between different substances and MIBC using a combination of Hansen solubility parameters (HSP).

[0069] In calculating the solubility distance of a combination of two or more materials relative to a target substance in the Hansen solubility space, the average solubility parameter of the mixture can be calculated first. In this context, "materials" is often used because a combination of two or more materials can include combinations of solvents, combinations of non-solvents, and / or combinations of non-solvents and / or solvents, which thus act as suitable solvents for a given application (e.g., relative to MIBC).

[0070] Assuming a mixture of two materials (material 1 and material 2) has volume fractions f1 and f2 (where f1 + f2 = 1), the combined solubility parameter (δD) of the HSP value can be calculated using equations 2-1, 2-2, and 2-3. mix δP mix ,δH mix ): Equation 2-1 Equation 2-2 Equation 2-3 Wherein, δD mix δD1 and δD2 represent the weighted dispersion forces of the mixture of materials 1 and 2, respectively, and δP represents the individual dispersion forces of materials 1 and 2. mix δP1 and δP2 represent the weighted dipole-dipole interactions between polar molecules in a mixture of materials 1 and 2, respectively, and δH represents the individual dipole-dipole interactions between polar molecules in materials 1 and 2. mix δH1 represents the weighted hydrogen bond potential of the molecules in the mixture of material 1 and material 2, and δH2 represents the individual hydrogen bond potential of the molecules in material 1 and material 2, respectively.

[0071] After determining the weighted average solubility parameters of the mixture, the same equation for the solubility distance (i.e., Equation 1 above) can be used in Equation 3, but the weighted mixture parameters mentioned above (i.e., Equations 2-1, 2-2, and 2-3) are used to calculate the combined solubility distance between the target material (e.g., MIBC) and the mixture (e.g., in the HSP space, which can be graphically represented in a 3D diagram): Equation 3 Where Dist represents the combined solubility distance, δDt represents the dispersion force of MIBC, δPt represents the dipole-dipole interaction between the polar molecules of MIBC, and δHt represents the hydrogen bonding potential of the MIBC molecule.

[0072] More generally, for mixtures of two or more materials, the process for calculating the combined solubility distance relative to the MIBC in HSP space is similar. First, the volume fraction (f) of each material in the mixture can be determined. i Secondly, the weighted average solubility parameter can be calculated using equations 4-1, 4-2, and 4-3: Equation 4-1 Equation 4-2 Equation 4-3 Wherein, δD mix δD represents the weighted dispersion force of a mixture of materials. i δP represents the individual dispersion force of each material in the mixture. mix δP represents the weighted dipole-dipole interaction between polar molecules in a mixture of materials. i δH represents the individual dipole-dipole interactions between the polar molecules of each material in the mixture. mixThe weighted hydrogen bond potential of molecules in a mixture of materials is represented by δH. i This represents the individual hydrogen bond potential of each molecule in the mixture.

[0073] Third, the combined solubility distance between the target material (e.g., MIBC) and the mixture can be calculated using the same equation for solubility distance, in Equation 3 (see above) using the aforementioned weighted mixture parameters (i.e., Equations 4-1, 4-2, and 4-3).

[0074] In embodiments, the determination or calculation of the combined solubility distance can be achieved by using the HSP computer program with different weighting techniques and / or equations different from any or all of the example equations described above, and / or by using numerical approximations or numerical methods to determine / calculate HSP information. For example, the HSP computer program can utilize lookup tables to obtain part or all of the data used to determine the combined solubility distance. For example, the HSP computer program can utilize numerical methods to approximate the results of the mathematical equations.

[0075] Figure 4 These are screenshots of an HSP computer program (which provides a list of materials including HSP information) according to an embodiment of this disclosure. More specifically, Figure 4 A list of materials (e.g., solvents) is shown, with MIBC at the top of the list. The rightmost column is labeled "Distance," which is the distance in HSP space for each listed material (see example...). Figure 3 The solubility distance relative to MIBC is calculated using Equation 1 (as described above) in the HSP space (as shown graphically). Therefore, the solubility distance of MIBC relative to MIBC is zero. Figure 4 All example materials listed have a solubility distance of less than seven relative to MIBC. Therefore, according to the embodiments of this disclosure, Figure 4 Each of the example materials listed can be a suitable developer for a given ROC layer material (or a suitable alternative to MIBC).

[0076] refer to Figure 4 The smaller the solubility distance value of the solvent in the Distance column, the more similar its solubility characteristics are to the MIBC. The MIBC can be set as the target (or the "distance" is zero). Therefore, the distance value can be compared with the MIBC used as a reference material / solvent / developer. It should be noted that... Figure 4 This list is not an exhaustive list of solvents, but merely an example list for illustrative purposes. Many other solvents and / or material / solvent combinations can be identified using the HSPiP software and other material / solvent combinations.

[0077] Figure 5 This is a flowchart illustrating a method for selecting a developer according to embodiments of this disclosure. In an embodiment of the method for formulating a developer for developing a patterned material having reversible solubility in a process for manufacturing a semiconductor device, the method may include identifying a list of materials, wherein each individual material in the list has a dispersion component (δD) between 14 and 18, a polar component (δP) between 2 and 8, and a hydrogen bonding component (δH) between 7 and 16, according to an HSP component system (box 501). In an embodiment of the method for formulating a developer, the method may include selecting a combination of two or more materials from the list and mixing the selected combination of the two or more materials at a selected ratio to formulate the developer such that the developer has a combined solubility distance relative to MIBC in the HSP space in the range of zero to seven (box 502).

[0078] In embodiments of the method for preparing a developer, the individual first solubility distance of one of the two or more materials may be greater than seven, while the combined solubility distance based on the combination of two or more materials is in the range of zero to seven in the HSP space relative to the MIBC. In embodiments of the method for preparing a developer, for a combination of two or more materials in the developer, none of the materials may be the MIBC.

[0079] Figure 6 This is a screenshot of an HSP computer program according to an embodiment of this disclosure (which provides example material combinations including HSP information for each of the listed materials). Figure 6 An example of a solvent mixture is shown, where the individual solubility distances of each solvent relative to the MIBC in the HSP space (3 and 11.8, respectively) are greater than the combined solubility distances relative to the MIBC in the HSP space. In this example case, the two solvents are mixed to give a combined solubility distance of 0.9 relative to the MIBC, for example, as shown below. Figure 6 As shown. In practice, two, three, or more solvents can be combined.

[0080] Many possible combinations may exist, but acceptable combinations can be identified, for example, using HSP software from a given supplier. Solvent mixtures can be selected based on practicality and the solubility distance of the combination relative to MIBC in the HSP space. Other solvent properties, such as toxicity and flammability, may limit or prevent solvent selection for the developer.

[0081] The embodiments of this disclosure can utilize the techniques disclosed herein to obtain methods and compositions for developing reversible outer coating films. Such techniques may include using 4-methyl-2-pentanol (MIBC / methyl isobutyl methanol CAS # 108-11-2) as a developer for certain reversible outer coating materials. Developers for such materials can be challenging because, in some embodiments, the developer should be able to dissolve the deprotected reversibly soluble material without dissolving the remaining reversibly soluble material or photoresist material on the substrate. Such techniques may also include solvent compositions and methods of using such compositions, having an HSP solubility distance close to or similar to that of MIBC.

[0082] The embodiments of this disclosure can be applied to the field of advanced patterning methods, wherein a pattern is formed by placing an outer coating with reverse solubility on a relief pattern of photoresist, and a reverse spacer is formed. Reverse spacer trenches can be formed using a trajectory-based patterning method. The embodiments of this disclosure offer the advantage of selecting a reverse spacer developer that is neither water-based tetramethylammonium hydroxide (TMAH) nor n-butyl acetate (nBA). Instead, the developer can be 4-methyl-2-pentanol (MIBC / methyl isobutyl methanol CAS # 108-11-2), or any solvent or combination of solvents / materials having the same or similar solubility characteristics as MIBC in the HSP solubility space. In the reverse spacer process flow, according to the embodiments of this disclosure, the developing operation that forms or exposes the trench can use MIBC or MIBC-like solvents as the developer, and this developer can be formulated / selected such that it does not readily dissolve the initial, trimmed photoresist pattern or the second layer pattern (e.g., a cross-linked reversible outer coating material) (e.g., having much greater or 100 times greater etch selectivity).

[0083] Therefore, according to embodiments of this disclosure, the techniques disclosed herein include using 4-methyl-2-pentanol solvent and its solvent space as a developer in the formation of reverse spacer trenches. This MIBC solvent space can include any solvent or solvent / material combination similar to the MIBC in the HSP space and has a mathematical distance relative to the MIBC in the range of zero to seven (e.g., according to the distance formula described herein). Having such a developer can be useful in reverse spacer processes to remove acid-diffused regions while preserving the material and structure forming the mandrel pattern (see, for example...). Figure 1I The mandrel pattern 144 includes the modified mandrel 122 and the sub-mandrel 136.

[0084] While MIBC can be used as a topcoat solvent or part of a topcoat composition, embodiments of this disclosure provide a method for using MIBC as a developer in different ways (for different purposes to address different problems / issues). MIBC typically does not dissolve commonly used or standard photoresist materials, and therefore MIBC can be used as a type of etchant to selectively remove a material without affecting the photoresist material (e.g., in trajectory-based reverse spacer processes). By creating a solubility switch in the ROC layer, MIBC can be used as a developer to selectively remove the switched / converted material for patterning. Even though developers are typically used after a material change following a photostep (e.g., a change in photoresist upon exposure to light or radiation), in the context of embodiments of this disclosure, the developer can be used after a material change performed by diffusion (e.g., patterning in the ROC layer is defined by chemical diffusion rather than a photostep).

[0085] Therefore, the embodiments of this disclosure are not necessarily limited to those described above and are... Figures 1A to 1I The process flow for the reverse spacer is illustrated. The developer according to embodiments of this disclosure can be used in any process flow or patterning operation where the layer has a solubility switching or chemical conversion portion, and the switching / converted material then becomes soluble in the MIBC, or becomes soluble in a combination of two or more materials within a given solubility distance of the MIBC in the HSP space, such that the developer can remove the switching / converted material while leaving the unconverted material and / or photoresist mandrel intact to produce a new mandrel pattern. For example, in embodiments, the switching / converted material can originate from a crosslinking-to-decrosslinking switch of the ROC material (as described above regarding...). Figures 1A to 1I (As described). However, in embodiments, the material being switched / converted can be switched / converted in an alternative manner or from a different starting point or material composition. For example, in embodiments, the solubility switching or conversion of a material can typically originate from the diffusion of a substance or element (e.g., an acid) from a first material to a second material, wherein the second material undergoes a solubility switching to a given depth within the second material, which allows the switched / converted material (or a portion thereof) to become soluble in the MIBC, or to become soluble in a combination of two or more materials within a given solubility distance of the MIBC in HSP space. Therefore, for other embodiments, the switching mechanism and / or process for making the switched / converted material soluble in the MIBC (or a MIBC-like solvent) can vary.

[0086] In the foregoing description, specific details, such as the particular geometry of the machining system and the description of various components and processes used therein as exemplary embodiments, have been set forth. However, it should be understood that the techniques described herein can be practiced in other embodiments and other processes that deviate from these specific exemplary details, and such exemplary details may be for illustrative purposes and not necessarily for limiting purposes. Exemplary embodiments disclosed herein have been described with reference to the accompanying drawings. Similarly, specific figures, materials, and configurations have been set forth for illustrative purposes to provide a thorough understanding, but other embodiments may be practiced without such specific details.

[0087] Various techniques have been described as multiple discontinuous operations to aid in understanding the various example embodiments. The order of description should not be interpreted as implying that these operations must be performed in a specific order. In fact, these operations do not need to be performed in the presented order. The described operations may be performed in an order different from the order of the described example embodiments. In other embodiments, various additional operations may be performed and / or the described operations may be omitted.

[0088] As used herein, “substrate” can generally refer to an object processed according to the present invention. A substrate can include any material portion or structure of a device, and can particularly include semiconductors or other electronic devices, and can be, for example, a base substrate structure (such as a semiconductor wafer, a photomask) and / or a layer on or overlying a base substrate structure (such as a thin film). Therefore, a substrate is not limited to any particular base structure, lower or upper layer, patterned or unpatterned structure, or intermediate structure, or combination thereof, during the manufacture of a semiconductor device, and can include any such layer or base structure, and any combination of layers and / or base structures. This disclosure may refer to specific types of substrates, but this may be for illustrative purposes only.

[0089] Further exemplary embodiments of this disclosure are summarized herein. Other embodiments can also be understood in light of the entire specification and the claims set forth herein.

[0090] Example 1. A developer configured to selectively remove a solubility switching region of a first material layer during a semiconductor manufacturing process to form a mandrel pattern in the layer on a substrate, wherein the developer has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter (HSP) space in the range of zero to seven.

[0091] Example 2. A developer as described in Example 1, wherein the developer is MIBC.

[0092] Example 3. A developer as described in either Example 1 or 2, wherein the developer comprises a combination of two or more materials, and wherein the solubility distance is based on the combined solubility distance of the combination of the two or more materials.

[0093] Example 4. A developer as described in any one of Examples 1 to 3, wherein, for the combination of the two or more materials, none of the materials are MIBC.

[0094] Example 5. A developer as described in any one of Examples 1 to 4, wherein the developer is a combination of two or more materials, wherein the solubility distance is a combined solubility distance based on the combination of the two or more materials, and wherein an individual first solubility distance of one of the two or more materials is greater than seven, but the combined solubility distance based on the combination of the two or more materials is in the range of zero to seven relative to MIBC in the HSP space.

[0095] Example 6. A developer as described in any one of Examples 1 to 5, wherein, for the combination of the two or more materials, none of the materials are MIBC.

[0096] Example 7. A developer as described in any one of Examples 1 to 6, wherein the developer is a combination of two or more materials, wherein the solubility distance is based on the combined solubility distance of the combination of the two or more materials, and wherein, according to the HSP component system, each individual material in the material list has a dispersion component between 14 and 18, a polar component between 2 and 8, and a hydrogen bonding component between 7 and 16.

[0097] Example 8. A developer as described in any one of Examples 1 to 7, wherein, for the combination of the two or more materials, none of the materials are MIBC.

[0098] Example 9. In a method for forming a semiconductor device, the method includes: coating a reversible outer coating layer on a first mandrel on a substrate; inducing a crosslinking reaction within the reversible outer coating layer, the crosslinking reaction rendering the reversible outer coating layer insoluble in a developer and forming a crosslinked outer coating layer; diffusing acid particles from the first mandrels into a first portion of the crosslinked outer coating layer; inducing a decrosslinking reaction within the first portion of the crosslinked outer coating layer to form decrosslinked regions, wherein unmodified regions of the crosslinked outer coating layer form second mandrels; and selectively removing the decrosslinked regions with the developer, such that the first mandrels and the second mandrels form a mandrel pattern on the substrate, wherein the developer has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter space in the range of zero to seven.

[0099] Example 10. The method as described in Example 9, wherein the developer is MIBC.

[0100] Example 11. The method as described in any one of Examples 9 or 10, further comprising selecting the developer, wherein the developer is a combination of two or more materials that are not MIBC, and wherein the solubility distance is based on the combined solubility distance of the combination of the two or more materials.

[0101] Example 12. The method as described in any one of Examples 9 to 11, wherein the selection of the developer further comprises: selecting a combination of the two or more materials; determining a combination solubility distance of the two or more materials; and determining whether the combination of the two or more materials is suitable as the developer based on whether the combination solubility distance of the two or more materials is in the range of zero to seven relative to MIBC in the Hansen solubility parameter space.

[0102] Example 13. The method as described in any one of Examples 9 to 12, wherein the selection of the developer is performed using a computer software program.

[0103] Example 14. The method of any one of Examples 9 to 13, further comprising selecting the developer, wherein the developer is a combination of two or more materials that are not MIBC, wherein the solubility distance is a combined solubility distance based on the combination of the two or more materials, and wherein an individual first solubility distance of one of the two or more materials is greater than seven, but the combined solubility distance based on the combination of the two or more materials is in the range of zero to seven relative to MIBC in the Hansen solubility parameter space.

[0104] Example 15. The method as described in any one of Examples 9 to 14, wherein the reversible outer coating layer comprises a first material with phenolic functional groups and a second material with vinyl ether functional groups.

[0105] Example 16. The method as described in any one of Examples 9 to 15, wherein the reversible outer coating layer comprises a first material with methacrylic acid functional groups and a second material with vinyl ether functional groups.

[0106] Example 17. The method of any one of Examples 9 to 16, further comprising forming the first mandrels on the substrate using a pre-lithography trimming process, and generating the acid particles within the first mandrels by exposure to photochemical radiation.

[0107] Example 18. In a method of formulating a developer for developing a patterned material having reversible solubility in a process for manufacturing a semiconductor device, the method includes: identifying a list of materials, wherein each individual material in the list has a dispersion component between 14 and 18, a polar component between 2 and 8, and a hydrogen bonding component between 7 and 16, according to a Hansen solubility parameter (HSP) component system; and selecting a combination of two or more materials from the list, and mixing the selected combination of the two or more materials in a certain ratio to formulate the developer such that the developer has a combined solubility distance relative to methyl isobutyl methanol (MIBC) in the HSP space in the range of zero to seven.

[0108] Example 19. The method as described in Example 18, wherein the individual first solubility distance of one of the two or more materials is greater than seven, but the combined solubility distance based on the combination of the two or more materials is in the range of zero to seven relative to MIBC in the HSP space.

[0109] Example 20. The method as described in one of Examples 18 or 19, wherein, for the combination of the two or more materials, none of the materials are MIBC.

[0110] Although illustrative exemplary embodiments have been described with reference to the accompanying drawings, this description is not intended to be construed in a limiting sense. Various modifications and combinations of the illustrative exemplary embodiments and other embodiments will be apparent to those skilled in the art from this disclosure. Therefore, the appended claims are intended to cover any and all such modifications, equivalents, or embodiments.

Claims

1. A developer comprising a developer composition configured to selectively remove a solubility switching region of a first material layer during a semiconductor manufacturing process to form a mandrel pattern in the layer on a substrate, wherein the developer composition has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter (HSP) space in the range of zero to seven.

2. The developer as claimed in claim 1, wherein, The developer composition includes MIBC.

3. The developer as described in claim 1, wherein, The developer composition comprises a combination of two or more materials, and the solubility distance is based on the combined solubility distance of the two or more materials.

4. The developer as described in claim 3, wherein, For combinations of two or more materials, none of these materials are MIBC.

5. The developer as claimed in claim 1, wherein, The developer composition comprises a combination of two or more materials, wherein the solubility distance is a combined solubility distance based on the combination of the two or more materials, and wherein the individual first solubility distance of one of the two or more materials is greater than seven, but the combined solubility distance based on the combination of the two or more materials is in the range of zero to seven relative to MIBC in the HSP space.

6. The developer as claimed in claim 5, wherein, For combinations of two or more materials, none of these materials are MIBC.

7. The developer as claimed in claim 1, wherein, The developer composition comprises a combination of two or more materials, wherein the solubility distance is based on the combined solubility distance of the two or more materials, and wherein, according to the HSP component system, each individual material in the material list has a dispersion component between 14 and 18, a polar component between 2 and 8, and a hydrogen bonding component between 7 and 16.

8. The developer as claimed in claim 7, wherein, For combinations of two or more materials, none of these materials are MIBC.

9. A method for forming a semiconductor device, the method comprising: A reversible outer coating layer is applied to the first mandrel on the substrate; A cross-linking reaction is induced within the reversible outer coating layer, which renders the reversible outer coating layer insoluble in the developer and forms a cross-linked outer coating layer. Acid particles are diffused from these first mandrels into the first portion of the cross-linked outer coating layer; A decrosslinking reaction is induced in the first portion of the crosslinked outer coating layer to form a decrosslinked region, wherein the unmodified region of the crosslinked outer coating layer forms a second mandrel; as well as The developer is used to selectively remove these decrosslinked regions, so that the first mandrels and the second mandrels form a mandrel pattern on the substrate, wherein the developer has a solubility distance relative to methyl isobutyl methanol (MIBC) in the Hansen solubility parameter space in the range of zero to seven.

10. The method of claim 9, wherein, The developer is MIBC.

11. The method of claim 9, further comprising selecting the developer, wherein the developer is a combination of two or more materials that are not MIBC, and wherein the solubility distance is based on the combined solubility distance of the combination of the two or more materials.

12. The method of claim 11, wherein, The choice of developer further includes: Choose a combination of two or more materials; Determine the combined solubility distance of the combination of the two or more materials; and Based on whether the combination of two or more materials is within the range of zero to seven relative to MIBC in the Hansen solubility parameter space, it is determined whether the combination of two or more materials is suitable as the developer.

13. The method of claim 11, wherein, The selection of the developer is performed using a computer software program.

14. The method of claim 9, further comprising selecting the developer, wherein the developer is a combination of two or more materials that are not MIBC, wherein the solubility distance is a combined solubility distance based on the combination of the two or more materials, and wherein an individual first solubility distance of one of the two or more materials is greater than seven, but the combined solubility distance based on the combination of the two or more materials is in the range of zero to seven relative to MIBC in the Hansen solubility parameter space.

15. The method of claim 9, wherein, The reversible outer coating layer comprises a first material with phenolic functional groups and a second material with vinyl ether functional groups.

16. The method of claim 9, wherein, The reversible outer coating layer comprises a first material with methacrylic acid functional groups and a second material with vinyl ether functional groups.

17. The method of claim 9, further comprising: These first mandrels were formed on the substrate using a matte lithography finishing process; as well as These acid particles are generated within these first mandrels by exposure to photochemical radiation.

18. A method for formulating a developer for developing a patterned material having reversible solubility in a process for manufacturing a semiconductor device, the method comprising: Identify a list of materials in which, according to the Hansen solubility parameter (HSP) component system, each individual material in the list has a dispersive component between 14 and 18, a polar component between 2 and 8, and a hydrogen bonding component between 7 and 16; and Select a combination of two or more materials from the list and mix the selected combination of the two or more materials in a certain ratio to formulate the developer such that the developer has a combined solubility distance relative to methyl isobutyl methanol (MIBC) in the HSP space in the range of zero to seven.

19. The method of claim 18, wherein, The individual first solubility distance of one of the two or more materials is greater than seven, but the combined solubility distance of the combination of the two or more materials is in the range of zero to seven relative to MIBC in the HSP space.

20. The method of claim 18, wherein, For combinations of two or more materials, none of these materials are MIBC.

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