PRIORITY CLAIM

This application claims the benefit of the filing date of United States Patent Application Serial No. 14/677,445, filed April 2, 2015, for "METHODS OF FORMING NANOSTRUCTURES USING SELF-ASSEMBLED NUCLEIC ACIDS, AND

NANOSTRUCTURES THEREOF."

FIELD

The present disclosure, in various embodiments, relates generally to methods of forming nanostructures using self-assembly of nucleic acids.

BACKGROUND

A continuing goal of integrated circuit fabrication is to decrease the dimensions thereof. Integrated circuit dimensions can be decreased by reducing the dimensions and spacing of the constituent features or structures. For example, by decreasing the dimensions and spacing of semiconductor features (e.g., storage capacitors, access transistors, access lines) of a memory device, the overall dimensions of the memory device may be decreased while maintaining or increasing the storage capacity of the memory device.

As the dimensions and spacing of semiconductor device features become smaller, conventional lithographic processes for forming the semiconductor device features become increasingly more difficult and expensive to conduct. Therefore, significant challenges are encountered in the fabrication of nanostructures, particularly structures having a feature dimension (e.g., critical dimension) less than a resolution limit of conventional photolithography techniques (currently about 40 nm). It is possible to fabricate semiconductor structures with such feature dimensions using a costly pitch division or double patterning technologies. However, use of such processes is limited because the exposure tools are extremely expensive or extremely slow and, further, may not be amenable to formation of structures having dimensions of less than 20 nm.

The development of new processes, as well as materials useful in such processes, is of increasing importance to make the fabrication of small-scale devices easier, less expensive, and more versatile. One example of a method of fabricating small-scale devices that addresses some of the drawbacks of conventional lithographic techniques is directed self-assembly (DSA) of phase separated block copolymers.

Although DSA block copolymer is useful for fabrication of semiconductor structures having dimensions of less than 40 run, the self-assembled block copolymer materials are generally restricted to periodic patterns and may not produce nanostructures exhibiting sufficiently low defect levels.

Self-assembled nucleic acids have been investigated for forming semiconductor devices. The specificity of complementary base pairing in nucleic acids provides self-assembled nucleic acids that may be used for self-assembled nucleic acid lithography processes.

U.S. Patent 8,501,923 discloses a self-assembled DNA origami structure. The DNA origami structure is formed from structural units, wherein each structural unit comprises a single stranded polynucleotide scaffold and a plurality of helper/staple strands. The helper/staple strands are designed to be at least partially complementary to the single stranded polynucleotide scaffold such that the helper/staple strands self-anneal with the single stranded polynucleotide scaffold into a structural unit. The DNA origami structure may have dimensions of 100-200 nm with a resolution of 6 nm.

Arbitrary two-dimensional (2D) patterns of self-assembled nucleic acids have been reported in Wei et al., "Complex shapes self-assembled from single stranded DNA tiles," Nature 485 (2012), 623-627. The arbitrary 2D patterns are created using self-assembled DNA molecular canvases that are formed from DNA subunits. The DNA subunit has dimension s of less than 10 nm The DNA subunit may be a single strand DNA having dimension of 3 nm The self-assembled DNA molecular canvas may have dimensions of 200 nm

Surwade et al. disclose a method of forming custom-shaped inorganic oxide nanostructures by using self-assembled DNA-nanostructure templates. Surwade et al., "Nanoscale Growth and Patterning of Inorganic Oxides Using DNA Nanostructure Templates," J. Am. Chem. Soc. 135 (2013), 6778-6781. The self-assembled DNA nanostructure is deposited on a substrate without registration, and then used as a template for a selective deposition of inorganic oxide material to provide an inorganic oxide nanostructure. The inorganic oxide nanostructure may be used as a hard mask for etching the substrate. Kershner et al. disclose the placement and orientation of individual self-assembled DNA structures on a lithographically patterned substrate. Kershner et al., "Placement and orientation of individual DNA shapes on lithographically patterned surfaces," Nature Nanotechnology 4 (2009), 557-561. DNA origami, in which a long single strand of DNA is folded into a shape using shorter "staple strands," is used as the self-assembled DNA structure. Electron beam lithography and dry oxidative etching are used to create DNA origami-shaped binding sites on the materials such as silicon dioxide (Si0 ₂ ) and diamond-like carbon (DLC). BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows top views of stages of forming a directed self-assembly of multiple DNA structures on a patterned substrate according to one embodiment of the present disclosure;

FIG. 2 shows a directed self-assembly of multiple isotropic DNA structures according to one embodiment of the present disclosure;

FIG. 3 shows a directed self-assembly of multiple anisotropic DNA structures according to one embodiment of the present disclosure;

FIG. 4 shows a directed self-assembly of multiple anisotropic DNA structures according to another embodiment of the present disclosure;

FIG. 5a is a top view of functionalized DNA structure;

FIG. 5b is a cross-sectional view of functionalized DNA structure;

FIG. 6 shows a semiconductor structure comprising a substrate, a sacrificial pattern material, and spacers;

FIG. 7 shows a patterned substrate comprising a substrate and functionalized spacers; and

FIG. 8 shows a semiconductor structure comprising a substrate, functionalized spacers, and a functionalized DNA structure.

MODE(S) FOR CARRYING OUT THE INVENTION The following description provides specific details, such as material types, material thicknesses, and processing conditions in order to provide a thorough description of embodiments of the disclosure. However, a person of ordinary skill in the art will understand that embodiments of the present disclosure may be practiced without employing these specific details. Indeed, the embodiments of the present disclosure may be practiced in conjunction with conventional fabrication techniques employed in the industry.

In addition, the description provided herein does not form a complete process flow for forming nanostructures. Only those process acts and structures necessary to understand the embodiments of the present disclosure are described in detail below. Additional acts to form the complete nanostructures may be performed by conventional fabrication techniques. Also the drawings accompanying the application are for illustrative purposes only, and are thus not necessarily drawn to scale. Elements common between figures may retain the same numerical designation. Furthermore, while the materials described and illustrated herein may be formed as layers, the materials are not limited thereto and may be formed in other three-dimensional configurations.

As used herein, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

As used herein, the term "substrate" means and includes a base material or construction upon which additional materials are formed. The substrate may be, for example, a semiconductor substrate, a base semiconductor material on a supporting structure, a metal electrode or a semiconductor substrate having one or more materials, structures or regions formed thereon. The substrate may be a conventional silicon substrate, or other bulk substrate comprising a layer of semiconductive material. As used herein, the term "bulk substrate" means and includes not only silicon wafers, but also silicon-on-insulator (SOI) substrates, such as silicon-on-sapphire (SOS) substrates and silicon-on-glass (SOG) substrates, epitaxial layers of silicon on a base semiconductor foundation, or other semiconductor or optoelectronic materials, such as silicon-germanium (Sii-xGex, where x is, for example, a mole fraction between 0.2 and 0.8), germanium (Ge), gallium arsenide (GaAs), gallium nitride (GaN), or indium phosphide (InP), among others. Furthermore, when reference is made to a "substrate" in the following description, previous process acts may have been conducted to form materials, regions, or junctions in the base semiconductor structure or foundation. In one embodiment, the substrate is a

silicon-containing material, such as a silicon substrate. The substrate may be doped or undoped.

As used herein, the term "nucleic acid" means and includes a polymeric form of nucleotides (e.g., polynucleotides and oligonucleotides) of any length that comprises purine and pyrimidine bases, or chemically or biochemically modified purine and pyrimidine bases. Nucleic acids may comprise single stranded sequences, double stranded sequences, or portions of both double stranded or single stranded sequences. As non-limiting examples, the nucleic acid may include ribonucleic acid (RNA), deoxyribonucleic acid (DNA), peptide nucleic acid (PNA), or combinations thereof. The backbone of the polynucleotide may comprise sugars and phosphate groups as may typically be found in RNA or DNA, or modified sugar and/or phosphate groups. Furthermore, the

polynucleotide may comprise modified nucleotides, such as methylated nucleotides and nucleotide analogs.

Disclosed embodiments relate generally to nanostructures comprising directed self-assemblies of nucleic acid structures on a patterned substrate, and to methods of forming the nanostructures. In some embodiments, the nucleic acid structure may be DNA structure. Non-limiting examples of such DNA structure may include those described in

Wei et al., supra, or the DNA origami structure disclosed in U.S. Patent 8,501,923. The patterned substrate comprises multiple regions. Upon bringing the nucleic acid structures into contact with the patterned substrate, the nucleic acid structures adsorb onto specific regions of the patterned substrate as directed by interactions between the nucleic acid structures and the patterned substrate to provide directed self-assembly of nucleic acid structures on the patterned substrate.

Accordingly, ananostructure comprises directed self-assembly of nucleic acid structures on a patterned substrate. The patterned substrate comprises regions, wherein each of the regions is configured to selectively adsorb one of the nucleic acid structures in the directed self-assembly.

As used herein, the term "directed self-assembly of multiple DNA structures" or

"DSA of multiple DNA structures" refers to a self-assembly of multiple DNA structures on the patterned substrate that is directed by interactions between the DNA structures and the patterned substrate to enable the selective adsorption of specific DNA structures to specific regions of the patterned substrate.

As shown in FIG. 1, DNA structure 100 may have different configurations, e.g.,

DNA structures A, B, C, D, E, F, G, H, I, L, M, and N. In some embodiments, the DNA structures 100 may be those DNA structures described in Wei et al., supra, that are composed of DNA subunits having dimensions of less man 10 nm In some embodiments, the DNA structures 100 may comprise the DNA origami disclosed in U.S. Patent 8,501,923 mat has dimensions of 100-200 nm As shown in FIG. 1, a patterned substrate 300 comprises patterned regions 310 of different configurations, e.g., patterned regions A', B', C, D', E, F, G', Η', Γ, L', M', and N'. The patterned substrate 300 is prepared by selectively patterning a substrate to create multiple regions 310, wherein each of the regions 310 is for a specific DNA structure. In some embodiments and as described in more detail below, the substrate is patterned to create regions that exhibit chemical specificity with the DNA structures. For example, the regions of the patterned substrate include chemical specificity for adsorbing the DNA structures, such as via Van der Waals, ionic and/or electrostatic interactions. In some embodiments, the substrate is patterned to create regions that have topological specificity with the DNA structures. For example, the regions of the patterned substrate have size and/or morphology corresponding to the size and/or morphology of the DNA structures. In some embodiments, the substrate is patterned to create regions that exhibit both chemical and topological specificity with the DNA structures. As shown in FIG. 1, the region A ¹ of the patterned substrate 300 corresponds in size and/or morphology to the size and/or morphology of the DNA structure A, and the region B' corresponds in size and/or morphology to the size and/or morphology of DNA structure B. Any conventional techniques may be used to pattern the substrate.

Accordingly, a method of forming a nanostructure comprises forming a directed self-assembly of nucleic acid structures on a patterned substrate. The patterned substrate comprises multiple regions. Each of the regions on the patterned substrate is specifically tailored for adsorption of specific nucleic acid structure in the directed self-assembly of nucleic acid structures.

In FIG. 2, a directed self-assembly 420 is formed from nine DNA structures 120 on a patterned substrate (not shown). As shown in FIG. 2, each of the DNA structures 120 has the same configuration, such as the same length and width with an opening 122 in the middle of the DNA structure 120. The dimensions of the opening 122 are at a

sublithographic scale. As with the embodiment described for FIG. 1, the patterned substrate may include regions that correspond in size and/or morphology to the size and/or morphology of the DNA structures 120. The DNA structure 120 is isotropic (i.e., the DNA structure has physical properties that are the same regardless of the direction of measurement). Since the DNA structures 120 are isotropic, the DSA 420 of DNA structures is not susceptible to orientational or sequential placement errors. Thus, each of the nine DNA structures 120 may adsorb to any region of the patterned substrate and neither orientational control nor sequential control is required for the formation of

DSA 420. Furthermore, the patterned substrate may include regions that correspond in size and/or shape of the array of the DNA structures 120.

By way of non-limiting example, in some embodiments, the nine isotropic DNA structures 120 may form a 3x3 array-DSA on the patterned substrate. Since each of the DNA structures 120 includes the opening 122, the DSA 420 of DNA structuresl20 may be used to create a contact hole pattern in a semiconductor device, with the holes having sublithographic dimensions. In some other embodiments, each of the DNA structures 120 includes plurality of openings at a sublithographic pitch. The DSA 420 of DNA structures 120 enables large array of sublithographic features or pillars at a sublithographic pitch.

In FIG. 3, a directed self-assembly is formed from nine anisotropic DNA structures 130 assembled into a 3x3 array on a patterned substrate (not shown). The arrow symbol on the DNA structures 130 indicates the required orientation of the structure containing the sublithographic pattern. As with the embodiment described for FIG. 1, the patterned substrate may include regions lhat correspond in size and/or morphology to the size and/or morphology of the DNA structures 130. The DNA structure 130 is anisotropic (i.e., the DNA structure has physical properties that differ based on the direction of measurement). Since the DNA structures 130 are anisotropic, the DSA of DNA structures 130 does not always provide a desired DSA unless orientational control is provided during the adsorption of the anisotropic DNA structures 130 to the patterned substrate. Without providing orientational control, the anisotropic DNA structures 130 may assemble into undesirable DSA 430A, where Ihe arrows pointing in different directions indicate orientation errors. With orientational control, the anisotropic DNA structures 130 may assemble into the desired DSA 430B, where the arrows pointing in same directions indicate the absence of orientation errors. By way of non-limited example, the nine anisotropic DNA structures 130 may form a 3x3 array-DSA on the patterned substrate. The DSA 430B may be used to create a sublithographic logic gate or interconnect patterns in semiconductor devices where sequence is not critical.

In FIG. 4, a directed self-assembly is formed from nine anisotropic DNA structures 140 assembled into a 3x3 array on a patterned substrate (not shown). The letter symbols on the DNA structures 140 indicate mat the sublithographic features to be transferred to the substrate require specific orientation and sequence control. The sublithographic features may include regular, periodic, patterns or irregular, i.e. sparse, patterns, corresponding to dense array features or peripheral routing, logic, interconnects, or contacts. As with the embodiment described for FIG. 1, the patterned substrate may include regions that correspond in size and/or morphology to the size and/or morphology of the DNA structures 140. Since the DNA structures 140 are anisotropic, the DSA of DNA structures 140 does not always provide a desired DSA unless orientational and sequential control is provided. If orientational control is provided but no sequential control is provided, the anisotropic DNA structures 140 may assemble into undesirable DSA 440A As shown, although all letters in the DSA 440A are in the desired upright orientation, the DSA 440A does not provide any discernible message. If sequential control is provided but no orientational control is provided, the anisotropic DNA structures 140 may assemble into undesirable DSA 440B. As shown, all letters in the DSA 440B are in the desired sequence. However, the DSA 440B does not provide any discernible message because some letters are not in the desirable upright orientation. When both orientational control and sequential control are provided, the anisotropic DNA structures 140 may assemble into the desired DSA 440C so that the message (e.g., "DNA DSA WIN") may be read. Thus, in the embodiment as shown in FIG. 4, both orientational control and sequential control are provided during assembling of DNA structures 140 to provide the directed

self-assembly 440C of multiple DNA structures with minimum orientational and sequential errors.

Accordingly, a nanostructure comprises directed self-assembly of DNA structures on a patterned substrate. The patterned substrate comprises regions, wherein each of the regions is configured to selectively adsorb a specific DNA structure in the directed self-assembly of DNA structures.

In some embodiments, the directed self-assembly of DNA structures is formed on the patterned substrate with an orientational control. In some embodiments, the directed self-assembly of DNA structures is formed on the patterned substrate with a sequential control. In some embodiments, the directed self-assembly of DNA structures is formed on the patterned substrate with both orientational and sequential controls.

Each of the regions on the patterned substrate corresponds to a DNA structure in the

DSA of multiple DNA structures. The selective adsorption of the specific DNA structure to the specific region on the patterned substrate is driven thermodynamically by an energy minimization of the resulting DSA of the multiple DNA structures. As described in more detail below, a specific DNA structure may adsorb to its corresponding region on the patterned substrate by achieving its lowest energy configuration. Adsorption between a specific DNA structure and its corresponding region of the patterned substrate may be energetically favorable, while adsorption between a specific DNA structure and other regions of the patterned substrate may be energetically unfavorable.

In some embodiments and as described in more detail below, the regions of the patterned substrate include chemical specificity for adsorbing to the DNA structures, such as via Van der Waals, ionic, and/or electrostatic interactions. In some embodiments, the regions of the patterned substrate include topological specificity to the DNA structures. In some embodiments, the regions of the patterned substrate include both topological and chemical specificity to the DNA structures.

FIGs. 5a, 5b, and 6-8 show various stages in the preparation of nanostructures according to some embodiments of the present disclosure.

FIGs. 5a and 5b show atop view and cross-sectional view, respectively, of a functionalized DNA structure 150. As shown, the functionalized DNA structure 150 comprises a DNA structure 1000 and multiple functional groups "A" on the DNA structure 1000. The functional groups "A" may include, but are not limited to, a phosphate linkage, a complementary RNA strand, a short DNA strand, or other reactive group. The DNA structure 1000 may include any of DNA structures 100, DNA structures 120, DNA structures 130, or DNA structures 140 as described above.

FIG. 6 shows a semiconductor structure 600 comprising a substrate 360, a sacrificial pattern material 610 on the substrate 360, and spacers 620. The sacrificial pattern material 610 and the spacers 620 may be formed on the substrate 360 by any conventional methods.

After removal of the sacrificial pattern material 610 from the semiconductor structure 600, the spacers 620 on the substrate 360 may be derivatized to include functional groups "B." The functional groups "B" have chemical specificity to the functional groups "A" of the functionalized DNA structure 150 in FIG. 5a or FIG. 5b.

As shown in FIG. 7, the patterned substrate 700 comprises the substrate 360 and functionalized spacers 670 protruding from the substrate 360. Each of the functionalized spacers 670 comprises a spacer 620 and multiple functional groups "B" on the spacer 620.

Upon contacting the functionalized DNA structure 150 with the patterned substrate 700, the chemical specificity between the functional groups "A" of the functionalized DNA structure 150 and the functional groups "B" on the functionalized spacers 670 of the patterned substrate 700 directs the selective absorption of the functionalized DNA structure 150 onto the specific region on the patterned substrate 700 to provide a semiconductor structure 800, as shown in FIG.8. Favorable interactions between the A and B functional groups may enable the functionalized DNA structure 150 to selectively adsorb onto the specific region on the patterned substrate 700.

Accordingly, a method of forming a nanostructure comprises patterning a substrate to create a patterned substrate and contacting the patterned substrate with DNA structures. The patterned substrate comprises regions. The method further comprises selectively adsorbing the DNA structures to a specific region on the patterned substrate to form a self-assembly of DNA structures on the patterned substrate.

The nanostructures of present disclosure may be used for fabrication of various semiconductor structures and devices. By way of non-limiting example, the

nanostructures, such as the DSA 400, the DSA 420, the DSA 430B, or the DSA 440C described in FIGs. 1-4, may be used to transfer the sublithographic features of the DNA structures 100, the DNA structures 120, the DNA structures 130, or the DNA

structures 140 into the substrate, such as for fabricating sublithographic feature devices, contacts, contact holes, interconnects, etc. In some embodiments, the DSA of DNA structures may be removed during further processing acts of the fabrication of

semiconductor structures and devices. In some embodiments, the DSA of DNA structures may remain during further processing acts of the fabrication.

The disclosed methods of forming nanostructures use the directed self-assembly of multiple DNA structures, and may provide the nanostructures having dimensions of less than 40 nm with reduced defect levels. Furthermore, the nanostructures may have any arbitrary structures depending on the designs of the DNA structures.

It is also understood that the directed self-assembly of DNA structures are used herein to exemplify the invention. The directed self-assembly of other nucleic acid structures may be used in the present disclosure, e.g., the directed self-assembly of RNA structures, the directed self-assembly of PNA structures, etc.

While the present disclosure is susceptible to various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and have been described in detail herein. However, the present disclosure is not intended to be limited to the particular forms disclosed. Rather, the present disclosure is to cover all modifications, equivalents, and alternatives falling within the scope of the present disclosure as defined by the following appended claims and their legal equivalents.