Methods for manufacture of sequence-defined, stochastic-controlled polymeric EUV photoresists

Abstract

Systems, compositions, and methods for manufacture of photoresist platforms based on polypeptoids that can be made with defined sequences are provided. The polymer chains of these sequence-defined, photoacid generator (PAG)-free polymer resists can be made with the same molecular weight, e.g., chain length, composition, and sequence. In this way, the stochastic properties of the photoresists can be improved. Further, this photoresist platform can also be intrinsically patternable, thereby removing the utilization of PAGs to trigger chemical reactions upon exposure to lithographic radiation.

Description

METHODS FOR MANUFACTURE OF SEQUENCE-DEFINED, STOCHASTIC- CONTROLLED POLYMERIC EUV PHOTORESISTSCROSS-REFERENCE TO RELATED APPLICATION

[0001] The present disclosure claims priority to and the benefit of U.S. Provisional Application No. 63 / 557,513, entitled “Systems, Compositions, and Methods for Manufacture of Sequence-Defined, Stochastic-controlled, PAG-Free Polymeric EUV Photoresist Platforms,'’ filed on February 24, 2024, the content of which is incorporated by reference herein in its entirety.GOVERNMENT RIGHTS

[0002] This invention was made with government support under OSP 14433 awarded by the Department of Energy. The government has certain rights in the invention.FIELD

[0003] The present disclosure relates to systems, compositions, and methods for manufacture of photoresist platforms, and more particularly relates to systems, compositions, and methods for manufacture of sequence-defined photoresists that are free of photoacid generators.BACKGROUND

[0004] EUV lithography is widely considered to be one of, if not, the most advanced methods today to fabricate microelectronics with very' tiny features. While the chemically amplified resist (CAR) system has been widely used in industry , it suffers from stochastic failures and the concern of using fluorochemicals in its formulation, more specifically, photoacid generators (PAGs).

[0005] Stochastics refer to events that originate from random composition and process variables, which includes molecular variations from polydisperse materials (so called chemical / compositional stochastics). In polymer-based systems including CAR, stochastic issues come from molecular weight dispersity, compositional dispersity and sequence dispersity'. When very small features are being printed, the molecular variations among different polymer chains can cause issues that lead to pattern imperfections.

[0006] Conventional CARs use PAGs in their formulation to trigger chemical reactions upon exposure to lithographic radiation. The acids being generated from PAGs then cause the chemical change in the photoresist layer (usually deprotection of certain acid-labile groups, for example, tert-butyloxycarbonyl protecting group (tBOC)). This causes two problems: first, the unbounded PAG molecules can randomly distribute across the photoresist film and contribute to inhomogeneity and stochastics problems. Second, most of the PAGs are fluorinated compounds, or per- and polyfluorinated substances (PF AS). This is a major problem in semiconductor manufacturing or even the materials industry. Health issues stemming from PFASs have led to lawsuits, with manufacturers agreeing to billion-dollar settlements over these claims. Globally, the regulation of PF AS usage is tightening, with strategies in place to completely eliminate their presence in products.

[0007] Accordingly, there is a need for a new class of photoresists that can be used in microelectronic applications.SUMMARY

[0008] The present disclosure is directed to photoresists that are based on polypeptoids that can be made with defined sequences. These polypeptoids can have polymer chains that are made with the same molecular weight, e.g., chain length, composition, and sequence. Moreover, the photoresists of the presents embodiments are substantially devoid of PAG, which results in improved stochastic properties of the resulting photoresists. The omission of PAGs allows relief from the problems associated with the PAG distribution, and for solving of environmental, health and regulation concerns, while still allowing for patterning of the photoresist.

[0009] Additional features of the present disclosure will become apparent to those skilled in the art upon consideration of illustrative embodiments exemplifying the best mode of carrying out the disclosure as presently perceived.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] This disclosure will be more fully understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

[0011] FIG. 1 A is a schematic of a photoresist of the present embodiments undergoing a chemical reaction when exposed to ultraviolet light (UV) or extreme ultraviolet (EUV) radiation;

[0012] FIG. IB is a schematic of a positive-tone product of the reaction of FIG. 1A;

[0013] FIG. 1C is a schematic of a negative-tone product of the reaction of FIG. 1A;

[0014] FIG. 2A is one example of a chemical structure of the prior art;

[0015] FIG. 2B is another example of a chemical structure of the prior art;

[0016] FIG. 2C is another example of a chemical structure of the prior art;

[0017] FIG. 3 A is one example of a chemical structure of building blocks of polypeptoids;

[0018] FIG. 3B is another example of a chemical structure of building blocks of polypeptoids;

[0019] FIG. 4A is one example polypeptoid sequence that is intrinsically pattemable under EUV and e-beam in negative-tone;

[0020] FIG. 4B is another exemplary embodiment of a chemical structure of a polypeptoid building block;

[0021] FIG. 4C is another exemplary' embodiment of a chemical structure of a polypeptoid building block;

[0022] FIG. 4D is another exemplary embodiment of a chemical structure of a polypeptoid building block;

[0023] FIG. 4E is another exemplar}' embodiment of a chemical structure of a polypeptoid building block;

[0024] FIG. 4F is another exemplary’ embodiment of a chemical structure of a polypeptoid building block;

[0025] FIG. 4G is another exemplary embodiment of a chemical structure of a polypeptoid building block;

[0026] FIG. 5 A is another exemplary embodiment of a chemical structure of a polypeptoid building block having alcohol groups;

[0027] FIG. 5B is a schematic of a pattern observed following e-beam exposure on a photoresist having the polypeptide building block of FIG. 5 A;

[0028] FIG. 5C is another schematic of a pattern observed following e-beam exposure on a photoresist having the polypeptide building block of FIG. 5 A;

[0029] FIG. 6A is another exemplary embodiment of a chemical structure of a polypeptoid building block having alcohol groups;

[0030] FIG. 6B is a schematic of a pattern observed following e-beam exposure on a photoresist having the polypeptide building block of FIG. 6A;

[0031] FIG. 7A is another exemplary embodiment of a chemical structure of a polypeptoid building block having thiol groups;

[0032] FIG. 7B is a schematic of a pattern observed following e-beam exposure on a photoresist having the polypeptide building block of FIG. 7A;

[0033] FIG. 7C is another schematic of a pattern observed following e-beam exposure on a photoresist having the polypeptide building block of FIG. 7A;

[0034] FIG. 8 is another exemplary' embodiment of a chemical structure of a polypeptoid building block;

[0035] FIG. 9A is another exemplary embodiment of a chemical structure of a polypeptoid building block having chain end groups involved in chemical reactions for development of patterns;

[0036] FIG. 9B is another exemplary’ embodiment of a chemical structure of a polypeptoid building block having chain end groups involved in chemical reactions for development of patterns;

[0037] FIG. 10 is a systematic study on lithographic performance with different polypeptoid sequences;

[0038] FIG. 11 A is an SEM image of one example e-beam pattern made from the abovementioned polypeptoid sequence having 24-nm half-pitch;

[0039] FIG. 1 IB is an SEM image of one example EUV pattern made from the abovementioned polypeptoid sequence having left to right 20-, 16-, 14-, 12-nm half pitch.

[0040] FIG. 12A is an SEM image of one example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0041] FIG. 12B is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0042] FIG. 12C is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0043] FIG. 12D is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0044] FIG. 12E is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0045] FIG. 12F is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0046] FIG. 12G is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to e-beam;

[0047] FIG. 13A is an SEM image of one example of negative-tone patterns that develop on photoresists exposed to EUV ;

[0048] FIG. 13B is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to EUV; and

[0049] FIG. 13C is an SEM image of another example of negative-tone patterns that develop on photoresists exposed to EUV.DETAILED DESCRIPTION

[0050] Certain exemplary embodiments will now be described to provide an overall understanding of the principles of the systems and methods disclosed herein. One or more examples of these embodiments are illustrated in the accompanying drawings. Those skilled in the art will understand that the systems and methods specifically described herein and illustrated in the accompanying drawings are non-limiting exemplary embodiments and that the scope of the present disclosure is defined solely by the claims. The features illustrated or described in connection with one exemplary embodiment may be combined with the features of other embodiments. Such modifications and variations are intended to be included within the scope of the present disclosure. To the extent that the instant disclosure includes various terms for components and / or processes of the disclosed systems, methods, and the like, one skilled in the art, in view of the claims, present disclosure, and knowledge of the skilled person, will understand such terms are merely examples of such components and / or processes, and other components, designs, processes, and / or actions are possible.

[0051] At least one novel feature of the present embodiments can include a new class of photoresists to be used in extreme ultraviolet (EUV) lithography, or electron beam (e- beam) lithography. For example, this new class of photoresist platforms is based on polypeptoids that can be made with defined sequences. The polymer chains of these sequence-defined, PAG-free polymer resists can be made with the same molecular weight, e.g., chain length, composition, and sequence. In this way, the stochastic properties of the photoresists can be improved. Further, this photoresist platform can also be intrinsically pattemable under EUV or e-beam, which means the addition of PAGs is unnecessary, which can differ from conventional systems recognized by one skilled in the art, which utilize PAGs to trigger chemical reactions upon exposure to lithographic radiation. The omission of PAGs allows relief from the problems associated with the PAG distribution, and for solving of environmental, health and regulation concerns. In addition, the present embodiments exhibit superior lithographic performance as compared to conventional systems and methods.During EUV patterning experiments, for example, the photoresist can be patterned at about a 13 to about a 16 nm half pitch node, or at approximately a 14 nm half pitch node, which is noteworthy due to the state-of-the-art record of a polymer resist being 13-nm. In some embodiments, the EUV radiation can have a dose from about 1 mJ / cmA2 to about 150 mJ / cmA2 or the e-beam radiation can have a dose from about 1 pC7cmA2 to about 1000 pC / cmA2.

[0052] A person skilled in the art will recognize that for the purposes of this disclosure, the photoresists of the present embodiments being PAG-free can be understood to mean that the photoresists are substantially devoid of PAG. The term “substantially devoid,” as pertaining to PAGs, or any other compound with which it is discussed in this disclosure will be understood to mean that the PAG, or the other compound, is contained within an amount that is present in trace amounts or absent from the composition.

[0053] FIGS. 1A-1C illustrate photolithography using a chemically amplified photoresist as provided for by the instant disclosure. As shown in FIG. 1 A, a system 100 of the present embodiments can include a photoresist 102 disposed on a substrate 104 that is exposed to a UV or EUV light 106 through a mask 108. When exposed to the light 106, the photoresist 102 undergoes a chemical reaction that enables a solubility switch. The chemical reaction can include baking of the photoresist 102, which results in positive-tone 102p and negative-tone dissolution 102n transfer photoresists.

[0054] As show n in FIG. 1 C, the photoresist of the present embodiments can be a negative-tone photoresist 102n, in which a region exposed to the EUV and / or e-beam 106 remains while the unexposed region is removed. This differs from the positive-tone photoresists of FIG. IB in which the exposed region is removed during the development process. The negative-tone exhibited by the unprotected phenols of the present embodiments under various kinds of exposure is an unanticipated behavior and is unexpected to one skilled in the art of photoresists. In some embodiments, the present embodiments can use tBOC- protected phenol groups or t-butyl ester groups to manufacture the negative-tone photoresists of the present embodiments.

[0055] In use, altering polypeptoid composition and / or sequence can generate patterns in negative-tone. For example, as mentioned above, conventional CARs are usually in positive-tone, while exposing the polypeptoid sequences of the present embodiments to electron beams in the absence of PAG can exhibit negative-tone behavior. The negative-tone behavior can be attributed to peptoid chains crosslinking upon exposure and becoming insoluble. Alternatively, or in addition, the peptoid backbone can have many amide groups, which may form intermolecular hydrogen bonds with deprotected solubility switches, leading to insolubility.

[0056] Conventional resist platforms for EUV lithography suffer from several shortcomings. First, conventional resist platforms can be fundamentally different due to use of metal-organic clusters in manufacture of photoresists as compared to those of the present embodiments. This differs from the systems and methods of the present embodiments whichcan use metal free, purely organic peptoids. Metal atoms can potentially introduce impurities in semiconductor fabrication processes as certain metals can diffuse into the silicon substrate and cause contamination. Moreover, conventional resists use organic solvents as developer (to remove the unexposed region from the substrate), while our resists are developable in a very7dilute aqueous base solution, which is more eco-friendly and does not lead to exposure to potentially toxic organic solvents.

[0057] In conventional building blocks, tBOC-protected phenol groups or t-butyl ester groups in the structure can act as solubility switches, which are very similar to the conventional chemically amplified photoresists, including environmentally stable chemically amplified photoresists (ESCAPs) and APEX, shown in FIGS. 2A-2C. Upon exposure, these groups can be deprotected by the acids generated by the photoacid generator, generating more hydrophilic side groups and becoming more soluble in the developer.

[0058] These conventional building blocks differ from those the present embodiments, which, while also containing t-butyl ester groups, contain a polypeptoid backbone, which was not disclosed in conventional photoresists. For example, the system of the present embodiments can be a one-component system that contains polypeptoids with a precise molecular structure, which includes molecular weight, e.g., chain length, composition and sequence. The polypeptoids can be made with a solid-phase submonomer synthesis method with molecular precision as photoresists in lithography to reduce stochastics. These photoresists can then be purified with high-performance liquid chromatography (HPLC) to form high resolution, high purity, low stochastic photoresists of the present embodiments. The specific sequence can include building blocks of polypeptoids, such as tyramine (or similar structure with phenol groups), along with other side groups including tBOC and t- butyl esters, the chemical structures of which are shown in FIGS. 3A-3B. In some embodiments, a plurality of units having different chemical structures, e.g, tyramine units, phenol derivatives, tBOC and t-butyl esters, and so forth, can be placed in combination along the polypeptoid chain. In such embodiments in which a plurality of these units are included on the chain, an amount of the first unit can approximately range from about 0% to about 100% with respect to the molecular weight of the chain, from about 0% to about 99% with respect to the molecular weight of the chain, or from about 1% to about 99% with respect to the molecular weight of the chain including any values therewithal or any subranges therebetw een, and an amount of the second unit can approximately range from about 0% to about 100% with respect to the molecular weight of the chain, from about 0% to about 99% with respect to the molecular weight of the chain, or from about 1% to about 99% withrespect to the molecular weight of the chain, including any values therewithin or any subranges therebetween.

[0059] For example, the polypeptoid sequence can cause tone switch due to metal elements having high EUV-absorption cross-sections binded to the polypeptoid sequences at precisely defined locations along the chain. An example of a polypeptoid sequence of the present embodiments that is intrinsically pattemable under EUV and e-beam is shown in FIG. 4A. As shown, the polypeptoid sequence includes unprotected tyramine and l-butyl ester groups of FIGS. 3A-3B that are placed at stochastically -controlled locations along the polypeptoid chain.

[0060] FIGS. 4B-4G illustrate additional non-limiting examples of chemical structures of building blocks that can be used in the polypeptoid sequences of the present embodiments to yield resist systems that exhibit resist systems or photoresists that exhibit superior performance. As show n in FIG. 4B (I)-(IV), the polypeptoid sequences of the present embodiments can include a chemical structure of a hydrophilic building block, as shown, wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H, an alkyl group (e.g. methyl group), or, for example, considering the metal chelated material, and wherein n is selected from 1-5, preferably 1-3, or 1.

[0061] FIGS. 4C (I)-(II) illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of a building block, as shown, wherein L2 (I) or L (II) is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4). - O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and an amide -CONH- linker, and optionally an -O- linker. In some embodiments, L2 can be a complex linker that includes the combination of two or more linker groups described above, and R2 is any chemical group that can be bonded and / or otherwise associated with L2. For the purposes of the present disclosure, R2 being any chemical group can refer to groups that are composed of one or more of all 118 know n elements in various combinations thereof that can be stably bonded to the polypeptoid sequence. It will be appreciated that, in some embodiments, some nonlimiting examples of R2 being any chemical group can include one or more of a hydrogenatom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, a methoxy group, and a tert-butyl group.

[0062] In some embodiments, R2 can be selected from a combination of any chemical group except the tert-Butyl (tBu) group.

[0063] In some embodiments, R2 can be selected from an alky l group, preferably a branched alkyl group (e.g. isopropyl group or tert-butyl group), or a hydrogen atom (H), as shown in (III)-(VI). It will be appreciated that if R2 is a hydrogen atom, then the combination of L2 and R2 will result in a carboxylic acid.

[0064] FIGS. 4D (I)-(II) illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of a metal-binding building block, as shown, wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1- 4), -O-, -COO-, or any combination thereof. A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group - OH linked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal.

[0065] In some embodiments, an ion of the metal can be selected from a 2+ cation, a 3+ cation, or a 4+ cation. In some embodiments, the ion can be selected from a Zn ion or an Sn ion.

[0066] FIGS. 4E (I)-(IV) illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of an inert hydrophobic building block, as shown, wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic ary l having 2 or 3 pheny l rings bonded to each other by single bonds, alkyl linkers, or fused together.

[0067] In some embodiments, iodine can be added as an EUV absorption enhancer and / or secondary' electron generator. The iodine can absorb EUV photons and kick off secondary' electrons to cause chemistry', thereby sensitizing the photoresist. FIG. 4F (I)-(VI) illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of some non-limiting examples of iodinated amines. These structures can include iodine attached to an aromatic ring, a phenyl ring, and / or bonded to a polycyclic aryl group. Attaching the iodine to an aromatic group can help w ith maintaining stability' of iodinated compounds for prolonged periods. It will be appreciated that the premises discussed above can extend to other halogens.

[0068] FIGS. 4G (I)-(VI) illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of some non-limiting examples of iodinated monomers. These structures can include one to five iodine molecules attached to an aromatic ring, a phenyl ring, and / or bonded to a polycyclic aryl group. The L5 group can be any of the linkers mentioned for the other monomers above, while A5 can be selected from an aromatic (or heteroaromatic) group, specifically, an aromatic or heteroaromatic group functionalized with 1 up to the maximum number of group X allowed by the chemical structure, wherein the functionalization group X is selected from F, Cl, Br, I, hydroxyl group (-OH), such as an iodine-containing aromatic or heteroaromatic ring functionalized with up to 1-5 (or up to the maximum allowed by the chemical structure) halogen atoms (e.g. iodine atoms), or a functionalized alkyl group, specifically, an alkyl group functionalized with 1 up to the maximum number of group X allowed by the chemical structure, wherein the functionalization group X is selected from F, Cl, Br, I, a hydroxyl group (-OH), or any combinations thereof, such as an iodine-containing alkyl group. These monomers can contain multiple functionalizations (i.e. hydroxyls and iodines, etc.). Attaching the iodine to an aromatic group can help with maintaining stability of iodinated compounds for prolonged periods. It will be appreciated that the premises discussed above can extend to other halogens.

[0069] FIG. 5A illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of some non-limiting examples of alcohol groups, e.g., the hydroxyl group (-OH), and FIGS. 5B-5C illustrates its corresponding patterns observed following e-beam exposure in the absence of PAGs. While hydroxyl groups are mentioned above with respect to FIG. 4G, where the L5 group can be any of the linkers mentioned for the other monomers above, while A5 can be a hydroxyl group that is linked to the alkyl group of L5 without an intervening aromatic group or being a functionalization group. In some embodiments, the hydroxyl group and the aromatic group can alternate as the end groups of A5 that branch of the nitrogen atoms of the polypeptoid sequence, as shown in FIG. 5A. Alternatively, or additionally, the hydroxyl group can alternate with an alkyl group as the end groups of A5 that branch of the nitrogen atoms of the polypeptoid sequence, as shown in FIG. 6A. The corresponding patterns following e-beam exposure in FIGS. 5B-5C and 6B, respectively, illustrate the polypeptoids patterned by e-beam lithography in negative tone, including large fiducial marks (about 100 pm) and line / space patterns, demonstrating the pattemability of these polypeptoids under e-beam.

[0070] FIG. 7A illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of some non-limiting examples of thiols, .e.g. the (-SH) group, and FIGS. 7B-7C illustrates its corresponding patterns observed following e-beam exposure in the absence of PAGs. The sequence of these embodiments resemble those of FIG. 5A with the modification being inclusion of a thiol group at the end of the alkyl group that branches off the nitrogen atoms, in lieu of the hydroxyl group, and a detailed discussion is therefore omitted for the sake of brevity. The patterns following e-beam exposure illustrate the polypeptoids patterned by e-beam lithography in negative tone, including large fiducial marks (about 100 pm) and small areas, demonstrating the pattemability of these polypeptoids under e-beam.

[0071] It will be appreciated that while the alkyl branch is shorter than that of FIG. 5 A, longer branched alkyls can be used. Moreover, the polypeptoid chain of the present embodiments can vary in length. For example, in some embodiments, the polypeptoid chain can have a number of units that is approximately in a range from about 3 units to about 100 units, about 4 units to about 100 units, about 5 units to about 100 units, about 3 units to about 50 units, about 3 units to about 30 units, about 4 units to about 30 units, and / or about 5 units to about 30 units. In some embodiments, the polypeptoid chain can have a number of units that is approximately in a range from about 3 units to about 29 units, about 4 units to about 29 units, and / or about 5 units to about 29 units. In some embodiments of the present invention, the polypeptoid chain can include units having a molar percentage of 0 mol % to 99 mol %, including any values therewithin or any subranges therebetween. In some embodiments, the polypeptoid chain can include a first type of unit and a second type of unit, and optionally a third type of unit, wherein the mol% of the first type of unit is 1-99 mol% (e.g. 30-99 mol%), including any values therewithin or any subranges therebetween, the mol% of the second type of unit is 1-99 mol% (e.g. 30-99 mol%), including any values therewithin or any subranges therebetween, and optionally the mol% of the third type of unit is 0-99 mol% (e.g. 0-40 mol%), including any values therewithin or any subranges therebetween.

[0072] Likewise, it will be appreciated that while the hydroxyl groups and the thiol groups of FIGS. 5A-7A are shown with respect to the polypeptoid structures of said figures, the hydroxyl and / or thiol groups can be used with any of the polypeptoid sequences shown in FIGS. 4A-4G.

[0073] FIG. 8 illustrates that the polypeptoid sequences of the present embodiments can include a chemical structure of a methoxyethyl group. The methoxyethyl group can take the place of the hydroxyl and / or the thiol groups as shown.

[0074] In some embodiments, chain end groups of the polypeptoid sequences of the present embodiments may be involved in chemical reactions for development of patterns, thereby leading to the pattemability of the polypeptoids. For example, FIGS. 9A-9B illustrate exemplary embodiments of polypeptoid sequences having chain end groups that can be involved in such reactions. Such groups can include carboxylic acids, as shown in FIG. 9A, or amides, as shown in FIG. 9B, among others. It will be appreciated that the sequences in FIGS. 9A-9B are merely exemplary and that the chain end groups of a variety of sequences disclosed in the present application can be involved in these reactions. Some nonlimiting examples of these chain end groups can include one or more of one or more of a hydrogen atom, a thiol group, a hydroxyl group, a carbon atom, a methoxy group, and so forth.

[0075] Uses of the systems, methods, and compositions can involve dissolving materials in casting solvents, spin-coating the solution on a silicon w afer to form a smooth film with certain thickness, soft baking to remove the residue solvents, exposure to UV or EUV light in lithographic tools (for example, a stepper), post-exposure baking, and / or development of the patterns in the developer. In some embodiments, the negative-tone can be observed following exposure to EUV light with 13.5-nm wavelength, or electron beam (e- beam). The photoresists of the present embodiments can be used in EUV lithography or e- beam lithography as a stochastically controlled (sequence-defined). PAG / PFAS free resists that can be developable in diluted aqueous base solution. The impact of different polypeptoid sequences on lithographic performance can be studied by screening large sequence space, as shown in FIG. 10.

[0076] FIG. 11 A illustrates an example scanning electron microscope (SEM) image of one example electron beam pattern made from the polypeptoid sequence of FIG. 4A, and FIG. 11 B illustrates an SEM image of one example EUV pattern made from the polypeptoid sequence of FIG. 4A. In some embodiments, 24-nm half-pitch resolution with e-beam lithography and 14-nm half-pitch resolution with EUV can be achieved on such photoresists. As shown, the number near each group of line / space patterns indicates the half-pitch resolution of each group of patterns. Additional examples of SEM images from photoresists exposed to electron beam and EUV are shown in FIGS. 12A-12G and 13A-13C respectively.

[0077] The following numbered clauses include embodiments that are contemplated and non-limiting:

[0078] Clause 1. A photoresist composition, comprising a polypeptoid chain of a defined molecular structure having one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic ar l having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5, preferably 1-3, or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is one or more of a hydrogen atom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, a methoxy group, and a tert-butyl group,formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- . x is 1 to 10, preferably 1-4), -O-. -COO-, or any combinationthereof, wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OH linked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal, andformula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together, formulawherein L5 a linker selected from an alkyl linker (e.g. - (CH2)X-, x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring), and wherein the photoresist is negative-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

[0079] Clause 2. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein R2 is selected from an alkyl group, preferably a branched alkyl group (e.g. isopropyl group or tert-butyl group), or a hydrogen atom (-H).

[0080] Clause 3. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein R2 is selected from a hydroxyl group, a thiol group, or a methoxy group.

[0081] Clause 4. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptide chain further comprises a chain end group that includes one or more of a carboxylic acid or an amide.

[0082] Clause 5. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is sufficiently devoid of photoacid generators (PAGs).

[0083] Clause 6. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is composed of metal free, organic peptoids.

[0084] Clause 7. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptoid chain further comprises one or more unprotected phenol groups.

[0085] Clause 8. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is pattemable under exposure to EUV light or e-beam light.

[0086] Clause 9. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein exposure to a light of the EUV lithography includes a 13.5 nm wavelength or e-beam.

[0087] Clause 10. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is substantially devoid of organic solvents as the developer during a development process.

[0088] Clause 11. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the defined molecular structure of the polypeptoid further comprises one or more of a predetermined molecular weight, composition, or sequence.

[0089] Clause 12. The photoresist of clause 11, wherein the sequence further comprises one or more of tyramine, tBOC, or t-butyl esters.

[0090] Clause 13. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein a length of the polypeptoid chain is approximately in a range from about 3 units to about 100 units.

[0091] Clause 14. The photoresist of clause 1313, wherein a length of the polypeptoid chain is approximately in a range from about 3 units to about 29 units.

[0092] Clause 15. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptoid chain comprises a plurality of units having different chemical structures, a first unit of the plurality of units being present in an amount approximately in a range from about 0% to about 100% with respect to the molecularweight of the chain, and an amount of the second unit approximately in a range from about 0% to about 100% with respect to the molecular weight of the chain.

[0093] Clause 16. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptoid chain comprises two or more of formulas (I)-(V).

[0094] Clause 17. The photoresist of clause 1, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptoid chain comprises formula (III) and one or more metal ions forming stable chelating bond(s) with formula III.

[0095] Clause 18. The photoresist of clause 17, any other suitable clause, or any other suitable combination of clauses, wherein the metal ion is selected from a 2+ cation, a 3+ cation, or a 4+ cation.

[0096] Clause 19. The photoresist of clause 17, any other suitable clause, or any other suitable combination of clauses, wherein the metal ion is selected from aZn ion or an Sn ion.

[0097] Clause 20. A method of fabricating photoresists, comprising synthesizing a first polypeptoid chain having a predetermined molecular structure by placing one or more compounds at a specific location along the first polypeptoid chain; exposing the first polypeptoid chain to ultraviolet (EUV) light or electron beam (e-beam) light; intrinsically patterning the photoresist under extreme ultraviolet (EUV) lithography or electron beam (e- beam) lithography; removing a region of the photoresist that is not exposed to EUV or e- beam; and developing the photoresist in an aqueous base developer, wherein the photoresist is negative-tone when exposed to EUV or e-beam light.

[0098] Clause 21. The method of clause 20, wherein the defined molecular structure comprises one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl nngs bonded to each other by single bonds or fused together, or their derivatives with one or morecarbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5. preferably 1-3. or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an ary l or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is one or more of a hydrogen atom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, a methoxy group, and a tert-butyl group,formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, or any combination thereof, and wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OH linked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal,formula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and formulawherein L5 a linker selected from an alky l linker (e.g. -(CH2)X- . x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together.

[0099] Clause 22. The method of clause 21, any other suitable clause, or any other suitable combination of clauses, wherein R2 is selected from an alkyl group, preferably a branched alkyl group (e.g. isopropyl group or / -but l group), or a hydrogen atom (-H).

[0100] Clause 23. The photoresist of clause 21, any other suitable clause, or any other suitable combination of clauses, wherein R2 is selected from a hydroxyl group, a thiol group, or a methoxy group.

[0101] Clause 24. The method of clause 21, any other suitable clause, or any other suitable combination of clauses, wherein intrinsically patterning the photoresist further comprises reacting the one or more compounds under EUV or e-beam lithography, the one or more compounds comprising of a carboxylic acid or an amide.

[0102] Clause 25. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, wherein synthesizing the first polypeptoid chain having a predetermined molecular structure further comprises predetemiining one or more of a molecular weight, composition, or sequence of the first polypeptoid chain.

[0103] Clause 26. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, wherein the one or more compounds further comprise one or more of tyramine, tBOC, or t-butyl esters.

[0104] Clause 27. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, wherein synthesizing the first polypeptoid chain further comprises solid-phase submonomer synthesis.

[0105] Clause 28. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, further comprising purifying the photoresist with high- performance liquid chromatography (HPLC).

[0106] Clause 29. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, wherein the EUV radiation has a dose from about 1 mJ / cmA2 to about 150 mJ / cmA2 or the e-beam radiation has a dose from about 1 pC / cmA2 to about 1000 pC / cmA2.

[0107] Clause 30. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, further comprising developing the photoresist in a dilute aqueous base solution.

[0108] Clause 31. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is composed of metal free, organic peptoids.

[0109] Clause 32. The method of clause 20, any other suitable clause, or any other suitable combination of clauses, further comprising synthesizing a second polypeptoid chain that has substantially the same predetermined molecular structure as the first polypeptoid chain.

[0110] Clause 33. A photoresist composition, comprising a polypeptoid chain of a defined molecular structure having one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic ar l having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or morecarbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5. preferably 1-3. or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is selected from one or more of a hydrogen atom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, and a methoxy group, except for a tert-butyl group,formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-. -COO-, or any combination thereof, wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OH linked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal, andformula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together, formula, wherein L5 a linker selected from an alkyl linker (e.g. - (CH2)X-, x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring).

[0111] Clause 34. The photoresist of clause 33, any other suitable clause, or any other suitable combination of clauses, wherein R2 is selected from an alkyl group, preferably a branched alkyl group (e.g. isopropyl group), or a hydrogen atom (-H).

[0112] Clause 35. The photoresist of clause 33, any other suitable clause, or any other suitable combination of clauses, wherein R2 is selected from a hydroxyl group, a thiol group, or a methoxy group.

[0113] Clause 36. The photoresist of clause 33, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptide chain further comprises a chain end group that includes one or more of a carboxylic acid or an amide.

[0114] Clause 37. The photoresist of clause 33, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is sufficiently devoid of photoacid generators (PAGs).

[0115] Clause 38. The photoresist of clause 33, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is negative-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

[0116] Clause 39. The photoresist of clause 33, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is positive-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

[0117] Clause 40. A photoresist composition, comprising a polypeptoid chain of a defined molecular structure having one or more of:formula (I): , wherein LI is a linker selected from an alkyd linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from pheny l ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5, preferably 1-3, or 1,formula (II): , wherein L2 or L is a linker selected from an alky l linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4). -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is a hydrogen atom (-H),formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, or any combination thereof, wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OH linked to the same or an adjacent aromatic or heteroaromatic ring(s). configured to form one or more stable chelating bond(s) with a metal, andformula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together. formulawherein L5 a linker selected from an alkyl linker (e.g. -(CH2)X-, x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring).

[0118] Clause 41. The photoresist of clause 40, any other suitable clause, or any other suitable combination of clauses, wherein R2 further comprises a hydroxyl group, a thiol group, or a methoxy group.

[0119] Clause 42. The photoresist of clause 40, any other suitable clause, or any other suitable combination of clauses, wherein the polypeptide chain further comprises a chain end group that includes one or more of a carboxylic acid or an amide.

[0120] Clause 43. The photoresist of clause 40, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is sufficiently devoid of photoacid generators (PAGs).

[0121] Clause 44. The photoresist of clause 40. any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is negative-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

[0122] Clause 45. The photoresist of clause 44, any other suitable clause, or any other suitable combination of clauses, wherein R2 further comprises an alkyl group, preferably a branched alkyl group (e.g. isopropyl group or tert-butyl group).

[0123] Clause 46. The photoresist of clause 40, any other suitable clause, or any other suitable combination of clauses, wherein the photoresist is positive-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

[0124] Some non-limiting claims that are supported by the contents of the present disclosure are provided below.

Claims

CLAIMSWhat is claimed is:

1. A photoresist composition, comprising: a polypeptoid chain of a defined molecular structure having one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5, preferably 1-3, or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or anycombinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is one or more of a hydrogen atom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, a methoxy group, and a tert-butyl group,formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, or any combination thereof, wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OH linked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal, andformula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), andwherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together, formula, wherein L5 a linker selected from an alkyl linker (e g. -(CH2)X-, x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring), and wherein the photoresist is negative-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

2. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein R2 is selected from an alkyl group, preferably a branched alkyl group (e.g. isopropyl group or tert-butyl group), or a hydrogen atom (-H).

3. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein R2 is selected from a hydroxyl group, a thiol group, or a methoxy group.

4. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the polypeptide chain further comprises a chain end group that includes one or more of a carboxylic acid or an amide.

5. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is sufficiently devoid of photoacid generators (PAGs).

6. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is composed of metal free, organic peptoids.

7. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the polypeptoid chain further comprises one or more unprotected phenol groups.

8. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is patternable under exposure to EUV light or e-beam light.

9. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein exposure to a light of the EUV lithography includes a 13.5 nm wavelength or e-beam.

10. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is substantially devoid of organic solvents as the developer during a development process.

11. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the defined molecular structure of the polypeptoid further comprises one or more of a predetermined molecular weight, composition, or sequence.

12. The photoresist of claim 11, wherein the sequence further comprises one or more of tyramine, tBOC, or t-butyl esters.

13. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein a length of the polypeptoid chain is approximately in a range from about 3 units to about 100 units.

14. The photoresist of claim 13, wherein a length of the polypeptoid chain is approximately in a range from about 3 units to about 29 units.

15. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the polypeptoid chain comprises a plurality of units having different chemical structures, a first unit of the plurality of units being present in an amount approximately in a range from about 0% to about 100% with respect to the molecular weight of the chain, and an amount of the second unit approximately in a range from about 0% to about 100% with respect to the molecular weight of the chain.

16. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the polypeptoid chain comprises two or more of formulas (I)-(V).

17. The photoresist of claim 1, any other suitable claim, or any other suitable combination of claims, wherein the polypeptoid chain comprises formula (III) and one or more metal ions forming stable chelating bond(s) with formula III.

18. The photoresist of claim 17, any other suitable claim, or any other suitable combination of claims, wherein the metal ion is selected from a 2+ cation, a 3+ cation, or a 4+ cation.

19. The photoresist of claim 17, any other suitable claim, or any other suitable combination of claims, wherein the metal ion is selected from a Zn ion or an Sn ion.

20. A method of fabricating photoresists, comprising: synthesizing a first polypeptoid chain having a predetermined molecular structure by placing one or more compounds at a specific location along the first polypeptoid chain;exposing the first polypeptoid chain to ultraviolet (EUV) light or electron beam (e-beam) light; intrinsically patterning the photoresist under extreme ultraviolet (EUV) lithography or electron beam (e-beam) lithography; removing a region of the photoresist that is not exposed to EUV or e-beam; and developing the photoresist in an aqueous base developer, wherein the photoresist is negative-tone when exposed to EUV or e-beam light.

21. The method of claim 20, wherein the defined molecular structure comprises one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5, preferably 1-3, or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is one or more of a hydrogen atom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, a methoxy group, and a tert-butyl group,formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, or any combination thereof, and wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OHlinked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal,formula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and formula, wherein L5 a linker selected from an alkyl linker (e g. -(CH2)X- , x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together.

22. The method of claim 21, any other suitable claim, or any other suitable combination of claims, wherein R2 is selected from an alkyl group, preferably a branched alkyl group (e.g. isopropyl group or te / 7-butyl group), or a hydrogen atom (-H).

23. The photoresist of claim 21, any other suitable claim, or any other suitable combination of claims, wherein R2 is selected from a hydroxyl group, a thiol group, or a methoxy group.

24. The method of claim 21, any other suitable claim, or any other suitable combination of claims, wherein intrinsically patterning the photoresist further comprises reacting the one or more compounds under EUV or e-beam lithography, the one or more compounds comprising of a carboxylic acid or an amide.

25. The method of claim 20, any other suitable claim, or any other suitable combination of claims, wherein synthesizing the first polypeptoid chain having a predetermined molecular structure further comprises predetermining one or more of a molecular weight, composition, or sequence of the first polypeptoid chain.

26. The method of claim 20, any other suitable claim, or any other suitable combination of claims, wherein the one or more compounds further comprise one or more of tyramine, tBOC, or t-butyl esters.

27. The method of claim 20, any other suitable claim, or any other suitable combination of claims, wherein synthesizing the first polypeptoid chain further comprises solid-phase submonomer synthesis.

28. The method of claim 20, any other suitable claim, or any other suitable combination of claims, further comprising purifying the photoresist with high- performance liquid chromatography (HPLC).

29. The method of claim 20, any other suitable claim, or any other suitable combination of claims, wherein the EUV radiation has a dose from about 1 mJ / cmA2 to about 150 mJ / cmA2 or the e-beam radiation has a dose from about 1 pC / cmA2 to about 1000 pC / cmA2.

30. The method of claim 20, any other suitable claim, or any other suitable combination of claims, further comprising developing the photoresist in a dilute aqueous base solution.

31. The method of claim 20, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is composed of metal free, organic peptoids.

32. The method of claim 20, any other suitable claim, or any other suitable combination of claims, further comprising synthesizing a second polypeptoid chain that has substantially the same predetermined molecular structure as the first polypeptoid chain.

33. A photoresist composition, comprising: a polypeptoid chain of a defined molecular structure having one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), and wherein n is selected from 1-5, preferably 1-3, or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e.g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is selected from one or more of a hydrogen atom, a carboxylic acid group, a thiol group, a hydroxyl group, a carbon atom, and a methoxy group, except for a zc / 7-butyl group,formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, or any combination thereof, wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OHlinked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal, andformula IV : , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together, formula, wherein L5 a linker selected from an alkyl linker (e g. -(CH2)X-, x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring).

34. The photoresist of claim 33, any other suitable claim, or any other suitable combination of claims, wherein R2 is selected from an alkyl group, preferably a branched alkyl group (e.g. isopropyl group), or a hydrogen atom (-H).

35. The photoresist of claim 33, any other suitable claim, or any other suitable combination of claims, wherein R2 is selected from a hydroxyl group, a thiol group, or a methoxy group.

36. The photoresist of claim 33, any other suitable claim, or any other suitable combination of claims, wherein the polypeptide chain further comprises a chain end group that includes one or more of a carboxylic acid or an amide.

37. The photoresist of claim 33, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is sufficiently devoid of photoacid generators (PAGs).

38. The photoresist of claim 33, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is negative-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

39. The photoresist of claim 33, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is positive-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

40. A photoresist composition, comprising: a polypeptoid chain of a defined molecular structure having one or more of:formula (I): , wherein LI is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), wherein Al is an aromatic or heteroaromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds or fused together, or their derivatives with one or more carbons in the ring(s) substituted with N, wherein R1 is selected from H or an alkyl group (e.g. methyl group), andwherein n is selected from 1-5, preferably 1-3, or 1,formula (II): , wherein L2 or L is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, an aryl or heteroaryl linker (e.g. a phenyl group or a phenol linker group), or any combinations thereof (e g. a combination of an alkyl linker like -CH2- or -C2H4-, an aryl linker like a phenyl or phenol linker, and an -COO- linker, and optionally an -O- linker, wherein L2 can be a complex linker that includes the combination of two or more linker groups described above, and wherein R2 is a hydrogen atom (-H),formula III: , wherein L3 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), -O-, -COO-, or any combination thereof, wherein A3 is selected from a heteroaromatic group, comprising at least one N in the heteroaromatic ring(s) and / or at least one hydroxyl group -OH linked to the same or an adjacent aromatic or heteroaromatic ring(s), configured to form one or more stable chelating bond(s) with a metal, andformula IV: , wherein L4 is a linker selected from an alkyl linker (e.g. -(CH2)X- , x is 1 to 10, preferably 1-4), and wherein A4 is selected from an alkyl group or an aromatic ring(s) selected from phenyl ring, polycyclic aryl having 2 or 3 phenyl rings bonded to each other by single bonds, alkyl linkers, or fused together, formula, wherein L5 a linker selected from an alkyl linker (e.g. -(CH2)X-, x is 1 to 10, preferably 1-4), and A5 is selected from a halogen-containing alkyl group (e.g. an iodine-containing alkyl group) or a halogen-containing aromatic group (e.g. an iodine-containing aromatic ring).

41. The photoresist of claim 40, any other suitable claim, or any other suitable combination of claims, wherein R2 further comprises a hydroxyl group, a thiol group, or a methoxy group.

42. The photoresist of claim 40, any other suitable claim, or any other suitable combination of claims, wherein the polypeptide chain further comprises a chain end group that includes one or more of a carboxylic acid or an amide.

43. The photoresist of claim 40, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is sufficiently devoid of photoacid generators (PAGs).

44. The photoresist of claim 40, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is negative-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

45. The photoresist of claim 44, any other suitable claim, or any other suitable combination of claims, wherein R2 further comprises an alkyl group, preferably a branched alkyl group (e.g. isopropyl group or Zc’ / V-butyl group).

46. The photoresist of claim 40, any other suitable claim, or any other suitable combination of claims, wherein the photoresist is positive-tone when exposed to an ultraviolet (EUV) light or an electron beam (e-beam) light.

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