TWI824680B - Self-aligned build-up processing - Google Patents

Abstract

A method of microfabrication includes providing a substrate having an existing pattern, wherein the existing pattern comprises features formed within a base layer such that a top surface of the substrate has features uncovered and the base layer is uncovered, depositing a selective attachment agent on the substrate, wherein the selective attachment agent includes a solubility-shifting agent, depositing a first resist on the substrate, activating the solubility shifting agent such that a portion of the first resist becomes insoluble to a first developer, developing the first resist using the first developer such that a relief pattern comprising openings is formed, wherein the openings expose the features of the existing layer, and executing a selective growth process that grows a selective-deposition material on the features and within the openings of the relief pattern to provide self-aligned selective deposition features.

Description

Self-aligned stacking method

The present invention relates to self-aligned deposition methods.

Background of the invention

Microfabrication of semiconductor devices includes various steps such as film deposition, patterning, and pattern transfer. Materials and films are deposited on the substrate by spin coating, vapor deposition and other deposition methods. Patterning is typically performed by exposing a photosensitive film called a photoresist to a pattern of actinic radiation and subsequently developing the photoresist to form a relief pattern. The relief pattern then acts as an etch mask that covers the portions of the substrate that will not be etched when one or more etching methods are applied to the substrate. After the first etch, the method may then continue with additional steps of material deposition, etching, annealing, photolithography, etc., where the various steps are repeated until a transistor or integrated circuit is fabricated.

There are multiple steps in semiconductor methods where critical topography must be precisely aligned with the underlying layer. Conventionally, different methods can be aligned by aligning the different mask layers, correcting their positioning, and then etching the layers into place.

Summary of the invention

This Summary is provided to introduce a selection of concepts that are further described below. This Summary is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

In one aspect, embodiments disclosed herein relate to a method of microfabrication that includes providing a substrate having an existing pattern, wherein the existing pattern includes features formed in a substrate such that the substrate A top surface has an uncovered topography and the base layer is uncovered; depositing a selective adhesive on the substrate, wherein the selective adhesive includes a solubility change agent; depositing a first resistor on the substrate agent; activating the solubility change agent so that a portion of the first resist becomes insoluble in a first developer; developing the first resist using the first developer to form a relief pattern including openings, wherein the openings expose the features of the existing layer; and performing a selective growth method that grows a selectively deposited material on the features and within the openings of the relief pattern to provide self-alignment Selective deposition of topographies.

Other aspects and advantages of the claimed subject matter will be apparent from the following description and appended claims.

Detailed description of preferred embodiments

In the microfabrication of devices and nodes, selective methods are required to achieve complete alignment of some features. A typical example is a through hole in a metal top. That is, the vias are ideally positioned precisely without extending into the oxide. Vias are electrical connections between metal layers in a device. In selective deposition methods, pre-selected materials need to be grown defect-free in pre-defined locations and in pre-defined directions. However, current directional growth techniques such as selective atomic layer deposition suffer from high defectivity. Additionally, such techniques are generally insufficient for more complex situations, such as selected growth areas extending to the sidewalls of spacers. Current self-aligned growth generally tends to grow in all directions. As the material grows in all (available) directions, growing specific topographies is difficult. Typically only very thin morphologies can be grown on demand. Furthermore, self-aligned growth often has a high defect rate. Even small amounts of unintentional deposits can cause problems for devices.

The present disclosure generally relates to a method of selective growth on a semiconductor substrate. As used herein, the terms "semiconductor substrate" and "substrate" are used interchangeably and can be any semiconductor material, including but not limited to semiconductor wafers, semiconductor material layers, and combinations thereof. The methods disclosed herein provide core self-aligned topographies for generating fully self-aligned topographies or partially self-aligned topographies. In one or more embodiments, the method combines selective topography placement and selective growth. This method may be able to fill various topographies and openings and facilitate shallow trench isolation deposition.

The methods disclosed herein provide a self-aligned deposition method that inherently protects areas that will not receive sediment. Such methods enable selective deposition with lower selectivity requirements. In one or more embodiments, partially aligned features or features without significant openings will still be contactable, for example as metal contacts. Furthermore, using the method of the present invention, low spatial density features can be coated and filled, which can lead to simpler integration via many microfabrication methods.

The methods of one or more embodiments, relying on both chemistry and diffusion properties, provide the unique ability to add control topography to the input chemicals themselves and to the process of measuring such chemicals.

Those skilled in the art should understand that the methods disclosed herein can be used to provide various self-aligned topographies, such as universal self-alignment, selective self-alignment, and topography self-alignment. Therefore, the specific embodiments described herein are not intended to limit the scope of the present disclosure. In one or more specific embodiments, a method for universal self-aligned vias is provided.

A general self-aligned method 100 in accordance with the present disclosure is shown in Figure 1 and discussed with reference to that figure. Initially, at block 102, an existing pattern including features within the substrate is provided on a substrate. At block 104, the substrate or a portion thereof is coated with a selective adhesive. Selective adhesion agents may include solubility shifting agents. Next, at block 106, the substrate is coated with a first resist. At block 108, the solubility shift agent can be activated to provide a region where the first resist is soluble in the first developer. Next, at block 110 the first resist is developed to provide gaps in the first resist that expose the existing pattern of features of the substrate. Finally, at block 112, selective growth on the topography is performed. In some embodiments, after selective growth, the substrate is etched to remove any residual coating, such as the selective adhesive and first resist.

Schematic representations of coated substrates at various time points during the methods described above are shown in Figures 2A-E. As used herein, "coated substrate" refers to a substrate coated with one or more layers, such as a first resist layer and a second resist layer. Figure 2A shows a substrate including an existing pattern. Figure 2B shows a substrate including an overcoat layer including a selective adhesive. Figure 2C shows a substrate including a selective adhesive overcoat layered with a first resistor. Figure 2D shows the coated substrate after the first resist has been developed such that the topography of the substrate is exposed. Finally, Figure 2E shows a substrate including a first resist and a selective growth layer on top of the topography of the substrate. The method of Figure 1 and the coated substrate shown in Figures 2A-E are discussed in detail below.

In Figure 1, at block 102, an existing pattern is provided on a substrate. Figure 2A shows a substrate including an existing pattern. In FIG. 2A , the existing pattern includes topography 202 formed in the base layer 201 . The base layer can be any suitable substrate known in the art. In one or more embodiments, the features formed in the base layer are in a large array. For example, on a square base layer, the topographies can be evenly spaced in a 4×4 array, a 5×5 array, a 6×6 array, etc. The shape and size of the array are not particularly limited and can be any shape and size suitable for photolithography tracks.

Topographies can be made from any material commonly used in this technology. In one or more embodiments, the topography includes metal, metalloid, or other conductive structures. As used herein, the term metal includes alloys, stacks, and other combinations of metals. For example, metal interconnect lines may include barrier layers, stacks of different metals or alloys, etc. Suitable metals and metalloids that may form the topographies include, but are not limited to, silicon, polycrystalline silicon, copper, cobalt, and tungsten. In one or more embodiments, the base layer is an interlayer dielectric. Suitable interlayer dielectrics may include silicon oxides (such as silicon dioxide (SiO ₂ )), silicon doped oxides, silicon fluorinated oxides, silicon carbon doped oxides, this technology Various low-k dielectric materials and combinations thereof are known in . The existing pattern may be the final topography or the intermediate topography in the patterning method. The substrate can be planarized so that the existing pattern of features within the substrate is exposed and accessible. In one or more embodiments, the substrate includes an etch stop layer over the metal lines, or a graphene coating.

Next, at block 104, a selective adhesive is applied to the substrate or a portion thereof. Figure 2B shows a substrate including an existing pattern coated with selective adhesive 203. The selective adhesive can be applied to the substrate by any coating method known in the art. Suitable coating methods include, but are not limited to, vapor phase deposition, liquid phase deposition, gas phase deposition, spin coating and Langmuir-Blodgett single layer coating. .

Selective adhesives preferentially adhere to one material over the existing pattern. In one or more embodiments, the selective adhesive adheres to the features of the existing pattern of the substrate. In such embodiments, the selective adhesive may adhere to the features of the pattern at a ratio of features to first layer of greater than 1:1. By way of example, and not limitation, the selective adhesive may adhere to the features of the pattern at a ratio of features to first layer ranging from about 2:1 to about 10:1 or higher.

In one or more embodiments, the selective adhesion agent is a chemical functional group that can be further functionalized. Exemplary selective adhesion agents include, but are not limited to, alcohols, silanols, amines, phosphines, phosphonic acids, and carboxylic acids. The specific selective adhesive applied to the existing pattern may depend on the specific chemistries used in the other components of method 100. For example, various phosphonic acids and esters are capable of reacting selectively or at least preferentially with native or oxidized metal surfaces to form strong bonds preferentially or even selectively relative to the surface of dielectric materials such as silicon oxides. Metal phosphonates, and therefore can be used as selective adhesion agents to the topography rather than the substrate. One specific example of a suitable phosphonic acid is octadecylphosphonic acid (ODPA). Such surface coatings generally tend to be stable in many organic solvents but can be removed using aqueous solutions of weak acids and bases. Phosphines (eg organophosphines) may also optionally be used. Other common acids such as sulfonic acid, sulfinic acid and carboxylic acid may optionally be used.

Another example of a reaction that is selective or at least preferential for metallic materials compared to dielectric materials or organic polymeric materials or other materials are various metal corrosion inhibitors, such as those used to protect interconnect structures during chemical mechanical polishing. They. Specific examples include benzotriazole, other triazole functional groups, other suitable heterocyclyl groups (eg, heterocycle-based corrosion inhibitors), and other metal corrosion inhibitors known in the art. In addition to triazolyl, other functional groups can be used to provide the desired attraction or reactivity toward the metal. Various metal chelating agents may also be suitable. Various amines (eg organic amines) may also be suitable.

Another example of reactions that are selective or at least preferential for metallic materials compared to dielectric materials or organic polymeric materials or other materials are various thiols. As another example, 1,2,4-triazole or similar aromatic heterocyclic compounds can be used to react selectively with metals compared to dielectrics and certain other materials. Selective adhesion agents may also contain functional groups capable of reacting with functional groups of the polymer to bond the polymer to the surface. Various other metal poisoning compounds known in the art may also potentially be used. It should be understood that these are only a few illustrative examples and that additional examples will be apparent to those skilled in the art and having the benefit of this disclosure. Selective adhesion agents may also include polymers containing any one of the aforementioned functional groups capable of selective attachment, wherein the polymer has functional groups along the main chain or as end groups and forms a polymer chain layer attached to the target material.

In one or more embodiments, the selective adhesion agent may include a solubility shifting agent. The composition of the solubility shift agent may depend on the selective adhesion agent. Those skilled in the art will appreciate that any suitable solubility shift agent may be included in the selective adhesion agent, with the proviso that the two materials do not react with each other. Generally speaking, a solubility shift agent can be any chemical substance that is activated by light or heat. For example, in some embodiments, the solubility shift agent includes an acid or acid generator. The acid, or acid generated in the case of TAG, should be heated enough to cause the breaking of bonds of the acid-decomposable groups of the polymer in the surface region of the first resist pattern so that the first resist polymer reacts with the particular developer to be applied. The solubility in increases. The acid or TAG is typically present in the conditioning composition in an amount of about 0.01 to 20 wt%, based on the total solids of the composition.

Preferred acids are organic acids, including non-aromatic acids and aromatic acids, each of which may optionally have fluorine substitution. Suitable organic acids include, for example: carboxylic acids, such as alkanoic acids, including formic acid, acetic acid, propionic acid, butyric acid, dichloroacetic acid, trichloroacetic acid, perfluoroacetic acid, perfluorooctanoic acid, oxalic acid, malonic acid and succinic acid. ; Hydroxyalkanoic acids, such as citric acid; Aromatic carboxylic acids, such as benzoic acid, fluorobenzoic acid, hydroxybenzoic acid and naphthoic acid; Organophosphoric acids, such as dimethylphosphoric acid, dimethylphosphinic acid; and sulfonic acids, such as Optionally fluorinated alkyl sulfonic acids, including methanesulfonic acid, trifluoromethanesulfonic acid, ethanesulfonic acid, 1-butanesulfonic acid, 1-perfluorobutanesulfonic acid, 1,1,2,2-tetrafluorobutanesulfonic acid Alkane-1-sulfonic acid, 1,1,2,2-tetrafluoro-4-hydroxybutane-1-sulfonic acid, 1-pentanesulfonic acid, 1-hexanesulfonic acid and 1-heptanesulfonic acid.

Exemplary fluorine-free aromatic acids include aromatic acids of general formula (I) wherein:

Where: R1 independently represents a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C5-C20 aryl group or a combination thereof, which optionally contains one or more carbonyl groups, carbonyl oxygen group, sulfonamide group, ether, thioether, substituted or unsubstituted alkylene group or a combination thereof; Z1 independently represents a group selected from carboxyl group, hydroxyl group, nitro group, cyano group, C1 to C5 alkoxy group a group, a formyl group and a sulfonic acid group; a and b are independently integers from 0 to 5; and a+b is 5 or less.

Exemplary aromatic acids may have general formula (II):

Wherein: 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, which optionally contains one or more carbonyl groups. , carbonyloxy group, sulfonamide group, ether, thioether, substituted or unsubstituted alkylene group or a combination thereof; Z2 and Z3 each independently represent a group selected from carboxyl, hydroxyl, nitro, cyano group , C1 to C5 alkoxy, formyl and sulfonic acid groups; c and d are independently an integer from 0 to 4; c+d is 4 or less; e and f are independently an integer from 0 to 3 ; and e+f is 3 or less.

Additional aromatic acids that may be included in the solubility shifting agent include those of general formula (III) or (IV):

Among them: 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, which optionally contains one or more options. A group consisting of a carbonyl group, a carbonyloxy group, a sulfonamide group, an ether, a thioether, a substituted or unsubstituted alkylene group or a combination thereof; Z4, Z5 and Z6 each independently represent a group selected from the group consisting of carboxyl, hydroxyl, nitro group, cyano group, C1 to C5 alkoxy group, formyl group and sulfonic acid group; g and h are independently an integer from 0 to 4; g+h is 4 or less; i and j are independently 0 to 2; i+j is 2 or less; k and l are independently integers from 0 to 3; and k+l is 3 or less;

Among them: 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, which optionally contains one or more options. A group consisting of a carbonyl group, a carbonyloxy group, a sulfonamide group, an ether, a thioether, a substituted or unsubstituted alkylene group or a combination thereof; Z4, Z5 and Z6 each independently represent a group selected from the group consisting of carboxyl, hydroxyl, nitro group, cyano group, C1 to C5 alkoxy group, formyl group and sulfonic acid group; g and h are independently an integer from 0 to 4; g+h is 4 or less; i and j are independently 0 to 1; i+j is 1 or less; k and l are independently integers from 0 to 4; and k+l is 4 or less.

Suitable aromatic acids alternatively have the general formula (V):

Wherein: 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, which optionally contains one or more carboxyl groups. , carbonyl group, carbonyloxy group, sulfonamide group, ether, thioether, substituted or unsubstituted alkylene group or a combination thereof; Z7 and Z8 each independently represent a group selected from hydroxyl, nitro, cyano group , C1 to C5 alkoxy, formyl and sulfonic acid groups; m and n are independently integers from 0 to 5; m+n is 5 or less; o and p are independently integers from 0 to 4 ; and o+p is 4 or less.

Additionally, exemplary aromatic acids may have general formula (VI):

Wherein: A group selected from carbonyl, carbonyloxy, sulfonamide, ether, thioether, substituted or unsubstituted alkylene or a combination thereof; Z9 independently represents a group selected from carboxyl, hydroxyl, nitro, cyano , C1 to C5 alkoxy group, carboxyl group and sulfonic acid group; q and r are independently integers from 0 to 3; and q+r is 3 or less.

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

Suitable TAGs include those capable of producing non-polymeric acids as described above. TAG can be non-ionic or ionic. Suitable nonionic thermal acid generators include, for example, cyclohexyl triflate, methyl triflate, cyclohexyl p-toluenesulfonate, methyl p-toluenesulfonate, 2,4,6- Cyclohexyl triisopropylbenzenesulfonate, nitrobenzene ester, benzoin tosylate, 2-nitrobenzene methyl toluenesulfonate, ginseng (2,3-dibromopropyl)-1,3, 5-Triketone-2,4,6-trione, alkyl ester of organic sulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, oxalic acid, phthalic acid, phosphoric acid, camphorsulfonic acid, 2,4,6-tritoluenesulfonic acid, triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid, 5-sulfosalic acid, 2,5-xylenesulfonic acid, 2-nitrobenzenesulfonate Acid, 3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 2-fluorodecanylsulfonic acid, dodecylbenzenesulfonic acid, 1-naphthol-5-sulfonic acid, 2-methoxy-4 -Hydroxy-5-benzoyl-benzenesulfonic acid and salts thereof, and combinations thereof. Suitable ionic thermal acid generators include, for example, triethylamine dodecylbenzene sulfonate, triethylamine dodecylbenzene disulfonate, ammonium p-toluenesulfonate, and pyridium salt of p-toluenesulfonate. , sulfonates, such as carbocyclic aryl and heteroaryl sulfonates, aliphatic sulfonates, and benzene sulfonates. Compounds which generate sulfonic acid upon activation are generally suitable. Preferred thermal acid generators include ammonium p-toluenesulfonate and heteroarylsulfonates.

Preferably, TAG is ionic, and the reaction flow for producing sulfonic acid is as follows:

Among them, RSO ₃ ⁻ is a TAG anion and X ⁺ is a TAG cation, preferably an organic cation. The cation may be a nitrogen-containing cation of general formula (I):

(BH) ⁺ (I)

It is the monoprotonated form of the nitrogenous base B. Suitable nitrogen-containing bases B include, for example: optionally substituted amines such as ammonia, difluoromethylamine, C1-20 alkylamines and C3-30 arylamines, for example nitrogen-containing heteroaromatic bases such as pyridine Or substituted pyridine (such as 3-fluoropyridine), pyrimidine and pyridine; nitrogen-containing heterocyclic group, such as oxazole, oxazoline or thiazoline. The aforementioned nitrogenous base B may be optionally substituted by, for example, one or more groups selected from alkyl, aryl, halogen atoms (preferably fluorine), cyano, nitro and alkoxy groups. Among them, base B is preferably a heteroaromatic base.

Base B typically has a pKa between 0 and 5.0, or between 0 and 4.0, or between 0 and 3.0, or between 1.0 and 3.0. As used herein, the term "pKa" is used according to its art-accepted meaning, i.e., pKa is about the negative of the dissociation constant of the conjugate acid (BH) ⁺ of the basic moiety (B) in aqueous solution at room temperature. Logarithm (base 10). In certain embodiments, Base B has a boiling point of less than about 170°C, or less than about 160°C, 150°C, 140°C, 130°C, 120°C, 110°C, 100°C, or 90°C.

Exemplary suitable nitrogen-containing cations (BH) ⁺ include NH ₄ ⁺ , CF ₂ HNH ₂ ⁺ , CF ₃ CH ₂ NH ₃ ⁺ , (CH ₃ ) ₃ NH ⁺ , (C ₂ H ₅ ) ₃ NH ⁺ , (CH ₃ ) ₂ (C ₂ H ₅ )NH ⁺ and below:

Wherein Y is an alkyl group, preferably methyl or ethyl.

In particular embodiments, the solubility shift agent can be an acid such as trifluoromethanesulfonic acid, perfluoro-1-butanesulfonic acid, p-toluenesulfonic acid, 4-dodecylbenzenesulfonic acid, 2,4-dinitrate benzene sulfonic acid and 2-trifluoromethylbenzenesulfonic acid; acid generators such as triphenylsulfonate antimonate, pyridinium perfluorobutanesulfonate, 3-fluoropyridium perfluorobutanesulfonate, 4 -Tertiary butylphenyl tetramethylene sulfonate perfluoro-1-butanesulfonate, 4-tertiary butylphenyl tetramethylene sulfonate 2-trifluoromethylbenzene sulfonate and 4-tertiary or its combination.

Alternatively, the solubility shift agent may include a base or base generator. In such embodiments, suitable solubility shift agents include, but are not limited to, hydroxides, carboxylates, amines, imines, amides, and mixtures thereof. Specific examples of bases include ammonium carbonate, ammonium hydroxide, ammonium hydrogenphosphate, ammonium phosphate, tetramethylammonium carbonate, tetramethylammonium hydroxide, tetramethylammonium hydrogenphosphate, tetramethylammonium phosphate, tetraethylammonium carbonate, tetraethylammonium hydroxide Ammonium, tetraethylammonium hydrogen phosphate, tetraethylammonium phosphate and combinations thereof. Amines include aliphatic amines, cycloaliphatic amines, aromatic amines and heterocyclic amines. The amine can be a primary, secondary or tertiary amine. The amine can 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 which may be strong bases such as hydroxides or alkoxides or weak bases such as carboxylates. Exemplary bases include amines, such as tripropylamine, dodecamine, gins(2-hydroxypropyl)amine, tetra(2-hydroxypropyl)ethylenediamine; arylamines, such as diphenylamine, triphenylamine, aminephenols, and 2-(4-Aminophenyl)-2-(4-hydroxyphenyl)propane, Troger's base, hindered amines such as diazabicycloundecene (DBU) or diazabicyclo Nonene (DBN), amides, such as 1,3-dihydroxy-2-(hydroxymethyl)propan-2-ylcarboxylic acid tertiary butyl ester and 4-hydroxypiperidine-1-carboxylic acid tertiary butyl ester ; or ion quenchers including quaternary alkylammonium salts such as tetrabutylammonium hydroxide (TBAH) or tetrabutylammonium lactate. In another embodiment, the amine is hydroxylamine. Examples of hydroxylamines include hydroxylamines having one or more hydroxyalkyl groups each having from 1 to about 8 carbon atoms, and preferably from 1 to about 5 carbon atoms, such as hydroxymethyl, hydroxyethyl, and hydroxybutyl. Specific examples of hydroxylamine include monoethanolamine, diethanolamine and triethanolamine, 3-amino-1-propanol, 2-amino-2-methyl-1-propanol, 2-amino-2-ethyl-1 , 3-propanediol, (hydroxymethyl)aminomethane, N-methylethanolamine, 2-diethylamino-2-methyl-1-propanol and triethanolamine.

A suitable base generator may be a thermal base generator. Thermal base generators form a base when heated above a first temperature, typically about 140°C or higher. Thermal base generators may include functional groups such as amide, sulfonamide, amide, imine, O-acyl oxime, benzyloxycarbonyl derivatives, quaternary ammonium salts, nifedipine , urethanes and combinations thereof. Exemplary thermal base 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}p-benzene Dicarboxylic acid, 2,4-bis{(β-(dimethylamino)ethyl)aminocarbonyl}isophthalic acid, 2,4-bis{(γ-(dimethylamino)propyl)amino Carbonyl}isophthalic acid and combinations thereof.

Alternatively, in one or more embodiments, the solubility shift agent includes a cross-linking agent. Suitable cross-linking agents that can be used as solubility shift agents include, but are not limited to, cross-linking agents used to cure diepoxides such as bisphenol A diglycidyl ether, 2,5-bis[(2-oxirane Methoxy)-methyl]-furan, 2,5-bis[(2-oxiranylmethoxy)methyl]-benzene, melamine, glycolurils such as tetramethoxymethyl glycoluril and Tetrabutoxymethyl glycoluril, a material based on benzoguanamine, such as benzoguanamine, hydroxymethylbenzoguanamine, methylated hydroxymethylbenzoguanamine, and ethylated hydroxymethylbenzoguanamine Benzoguanamine, and materials based on urea.

In one or more embodiments, the selective adhesion agent includes a solvent. The solvent is usually selected from water, organic solvents and mixtures thereof. In some embodiments, the solvent may include an organic-based solvent system including one or more organic solvents. The term "organic-based" means that the solvent system includes greater than 50 wt% organic solvent based on the total solvent of the solubility change agent composition, and more typically greater than 90 wt% based on the total solvent of the solubility change agent composition. , greater than 95 wt%, greater than 99 wt% or 100 wt% organic solvent. The solvent component is typically present in an amount of 90 to 99 wt% based on the solubility shift agent composition.

Organic solvents suitable for use in selective adhesion agent compositions include, for example: alkyl esters, such as alkyl propionates, such as n-butyl propionate, n-pentyl propionate, n-hexyl propionate, and n-heptyl propionate, and Alkyl butyrate, such as n-butyl butyrate, isobutyl butyrate and isobutyl isobutyrate; ketones, such as 2,5-dimethyl-4-hexanone and 2,6-dimethyl- 4-Heptanone; aliphatic hydrocarbons such as n-heptane, n-nonane, n-octane, n-decane, 2-methylheptane, 3-methylheptane, 3,3-dimethylhexane and 2,3,4-trimethylpentane, and fluorinated aliphatic hydrocarbons, such as perfluoroheptane; alcohols, such as linear, branched chain or cyclic C ₄ -C ₉ monohydric alcohols, such as 1-butanol, 2-Butanol, isobutanol, tertiary butanol, 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-octanol; 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, and C ₅ -C ₉ fluorinated diols such 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-1,8-octanediol; ethers, such as isopentyl ether and propylene glycol monomethyl ether; esters, such as alkyl esters with a total carbon number of 4 to 10, such as propylene glycol monomethyl ether acetate, Alkyl propionates, such as n-butyl propionate, n-amyl 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; and polyethers, such as dipropylene glycol monomethyl ether and tripropylene glycol mono Methyl ether; and mixtures containing one or more of these solvents.

In some embodiments, after coating the substrate with the selective adhesive agent, the substrate is pretreated. The matrix can be pretreated to ensure that the selective adhesive adheres to the surface of the topography. The pretreatment may be soft baking at a temperature ranging from 50 to 150°C for about 30 seconds to 90 seconds.

After the selective attachment material is attached to the topography, any excess material can be removed. Accordingly, in one or more embodiments, after applying the selective adhesive to the substrate and optionally pretreating it, the substrate is rinsed to remove unused material.

Next, at block 106 of method 100, a first resist is deposited on the substrate. Figure 2C shows the substrate 201 coated with the selective adhesive 203 and the first resistor 204. Generally speaking, a resist is a chemically amplified photosensitive composition including a polymer, a photoacid generator and a solvent. In one or more embodiments, the first resistor includes a polymer. The polymer may be any standard polymer commonly used in resist materials, and may especially be polymers having acid labile groups. The polymer may be a polymer made from monomers including vinyl aromatic monomers such as styrene and p-hydroxystyrene, acrylates, methacrylates, norbornene, and combinations thereof. For example, the polymer may be a polymer made from monomers including styrene, parahydroxystyrene, acrylates, methacrylates, norbornene, and combinations thereof. Monomers including reactive functional groups may be present in the polymer in protected form. For example, the -OH group of p-hydroxystyrene can be protected with a tertiary butoxycarbonyl protecting group. Such protecting groups can alter the reactivity and solubility of the polymer included in the first resistor. Those skilled in the art will appreciate that a variety of protecting groups may be used for this purpose. Acid-labile groups include, for example: tertiary alkyl ester groups, secondary or tertiary aryl ester groups, secondary or tertiary ester groups having a combination of alkyl and aryl groups, tertiary alkoxy groups, acetals base or ketal base. Acid-labile groups are also commonly referred to as "acid-decomposable groups", "acid-cleavable groups", "acid-cleavable protecting groups", "acid-labile protecting groups", and "acid-leaving groups" in this technology. ” and “acid-sensitive groups”.

The acid-labile group that forms carboxylic acid on the polymer during decomposition is preferably the tertiary ester group of the formula -C(O)OC(R ¹ ) ₃ or the formula -C(O)OC(R ² ) ₂ OR ³ Acetal group, wherein: R ¹ is each independently a straight chain C _{1 -20} alkyl group, a branched chain C _{3 -20} alkyl group, a monocyclic or polycyclic C _{3 -20} cycloalkyl group, or a straight chain C _{2 -20} Alkenyl, branched chain 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} heteroaryl, Preferred linear C _{1 -6} alkyl, branched chain C _{3 -6} alkyl or monocyclic or polycyclic C _{3 -10} cycloalkyl, each of which is substituted or unsubstituted, each R ¹ optionally includes a or more groups selected from -O-, -C(O)-, -C(O)-O- or -S- as part of its structure, and any two R ¹ groups together optionally form Ring; R ² is independently hydrogen, fluorine, linear C _{1 -20} alkyl, branched chain C _{3 -20} alkyl, monocyclic or polycyclic C _{3 -20} cycloalkyl, linear C _{2 -20} alkenyl , branched chain 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} heteroaryl, preferably Hydrogen, linear C _{1 -6} alkyl, branched chain C _{3 -6} alkyl or monocyclic or polycyclic C _{3 -10} cycloalkyl, each of which is substituted or unsubstituted, each ^R optionally includes a or more groups selected from -O-, -C(O)-, -C(O)-O- or -S- as part of its structure, and the R ² groups together optionally form a ring; and R ³ is linear C _{1 -20} alkyl, branched chain C _{3 -20} alkyl, monocyclic or polycyclic C _{3 -20} cycloalkyl, linear C _{2 -20} alkenyl, branched chain C _{3 -20} alkene base, monocyclic or polycyclic C _{3 -20} cycloalkenyl, monocyclic or polycyclic C _{6 -20} aryl or monocyclic or polycyclic C _{2 -20} heteroaryl, preferably linear C _{1 -6} alkyl , branched chain C _{3 -6} alkyl or monocyclic or polycyclic C _{3 -10} cycloalkyl, each of which is substituted or unsubstituted, R ³ optionally includes one or more selected from -O-, -C (O)-, -C(O)-O- or -S- groups as part of its structure, and one R ² and R ³ together optionally form a ring. Such monomers are typically vinylaromatic, (meth)acrylate or norbornyl monomers. The total content of polymerized units including acid-decomposable groups forming carboxylic acid groups on the polymer is generally 10 to 100 mol%, more typically 10 to 90 mol% or 30 to 30 mol%, based on the total polymerized units of the polymer. 70 mol%.

The polymer may further comprise as polymerized monomers containing acid labile groups, the decomposition of which forms alcohol or fluoroalcohol groups on the polymer. Suitable such groups include, for example, ^{an acetal group of the formula -COC(R2)2OR3- or} _a carbonate group of the formula -OC(O)O-, where R is as defined above. Such monomers are typically vinylaromatic, (meth)acrylate or norbornyl monomers. If present in the polymer, the total content of polymerized units including acid-decomposable groups whose groups decompose to form alcoholic or fluoroalcoholic groups on the polymer is typically from 10 to 90 moles based on the total polymerized units of the polymer. %, more typically 30 to 70 mol%.

In some embodiments, the composition of the first resist is similar to that of a positive tone development (PTD) resist. In such embodiments, the first resistor may include a polymer made from the monomers described above, wherein one or more of the monomers including reactive functional groups are protected. Therefore, the PTD-like first resistor can be organically soluble.

In other embodiments where the solubility shift agent is a cross-linking agent, the first resistor is a negative resistor. In such embodiments, the first resistor may include a polymer made from the monomers described above, wherein any monomers that include reactive functional groups are unprotected. Suitable reactive functional groups include, but are not limited to, alcohols, carboxylic acids, amines, and epoxides. Exposure to the cross-linking agent causes the polymer to cross-link, rendering the polymer insoluble in the developer. The non-crosslinked areas can then be removed using an appropriate developer.

In other embodiments, the first resist is a negative developing (NTD) resist. Similar to PTD resistors, NTD resistors may include polymers made from the monomers described above, in which one or more of the monomers including reactive functional groups are protected. Therefore, the NTD first resistor can be organically soluble, but instead of developing the solubility transition zone with an alkaline first resist developer, the solubility transition zone remains while the zone containing protected functional groups is developed using an organic-containing first resistor. Solvent first resist developer removal. Suitable organic solvents that can be used as the first resist developer include n-butyl acetate (NBA) and 2-heptanone. The type of resist (ie, PTD vs. negative vs. NTD) can affect final pattern placement.

In one or more embodiments, the first resist is layered on the substrate such that it has a thickness of about 300 Å to about 3000 Å.

At block 108 of method 100, the solubility shift agent is activated. In embodiments where the solubility change agent is an acid, an acid generator, a base, or a base generator, activation of the solubility change agent includes diffusing the solubility change agent into the first resistor to provide a solubility change zone of the first resistor. The solubility transition zone of the first resistor can be determined by the preferential adhesion of the selective adhesive. For example, a selective adhesive that preferentially adheres to existing patterned features can provide a solubility transition zone of the first resistor above the topography. In one or more embodiments, the solubility transition zone of the first resistor extends vertically from the surface of the selective adhesive coated on the topography to the surface of the first resistor. In one or more embodiments, the solubility transition zone extends in an oblique direction. When the solubility transition zone extends in an oblique direction, it may be necessary to prevent the topographies from merging together. In order to achieve this goal, the thickness of the topography can be controlled to be thin enough.

In one or more embodiments, diffusion of the solubility shift agent into the first resist is accomplished by baking. Baking can be done on a hot plate or in an oven. The temperature and time of baking will depend on the properties of the second resist and the amount of solubility changing agent required to diffuse into the second resist. Suitable conditions for baking may include a temperature in the range of about 50°C to about 160°C and a time in the range of about 30 seconds to about 90 seconds.

In embodiments where the solubility converting agent is a cross-linking agent, activation of the solubility converting agent includes initiating polymerization of the cross-linking agent into the first resistor. Activation of the cross-linking agent provides a cross-linked region of the first resistor. The cross-linked area of the first resistor can be determined by the preferential adhesion of the selective adhesive. For example, when the selective adhesive preferentially adheres to existing patterned features, as in selectively patterned self-alignment, the cross-linked regions of the first resist can be above the features.

Next, at block 110 of method 100, the first resist is developed using a specific developer. The specific developer can be any developer commonly used in the art. The composition of a particular developer will depend on the type and solubility characteristics of the first resist. For example, if the first resist is a positive developing resist, the specific developer may be a base, such as tetramethylammonium hydroxide. On the other hand, if the first resist is a negative developing resist, the specific developer may be a non-polar organic solvent, such as n-butyl acetate or 2-heptanone.

In one or more embodiments, the solubility transition zone or cross-linking zone is insoluble in the first developer. Therefore, after developing the first resist, the solubility transition zone or cross-linking zone of the first resist can remain on the substrate. Alternatively, in one or more embodiments, the solubility transition zone becomes soluble in the first developer. In such embodiments, the solubility transition zone of the first resist is removed from the substrate after developing the first resist. This type of pattern may be called an anti-selective pattern because the resist topography remains above the base layer and the pattern is not coated with the selective adhesive.

In one or more embodiments, the solubility transition region of the first resist is soluble in the first developer. In such embodiments, development of the first resist produces a pattern of the first resist that includes gaps exposing topography of the existing pattern. Thus, the selective adhesive is exposed and accessible for further coating. Figure 2D shows a coated substrate with gaps 205 in the first resist 204 exposing the existing pattern of features 202. In one or more embodiments, residual selective adhesion agent is removed by rinsing prior to metallization.

Finally, at block 112 of method 100, selective growth is performed on the topography of the existing pattern. Any suitable selective growth technique known in the art can be used to provide the second set of features directly on top of the existing patterned features. In Figure 2E, a substrate is shown that includes a topography 201, a first resist 204 offset to form the topography, and a selective growth material 206 on top of the topography.

In one or more embodiments, the second set of features includes selective growth material. Many different types of selective growth deposition materials known in the art are suitable for the various embodiments disclosed herein. In some embodiments, selective metal-to-metal reactive deposition can be achieved in solution using techniques such as electroless metal deposition and/or electrochemical atomic layer deposition. Examples of metals suitable for such metal-to-metal reactive deposition include, but are not limited to, copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), titanium ( Ti), tantalum (Ta), ruthenium (Ru), palladium (Pd) and their various alloys, stacks or other combinations. Other metals that can be deposited by selective reactions using electroless metal deposition and/or electrochemical atomic layer deposition generally should also be suitable.

In some embodiments, selective metal-to-metal reactive deposition can be performed using an isotactic ligand metaldiazetidine complex [M{N(R)C(H)C(H)N(R') }2]Proceed. In this formula, M may represent a metal atom selected from nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn) or chromium (Cr). The organic functional groups R and R' may represent any of a variety of substituted or unsubstituted alkyl or aryl functional groups. Examples of R and R' include, but are not limited to, substituted or unsubstituted two to eight carbon alkyl groups, phenyl and similar groups. Combinations of different complexes (eg with different metal atoms) may also optionally be used. Metals (e.g., pure metals or alloys or stacks of multiple metals) can be deposited by using chemical vapor deposition (CVD) with or without coreactants (e.g., hydrogen (H ₂ ), ammonia (NH ₃ ), hydrazine, etc.) In this case, it is deposited on the starting metal and/or on the metal deposited from such complexes. Atomic layer deposition (ALD) may alternatively be used. Such deposition will generally be selective compared to dielectric, semiconductor, and organic polymeric materials.

In some embodiments, applied voltage and/or the photoelectric effect can be used to promote metal deposition and/or increase the selectivity of metal deposition on a metal compared to another material (eg, a dielectric). In some embodiments, a bias voltage may be applied between a wafer or other substrate and conductive hardware in a metal deposition apparatus, such as a wafer chuck and a coil on the wafer chuck above the wafer. This bias voltage can be direct current (DC) or alternating current (AC), such as radio frequency AC. Applying a bias may tend to produce relatively more electrons from a metal (such as an interconnect or a metal material formed over an interconnect) than from another material (such as a dielectric), reducing the energy required to release electrons or otherwise provide electrons (such as secondary electrons), for example due in part to the photoelectric effect. In some embodiments, a forward bias may be applied to help accelerate electrons away from the metal. When using a DC bias, it is possible that after some electrons are emitted from the metal and the metal begins to have a net positive charge, the electron release may slow down unless there is a conductive path to the metal. However, applying an AC bias can generally help avoid this by loading electrons back into the metal between cycles. The electrons can be used to promote metal deposition and/or increase the selectivity of metal deposition on a metal compared to another material (eg, a dielectric). The electrons can help provide energy to drive or promote selective metal deposition reactions, such as ALD or CVD deposition of metals or other metal deposition methods that can be facilitated by such generated electrons. In some embodiments, a UV light source may be used with a bias voltage to help further generate photoelectrons near the metal. This can further help promote metal deposition and metal deposition selectivity.

In some embodiments, selective dielectric-to-dielectric reactive deposition may be accomplished by solution phase techniques such as sol-gel methods. Selective dielectric-to-dielectric reactive deposition can also be achieved by CVD, ALD, MLD or other vapor phase technologies. Examples of materials suitable for such dielectric-to-dielectric reactive deposition include, but are not limited to, silicon oxides (e.g., silicon dioxide ( _SiO2 )), silicon carbon-doped oxides, silicon nitrogen compounds (such as silicon nitride (SiN)), silicon carbides (such as silicon carbide (SiC)), silicon carbonitrides (such as SiCN), aluminum oxides (such as aluminum oxide (Al ₂ O ₃ )), Oxides of titanium (such as titanium oxide (TiO ₂ )), oxides of zirconium (such as zirconium oxide (ZrO ₂ )), oxides of hafnium (such as hafnium oxide (HfO ₂ )), and combinations thereof, to name just a few sexual examples. Other dielectrics and low-k dielectric materials known in the art may also be suitable. Carbosiloxane materials can also optionally be used. Various examples of reactions that deposit such materials selectively or at least preferentially compared to metals are known in the art using techniques such as sol-gel, ALD, CVD and MLD.

In some embodiments, one or more of carbon nanotubes, graphene, and graphite can be grown or formed on the metal surface material. The metal surface material may represent a catalytic metal surface material that is catalytic for the growth of carbon nanotubes, graphene or graphite. The catalytic metal surface material can be heated and exposed to suitable hydrocarbons and any other co-reactants using techniques known in the art. An example of a suitable catalytic surface and reactant assembly is a cobalt surface exposed to carbon monoxide and hydrogen. The biasing methods described above can also potentially be used to help promote such responses.

In some embodiments, a passivation material or layer may optionally be applied or formed on one of the different surface materials to help increase the selectivity or priority of response to the other of the surface materials. The use of such passivation materials generally helps to expand the number of possible selective/preferential reactions that can be used to form the layer. A reaction that is not necessarily selective/preferential for one surface material over another can still be selective for one of the surface materials compared to a passivating material. For example, a passivating material may be applied to a first surface material rather than a second surface material to increase the selectivity/priority of a given deposition reaction to the second surface material compared to the passivating material. Most passivating materials that can be manipulated to form selectively on a material and that can be manipulated to increase the selectivity/priority of the reaction should generally be suitable. Such passivating agents can be applied in the gas phase or in the solution phase. Such passivating agents may be applied one or more times during the selective deposition process. After the layer has been formed by the selective/preferential reaction, the passivating material can be removed. For example, passivating materials can be removed via thermal, photolytic, chemical or electrochemical treatments. In some embodiments, another passivation material can optionally be applied to other surface materials, but this is not required. Likewise, the use of optional such passivation materials can help expand the number of possible selective or at least preferential chemical reactions that can be used to form the various layers mentioned herein.

In one or more embodiments, after selective growth is performed on the existing patterned features, the substrate can be etched to remove any residual organic materials, including selective adhesion agents, solubility shifters, and resists. Next, dielectric isolation material can be deposited to fill the new features formed by the selective growth method. Examples of materials suitable for such dielectric deposition include, but are not limited to, oxides of silicon (e.g., silicon dioxide (SiO2)), carbon-doped oxides of silicon, nitrides of silicon (e.g., silicon nitride (SiO2)). SiN)), silicon carbides (such as silicon carbide (SiC)), silicon carbonitrides (such as SiCN), aluminum oxides (such as aluminum oxide (Al2O3)), titanium oxides (such as titanium oxide (TiO2) )), zirconium oxides (eg, zirconium oxide (ZrO2)), hafnium oxides (eg, hafnium oxide (HfO2)), and combinations thereof, to name just a few illustrative examples. Subsequently, chemical mechanical polishing methods can be used to planarize the surface. For example, if silicon dioxide is deposited and such deposition provides a capping layer, the capping layer can be removed by chemical mechanical polishing.

Thus, method 100 can provide self-aligned vias or metal contacts with generally vertical growth directions due to the constraints imposed by the surrounding first resist. Resistant.

In an alternative embodiment, the topography is coated with a first selective adhesive agent containing a first solubility changing agent, and the base layer is coated with a second selective adhesive agent containing a second solubility changing agent. In some embodiments, the first solubility shift agent includes an acid or acid generator and the second solubility shift agent includes a base or base generator. The resist is then deposited on the substrate and the solubility shift agent is simultaneously activated. The first solubility change agent diffuses from the top of the topography and the second solubility change agent diffuses from the top of the base layer. At the interface of the diffusion front, the solubility shift agents may interact with each other to prevent solubility switching of the resist in side regions outside the vertical plane perpendicular to the substrate and at the interface of the topography and the exposed substrate. This helps limit solubility switching to the resist region above the topography, thereby limiting lateral growth of the openings and producing a generally straight edge rather than a sloped profile.

In one or more embodiments, a method includes a photolithography step. The photolithographic step can be used to select specific features, portions of features, or other areas. For example, selective placement and growth may be achieved using directional growth methods as described in method 100 above. Next, the first resist can be exposed to form a patterned array, which exposes the target area and activates the solubility shift agent in that area. The heat treatment then causes the solubility shift agent to diffuse through the resist layer and promotes the solubility shift reaction. A solubility changing agent (eg acid) makes the resist soluble and this part is removed. Next, selective growth can be performed on the metal/substrate. Selective growth may be preceded by an etching step to remove any residual coating of selective adhesion agent and/or solubility shift agent from the top of the uncovered features.

Although only a few example embodiments have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the example embodiments without materially departing from the invention. Accordingly, all such modifications are intended to be included within the scope of this disclosure as defined in the claims below.

100:Method

102,104,106,108,110,112: Square

201: base layer, matrix

202:Topography

203:Selective adhesive

204:First Resistor

205: Gap

206: Selective growth materials

FIG. 1 is a process block diagram of a method according to one or more embodiments of the present disclosure.

2A-E are schematic illustrations of a coated substrate at various points in time according to a method according to one or more embodiments of the present disclosure.

201: base layer, matrix

202:Topography

203:Selective adhesive

204:First Resistor

206: Selective growth materials

Claims (14)

A method of microfabrication, comprising: providing a substrate having an existing pattern, wherein the existing pattern includes features formed in a first layer such that a top surface of the substrate has uncovered features and the first layer is not covered; depositing a selective adhesive agent on the substrate, wherein the selective adhesive agent includes a solubility changing agent; depositing a first resistor on the substrate; activating the solubility changing agent so that A portion of the first resist becomes insoluble in a first developer; and developing the first resist using the first developer to form a relief pattern including openings, wherein the openings expose the first the features of the layer; and performing a selective growth method that grows a selective deposition material on the features and within the openings of the relief pattern to provide self-aligned selective deposition features . The method of claim 1, wherein the adhesion of the selective adhesive agent to the surface of the topography exceeds the adhesion to the surface of the first layer. The method of claim 1 or 2, wherein the topographic bodies formed in the first layer form a large array. The method of claim 1 or 2, wherein the selective adhesion agent includes a phosphonic acid, a phosphonate ester, a phosphine, a sulfonic acid, a sulfinic acid, a carboxylic acid, a triazole, a thiol or one thereof combination. The method of claim 1 or 2, wherein the solubility change agent includes an acid generator. The method of claim 5, wherein the acid generator does not contain fluorine. The method of claim 5, wherein the acid generating agent is selected from the group consisting of: triphenylsulfonate antimonate, pyridinium perfluorobutanesulfonate, 3-fluoropyridium perfluorobutanesulfonate, 4 -Tertiary butylphenyl tetramethylene sulfonate perfluoro-1-butanesulfonate, 4-tertiary butylphenyl tetramethylene sulfonate 2-trifluoromethylbenzene sulfonate, 4-tertiary Butylphenyltetramethylenesulfonium 4,4,5,5,6,6-hexafluorodihydro-4H-1,3,2-dithithiane

1,1,3,3-tetraoxide and combinations thereof. The method of claim 1 or 2, wherein the solubility change agent includes an acid. The method of claim 8, wherein the acid does not contain fluorine. The method of 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-Dinitrophenylsulfonic acid, 2-trifluoromethylbenzenesulfonic acid and combinations thereof. The method of claim 1 or 2, further comprising pretreating the substrate before depositing the first resist on the substrate. The method of claim 1 or 2, wherein the morphologies include one metal or metalloid selected from the group consisting of silicon, polycrystalline silicon, copper, cobalt, tungsten and combinations thereof. The method of claim 1 or 2, wherein the first layer includes a dielectric. A method of micromanufacturing, the method comprising: receiving a substrate having a topography formed in a first layer, such that a top surface of the substrate has an uncovered topography and an uncovered first layer; depositing a first solubility change agent on the substrate, the first solubility change agent selected such that the first solubility change agent adheres to the uncovered surface of the topographies and does not adhere to the first the uncovered surface of the layer; depositing a second solubility change agent on the substrate, the second solubility change agent selected such that the second solubility change agent adheres to the uncovered surface of the first layer without adhering to the uncovered surface of the features; depositing a first photoresist on the substrate; activating the first solubility change agent sufficient to cause the first photoresist above the features to Region change of agents be soluble in a specific developer; activate the second solubility change agent so that the second solubility change agent increases the insolubility of the first photoresist above the first layer; develop the first photoresist, generating a relief pattern defining openings exposing the features; and performing a selective growth method that grows a selectively deposited material on the features and within the defined openings of the relief pattern, thereby producing a self-produced Align selectively deposited topographies.

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