Assisted Feature Placement in Semiconductor Patterning

Abstract

The challenges in PCB patterning include precisely positioning the designed pattern relative to the underlying features, thereby accurately forming the final pattern. Another challenge is precisely sizing the final pattern as designed. [Solution] The present invention relates to a microfabrication method comprising: providing a substrate having an existing pattern, wherein the existing pattern includes features formed in a base layer such that the upper surface of the substrate has uncovered features and the base layer is uncovered; depositing a selective binder on the substrate, wherein the selective binder includes a solubility modifier; depositing a first resist on the substrate; activating the solubility modifier so that a portion of the first resist becomes soluble in a first developer; and developing the first resist using the first developer so that a portion of the first resist that is soluble in the first developer is removed.

Description

[Background technology]

[0001] Microfabrication of semiconductor devices involves various processes such as film deposition, pattern formation, and pattern transfer. Materials and films are deposited on a substrate by spin coating, vapor deposition, and other deposition processes. Pattern formation is typically carried out by exposing a photosensitive film, known as a photoresist, to chemical radiation in a certain pattern, and then developing the photoresist to form a relief pattern. The relief pattern then acts as an etching mask, covering the areas of the substrate that are not etched when one or more etching processes are applied to the substrate. Thus, patterns constituting functional elements (such as transistors and diodes) are formed on the substrate, which are then further processed.

[0002] Semiconductor patterning involves a routine process flow. A substrate layer is received with several patterns. These patterns are smoothed, and a transfer layer is placed to improve the pattern shape. Next, a photoresist and related layers are deposited on the surface. The photoresist layer is exposed to the patterns by lithography, thereby generating a latent pattern. The latent pattern is then developed to form a relief pattern resistant to the etching solution used as an etching mask. Finally, this relief pattern is etched onto the transfer layer and then onto the final substrate. [Overview of the project] [Means for solving the problem]

[0003] This summary is provided to introduce a selection of concepts that will be further explained in the detailed description below. This summary is not intended to identify any important or essential features of the claimed subject matter, nor is it intended to be used to help limit the scope of the claimed subject matter.

[0004] In one aspect, an embodiment disclosed herein is to provide a substrate having an existing pattern, wherein the upper surface of the substrate has uncovered features and the existing pattern includes features formed in a base layer such that the base layer is not covered, and depositing a selective binder on the substrate, wherein the selective binder includes a solubility modifier, depositing a first resist on the substrate, activating the solubility modifier such that a portion of the first resist becomes insoluble in a first developer, and developing the first resist using the first developer such that a portion of the first resist that is insoluble in the first developer remains.

[0005] In another aspect, an embodiment of the present disclosure is to provide a substrate having an existing pattern, wherein the upper surface of the substrate has uncovered features and the existing pattern includes features formed in a base layer such that the base layer is not covered, and depositing a selective binder on the substrate, wherein the selective binder includes a solubility modifier, depositing a first resist on the substrate, activating the solubility modifier such that a portion of the first resist becomes soluble in a first developer, and developing the first resist using the first developer such that a portion of the first resist that is soluble in the first developer is removed.

[0006] Other aspects and advantages of the claimed subject matter will become apparent from the following description and appended claims.

Brief Description of the Drawings

[0007] [Figure 1A] It is a schematic diagram of a selective self-aligned pattern on a substrate according to one or more embodiments of the present disclosure.

[0008] [Figure 1B] It is a schematic diagram of an anti-selective self-aligned pattern on a substrate according to one or more embodiments of the present disclosure.

[0009] [Figure 2]This is a block flow diagram of a method according to one or more embodiments of the present disclosure.

[0010] [Figure 3A] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 3B] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 3C] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 3D] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 3E] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure.

[0011] [Figure 4] This is a block flow diagram of a method according to one or more embodiments of the present disclosure.

[0012] [Figure 5A] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 5B] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 5C] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Figure 5D] These are schematic diagrams of the coated substrate at each point in time according to one or more embodiments of the present disclosure. [Modes for carrying out the invention]

[0013] The challenges in PCB patterning include precisely positioning the designed pattern relative to the underlying features, thereby accurately shaping the final pattern. Another challenge is precisely sizing the final pattern as designed. Even small variations in size and shape can lead to both short-term and long-term device failures.

[0014] As will be understood by those skilled in the art, films and materials added to and removed from a given substrate can expose the substrate to internal compressive and tensile stresses based on the structure of the formed material and shape. These internal stresses can cause the substrate to flex and bend. Furthermore, printing patterns at a resolution below that of a given photolithography tool often means a high probability of misplacement of the pattern. Therefore, a significant challenge is that the placed (exposed) pattern may be offset from the preceding pattern. This "alignment" error or "overlay" error is one of the most important challenges in the microfabrication of devices. This challenge applies to each layer on top of each other and each layer adjacent to each other.

[0015] Therefore, improvement of pattern placement on a given subsequent layer is highly desirable. Conventional attempts to improve pattern placement in lithography systems tend to involve highly accurate measurements and the use of complex feedback loops.

[0016] This disclosure relates, in general terms, to methods for patterning on a semiconductor substrate. Herein, the terms “semiconductor substrate” and “substrate” are used interchangeably and may include, but are not limited to, any semiconductor material including, semiconductor wafers, semiconductor material layers, and combinations thereof. The methods disclosed herein provide pattern placement and overlays that are locally and directly improved by forming patterns at precise locations (e.g., target locations or target regions). To achieve self-aligned pattern placement, the methods may include either indicating where patterns are to be formed or preventing pattern formation at undesirable locations. In one or more embodiments, the methods include depositing or forming auxiliary layers on target locations.

[0017] The methods relating to this disclosure may include providing a substrate having an existing pattern, and then selectively forming a material for a certain pattern on or alternately with the existing pattern. A material for a certain pattern selectively formed on an existing pattern according to one or more embodiments is shown in Figure 1A. A material for a certain pattern selectively formed alternately with or offset from an existing pattern contained on a substrate according to one or more embodiments is shown in Figure 1B.

[0018] A method 200 for selective pattern self-alignment (e.g., the pattern shown in Figure 1A) according to this disclosure is shown in Figure 2 and will be discussed with reference to Figure 2. First, in block 202, an existing pattern is provided on a substrate. In block 204, the substrate or a portion thereof is coated with a selective binder. The selective binder may covalently bond to the surface. The selective binder coating may optionally be pre-treated. The optional pre-treatment may be heat treatment. Heat treatment may promote a condensation reaction between the selective binder and the surface. Next, in block 206, the substrate is coated with a first resist. A solubility modifier may be provided on the first resist, and then, as shown in block 208, the solubility modifier may be activated to provide a region of the first resist that is soluble in the first developer. Finally, in block 210, the first resist is developed to provide a selective pattern of the first resist.

[0019] Schematic diagrams of the coated substrate at various points in time during the method described above are shown in Figures 3A to 3E. In this specification, “coated substrate” refers to a substrate coated with one or more layers, such as a first resist layer and a second resist layer. Figure 3A shows a substrate with an existing pattern. Figure 3B shows a substrate with an overcoat containing a selective binder. Figure 3C shows a substrate with a selective binder overcoat laminated with the first resist. Finally, Figure 3D shows the coated substrate after the first resist has been developed, resulting in the exposure of a portion of the substrate. The method in Figure 2 and the coated substrates shown in Figures 3A to 3D are discussed in detail below.

[0020] In Figure 2, block 202 provides an existing pattern on the substrate. Figure 3A shows the substrate containing the existing pattern. In Figure 3A, the existing pattern includes a feature 302 formed on a base layer 301. The base layer can be any suitable substrate known in the art. In one or more embodiments, the feature includes a metal or other conductive structure. As used herein, the term metal includes alloys, laminates, and other combinations of multiple metals. For example, a metal interconnect line may include a barrier layer, a laminate of various metals or alloys, etc. Suitable metals that may be present in the feature include, but are not limited to, copper, cobalt, and tungsten. In one or more embodiments, the base layer is an interlayer dielectric. Suitable interlayer dielectrics may include silicon oxides (e.g., silicon dioxide (SiO2)), doped silicon oxides, fluorinated silicon oxides, carbon-doped silicon oxides, various low-k dielectric materials known in the art, and combinations thereof. The existing pattern may be a final or intermediate feature in the patterning process. In some embodiments, the existing pattern is flattened so that it is not covered and remains accessible.

[0021] Next, in block 204, a selective binder is coated onto the substrate or a portion thereof. The selective binder can be coated onto the substrate by any coating method known in the art. Preferred coating methods include, but are not limited to, vapor deposition, spin-on coating, and Langmuir-Bludget monolayer coating. In one or more embodiments, the selective binder is coated onto a target region. In this specification, “target region” or “target location” refers to a region on the substrate that will receive the pattern.

[0022] A selective binder may preferentially adhere to one material of an existing pattern. In one or more embodiments, the selective binder adheres to features of an existing pattern. Figure 3B shows a substrate coated with selective binder 303 that adheres to features of an existing pattern. The selective binder may adhere to features of a pattern in a ratio greater than 1:1. For example, but not limited to, the selective binder may adhere to features of a pattern where the feature-to-base layer ratio is in the range of 2:1 to 10:1.

[0023] In one or more embodiments, the selective binder is a chemically functionalized group that can be further functionalized. Exemplary selective binders include, but are not limited to, silanes, alkenes, alkynes, alcohols, silanols, amines, phosphines, phosphonic acids, and carboxylic acids. A particular selective binder coated on an existing pattern may depend on specific chemical reactions used in other components of Method 200. For example, various phosphonic acids and esters can react selectively or at least preferentially with untreated or oxidized metal surfaces to form metal phosphonates that are preferentially or even selectively strongly bonded to the surface of dielectric materials (e.g., silicon oxides), thereby being used as selective binders coated on features in the base layer. A specific example of a preferred phosphonic acid is octadecylphosphonic acid (ODPA). Such surface coatings generally tend to be stable in many organic solvents, but can be removed using weakly acidic and weakly basic aqueous solutions. Phosphines (e.g., organophosphines) can also be used optionally. Other common acids, such as sulfonic acids, sulfinic acids, and carboxylic acids, may also be used optionally.

[0024] Another example of a reaction that is selective or at least preferential to metallic materials compared to dielectric materials, organic polymer materials, or other materials is a variety of metal corrosion inhibitors, such as those used in chemical mechanical polishing to protect interconnected structures. Specific examples include benzotriazoles, other triazole functional groups, other suitable heterocyclic groups (e.g., heterocyclic corrosion inhibitors), and other metal corrosion inhibitors known in the art. In addition to triazole groups, other functional groups may be used to provide the desired attraction or reactivity to metals. Various metal chelating agents are also potentially suitable. Various amines (e.g., organic amines) are also potentially suitable.

[0025] Another example of a reaction that is selective or at least preferential to metallic materials compared to dielectric materials, organic polymer materials, or other materials is a variety of thiols. As another example, 1,2,4-triazoles or similar aromatic heterocyclic compounds may be used to react selectively with metals compared to dielectrics and certain other materials. Selective binders may also contain functional groups that are reactive with the functional groups of a polymer to bond the polymer to a surface. Various other metal-poisoning compounds known in the art may also be potentially used. These are merely some illustrative examples, and it should be understood that further examples will be apparent to those skilled in the art who are interested in this disclosure. Selective binders may also contain polymers containing any of the aforementioned functional groups capable of selective bonding, where the functional groups are along the main chain or as terminal groups, forming a layer of polymer chains bonded to the target material.

[0026] In one or more embodiments, the selective binder includes a solubility modifier. The composition of the solubility modifier may depend on the selective binder. As will be understood by those skilled in the art, any suitable solubility modifier may be included in the selective binder, as long as the two materials do not react with each other. Generally, the solubility modifier may be any chemical substance that is activated by light or heat. For example, in some embodiments, the solubility modifier includes an acid or a thermal acid generator (TAG). The acid, or in the case of a TAG, the generated acid, should be sufficient, by heat, to decompose the bonds of the acid-degradable groups of the polymer in the surface region of the first resist pattern, thereby increasing the solubility of the first resist polymer in the particular developer applied. The acid or TAG is typically present in the composition in an amount of about 0.01 to 20% by weight based on the total solids content of the trimming composition.

[0027] Preferred acids include organic acids, including non-aromatic and aromatic acids, each of which may optionally have fluorine substitution. Suitable organic acids include, for example, carboxylic acids such as alkanos including formic acid, acetic acid, propionic acid, butyric acid, dichloroacetic acid, trichloroacetic acid, perfluoroacetic acid, perfluorooctanoic acid, oxalic acid, malonic acid, and succinic acid; hydroxyalkanoics such as citric acid; aromatic carboxylic acids such as benzoic acid, fluorobenzoic acid, hydroxybenzoic acid, and naphthoic acid; organic phosphoric acids such as dimethyl phosphoric acid and dimethylphosphinic acid; and sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, 1-butanesulfonic acid, 1-perfluorobutanesulfonic acid, 1,1,2,2-tetrafluorobutane-1-sulfonic acid, 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid, and 1-heptanesulfonic acid, which are optionally fluorinated alkylsulfonic acids.

[0028] Examples of fluorine-free aromatic acids include those of the following general formula (I):

[0029] [ka]

[0030] [In the formula, R1 independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group, or a combination thereof, optionally containing one or more groups selected from carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene group, or a combination thereof; Z1 independently represents a group selected from carboxyl, hydroxy, nitro, cyano, C1-C5 alkoxy, formyl, and sulfonic acid; and a and b independently are integers from 0 to 5, with a+b being 5 or less.]

[0031] An exemplary aromatic acid may be represented by the following general formula (II).

[0032] [ka]

[0033] [In the formula, R2 and R3 each independently represent a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C16 aryl group, or a combination thereof, optionally containing one or more groups selected from carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene group, or a combination thereof; Z2 and Z3 each independently represent a group selected from carboxyl, hydroxy, nitro, cyano, C1-C5 alkoxy, formyl, and sulfonic acid; c and d are independently integers from 0 to 4, with c+d being 4 or less; and e and f are independently integers from 0 to 3, with e+f being 3 or less.]

[0034] Additional aromatic acids that may be included in the solubility modifier include those of the following general formulas (III) or (IV).

[0035] [ka]

[0036] [In the formula, R4, R5, and R6 each independently represent a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C12 aryl group, or a combination thereof, and optionally contain one or more groups selected from carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene group, or a combination thereof; Z4, Z5, and Z6 each independently represent a group selected from carboxyl, hydroxy, nitro, cyano, C1-C5 alkoxy, formyl, and sulfonic acid; g and h are independently integers from 0 to 4, with g+h being 4 or less; i and j are independently integers from 0 to 2, with i+j being 2 or less; k and 1 are independently integers from 0 to 3, with k+l being 3 or less]

[0037] [ka]

[0038] [In the formula, R4, R5, and R6 each independently represent a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C12 aryl group, or a combination thereof, and optionally contain one or more groups selected from carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene group, or a combination thereof; Z4, Z5, and Z6 each independently represent a group selected from carboxyl, hydroxy, nitro, cyano, C1-C5 alkoxy, formyl, and sulfonic acid; g and h are independently integers from 0 to 4, with g+h being 4 or less; i and j are independently integers from 0 to 1, with i+j being 1 or less; k and l are independently integers from 0 to 4, with k+l being 4 or less]

[0039] A suitable aromatic acid may alternatively be one of the following general formulas (V).

[0040] [ka]

[0041] [In the formula, R7 and R8 each independently represent a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C14 aryl group, or a combination thereof, and optionally contain one or more groups selected from carboxyl, carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene group, or a combination thereof; Z7 and Z8 each independently represent a group selected from hydroxy, nitro, cyano, C1-C5 alkoxy, formyl, and sulfonic acid; m and n are independently integers from 0 to 5, with m+n being 5 or less; and o and p are independently integers from 0 to 4, with o+p being 4 or less.]

[0042] Furthermore, exemplary aromatic acids may have the following general formula (VI).

[0043] [ka]

[0044] [In the formula, X is O or S, R9 independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group, or a combination thereof, optionally containing one or more groups selected from carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene group, or a combination thereof, Z9 independently represents a group selected from carboxyl, hydroxy, nitro, cyano, C1-C5 alkoxy, formyl, and sulfonic acid, and q and r independently are integers from 0 to 3, with q + r being 3 or less]

[0045] In one or more embodiments, the acid is a free acid having a fluorine substitution. Suitable free acids having a fluorine substitution may be aromatic or non-aromatic. For example, free acids having a fluorine substitution that can be used as solubility modifiers include, but are not limited to, the following:

[0046]

change

[0047]

change

change

change

change

[0048] Suitable TAGs include those capable of generating non-polymerizable acids, as described above. TAGs can be nonionic or ionic. Suitable nonionic thermal acid generators include, for example, cyclohexyl trifluoromethyl sulfonate, methyl trifluoromethyl sulfonate, cyclohexyl p-toluenesulfonate, methyl p-toluenesulfonate, cyclohexyl 2,4,6-triisopropylbenzenesulfonate, nitrobenzyl ester, benzoin tosylate, 2-nitrobenzyl tosylate, tris(2,3-dibromopropyl)-1,3,5-triazine-2,4,6-trione, alkyl esters of organic sulfonic acids, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, Examples of suitable ionic thermoacids include phthalic acid, phosphoric acid, camphor sulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalicylic acid, 2,5-dimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4-hydroxy-5-benzoylbenzenesulfonic acid and their salts, as well as combinations thereof. Suitable ionic thermoacid generators include, for example, triethylamine dodecylbenzenesulfonic acid salt, triethylamine dodecylbenzenedisulfonic acid salt, p-toluenesulfonic acid-ammonium salt, p-toluenesulfonic acid-pyridinium salt, sulfonates such as carbocyclic aryl and heteroaryl sulfonates, aliphatic sulfonates, and benzenesulfonates. Compounds that generate sulfonic acid upon activation are generally preferred. Preferred thermal acid generators include ammonium p-toluenesulfonate and heteroarylsulfonates.

[0049] Preferably, in the reaction scheme for generating sulfonic acid as shown below, the TAG is ionic.

[0050] [ka]

[0051] In the formula, RSO3 - It is a TAG anion, X + is a TAG cation, preferably an organic cation. The cation can be a nitrogen-containing cation of the following general formula (I).

[0052] (BH) + (I)

[0053] This is the monoprotonated form of nitrogen-containing base B. Suitable nitrogen-containing base B include, for example, ammonia, difluoromethylammonia, optionally substituted amines such as C1-20 alkylamines and C3-30 arylamines, such as pyridine or substituted pyridine (e.g., 3-fluoropyridine), nitrogen-containing heteroaromatic bases such as pyrimidine and pyrazine, and nitrogen-containing heterocyclic groups such as oxazole, oxazoline, or thiazoline. The aforementioned nitrogen-containing base B can be optionally substituted with one or more groups selected from alkyl, aryl, halogen atoms (preferably fluorine), cyano, nitro, and alkoxy. Of these, base B is preferably a heteroaromatic base.

[0054] Base B typically has a pKa of 0–5.0, 0–4.0, 0–3.0, or 1.0–3.0. Where used herein, the term "pKa" is used in accordance with its meaning as recognized in the art. That is, pKa is the pKa of the conjugate acid (BH) of the basic moiety (B) in an aqueous solution at approximately room temperature. + It is the negative logarithm (base 10) of the dissociation constant. In certain embodiments, base B has a boiling point of less than about 170°C, less than about 160°C, 150°C, 140°C, 130°C, 120°C, 110°C, 100°C, or less than 90°C.

[0055] Suitable exemplary nitrogen-containing cations (BH) + For example, NH4 + CF2HNH2 + CF3CH2NH3+ 、(CH3)3NH + 、(C2H5)3NH + 、(CH3)2(C2H5)NH + and the following may be mentioned.

[0056]

Chemical formula

[0057] [In the formula, Y is alkyl, preferably methyl or ethyl]

[0058] In certain embodiments, the solubility modifier may be an acid such as trifluoromethanesulfonic acid, perfluoro-1-butanesulfonic acid, p-toluenesulfonic acid, 4-dodecylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, and 2-trifluoromethylbenzenesulfonic acid; an acid generator such as triphenylsulfonium antimonate, pyridinium perfluorobutanesulfonate, 3-fluoropyridinium perfluorobutanesulfonate, 4-t-butylphenyltetramethylenesulfonium perfluoro-1-butanesulfonate, 4-t-butylphenyltetramethylenesulfonium 2-trifluoromethylbenzenesulfonate, and 4-t-butylphenyltetramethylenesulfonium 4,4,5,5,6,6-hexafluorodihydro-4H-1,3,2-dithiazine 1,1,3,3-tetraoxide; or a combination thereof.

[0059] Alternatively, the solubility modifier may include a base or a base generator. In such embodiments, suitable solubility modifiers include, but are not limited to, hydroxides, carboxylates, amines, imines, amides, and mixtures thereof. Specific examples of bases include ammonium carbonate, ammonium hydroxide, ammonium hydrogen phosphate, ammonium phosphate, tetramethylammonium carbonate, tetramethylammonium hydroxide, tetramethylammonium hydrogen phosphate, tetramethylammonium phosphate, tetraethylammonium carbonate, tetraethylammonium hydroxide, tetraethylammonium hydrogen phosphate, tetraethylammonium phosphate, and combinations thereof. Examples of amines include aliphatic amines, alicyclic amines, aromatic amines, and heterocyclic amines. The amine may be a primary amine, a secondary amine, or a tertiary amine. The amine may be a monoamine, a diamine, or a polyamine. Suitable amines may include C1-30 organic amines, imines, or amides, or C1-30 quaternary ammonium salts of strong bases (e.g., hydroxides or alkoxides) or weak bases (e.g., carboxylates). Examples of bases include amines such as tripropylamine, dodecylamine, tris(2-hydroxypropyl)amine, and tetrakis(2-hydroxypropyl)ethylenediamine; arylamines such as diphenylamine, triphenylamine, aminophenol, and 2-(4-aminophenyl)-2-(4-hydroxyphenyl)propane; Traeger bases; hindered amines such as diazabicycloundecene (DBU) or diazabicyclononene (DBN); amides such as tert-butyl 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarbamate and tert-butyl 4-hydroxypiperidine-1-carboxylate; or ionic quenchers containing quaternary alkylammonium salts such as tetrabutylammonium hydroxide (TBAH) or tetrabutylammonium lactate. In another embodiment, the amine is a hydroxyamine.Examples of hydroxyamines include hydroxyamines having one or more hydroxyalkyl groups (e.g., hydroxymethyl group, hydroxyethyl group, and hydroxybutyl group) having 1 to about 8 carbon atoms, preferably 1 to about 5 carbon atoms. Specific examples of hydroxyamines include monoethanolamine, diethanolamine, triethanolamine, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1,3-propanediol, tris(hydroxymethyl)aminomethane, N-methylethanolamine, 2-diethylamino-2-methyl-1-propanol, and triethanolamine.

[0060] A suitable base generator may be a thermal base generator. Thermal base generators form a base when heated above a first temperature, typically above about 140°C. Thermal base generators may contain functional groups such as amides, sulfonamides, imides, imines, O-acyloximes, benzoyloxycarbonyl derivatives, quaternary ammonium salts, nifedipines, carbamates, and combinations thereof. Examples of thermobase generators include o-{(β-(dimethylamino)ethyl)aminocarbonyl}benzoic acid, o-{(γ-(dimethylamino)propyl)aminocarbonyl}benzoic acid, 2,5-bis{(β-(dimethylamino)ethyl)aminocarbonyl}terephthalic acid, 2,5-bis{(γ-(dimethylamino)propyl)aminocarbonyl}terephthalic acid, 2,4-bis{(β-(dimethylamino)ethyl)aminocarbonyl}isophthalic acid, 2,4-bis{(γ-(dimethylamino)propyl)aminocarbonyl}isophthalic acid, and combinations thereof.

[0061] Alternatively, in one or more embodiments, the solubility modifier includes a crosslinking agent. Suitable crosslinking agents that can be used as solubility modifiers include, but are not limited to, crosslinking agents used to cure bisepoxides such as bisphenol A diglycidyl ether, glycuryls such as 2,5-bis[(2-oxyranylmethoxy)-methyl]-furan, 2,5-bis[(2-oxyranylmethoxy)methyl]-benzene, melamine, tetramethoxymethyl glycoluryl and tetrabutoxymethyl glycoluryl, benzoguanamine-based materials such as benzoguanamine, hydroxymethylbenzoguanamine, methylated hydroxymethylbenzoguanamine, and ethylated hydroxymethylbenzoguanamine, and urea-based materials.

[0062] In one or more embodiments, the selective binder comprises a solvent. The solvent is typically selected from water, organic solvents, and mixtures thereof. In some embodiments, the solvent may comprise an organic solvent system comprising one or more organic solvents. The term “organic system” means that the solvent system comprises more than 50% by weight of an organic solvent based on the total solvent of the solubility modifier composition, and more typically, more than 90% by weight, more than 95% by weight, more than 99% by weight, or 100% by weight of an organic solvent based on the total solvent of the solubility modifier composition. The solvent component is typically present in an amount of 90–99% by weight based on the solubility modifier composition.

[0063] Suitable organic solvents for selective binder compositions include, for example, alkyl esters such as n-butyl propionate, n-pentyl propionate, n-hexyl propionate, and n-heptyl propionate, and alkyl butyrates such as n-butyl butyrate, isobutyl butyrate, and isobutyl isobutyrate; ketones such as 2,5-dimethyl-4-hexanone and 2,6-dimethyl-4-heptanone; n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, and 3-methylheptane. Aliphatic hydrocarbons such as butane, 3,3-dimethylhexane and 2,3,4-trimethylpentane, and fluorinated aliphatic hydrocarbons such as perfluoroheptane; 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 3-methyl-1-butanol, 1-pentanol, 2-pentanol, 4-methyl-2-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol and 4- Alcohols such as linear, branched, or cyclic C4-C9 monohydric alcohols such as kutanol; 2,2,3,3,4,4-hexafluoro-1-butanol, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol and 2,2,3,3,4,4,5,5,6,6-decafluoro-1-hexanol, as well as 2,2,3,3,4,4-hexafluoro-1,5-pentanediol, 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol and 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro-1, C5-C9 fluorinated diols such as 8-octanediol; ethers such as isopentyl ether and propylene glycol monomethyl ether; alkyl esters having a total of 4 to 10 carbon atoms, such as alkyl propionates such as propylene glycol monomethyl ether acetate, n-butyl propionate, n-pentyl propionate, n-hexyl propionate and n-heptyl propionate, and alkyl butyrates such as n-butyl butyrate, isobutyl butyrate and isobutyl isobutyrate;Examples include ketones such as 2,5-dimethyl-4-hexanone and 2,6-dimethyl-4-heptanone; polyethers such as dipropylene glycol monomethyl ether and tripropylene glycol monomethyl ether; and mixtures containing one or more of these solvents.

[0064] In some embodiments, the substrate is pre-treated after being coated with a selective binder. The substrate may be pre-treated to ensure that the selective binder adheres to the surface of the features. The pre-treatment may be a soft bake carried out at a temperature in the range of 50–150°C for about 30–90 seconds.

[0065] After the selective bonding material has been bonded to the features, any excess material can be removed. Thus, in one or more embodiments, a selective bonding agent is applied to the substrate, and after optional pretreatment, the substrate is rinsed to remove any unused material.

[0066] Next, in block 206 of method 200, the first resist is deposited on the substrate. Figure 3C shows the substrate coated with the selective binder 303 and the first resist 304. The first resist may be a photoresist. Generally, a photoresist is a chemically amplified photosensitive composition comprising a polymer, a photoacid generator, and a solvent. In one or more embodiments, the first resist comprises a polymer. The polymer may be any standard polymer typically used in resist materials, but may particularly be a polymer having acid-unstable groups. For example, the polymer may be a polymer made from monomers including aromatic vinyl monomers such as styrene and p-hydroxystyrene, acrylates, methacrylates, norbornene, and combinations thereof. Monomers containing reactive functional groups may be present in the polymer in a protected form. For example, the -OH group of p-hydroxystyrene may be protected with a tert-butyloxycarbonyl protecting group. Such protecting groups may alter the reactivity and solubility of the polymer contained in the first resist. As will be understood by those skilled in the art, various protecting groups may be used for this reason. Examples of acid-unstable groups include tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of an alkyl group and an aryl group, tertiary alkoxy groups, acetal groups, or ketal groups. Acid-unstable groups are also commonly referred to in this art as "acid-degradable groups," "acid-dissociable groups," "acid-dissociable protecting groups," "acid-unstable protecting groups," "acid-leaving groups," and "acid-sensitive groups."

[0067] The acid-unstable group that forms a carboxylic acid in the polymer during decomposition is preferably of the formula -C(O)OC(R 1 )3 tertiary ester group, or formula -C(O)OC(R 2 )2OR 3 It is an acetal group, in the formula R 1 Each of them is independently a linear C 1-20 Alkyl, branched C 3-20 Alkyl, monocyclic, or polycyclic C 3-20 Cycloalkyl, linear C 2-20 Alkenil, Branch C 3-20 Alkenyl, monocyclic or polycyclic C3-20 Cycloalkenyl, monocyclic or polycyclic C 6-20 Aryl, or monocyclic or polycyclic C 2-20 It is a heteroaryl, preferably a linear C chain. 1-6 Alkyl, branched C 3-6 Alkyl, or monocyclic or polycyclic C 3-10 They are cycloalkyl, and each of them is substituted or unsubstituted, and each R 1 It optionally includes one or more groups selected from -O-, -C(O)-, -C(O)-O-, or -S- as part of its structure, and any two R 1 Both elements optionally form a ring, R 2 These are, independently, hydrogen, fluorine, and linear carbon. 1-20 Alkyl, branched C 3-20 Alkyl, monocyclic, or polycyclic C 3-20 Cycloalkyl, linear C 2-20 Alkenil, Branch C 3-20 Alkenyl, monocyclic or polycyclic C 3-20 Cycloalkenyl, monocyclic or polycyclic C 6-20 Aryl, or monocyclic or polycyclic C 2-20 It is a heteroaryl compound, preferably with hydrogen and a linear carbon chain. 1-6 Alkyl, branched C 3-6 Alkyl, or monocyclic or polycyclic C 3-10 They are cycloalkyl, and each of them is substituted or unsubstituted, and each R 2 It optionally includes one or more groups selected from -O-, -C(O)-, -C(O)-O-, or -S- as part of its structure, R 2 Both elements optionally form a ring, R 3 is a linear C 1-20 Alkyl, branched C 3-20 Alkyl, monocyclic, or polycyclic C 3-20 Cycloalkyl, linear C 2-20 Alkenil, Branch C 3-20 Alkenyl, monocyclic or polycyclic C 3-20 Cycloalkenyl, monocyclic or polycyclic C 6-20 Aryl, or monocyclic or polycyclic C 2-20It is a heteroaryl, preferably a linear C chain. 1-6 Alkyl, branched C 3-6 Alkyl, or monocyclic or polycyclic C 3-10 They are cycloalkyl, and each of them can be substituted or unsubstituted, R 3 It optionally includes one or more groups selected from -O-, -C(O)-, -C(O)-O-, or -S- as part of its structure, and one R 2 is R 3 In addition, rings are optionally formed. Such monomers are typically aromatic vinyl, (meth)acrylate, or norbornyl monomers. The total content of polymerization units containing acid-degradable groups that form carboxylic acid groups in the polymer is typically 10 to 100 mol%, more typically 10 to 90 mol%, or 30 to 70 mol%, based on the total polymerization units of the polymer.

[0068] The polymer may further contain monomers that have an acid-unstable group that decomposes to form an alcohol group or a fluoroalcohol group in the polymer during polymerization. Suitable such groups include, for example, the group of formula -COC(R 2 )2OR 3 Examples include an acetal group of the formula -OC(O)O-, or a carbonate ester group of the formula -OC(O)O-, where R is as defined above. Such monomers are typically aromatic vinyl, (meth)acrylate, or norbornyl monomers. When present in the polymer, the total content of polymer units containing acid-degradable groups that form alcohol or fluoroalcohol groups in the polymer by decomposition is typically 10 to 90 mol%, and more typically 30 to 70 mol%, based on the total polymer units of the polymer.

[0069] Photoacid generators are compounds capable of generating acid upon irradiation with chemical rays or radiation. Photoacid generators can be selected from known compounds capable of generating acid upon irradiation with chemical rays or radiation, and are used as photoinitiators for cationic photopolymerization, photoinitiators for radical photopolymerization, photodecolorizers and photochromicants for dyes, and microresists, or mixtures thereof can be used. Examples of photoacid generators include diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imidosulfonates, oximesulfonates, diazodisulfones, disulfones, and o-nitrobenzylsulfonates.

[0070] Suitable photoacids include onium salts, such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, tris(p-tert-butoxyphenyl)sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate; di-t-butiphenyliodonium perfluorobutanesulfonate, and di-t-butiphenyliodonium camphorsulfonate. Nonionic sulfonates and sulfonyl compounds are photoacid generators. It is also known to function as a generator, for example, nitrobenzyl derivatives, e.g., 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate and 2,4-dinitrobenzyl-p-toluenesulfonate; sulfonic acid esters, e.g., 1,2,3-tris(methanesulfonyloxy)benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; diazomethane derivatives, e.g., bis(benzenesulfonyl)diazomethane, bis(p-toluenesulfonyl)diazomethane; Examples include rioxime derivatives, such as bis-O-(p-toluenesulfonyl)-α-dimethylglyoxime and bis-O-(n-butanesulfonyl)-α-dimethylglyoxime; sulfonic acid ester derivatives of N-hydroxyimide compounds, such as N-hydroxysuccinimodomethanesulfonic acid and N-hydroxysuccinimodotrifluoromethanesulfonic acid; and halogen-containing triazine compounds, such as 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine. Preferred non-polymerized photoacid generators are further described in U.S. Patent No. 8,431,325 to Hashimoto et al. (column 37, lines 11-47 and columns 41-91).Other suitable sulfonate PAGs include sulfonated esters and sulfonyloxyketones, nitrobenzyl esters, s-triazine derivatives, benzointosylates, t-butylphenyl α-(p-toluenesulfonyloxy)-acetate and t-butyl α-(p-toluenesulfonyloxy)-acetate, as described in U.S. Patents 4,189,323 and 8,431,325. PAGs that are onium salts typically include anions having sulfonate or non-sulfonate-type groups such as sulfonamide, sulfonimidate, methide, or borate groups.

[0071] The resist composition may optionally contain multiple PAGs. These PAGs may be polymerizable, nonpolymerizable, or may contain both polymerizable and nonpolymerizable PAGs. Preferably, each of the PAGs is nonpolymerizable. Preferably, when multiple PAGs are used, the first PAG contains an anion with a sulfonate group, and the second PAG contains an anion without a sulfonate group, such an anion containing, for example, a sulfonamide group, sulfonimidate group, methide group, or borate group as described above. In some embodiments, the first resist has a composition similar to that of a positive tone developed (PTD) resist. In such embodiments, the first resist may be a polymer made from the monomers described above, in which any monomer containing a reactive functional group is protected. Thus, the first PTD resist may be organically soluble.

[0072] In other embodiments where the solubility modifier is a crosslinking agent, the first resist is a negative-type resist. In such embodiments, the first resist is a polymer made from the monomers described above, and may include polymers in which any monomers containing reactive functional groups are not protected. Suitable reactive functional groups include, but are not limited to, alcohols, carboxylic acids, and amines. Exposure to the crosslinking agent causes crosslinking of the polymer, making the polymer insoluble in the developer. The uncrosslinked areas can then be removed using a suitable developer.

[0073] In one or more embodiments, the first resist is a negative-type resist. In such embodiments, the first relief pattern may include a polymer made from the monomers described above, wherein any monomer containing reactive functional groups is not protected. Thus, the first resist may be soluble in either an organic solvent or an aqueous base. The tone of the resist (i.e., positive or negative) may affect the final pattern arrangement. For example, if the resist is similar to a PTD photoresist and the selective binder contains an acid, the resist polymer on the features is deprotected and thus becomes soluble in an aqueous base (e.g., TMAH), while the resist on the substrate remains soluble in an organic solvent. If the resist is similar to a negative-type photoresist and the selective binder contains a crosslinking agent, the resist polymer on the features is crosslinked and becomes insoluble, while the resist on the substrate remains soluble.

[0074] In one or more embodiments, the first resist is laminated on the substrate to have a thickness of approximately 300 Å to approximately 3000 Å.

[0075] Next, in block 208 of Method 200, the solubility modifier is activated. In embodiments where the solubility modifier is an acid, an acid generator, a base, or a base generator, the activation of the solubility modifier includes diffusing the solubility modifier into the first resist to provide a region of the first resist whose solubility has been altered. The region of the first resist whose solubility has been altered may be determined by the preferential adhesion of a selective binder. For example, a selective binder that preferentially adheres to features of an existing pattern may provide a region of the first resist whose solubility has been altered on the features, such as selective patterning self-alignment as in Method 200. In one or more embodiments, the region of the first resist whose solubility has been altered extends perpendicularly from the surface of the selective binder coated on the features to the surface of the first resist. In one or more embodiments, the region of altered solubility extends in a sloping direction. When the region of altered solubility extends in a sloping direction, it may be desirable to prevent each feature from bonding together. To achieve this, the thickness of the features may be controlled to be sufficiently thin.

[0076] The diffusion of the solubility modifier into the first resist is achieved by baking. Baking can be performed on a hot plate or in an oven. The baking temperature and time may depend on the characteristics of the second resist and the desired amount of diffusion of the solubility modifier into the second resist. Suitable baking conditions may include temperatures in the range of about 50°C to about 160°C and times in the range of about 30 seconds to about 90 seconds.

[0077] The regions in which the solubility of the first resist is altered may be determined by the preferential adhesion of the selective binder. For example, if the selective binder preferentially adheres to features of an existing pattern, such as in selective patterning self-alignment as in Method 200, the regions in which the solubility of the first resist is altered may be on top of the features. In one or more embodiments, the regions in which the solubility of the first resist is altered may extend perpendicular to the surface of the first resist layer.

[0078] In embodiments where the solubility modifier is a crosslinking agent, activation of the solubility modifier includes initiating polymerization of the crosslinking agent onto the first resist. Activation of the crosslinking agent may provide crosslinked regions of the first resist. The crosslinked regions of the first resist may be determined by the preferential adhesion of the selective binder. For example, if the selective binder preferentially adheres to features of an existing pattern, such as in selective patterning self-alignment, the crosslinked regions of the first resist may be on top of the features.

[0079] Finally, in block 210 of Method 200, the first resist is developed using a first developer. The first developer can be any developer commonly used in the art. The composition of the first developer may depend on the solubility of the first resist. For example, if the first resist is a positivetone-developable resist, a particular developer may be a base such as tetramethylammonium hydroxide. On the other hand, if the first resist is a negativetone-developable resist, a particular developer may be a nonpolar organic solvent such as n-butyl acetate or 2-heptanone. In one or more embodiments, the regions with altered solubility or crosslinked regions are insoluble in the first developer. Therefore, after developing the first resist, the regions with altered solubility or crosslinked regions of the first resist may remain on the substrate. Thus, Method 200 may provide a substrate containing a first resist 305 with altered solubility of a pattern, as shown in Figure 3D, but the altered first resist is directly on top of the existing pattern feature 302.

[0080] Alternatively, in one or more embodiments, the regions whose solubility has been altered become soluble in the first developer. In such embodiments, after developing the first resist, the regions of the first resist whose solubility has been altered are removed from the substrate. A coated substrate according to such an embodiment is shown in Figure 3E. In Figure 3E, the substrate includes a first resist 306 in a pattern offset from features 302 coated with the selective binder 303. Such a pattern may be called an anti-selective pattern because features of the resist remain on the base layer that was not coated with the selective binder.

[0081] As described above, in one or more embodiments, the method includes selectively forming a resist pattern alternately with features in the base layer. Similar to method 200, such a method can be considered selective patterning because it forms a first relief pattern according to the arrangement of a selective binder. However, a method of selectively forming a pattern or a first relief alternately with an existing pattern of features can be called selective anti-alignment because the two patterns are not aligned. Method 400 of selective anti-alignment patterning according to the present disclosure (e.g., the pattern shown in Figure 1B) is shown in Figure 4 and will be discussed with reference to Figure 4. Schematic diagrams of the coated substrate at various points in time during the above method are shown in Figures 5A to 5D.

[0082] In method 400, block 402 provides an existing pattern on a substrate. A coated substrate having the existing pattern is shown in Figure 5A. In Figure 5A, the existing pattern may include a feature 502 in a base layer 501. The feature and base layer are as described above with reference to method 200.

[0083] Next, in block 404 of method 400, the substrate is coated with a selective binder. In one or more embodiments, the selective binder is coated over the entire substrate except for the target region (i.e., the selective binder is coated over the entire base layer except for the features). As described above, the selective binder may preferentially adhere to one material of the existing pattern. In one or more embodiments, in method 400, the selective binder adheres to the base layer of the existing pattern. Figure 5B shows a substrate containing a selective binder 503 that coats the first layer rather than the features of the existing pattern. The selective binder may adhere to the features of the pattern in a ratio greater than 1:1. As an example, but not limited to, the selective binder may adhere to the base layer of the existing pattern where the feature-to-base layer ratio is in the range of 1:2 to 1:10.

[0084] In one or more embodiments, the selective binder is a chemically functionalized group that can be further functionalized. Examples of selective binders that are selective for dielectric materials on metals include, but are not limited to, silanes and alcohols. The specific selective binder to be coated on an existing pattern may depend on the specific chemical reactions used in other components of Method 200. For example, aminosilanes, halosilanes (e.g., chlorosilanes, fluorosilanes, etc.) and alkoxysilanes (e.g., methoxysilanes, ethoxysilanes, and other alkoxysilanes) can react selectively or at least preferentially with hydroxylation groups on the surface of dielectric materials compared to metallic materials. Specific examples of suitable silanes include, but are not limited to, trichlorooctadecylsilane, octadecylchlorosilane, diethylaminotrimethylsilane, bis(dimethylamino)dimethylsilane, methoxysilane, ethoxysilane, and other similar silanes, as well as combinations thereof. The reaction products of these reactions can be used to selectively coat exposed surfaces of dielectric materials. If certain, generally small amounts of reactants are produced on the metallic material, they can be removed by washing with water or the like. Silanes may contain one or more other groups, such as linear alkanes, branched alkanes, other linear or branched organic chains, benzyl groups or other organic groups, or various other known functional groups, in order to modify the chemical properties of the silane and achieve the desired chemical properties. Compounds containing hydroxyl groups, such as alcohols and catechols, are also known to react with the hydroxylation groups of dielectric materials. As another example, a difunctional, trifunctional, polyfunctional electrophile or a combination thereof may be reacted with the hydroxylation groups of a material (e.g., ILD), and then the resulting activated reaction product may be reacted with the functional groups of a polymer. Selective binders may also contain polymers containing any of the above-mentioned functional groups that are capable of selective bonding, in which case the polymer has functional groups along the main chain or as terminal groups, forming a layer of polymer chains bonded to the target material. Various other selective binders known in the art may also be potentially used. These are only a few illustrative examples, and it should be understood that further examples will be apparent to those skilled in the art who are interested in this disclosure.

[0085] In one or more embodiments, the selective binder includes a solubility modifier. The solubility modifier may be one of the solubility modifiers described above with reference to Method 200.

[0086] In some embodiments, the substrate is coated with a selective binder and then pre-treated. The pre-treatment may be a bake carried out at 50–150°C for about 30–90 minutes.

[0087] In method 400, in block 406, the first resist is deposited on the substrate. A substrate coated with the first resist 504 is shown in Figure 5C. In one or more embodiments, the first resist is as described above with reference to method 200. In one or more embodiments, the first resist is laminated on the substrate to have a thickness of about 300 Å to about 3000 Å.

[0088] In block 408 of method 400, the solubility modifier is activated. In embodiments where the solubility modifier is an acid, an acid generator, a base, or a base generator, the activation of the solubility modifier includes diffusing the solubility modifier into the first resist, as described above, to provide a region of the first resist in which the solubility has been altered.

[0089] The region in which the solubility of the first resist is altered may be determined by the preferential adhesion of the selective binder. For example, if the selective binder preferentially adheres to the base layer of the existing pattern, such as in anti-selective pattern self-alignment as in Method 400, the region in which the solubility of the first resist is altered may be above the base layer. In one or more embodiments, the region in which the solubility of the first resist is altered may extend perpendicular to the surface of the first resist layer.

[0090] In embodiments where the solubility modifier is a crosslinking agent, activation of the solubility modifier includes initiating polymerization of the crosslinking agent onto the first resist. Activation of the crosslinking agent may provide a crosslinked region of the first resist. The crosslinked region of the first resist may be determined by the preferential adhesion of the selective binder. For example, if the selective binder preferentially adheres to the base layer of an existing pattern, such as in anti-selective pattern self-alignment, the crosslinked region of the first resist may be above the base layer. The crosslinked region of the first resist may extend perpendicularly from the base layer to the surface of the first resist.

[0091] Finally, in method 400, the first resist is developed in block 410. The first resist may be developed using a first developer. The first developer may be selected based on the solubility characteristics of the first resist. In one or more embodiments, the regions of the first resist whose solubility has been altered or the crosslinked regions are insoluble in the first developer. Therefore, after developing the first resist, the regions of the first resist whose solubility has been altered or the crosslinked regions may remain on the substrate. Thus, method 400 may provide a substrate containing a first resist 505 with altered solubility of a pattern, as shown in Figure 5D, in which case the altered first resist is offset from the feature 502 of the existing pattern.

[0092] In one or more embodiments, the anti-selective pattern self-alignment process may be modified so that the regions whose solubility has been altered become soluble in the first developer. In such alternative embodiments, after development, the remaining modified first resist is positioned on top of existing pattern features, such as selective pattern self-alignment.

[0093] Similarly, in one or more embodiments, the selective pattern self-alignment process may be modified so that the regions whose solubility has been altered become soluble in the first developer. In such alternative embodiments, after development, the remaining modified first resist is offset from the features of the existing pattern, such as in anti-selective pattern self-alignment.

[0094] In one or more embodiments, the methods disclosed herein may be used for double patterning features on or adjacent to an existing pattern. Such methods may achieve double patterning by performing two selective pattern self-alignment processes, two non-selective pattern self-alignment processes, or one selective pattern self-alignment process and one non-selective pattern self-alignment process.

[0095] In alternative embodiments, the feature is coated with a first selective binder containing a first solubility modifier, and the base layer is coated with a second selective binder containing a second solubility modifier. In some embodiments, the first solubility modifier includes an acid or acid generator, and the second solubility modifier includes a base or base generator. The resist is then deposited on the substrate, and each solubility modifier is activated simultaneously. The first solubility modifier diffuses from above the feature, and the second solubility modifier diffuses from above the base layer. At the diffusion front interface, the solubility modifiers interact with each other to prevent changes in the solubility of the resist in the side area outside the vertical plane that is perpendicular to the substrate and located at the interface between the feature and the exposed base layer. This helps to suppress changes in solubility to the area of ​​resist above the feature, thereby limiting lateral growth of the opening and creating a nearly straight edge rather than a sloped profile.

[0096] Although only a few exemplary embodiments have been described in detail above, those skilled in the art will readily understand that many modifications are possible in the exemplary embodiments without substantially departing from the present invention. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the following claims.

Claims

1. The present invention provides a substrate having an existing pattern, wherein the upper surface of the substrate has uncovered features, and the existing pattern includes features formed within the base layer such that the base layer is uncovered. The process involves depositing a selective binder on the above-mentioned substrate, wherein the selective binder includes a solubility modifier. Depositing a first resist onto the above substrate, Activating the solubility modifier so that a portion of the first resist becomes soluble in the first developer, Developing the first resist using the first developer such that a portion of the first resist that is soluble in the first developer is removed. Microfabrication methods including

2. The method according to claim 1, wherein the selective binder is more readily adhered to the surface of the feature than to the surface of the base layer.

3. The method according to claim 1 or 2, wherein a portion of the first resist that is insoluble in the first developer is located on the feature.

4. The method according to claim 1 or 2, wherein the selective binder comprises a phosphonic acid, a phosphonic acid ester, a phosphine, a sulfonic acid, a sulfinic acid, a carboxylic acid, a triazole, a thiol, or a combination thereof.

5. The method according to claim 1 or 2, wherein the solubility modifier includes an acid generator.

6. The method according to claim 5, wherein the acid generator does not contain fluorine.

7. The method according to claim 5, wherein the acid generating agent is selected from the group consisting of triphenylsulfonium antimonate, pyridinium perfluorobutanesulfonate, 3-fluoropyridinium perfluorobutanesulfonate, 4-t-butylphenyltetramethylenesulfonium perfluoro-1-butanesulfonate, 4-t-butylphenyltetramethylenesulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butylphenyltetramethylenesulfonium 4,4,5,5,6,6-hexafluorodihydro-4H-1,3,2-dithiazine 1,1,3,3-tetraoxide and combinations thereof.

8. The method according to claim 1 or 2, wherein the solubility modifier includes an acid.

9. The method according to claim 8, wherein the above acid does not contain fluorine.

10. The method according to claim 8, wherein the acid is selected from the group consisting of trifluoromethanesulfonic acid, perfluoro-1-butanesulfonic acid, p-toluenesulfonic acid, 4-dodecylbenzenesulfonic acid, 2,4-dinitrobenzenesulfonic acid, 2-trifluoromethylbenzenesulfonic acid, and combinations thereof.

11. The method according to claim 1 or 2, further comprising pre-treating the substrate before depositing the first resist onto the substrate.

12. The present invention provides a substrate having an existing pattern, wherein the upper surface of the substrate has uncovered features, and the existing pattern includes features formed within the base layer such that the base layer is uncovered. The method involves depositing a first selective binder on the substrate, wherein the first selective binder contains a first solubility modifier, and the first selective binder adheres more readily to the surface of the feature than to the surface of the base layer. The method involves depositing a second selective binder on the substrate, wherein the second selective binder contains a second solubility modifier, and the second selective binder adheres more readily to the surface of the base layer than to the surface of the feature. Depositing a first resist onto the above substrate, Activating the first solubility modifier and the second solubility modifier so that a portion of the first resist becomes insoluble in the first developer, Developing the first resist using the first developer such that a portion of the first resist that is insoluble in the first developer remains. Microfabrication methods including

13. The method according to claim 12, wherein the first solubility modifier comprises an acid or an acid generator, and the second solubility modifier comprises a base or a base generator.

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