KR20210128344A - 2-dimensional polymer nanosheet and width, length, and height tunable method of preparing the same - Google Patents

Abstract

A semi-conductive two-dimensional (2D) nanomaterial obtained by the self-assembly of a conjugated polymer is a promising material in the optoelectronic applications. However, there has been no example of a 2D nanosheet capable of controlling the length and aspect ratio at the same time through self-assembly. The present invention provides a uniform semi-conductive 2D sheet by blending and heating a conjugated poly(cyclopentenylenevinylene) homopolymer and a block copolymer thereof. In addition, the homopolymer is used as a 2D seed and added as a unimer to accomplish living crystallization-driven self-assembly (CDSA). It is interesting that the homopolymer is assembled in only one direction, unlike conventional 2D CDSA examples. Due to such uniaxial growth, the length of the 2D nanosheet can be adjusted precisely with a narrow degree of dispersion according to the unimer-to-seed ratio. In addition, after studying the growth dynamics of the living 2D CDSA, it is shown to be linear dynamics. The present invention further provides various 2D block comicelles (BCM) including penta-BCM through a one-shot process.

Description

Two-dimensional polymer nanosheet and its width, length, and height-adjustable manufacturing method {2-DIMENSIONAL POLYMER NANOSHEET AND WIDTH, LENGTH, AND HEIGHT TUNABLE METHOD OF PREPARING THE SAME}

The present application relates to a two-dimensional polymer nanosheet and a manufacturing method capable of adjusting the width, length, and height thereof.

Two-dimensional (2D) organic nanostructures based on soft materials, especially conjugated 2D materials such as graphene, have unique properties based on their ultra-thin and flat shapes, which have potential applications as electron transport platforms. has been noticed Self-assembly of semi-crystalline polymers is one of the efficient bottom-up approaches for synthesizing these synthetic 2D nanostructures. By self-assembly of a block copolymer (BCP) containing a semi-crystalline polymer and a soluble shell block, he succeeded in synthesizing 2D nanostructures of various shapes such as rectangles, hexagons, diamonds, and squares. Semi-crystalline conjugated polymers such as P3HT, PPV, and PF have also been utilized as conjugated 2D materials with various applications such as sensors, imaging agents, light emitting diodes, and photovoltaic cells.

For higher applicability of these 2D polymer materials, it is essential to control the shape and size of the structure, and accordingly, strategies for diversifying the shape of nanostructures as well as strategies for controlling the size and shape have been actively developed. From simple strategies such as heating and blending with semi-crystalline homopolymers to crystallization-driven self-assembly (CDSA) strategies including seeded-growth and self-seeding, strategies have been developed. It was utilized for the synthesis of uniform 2D nanostructures. However, in conventional polymer self-assembly, unlike the self-assembly of inorganic or organic planar molecules, the core-block forms a lamellae arrangement through chain-folding of crystalline polymers and grows radially. Therefore, fine control of each length other than the aspect ratio of the 2D nanostructure is limited. In addition, in the case of a conjugated 2D material, there is a limitation in that the strong π-π (pi-pi) interaction of the conjugated polymer lowers the solubility of the 2D nanostructure, resulting in irregular aggregation. In order to solve this problem, so far, conductive 2D polymer nanostructures have been synthesized from the self-assembly of BCP in which a soluble shell block is introduced into a conjugated core block. It was difficult to precisely control the length through the introduction of the growth method.

As such, it has succeeded in forming various 2D nanostructures through a high level of overall control, but on the other hand, the understanding of the two-dimensional crystallization process in solution is still insufficient. Understanding the crystallization process is very important because it will enable the prediction of novel 2D nanostructures through various polymer designs. Regarding the one-dimensional crystallization process, growth kinetic studies have been reported in earnest based on the living CDSA of PFS-b-PDMS BCP. It has a chain conformational effect and is inevitably different from analogous living polymerization or monomolecular assembly growth kinetics. On the other hand, self-assembly of homopolymers, which are easy to synthesize, is the simplest method to form nanostructures and is a suitable tool for 2D growth kinetics studies. Recently, a 2D self-assembly strategy of homopolymers introduced with charged-groups, led by Manners group, has been developed, and it has been revealed that the shape of 2D nanostructures is determined by the relative difference in the growth rate with respect to the crystallographic direction. Growth kinetics have not yet been studied.

Korean Patent Laid-Open Publication No. 10-2013-0036856.

The present application relates to a two-dimensional polymer nanosheet and a manufacturing method capable of adjusting the width, length, and height thereof.

However, the problems to be solved by the present application are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

A first aspect of the present application, a block copolymer represented by the following Chemical Formula 1 or Chemical Formula 2; And it provides a two-dimensional polymer nanosheet comprising a homopolymer represented by the following formula 3:

[Formula 1]

;

;

[Formula 2]

;

;

[Formula 3]

;

;

In Formula 1, Formula 2 and Formula 3,

R ¹ to R ³ are each independently, a substituted or unsubstituted linear or branched C _1-8 alkyl group,

When ^{one or more of R 1} to R ³ is substituted, it is substituted with -SiR ^a R ^b R ^c ,

R ^a , R ^b and R ^c are each independently a linear or branched C _1-4 alkyl group,

m and o are each independently an integer of 20 to 70,

n and p are each independently an integer of 5 to 70,

q is an integer from 5 to 70;

A second aspect of the present application is to obtain a two-dimensional seed by mixing (a) a block copolymer represented by the following Chemical Formula 1 or Chemical Formula 2 and a homopolymer represented by the following Chemical Formula 3; and (b) adding a unimer including a homopolymer represented by the following Chemical Formula 3 to the two-dimensional seed to obtain a two-dimensional polymer nanosheet, the method for producing a two-dimensional polymer nanosheet according to the first aspect provides:

[Formula 1]

;

;

[Formula 2]

;

;

[Formula 3]

;

;

In Formula 1, Formula 2 and Formula 3,

R ¹ to R ³ are each independently, a substituted or unsubstituted linear or branched C _1-8 alkyl group,

When ^{one or more of R 1} to R ³ is substituted, it is substituted with -SiR ^a R ^b R ^c ,

R ^a , R ^b and R ^c are each independently a linear or branched C _1-4 alkyl group,

m and o are each independently an integer of 20 to 70,

n and p are each independently an integer of 5 to 70,

q is an integer from 5 to 70;

A third aspect of the present application provides a device comprising the two-dimensional polymer nanosheet according to the first aspect.

According to embodiments herein, the successful formation of uniform semiconductor 2D nanosheets without lamination using a blending strategy. Living 2D CDSA by the seed-growth mechanism was possible by adding the homopolymer as the unimer to the initial 2D seed formed by the manufacturing method. Interestingly, the homopolymer was uniaxially assembled to the 2D seed to form 2D nanorectangles with sharp edges with controlled length and area. A kinetic study of uniaxial growth of 2D assemblies based on real-time imaging of living CDSAs confirmed that it obeys the first-order rate law that precisely follows the living polymerization-like kinetics. In addition, it succeeded in forming a complex and diversified block comicelle (BCM) structure using unimers of various molecular weights.

According to the embodiments of the present application, in the process of forming the 2D seed, a second solvent (co-solvent) different from the first solvent is added to form the 2D seed according to the addition ratio of the second solvent. The width and/or length can be adjusted. In addition, according to the U/S (unimer to seed) ratio of the unimer, the length of the finally formed 2D nanosheet can be adjusted. Finally, depending on the molecular weight of the unimer, it is possible to form block comicelles of various heights.

According to an example of the present application, FIG. 1A is a TEM image of a uniform 2D seed produced by a heating and aging method _{of P1 50} -b-P2 ₂₂ and P2 _{22 homopolymers in a 2: 1 mixing ratio (the values in the images are the average} width (W _n ), length (L _n ) and scatter plots), and Fig. 1b is the HR- of a single 2D seed showing the three main d-spacings of 10.3 Å, 18.5 Å and 16.1 Å and the corresponding (hkl) plane. FFT patterns obtained from TEM images, Fig. 1c is a schematic diagram of a 2D seed and its proposed detailed structure, showing its crystalline array and observed crystal growth rate. Also, FIG. 1D is an AFM image of a 2D seed, and FIG. 1E shows a height profile along a white line in the AFM image.
2A shows TEM images of controlled length and area 2D rectangles with U/S ratios of 2, 3, 5, 10 and 15, respectively [numbers in images represent average area (A _n ) and variance], and FIGS. 2B and 2C are plots showing the linear dependence of area (An) and mean length (Ln) in the (010) direction according to the U/S ratio, respectively, demonstrating the living 2D CDSA. . _{In addition, FIG. 2D is a DLS profile showing an increase in D h} according to a U/S ratio from 2 to 15 after 3 weeks of aging, and FIG. 2E is a 2D rectangle prepared with a U/S ratio of 3, 10, and 15, respectively. AFM images and height profile showing the height difference of a 2D rectangle with a U/S ratio of 15 (7.8 nm of the newly formed 2D sheet vs. 14.4 nm of the original 2D seed), Figure 2f is a single axis along the (010) direction. As a schematic diagram of a living 2D CDSA through (uniaxial) seed-growth, the 2D schematic diagram of the prepared 2D rectangle is based on the interdigitating slip-stack packing model of P2 homopolymer with a simplified structure in the ab plane. do it with
In the examples herein, FIGS. 3A and 3B are plots (monitored for 3 weeks) and primary plots showing _{the length (L n} ) of a 2D rectangle over time at various U/S ratios from 2 to 15, respectively. A plot showing the initial reaction rate versus unimer concentration [U] confirming the kinetics. 3c and 3d are Eyring plots for rate constant k' extracted from seed-growth experiments at various temperatures, respectively, and Ln (L _final - L) from primary growth of various unimers with different DPs at 25°C. (time)) versus time.
In the example of the present application, FIG. 4a is a scheme for a method for producing a complex 2D BCM by sequential addition of _{two unimers (P2 10} and P2 _{15 ). By changing the order of addition of unimers, two} A symmetrical penta-BCM of the type was obtained. Figures 4b, 4c, and 4d are TEM images, electron density profiles, and 2D and 3D height AFM images of penta-BCM showing the clear difference between the two types of penta-BCM prepared by the sequential addition, respectively. In addition, FIG. 4e is a scheme for preparing one 2D BCM by one-shot addition of two unimers, and FIG. 4f is a TEM image and electron density of penta-BCM obtained with one-shot living CDSA. profile [numbers in image indicate mean length (L _n ) and variance].
5 is a schematic diagram of a method for controlling the width of a 2D nanosheet according to the addition of a cosolvent, according to an embodiment of the present application.
6A to 6G are TEM images of 2D nanosheets, each of which length and width are variously adjusted, according to an embodiment of the present application.
7A to 7L are AFM images and profiles of 2D nanosheets with various lengths and widths, respectively, according to an embodiment of the present application.
8a to 8e, according to an embodiment of the present application, DLS analysis, UV-vis absorption analysis, changes in width and length according to the ratio of the co-solvent, according to the ratio of the co-solvent for the structure of each 2D nanosheet This is the analysis result of the change in aspect ratio according to the change in area and the ratio of co-solvent.
9a to 9e are TEM images of 2D nanosheets obtained by adjusting the length to 1.9 μm to 4.2 μm according to the U/S ratio for 2D seeds each having a width of 910 nm in an embodiment of the present application. In addition, Figures 9f and 9g, in an embodiment of the present application, for a 2D seed having a width of 910 nm, respectively, U / of a 2D nanosheet obtained by adjusting the length to 1.9 μm to 4.2 μm according to the U / S ratio _{It is a plot showing the change of L n} in the (010) direction according to the S ratio for 67 hours of aging, or 45 hours and 67 hours of aging.
10a to 10e are TEM images of 2D nanosheets obtained by adjusting the length to 3.3 μm to 5.3 μm according to the U/S ratio for 2D seeds each having a width of 850 nm in an embodiment of the present application. In addition, Figure 10f, in one embodiment of the present application, the U / S ratio of the 2D nanosheet obtained by adjusting the length to 3.3 μm to 5.3 μm according to the U / S ratio with respect to the 2D seeds each having a width of 850 nm A plot showing the change in _{L n} in the (010) direction according to
11A to 11C are TEM images of 2D nanosheets obtained by adjusting the length to 5.1 μm to 8.0 μm according to the U/S ratio for 2D seeds each having a width of 650 nm, and It is a plot showing the change _{of L n} in the (010) direction according to the U/S ratio. Figure 11d, according to the U / S ratio of the 2D nanosheet obtained by adjusting the length to 5.1 μm to 8.0 μm according to the U / S ratio for the 2D seeds each having a width of 650 nm in an embodiment of the present application It is a plot showing _{L n} change in (010) direction _{and W n} change in (100) direction.
12A to 12E are TEM images of 2D nanosheets obtained by adjusting the length to 1.7 μm to 4.9 μm according to the U/S ratio for 2D seeds each having a width of 510 nm in an embodiment of the present application. In addition, Figure 12f, in one embodiment of the present application, the U / S ratio of the 2D nanosheet obtained by adjusting the length to 1.7 μm to 4.9 μm according to the U / S ratio with respect to the 2D seeds each having a width of 510 nm A plot showing the change in _{L n} in the (010) direction according to
13 is a schematic diagram illustrating a 2D nanosheet with an additionally adjusted length based on a 2D seed whose width and length are adjusted according to an embodiment of the present application.

Hereinafter, embodiments and examples of the present invention will be described in detail with reference to the accompanying drawings so that those of ordinary skill in the art to which the present invention pertains can easily carry out. However, the present application may be embodied in several different forms and is not limited to the embodiments and examples described herein. And in order to clearly explain the present invention in the drawings, parts irrelevant to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification.

Throughout this specification, when a part is said to be "connected" with another part, it includes not only the case where it is "directly connected" but also the case where it is "electrically connected" with another element interposed therebetween. do.

Throughout this specification, when a member is said to be “on” another member, this includes not only a case in which a member is in contact with another member but also a case in which another member is present between the two members.

Throughout this specification, when a part "includes" a certain component, it means that other components may be further included, rather than excluding other components, unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used in a sense at or close to the numerical value when the manufacturing and material tolerances inherent in the stated meaning are presented, and to aid in the understanding of the present application. It is used to prevent an unconscionable infringer from using the mentioned disclosure in an unreasonable manner.

As used throughout this specification, the term “step of doing” or “step of” does not mean “step for”.

Throughout this specification, the term "combination(s)" included in the expression of the Markush form means one or more mixtures or combinations selected from the group consisting of the components described in the expression of the Markush form, It means to include one or more selected from the group consisting of the above components.

Throughout this specification, reference to “A and/or B” means “A or B, or A and B”.

Throughout this specification, the term "alkyl" or "alkyl group" refers to a linear or branched alkyl group having 1 to 12 carbon atoms, 1 to 10 carbon atoms, 1 to 8 carbon atoms, or 1 to 5 carbon atoms. and all possible isomers thereof. For example, the alkyl or alkyl group is a methyl group (Me), an ethyl group (Et), an n-propyl group ( ⁿ Pr), an iso-propyl group ( ⁱ Pr), an n-butyl group ( ⁿ Bu), an iso-butyl group ( ⁱ Bu), tert-butyl group (tert-Bu, ^t Bu), sec-butyl group (sec-Bu, ^sec Bu), n-pentyl group ( ⁿ Pe), iso-pentyl group ( ^iso Pe), sec -pentyl group ( ^sec Pe), tert-pentyl group ( ^t Pe), ^neo- pentyl group ( neo Pe), 3-pentyl group, n-hexyl group, iso-hexyl group, heptyl group, 4,4-dimethylphen a tyl group, an octyl group, a 2,2,4-trimethylpentyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and isomers thereof, but may not be limited thereto.

Hereinafter, embodiments of the present application have been described in detail, but the present application may not be limited thereto.

A first aspect of the present application, a block copolymer represented by the following Chemical Formula 1 or Chemical Formula 2; And it provides a two-dimensional polymer nanosheet comprising a homopolymer represented by the following formula 3:

[Formula 1]

;

;

[Formula 2]

;

;

[Formula 3]

;

;

In Formula 1, Formula 2, and Formula 3, R ¹ to R ³ are each independently a substituted or unsubstituted linear or branched C _1-8 alkyl group, and at least one of ^{R 1} to R ³ When substituted, it is substituted with -SiR ^a R ^b R ^c , R ^a , R ^b and R ^c are each independently a linear or branched C _1-4 alkyl group, m and o are each independently, an integer from 20 to 70, n and p are each independently an integer from 5 to 70, and q is an integer from 5 to 70.

In one embodiment of the present application, R ¹ and R ³ are each independently, a substituted or unsubstituted, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso -Butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, 3-pentyl group, iso-pentyl group, tert-pentyl group, neo-pentyl group, sec-isopentyl group, 2-methylbutyl group , n-hexyl group, sec-hexyl group, 3-hexyl group, iso-hexyl group, tert-hexyl group, sec-isohexyl group, 3-isohexyl group, 2-methylpentyl group, 3,3-dimethyl Butyl group, 3-ethylbutyl group, 2,2-dimethylbutyl group, n-heptyl group, iso-heptyl group, neo-heptyl group, tert-heptyl group, sec-heptyl group, n-octyl group, iso- It may be an octyl group or a 2-ethylhexyl group, but may not be limited thereto. In one embodiment of the present application, R ¹ and R ³ are, each independently, a methyl group, an ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, n- pentyl group, sec-pentyl group, 3-pentyl group, iso-pentyl group, tert-pentyl group, neo-pentyl group, sec-isopentyl group, 2-methylbutyl group, or n-hexyl group.

In one embodiment of the present application, R ² is a substituted or unsubstituted, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec-pentyl group, 3-pentyl group, iso-pentyl group, tert-pentyl group, neo-pentyl group, sec-isopentyl group, 2-methylbutyl group, n-hexyl group, sec -Hexyl group, 3-hexyl group, iso-hexyl group, tert-hexyl group, sec-isohexyl group, 3-isohexyl group, 2-methylpentyl group, 3,3-dimethylbutyl group, 3-ethylbutyl group group, or a 2,2-dimethylbutyl group, but may not be limited thereto. In one embodiment of the present application, R ² may be a 3,3-dimethylbutyl group or a trimethylsilylethyl group.

In one embodiment of the present application, the -SiR ^a R ^b R ^c is -SiMe ₃ , -SiEt ₃ , -SiPr ₃ , -SiBu ₃ , -SiEtMe ₂ , -SiEt ₂ Me, -SiMe ₂ Pr, -SiMePr ₂ , -SiBuMe ₂ , -SiBu ₂ Me, -SiEt ₂ Pr, -SiEtPr ₂ , -SiBuEt ₂ , -SiBu ₂ Et, -SiBuPr ₂ , or -SiBu ₂ Pr.

In one embodiment of the present application, the width 100 of the two-dimensional polymer nanosheet may be about 100 nm to about 10 μm, but may not be limited thereto. For example, the width 100 of the two-dimensional polymer nanosheet is about 100 nm to about 10 μm, about 100 nm to about 5 μm, about 100 nm to about 1 μm, about 100 nm to about 900 nm, about 100 nm to about 800 nm, about 100 nm to about 700 nm, about 100 nm to about 600 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm, about 200 nm to about 10 μm, about 200 nm to about 5 μm, about 200 nm to about 1 μm, about 200 nm to about 900 nm, about 200 nm to about 800 nm, about 200 nm to about 700 nm, about 200 nm to about 600 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm, about 300 nm to about 10 μm, about 300 nm to about 5 μm, about 300 nm to about 1 μm, about 300 nm to about 900 nm, about 300 nm to about 800 nm, about 300 nm to about 700 nm, about 300 nm to about 600 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, about 400 nm to about 10 μm, about 400 nm to about 5 μm, about 400 nm to about 1 μm, about 400 nm to about 900 nm, about 400 nm to about 800 nm, about 400 nm to about 700 nm, about 400 nm to about 600 nm, about 400 nm to about 500 nm, about 500 nm to about 10 μm, about 500 nm to about 5 μm, about 500 nm to about 1 μm, about 500 nm to about 900 nm, about 500 nm to about 800 nm, about 500 nm to about 700 nm, about 500 nm to about 600 nm, about 600 nm to about 10 μm, about 600 nm to about 5 μm, about 600 nm to about 1 μm, about 600 nm to about 900 nm, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm to about 10 μm, about 700 nm to about 5 μm, about 700 nm to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 10 μm, about 800 nm to about 5 μm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, about 900 nm to about 10 μm, about 900 nm to about 5 μm, about 900 nm to about 1 μm, about 1 μm to about 10 μm , about 1 μm to about 5 μm, or about 5 μm to about 10 μm, but may not be limited thereto.

In one embodiment of the present application, the length 010 of the two-dimensional polymer nanosheet may be about 500 nm to about 20 μm, but may not be limited thereto. For example, the length 010 of the two-dimensional polymer nanosheet is about 500 nm to about 20 μm, about 500 nm to about 15 μm, about 500 nm to about 10 μm, about 500 nm to about 5 μm, about 500 nm to about 1 μm, about 500 nm to about 900 nm, about 500 nm to about 800 nm, about 500 nm to about 700 nm, about 500 nm to about 600 nm, about 600 nm to about 20 μm, about 600 nm to about 15 μm, about 600 nm to about 10 μm, about 600 nm to about 5 μm, about 600 nm to about 1 μm, about 600 nm to about 900 nm, about 600 nm to about 800 nm, about 600 nm to about 700 nm, about 700 nm to about 20 μm, about 700 nm to about 15 μm, about 700 nm to about 10 μm, about 700 nm to about 5 μm, about 700 nm to about 1 μm, about 700 nm to about 900 nm, about 700 nm to about 800 nm, about 800 nm to about 20 μm, about 800 nm to about 15 μm, about 800 nm to about 10 μm, about 800 nm to about 5 μm, about 800 nm to about 1 μm, about 800 nm to about 900 nm, about 900 nm to about 20 μm, about 900 nm to about 15 μm, about 900 nm to about 10 μm, about 900 nm to about 5 μm, about 900 nm to about 1 μm, about 1 μm to about 20 μm, about 1 μm to about 15 μm, about 1 μm to about 10 μm, about 1 μm to about 5 μm, about 5 μm to about 20 μm, about 5 μm to about 15 μm, about 5 μm to about 10 μm, about 10 μm to about 20 μm, about 10 μm to about 15 μm, or about 15 μm to about 20 μm, but may not be limited thereto.

In one embodiment of the present application, the height of the two-dimensional polymer nanosheet may be about 1 nm to about 500 nm, but may not be limited thereto. For example, the height of the two-dimensional polymer nanosheet is about 1 nm to about 500 nm, about 1 nm to about 400 nm, about 1 nm to about 300 nm, about 1 nm to about 200 nm, about 1 nm to about 100 nm, about 1 nm to about 50 nm, about 1 nm to about 10 nm, about 10 nm to about 500 nm, about 10 nm to about 400 nm, about 10 nm to about 300 nm, about 10 nm to about 200 nm, about 10 nm to about 100 nm, about 10 nm to about 50 nm, about 50 nm to about 500 nm, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, about 50 nm to about 100 nm, about 100 nm to about 500 nm, about 100 nm to about 400 nm, about 100 nm to about 300 nm, about 100 nm to about 200 nm, about 200 nm to about 500 nm, about 200 nm to about 400 nm, about 200 nm to about 300 nm, about 300 nm to about 500 nm, about 300 nm to about 400 nm, or 400 nm to about 500 nm, but may not be limited thereto.

In one embodiment of the present application, the two-dimensional polymer nanosheet may have conductivity and/or fluorescence.

A second aspect of the present application is to obtain a two-dimensional seed by mixing (a) a block copolymer represented by the following Chemical Formula 1 or Chemical Formula 2 and a homopolymer represented by the following Chemical Formula 3; and (b) adding a unimer including a homopolymer represented by the following Chemical Formula 3 to the two-dimensional seed to obtain a two-dimensional polymer nanosheet, the method for producing a two-dimensional polymer nanosheet according to the first aspect provides:

[Formula 1]

;

;

[Formula 2]

;

;

[Formula 3]

;

;

In Formula 1, Formula 2, and Formula 3, R ¹ to R ³ are each independently a substituted or unsubstituted linear or branched C _1-8 alkyl group, and at least one of ^{R 1} to R ³ When substituted, it is substituted with -SiR ^a R ^b R ^c , R ^a , R ^b and R ^c are each independently a linear or branched C _1-4 alkyl group, m and o are each independently, an integer from 20 to 70, n and p are each independently an integer from 5 to 70, and q is an integer from 5 to 70.

Although detailed descriptions of parts overlapping with the first aspect of the present application are omitted, the contents described with respect to the first aspect of the present application may be equally applied even if the description thereof is omitted in the second aspect of the present application.

In one embodiment of the present application, in (a), the two-dimensional seed may be formed by co-assembly of the block copolymer and the homopolymer.

In one embodiment of the present application, in (b), the two-dimensional polymer nanosheet may be formed by seed-growth.

In one embodiment of the present application, (a) is performed in the presence of a first solvent, and in (a), a second solvent different from the first solvent is added to adjust the width of the two-dimensional seed. Here, the first solvent is at least one selected from chloroform, dichloromethane, and tetrahydrofuran, and the second solvent is methyl chloride, dichloromethane (dichloromethane, DCM; or methylene chloride, methylene chloride, MC), chloroform , tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, and ortho- may be at least one selected from dichlorobenzene, but may not be limited thereto. In one embodiment of the present application, the first solvent may be chloroform, and the second solvent may be dichloromethane.

In one embodiment of the present application, the width of the two-dimensional seed may be adjusted according to the amount of the second solvent added. In particular, the width of the two-dimensional seed may be adjusted according to the volume ratio of the second solvent.

In one embodiment of the present application, in (b), the length of the two-dimensional polymer nanosheet may be adjusted according to the mass ratio of the unimer to the seed.

In one embodiment of the present application, in (b), the height of the two-dimensional polymer nanosheet may be adjusted according to the degree of polymerization of the unimer added. Here, two or more monomers having different degrees of polymerization may be added to form a block comicelle, but the present invention may not be limited thereto. For example, the penta-block comichel may be formed by adding the monomers having two different polymerization degrees.

In one embodiment of the present application, the two or more monomers having different degrees of polymerization may be added simultaneously or sequentially, but may not be limited thereto. Here, even if the unimers are added at the same time, since the seed-growth of one type of unimer occurs preferentially, a one-shot block comicelle can be formed.

In one embodiment of the present application, (a) and / or (b) may be to further include a heating step and / or aging step, but may not be limited thereto. In one embodiment of the present application, in (a), the block copolymer represented by Formula 1 or Formula 2 and the homopolymer represented by Formula 3 are mixed and heated, and then aged. In one embodiment of the present application, in (b), the two-dimensional seed may be aged by adding a unimer including the homopolymer represented by Chemical Formula 3 above.

A third aspect of the present application provides a device comprising the two-dimensional polymer nanosheet according to the first aspect.

Although detailed descriptions of parts overlapping with the first and second aspects of the present application are omitted, the descriptions of the first and second aspects of the present application are equally applicable even if the description is omitted in the third aspect of the present application. can

In one embodiment of the present application, the device may include and/or apply the two-dimensional polymer nanosheet of the present disclosure without limitation, as long as it is a device using electrical/thermal conductivity and/or fluorescence.

In one embodiment of the present application, the device may be, but is not limited to, a transistor, a sensor, an imaging agent, a light emitting diode, a photovoltaic cell, or a conductive display.

Hereinafter, the present application will be described in more detail using examples, but the following examples are only illustrative to help the understanding of the present application, and the content of the present application is not limited to the following examples.

[Example]

1. Common Substances and Polymers

Without further reference, all reagents were obtained from Sigma-Aldrich, Tokyo Chemical Industry Co. Ltd., Acros Organics, or Alfa Aesar® and used without further purification. A solvent for monomer synthesis is also commercially available, but was used for polymerization after further distillation under Ar (g). All reactions were performed under Ar (g) and monitored by thin layer chromatography performed on pre-coated plates (MERCK TLC silica gel 60, F254). For purification, flash column chromatography was performed using MERCK silica gel 60 (0.040 ~ 0.063 mm). For polymerization, a Grubbs 3rd generation (G3) catalyst was prepared according to a previously published method.

polymers

Sample block rate Mn (kDa) Ð P1 ₅₀ - b -P2 ₂₂ 50:22 38.6 1.10 P2 ₂₂ - 9.01 1.13 P2 ₁₀ - 4.98 1.15 P2 ₁₃ - 5.61 1.18 P2 ₁₅ - 6.05 1.13

2. Method

(1) polymerization process

A 4 mL screw cap vial with a septum was flame dried and filled with monomer and magnetic bar. The vial was purged 3 times with Ar (g) and degassed anhydrous THF was added (M1: monomer of P1, M2: monomer of P2, [M1] ₀ = 0.5 M or [M2] ₀ = 0.1 M). In another 4 mL vial, Ar (g) purged G3 catalyst was dissolved in 50 μL THF, and then the solution was rapidly injected into the monomer solution at 0° C. with vigorous stirring. After complete conversion of M1 to P1 (or M2 to P2 in the case of P2 homopolymer), a second monomer (M2) was added to the vial at 0 °C for block copolymer (BCP) formation ([M2 ] ₀ = 0.1 M). After the desired reaction time, the reaction was quenched with an excess of ethyl vinyl ether (EVE) and precipitated in methanol at room temperature. The obtained purple solid was filtered and dried in vacuo. The conversion of the monomer was calculated from ^{the 1 H NMR spectrum of the remaining crude mixture.}

(2) P1 ₅₀ - b -P2 ₂₂ and P2 ₂₂ Preparation of blends of

Each polymer (P1 ₅₀ -b -P2 ₂₂ and P2 ₂₂ ) was dissolved in 0.5 g/L chloroform (at least 0.5 mL in a 4 mL vial). _{Without aging, two solutions of various P1 50} -b -P2 ₂₂ and P2 ₂₂ with a ratio of 2 : 1 (or a molar ratio of 1 : 2) were mixed at room temperature.

(3) Preparation of 2D seeds from the blend by heating and aging

The blended solution was sealed with a Teflon line cap and heated at 50° C. for 1 hour, then cooled to 25° C. and aged for 3 days. The resulting 2D nanoparticles were observed by AFM and TEM imaging. Specifically, samples for TEM and AFM imaging were prepared by spin coating a drop of the 2D seed colloidal solution (about 0.05 mL) onto a carbon-coated copper grid (for TEM imaging) or freshly cut mica (for AFM imaging). (rotation speed = 3,000 rpm for 30 sec).

(4) P2 _n Manufacture of adjustable 2D rectangles with living 2D CDSA

After diluting the 2D seed solution with 0.03 g/L chloroform, a solution of low molecular weight P2 _n (unimer, M _n = 5.0 - 6.1 kDa, Ð < 1.18) of 10 g/L chloroform was added to the 2D seed solution with various unimers. It was added in a -to-seed (U/S) mass ratio. The samples were then aged at X°C (variable temperature).

(5) Study of growth kinetics of living 2D CDSA

In order to study the growth kinetics of the 2D assembly in the solution phase, the present inventors monitored the living 2D assembly according to the aging time after adding the unimer solution to the seed solution. For each nanostructure, the distributions of length, width, height, area, aspect ratio, and angle were manually estimated from TEM and AFM images using the ImageJ software package developed by the National Institutes of Health. For statistical length analysis, more than 30 randomly selected subjects were processed to determine mean values according to the data set. All particles in each image were counted to reduce subjectivity.

3. Results and Discussion

(1) The idea of this study

The present inventors have reported in a previous study that conjugated PCPV homopolymers containing fluorene and bulky substituents were successfully self-assembled into their uniform orthorhombic crystalline arrays. For example, P2 ₂₂ homopolymer (M _n = 9.01 kDa, Ð = 1.13) assembles into 2D rectangles directly in chloroform, but no control over the structure was possible due to its low solubility. The present inventors have BCP microstructure consisting of a core formed of the same block ₂₂ P2 moiety and a soluble ₅₀ P1 blocks _{(BCP, P1 50 - b -P2} 22, M _n = 38.6 kDa, Ð = 1.10). This modification stabilizes the P2 crystalline block, enabling precise control of width and length through living CDSA, but there is a limitation in that only 1D nanofibers are manufactured by this method. Based on previous studies, we attempted to form a uniform 2D nanosheet by blending _{P2 22} and P1 ₅₀ -b -P2 _{22 to achieve controlled co-assembly.} The partially introduced P1 shell block in the blend _{stabilizes the main crystalline array of the P2 22} homopolymer, which can overcome the solubility issue of 2D nanorectangles in solution. To achieve this co-assembly, the present inventors used a simple heating and aging method using the blend in chloroform and screened various conditions by changing the mass ratio, concentration, and temperature of the two polymers.

(2) Preparation of uniform monolayer 2D seeds

_{After several optimizations, a blend solution of P1 50} - b -P2 ₂₂ and P2 ₂₂ 0.5 g/L chloroform in a weight ratio of 2 : 1 (molar ratio = 1 : 2) of 2 : 1 was heated at 50 ° C. for 1 hour to provide excellent co- Co-assembly was achieved. After cooling to 25°C and aging for 3 days, TEM imaging confirmed uniform 2D rectangular monolayers with an aspect ratio of 1.73 and an average angle of 92.9°, demonstrating excellent self-assembly by the self-seeding mechanism. (Fig. 1a). In addition, the resulting 2D seeds were uniformly 790.7 nm (± 104.8) wide ( W _n ), 456.7 nm (± 39.6) long ( L _n ) and 0.36 of a very narrow length and areal dispersion (<1.02). It has an average area value of (±0.063) ν m ^{2 .} By freezing a low concentration of 0.05 g/L in chloroform, it was confirmed through cryogenic TEM imaging that the 2D self-assembly occurred in solution, not solvent evaporation. To gain insight into these co-assembled 2D seeds, we analyzed electron diffraction patterns by fast Fourier transform (FFT) in high-resolution TEM (HR-TEM) images (Fig. 1b). The diffraction analysis results show an orthorhombic crystal lattice with major d-spacing values of 10.3 Å, 16.1 Å and 18.5 Å, which is identical to the reported P2 homopolymer. This supports the conclusion that a blend of two polymers with a common P2 core was co-assembled as a 2D seed (Fig. 1c). Interestingly, the longer side of the 2D rectangle coincided with the orientation of the (100) plane of the crystalline array. During the aging process, polymer nucleation first formed small nuclei and then grew in both directions, growing slightly faster along the (100) plane than the (010) plane of the crystalline P2 core (cf. (110)>(100)>(010), Fig. 1c). Finally, a uniform 2D seed with a rectangular shape with two distinct, well-defined crystalline surfaces was formed. In addition, the fact that the P2 core block stands on the surface along the (001) direction of the 2D crystal lattice suggests that the P1 shell block occupies the top and bottom of the 2D seed from the BCP, which in the conventional P2 single assembly It suppresses the frequently observed problem of multiple stacking and makes the 2D seeds colloidally stable. This orientation also affected the height of the 2D seed as measured according to AFM analysis. Its average height (H _n ) was 14.4 ± 0.4 nm, which is 3 nm higher than the height of the 2D rectangle from only the P2 homopolymer without the conventional additional P1 shell block ( FIGS. 1D and 1E ).

(3) Control of area (length) of 2D nanosheets

With the obtained uniform 2D seeds, we investigated the possibility of CDSA through seed growth to further control the area of 2D nanosheets. _{Low molecular weight P2 10} in 10 g/L chloroform with various unimer-to-seed (U/S) mass ratios of 2 to 15 in 2D seed (0.32 (± 0.059) μm ² of A _{n ) solution in 0.03 g/L chloroform} (Unimer, M _n = 5.0 kDa, Ð = 1.15) solution was added. After optimization, P2 ₁₀ was successfully subjected to CDSA to form a uniform 2D rectangle, whose area changed from 1.2 μm ² to 7.1 μm ² (Ð <1.02) according to the U/S ratio after 3 weeks of aging at -13°C. increased linearly (Figs. 2a and 2b). In the TEM image of the resulting 2D rectangle, the central part of the 2D seed is displayed darker, easily distinguishable from the newly formed 2D sheet derived from the _{P2 10 unimer (Fig. 2a).} Surprisingly, unlike other 2D platelets that grew radially (both distal and lateral) to the seed _{, the 2D rectangle of the P2 10} unimer only grew in one direction along the (010) plane of the 2D seed. . Due to the uniaxial growth, _{the L n} (010) of the 2D rectangle generated while maintaining _{the width (W n} ) in the (100) direction could be controlled from 1.5 μm to 8.8 μm ( FIG. 2c ). The low magnification TEM image shows that the length dispersion is less than 1.03, indicating a successful living 2D CDSA. In addition, living CDSA was qualitatively supported by DLS analysis, and the D _h value in chloroform solution gradually increased from 454 nm to 4.9 μm with increasing U/S ratio (Fig. 1d). The height of the 2D rectangle in the (001) direction by AFM analysis also showed that the 2D seed and the newly formed 2D sheet (approximately 14.4 ± 0.4 nm vs. 7.8 ± 0.6 nm) (Fig. 2e). To understand the intrinsic uniaxial growth of a 2D rectangle along the (010) direction of the seed as opposed to the faster growth in the (100) direction of the seed formation process, which can be thermodynamically affected, we present the 2D seed The orientation of the orthorhombic crystal lattice of the P2 homopolymer was closely investigated (Fig. 2f). That (010) plane was occupied by the rigid fluorene moiety of the P2 chain and probably has a much higher surface energy than the (100) plane exposing the neohexyl group. Thus, during the elongation process, this distinct crystal plane of the 2D seed allows the P2 unimers to crystallize kinetically in the direction of higher surface energy, thereby leading to preferential crystallization of the unimers along the (010) direction. can do. Similarly, in our previous study, 2D rectangular nanosheets of other PCPV homopolymers containing silyl groups also grew faster in the (010) direction than in the (100) direction with 2D seeds with distinct crystal surfaces. In addition, the P2 chain containing the transalkene exclusively appeared to exhibit a fully extended conformation without chain folding in the 2D array, thereby maximizing the selective assembly of the unimer to the seed. These flawless CDSAs could have produced 2D sheets with sharp edges with near-perfect right angles.

(3) Kinetic study of 2D CDSA

In particular, this uniaxially-living 2D CDSA is an excellent system for conducting kinetic studies of 2D assembly in solution. Through real-time monitoring using TEM analysis, as described in Fig. 3a, the present inventors added _{P2 10} homopolymer at various U/S ratios under the aforementioned conditions (0.03 g/L seeds in chloroform solution at -13°C). and the growth kinetics study was performed by measuring the length increase. As expected, the higher the U/S ratio and the _{higher unimeric [U] 0} concentration, the faster the elongation. Interestingly, the plots for Ln growth versus time corresponded very well to the first-order kinetic function of [U] ₀ ^{with R 2 values greater than 0.991, similar to conventional living polymerization (Table 2, entries 1-5).} ). The rate constant (k') was also consistent within the experimental error regardless of the U/S ratio. Using the alternating method, the response order of [U] calculated at the initial rate by analyzing the _{L n increase in the initial phase was 0.964 (± 0.085) (Fig. 3b).} We further confirmed the first-order kinetics of living 2D CDSA of P2 homopolymer. This is an interesting result because previous studies of living 1D CDSA of P1- b- P2 or PFS BCP showed significant deviations in first-order kinetics. The main difference in the present study is probably due to the homopolymer microstructure of unimers, unlike BCPs with shell blocks in the previous case. Thus, the P2 homopolymer has a negligible morphological effect due to the absence of a shell block. Finally, P2, which does not undergo chain folding, directly forms a crystalline array, making this 2D CDSA similar to ideal crystallization, which is analogous to living supramolecular polymerization of small organic molecules such as porphyrin derivatives.

To investigate the effect of temperature on CDSA, rates were measured again at four temperatures: 0 °C, -10 °C, -20 °C and -25 °C. After the first fitting, it was found that the initial rate constant k' increased from 3.0x10 ^{-3 to 1.1x10 -2} as the temperature decreased from 0°C to -25°C. Using these values, an Eyring plot was generated to determine the activation enthalpy and entropy for the seed-growth process, with negative values of -31.7 kJ/mol and -384 J/Kmol, respectively, for faster growth at lower temperatures. (Table 2, entries 6-9, Fig. 3c). In addition, another kinetic study was performed using the longer P2 unimers of DP 13 (5.6 kDa (Ð = 1.18)) and 15 (6.1 kDa (Ð = 1.13)). Since the longer P2 unimers exhibiting high crystallinity readily undergo self-nucleation at low temperatures, all kinetic experiments were performed at 25°C for proper comparison. Another first-order fit of [U] ₀ ^{is 1.3x10 -4} (h ^-1 ), ^{1.5x10 -3} (h ^-1 ) and 2.5x10 ^-3 ( h ⁻¹ ) gave an initial rate constant k′ (Table 2, entries 10-12, FIG. 3d ). P2 ₁₀ than 20 times faster growth of P2 ₁₅ may also be due to the higher crystal of P2 _15. Similar to the previous report for P2, the average height of the new 2D sheets increased from 7.8 nm to 10.4 nm depending on the DP of P2. Using the longer P2 unimer, it was possible to perform living 2D CDSA at 25 °C with various U/S ratios from 1 to 10, which ranged from 0.64 μm to 5.5 μm for _{P2 13} and 0.80 μm to 0.80 μm for _{P2 15 .} Each prepared 2D rectangle of 3.3 μm provided an _{adjustable L n .}

entry Unimer (kDa) ripening temperature
(℃) U/S ratio k' (h ^-One ) error (h ^-One ) R ² One 5.0 -13 2 6.5×10 ^-3 6.1×10 ^-4 0.991 2 3 5.1×10 ^-3 4.0×10 ^-4 0.993 3 5 4.9x10 ^-3 4.2×10 ^-4 0.991 4 10 5.4×10 ^-3 4.6×10 ^-5 0.995 5 15 4.4×10 ^-3 2.5×10 ^-5 0.997 6 5.0 0 10 3.0×10 ^-3 8.4×10 ^-5 0.999 7 -10 3.8×10 ^-3 1.4×10 ^-4 0.999 8 -20 7.3×10 ^-3 2.2×10 ^-4 0.999 9 -25 1.1×10 ^-2 2.7×10 ^-4 0.999 10 5.0 25 10 1.3×10 ^-4 4.3×10 ^-5 0.999 11 5.6 1.5×10 ^-3 5.9×10 ^-5 0.999 12 6.1 2.5×10 ^-3 1.4×10 ^-4 0.999

(4) Preparation of multi-block comicelles with controlled length and height

Interestingly, uniaxial living 2D CDSA can produce more complex multi-block comicelles (BCMs) via serial seed-growth from various P2 unimers. Similar to block copolymerization via living polymerization, _{sequential addition of P2 10} and P2 ₁₅ gave penta-BCM with controlled length and height along the (010) direction (unimer in 10 g/L chloroform, 3 U/S ratio, [2D seed] = 0.03 g/L in chloroform, Figure 4a). By changing the order of addition, two types of symmetric penta-BCM, A(P2 ₁₅ )-B(P2 ₁₀ )-S (seed)-BA and BASAB were produced with uniform length and narrow dispersion ( FIG. 4b ). As the A block of _{P2 15 appears darker than the B block of P2 10} due to the higher electron density, a distinct difference is observed in the TEM image (Fig. 4c). In addition, AFM analysis confirms the block structure of penta-BCM, which shows another clear difference in the height of the 2D sheet (Fig. 4d). The present inventors attempted to form a more difficult but simple one-shot BCM by adding two P2 unimers to the 2D seed at 25°C with each U/S ratio of 3 at the same time. Because the more crystalline P2 ₁₅ grew much faster than P2 _{10 , the longer P2 15} preferentially assembles into the 2D seed. After that, lowering the temperature to 0 °C _{initiates the self-assembly of shorter P2 10} through the seed-growth mechanism to form BASAB penta-BCM identical to that prepared by sequential addition (Fig. 4e). These results represent an excellent example of these novel strategies that can be used to construct complex nanostructures based on a deep understanding of the 2D assembly process.

Since these precisely controlled 2D rectangles were composed of fluorescently conjugated PCPV, they could be viewed in super-resolution structured illumination microscopy (SR-SIM) without additional dyes. Interestingly, the central portion of the 2D seed exhibited much higher fluorescence than the rest of the 2D sheet newly formed from the P2 unimer, indicating that the longer P2 emits more intense light. In addition, video of the micellar solution recorded with confocal laser scanning microscopy (CLSM) shows persistent morphology and fluorescence stability without degradation and photobleaching.

(5) Preparation of 2D nanosheets with controlled width and length

The present inventors have extended this study to further control the width of the successfully adjusted 2D nanosheets. In particular, when THF or chloroform is added as a co-solvent in a simple heating and aging method in a dichloromethane (DCM) solution of an example of one of the PCPV homopolymers containing fluorene and bulky substituents in previous studies. , observed that the aspect ratio was controlled at 18 different content ratios. The crystallinity of the 2D sheets was analyzed from film X-ray diffraction patterns and electron diffraction patterns using high-resolution TEM, and the linear dependence of the aspect ratio of the nanosheets on the co-solvent % was determined by the difference between the surface energy of each plane and the crystal growth rate. was inferred to be due to

Accordingly, the present inventors used the linear dependence of the aspect ratio of the nanosheets due to the co-solvent effect described above to achieve the production of 2D nanosheets in which the width and length were simultaneously controlled using the blend, and a method for adding and aging a cosolvent after simple heating was used. In this regard, various conditions were screened by changing the cosolvent % and concentration in the method for preparing uniform monolayer 2D seeds previously.

_{As shown in FIG. 5 , after several optimizations, a blend solution of P1 50} - b -P2 ₂₂ and P2 ₂₂ 0.75 g/L chloroform of the same weight ratio of 2 : 1 (molar ratio = 1 : 2) was mixed at 50° C. for 1 hour. After heating under heating conditions, 10, 20, 30, 40, 50, 60, and 70% of the final volume % of the cosolvent DCM (volume % of the cosolvent DCM added during seed formation = SMC%) was added to the solvent. . After aging at 25 °C for 2 days, changes in width (Wn) and length (Ln) of the 2D rectangle prepared by TEM and AFM imaging were confirmed. It was confirmed that the average width was controlled from 950 nm to 230 nm according to the volume % of the total solution of the cosolvent DCM (MC), and it was confirmed that the average length was controlled from 570 nm to 3,220 nm. In addition, the aspect ratio increased more than 20-fold from 0.6 to 14, demonstrating the linear dependence of the aspect ratio of the nanosheets due to the cosolvent effect. Specifically, it can be seen that as the concentration of added DCM (MC) increases, the width along the (100) direction decreases and the length along the (010) direction increases ( FIGS. 6A to 6G , and FIGS. 7A to 7L ) ). In addition, after aging at 25° C. for 3 days and diluting to 0.05 g/L, DLS analysis, UV-vis absorption analysis, and statistical analysis were performed on the structure of each 2D nanosheet. As a result, the width of the 2D nanosheet and It was confirmed that the length can be adjusted linearly according to the percentage of cosolvent, and the resulting 2D seeds have very narrow length and area dispersion of 1.1 or less ( FIGS. 8a to 8e ).

(6) Formation of length-controlled 2D nanostructures by self-assembly that selectively grows in the longitudinal direction from width-controlled 2D seeds

With the obtained uniform 2D seeds with controlled width, the present inventors performed CDSA through seed growth with further controlled length to provide an environment in which width and length were simultaneously controlled. 2D seeds whose width was adjusted according to the volume ratio (represented as "SMC") of the cosolvent DCM added during seed formation (represented as "SMC") 0%, 10%, 20%, and 30% were used, and by adjusting the U/S ratio Accordingly, 2D nanosheets with controlled length were prepared by selectively growing in the (010) direction. In addition, the present inventors controlled the length of the nanosheets by adding cosolvent DCM (represented as "CMC") during the CDSA process through seed growth in order to increase the length control speed. In this case, the volume % of DCM is set to 50%. Conditions other than the volume ratio of SMC and the U/S ratio in the conditions of each experiment were set the same:

1) Concentration of 2D seeds: 0.2 g/L (in chloroform)

2) Molecular weight of unimer (M _w ): 6.05 kDa

3) CMC%: 50%

4) Aging temperature and time: 25℃ and 1-3 days

Interestingly, uniaxial living 2D CDSA occurred irrespective of the CMC 50%, and the length increased linearly with the U/S ratio. First, the length control of the 2D seed of 0% SMC having a width of 970 nm was successful from 1,890 nm to 4,160 nm ( FIGS. 9a to 9g ). Length control of 2D seeds with a width of 850 nm was successful from 3,300 nm to 5,300 nm ( FIGS. 10a to 10f ). Length control of 2D seeds with a width of 650 nm was successful from 5,100 nm to 8,000 nm ( FIGS. 11a to 11d ). Finally, the length control of the 2D seed having a width of 510 nm was successful from 1,700 nm to 4,900 nm ( FIGS. 12a to 12f ). The present inventors have succeeded in creating an environment for creating 2D nanosheets in which the width and length are simultaneously controlled through the length-controlled CDSA of the 2D seed with the controlled width.

As a result, 7 types of 2D seed structures could be formed depending on the SMC%, and the width in the (100) direction was adjustable from 970 nm to 230 nm, and the length in the (010) direction was in the range of 570 nm to 3,220 nm. appeared as Additionally, it was possible to adjust the length of 2 μm to 8 μm on average based on 2D seeds with a width of 970 nm to 510 nm through the 2D CDSA process under the control of the U/S ratio. The results of overall width and length control of the 2D nanosheet are shown in FIG. 13 . The above results show an excellent example of a combination of strategies that can be used to construct more precisely designed nanostructures based on a deep understanding of the 2D assembly process and control of width and length.

4. Conclusion

In conclusion, we have successfully fabricated the formation of uniform semiconductor 2D rectangles with sharp edges from semi-crystalline conjugated homopolymers by a uniaxial seed-growth approach. This exciting direction-selective assembly allows for the first time to control the length of 2D rectangles with narrow dispersion via 2D CDSA. Using uniaxial growth from these homopolymers, 2D growth kinetics studies showed that homopolymer self-assembly follows ideal first-order kinetics similar to living polymerization. These results indicate that the polymer self-assembly follows the ideal crystallization, since interfering factors such as the morphological effects of shell blocks or backbone chain folding have been removed. Finally, 2D CDSA prepared several complex but well-controlled penta-BCMs using P2 of various sizes. Ultimately, we succeeded in forming one-shot BCMs based on our understanding of growth kinetics, which provided excellent guidelines for optimizing self-assembly conditions. These precisely controlled uniform fluorescent 2D nanostructures have great potential for optoelectronic applications.

The above description of the present application is for illustration, and those of ordinary skill in the art to which the present application pertains will understand that it can be easily modified into other specific forms without changing the technical spirit or essential features of the present application. Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive. For example, each component described as a single type may be implemented in a distributed manner, and likewise components described as distributed may also be implemented in a combined form.

The scope of the present application is indicated by the following claims rather than the above detailed description, and all changes or modifications derived from the meaning and scope of the claims, and their equivalents should be construed as being included in the scope of the present application. .

Claims (20)

a block copolymer represented by the following Chemical Formula 1 or the following Chemical Formula 2; and
A homopolymer represented by the following formula (3)
A two-dimensional polymer nanosheet comprising:
[Formula 1]

;
[Formula 2]

;
[Formula 3]

;
In Formula 1, Formula 2 and Formula 3,
R ¹ to R ³ are each independently, a substituted or unsubstituted linear or branched C _1-8 alkyl group,
When ^{one or more of R 1} to R ³ is substituted, it is substituted with -SiR ^a R ^b R ^c ,
R ^a , R ^b and R ^c are each independently a linear or branched C _1-4 alkyl group,
m and o are each independently an integer of 20 to 70,
n and p are each independently an integer of 5 to 70,
q is an integer from 5 to 70;
The method of claim 1,
R ¹ and R ³ are each independently a substituted or unsubstituted, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, iso-butyl group, tert-butyl group , n-pentyl group, sec-pentyl group, 3-pentyl group, iso-pentyl group, tert-pentyl group, neo-pentyl group, sec-isopentyl group, 2-methylbutyl group, n-hexyl group, sec- Hexyl group, 3-hexyl group, iso-hexyl group, tert-hexyl group, sec-isohexyl group, 3-isohexyl group, 2-methylpentyl group, 3,3-dimethylbutyl group, 3-ethylbutyl group , 2,2-dimethylbutyl group, n-heptyl group, iso-heptyl group, neo-heptyl group, tert-heptyl group, sec-heptyl group, n-octyl group, iso-octyl group, or 2-ethylhexyl group A two-dimensional polymer nanosheet that is an actual machine.
The method of claim 1,
R ² is a substituted or unsubstituted, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, sec -pentyl group, 3-pentyl group, iso-pentyl group, tert-pentyl group, neo-pentyl group, sec-isopentyl group, 2-methylbutyl group, n-hexyl group, sec-hexyl group, 3-hexyl group , iso-hexyl group, tert-hexyl group, sec-isohexyl group, 3-isohexyl group, 2-methylpentyl group, 3,3-dimethylbutyl group, 3-ethylbutyl group, or 2,2-di A two-dimensional polymer nanosheet that is a methylbutyl group.
The method of claim 1,
The -SiR ^a R ^b R ^c is -SiMe ₃ , -SiEt ₃ , -SiPr ₃ , -SiBu ₃ , -SiEtMe ₂ , -SiEt ₂ Me, -SiMe ₂ Pr, -SiMePr ₂ , -SiBuMe ₂ , -SiBu ₂ Me, -SiEt ₂ Pr, -SiEtPr ₂ , -SiBuEt ₂ , -SiBu ₂ Et, -SiBuPr ₂ , or -SiBu ₂ Pr, the two-dimensional polymer nanosheet.
The method of claim 1,
The width 100 of the two-dimensional polymer nanosheet is 100 nm to 10 μm, the two-dimensional polymer nanosheet.
The method of claim 1,
The length (010) of the two-dimensional polymer nanosheet is 500 nm to 20 μm, the two-dimensional polymer nanosheet.
The method of claim 1,
The height of the two-dimensional polymer nanosheet is 1 nm to 500 nm, the two-dimensional polymer nanosheet.
The method of claim 1,
The two-dimensional polymer nanosheet is a two-dimensional polymer nanosheet having conductivity and / or fluorescence.
(a) mixing a block copolymer represented by the following Chemical Formula 1 or Chemical Formula 2 and a homopolymer represented by the following Chemical Formula 3 to obtain a two-dimensional seed; and
(b) obtaining a two-dimensional polymer nanosheet by adding a unimer including a homopolymer represented by the following formula (3) to the two-dimensional seed
A method for producing a two-dimensional polymer nanosheet according to any one of claims 1 to 8, comprising:
[Formula 1]

;
[Formula 2]

;
[Formula 3]

;
In Formula 1, Formula 2 and Formula 3,
R ¹ to R ³ are each independently, a substituted or unsubstituted linear or branched C _1-8 alkyl group,
When ^{one or more of R 1} to R ³ is substituted, it is substituted with -SiR ^a R ^b R ^c ,
R ^a , R ^b and R ^c are each independently a linear or branched C _1-4 alkyl group,
m and o are each independently an integer of 20 to 70,
n and p are each independently an integer of 5 to 70,
q is an integer from 5 to 70;
10. The method of claim 9,
In (a), the two-dimensional seed will be formed by co-assembly (co-assembly) of the block copolymer and the homopolymer, a method of manufacturing a two-dimensional polymer nanosheet.
10. The method of claim 9,
In (b), the two-dimensional polymer nanosheet is a method for producing a two-dimensional polymer nanosheet is formed by seed-growth.
12. The method of claim 11,
The seed-growth is a primary reaction, the method for producing a two-dimensional polymer nanosheets.
10. The method of claim 9,
(a) is carried out in the presence of a first solvent,
In (a), by adding a second solvent different from the first solvent to control the width of the two-dimensional seed, a method for producing a two-dimensional polymer nanosheet.
14. The method of claim 13,
The first solvent is at least one selected from chloroform, dichloromethane, and tetrahydrofuran,
The second solvent is at least one selected from methyl chloride, dichloromethane, chloroform, tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, and ortho-dichlorobenzene, a method for producing a two-dimensional polymer nanosheet.
10. The method of claim 9,
In (b), the method for producing a two-dimensional polymer nanosheet, to control the length of the two-dimensional polymer nanosheet according to the mass ratio of the unimer to the seed.
10. The method of claim 9,
In (b), the method for producing a two-dimensional polymer nanosheet to control the height of the two-dimensional polymer nanosheet according to the polymerization degree of the unimer to be added.
17. The method of claim 16,
A method for producing a two-dimensional polymer nanosheet, which forms a block comichel by adding the unimers having at least two different polymerization degrees.
10. The method of claim 9,
(a) and / or (b) further comprising a heating step and / or aging step, a method for producing a two-dimensional polymer nanosheets.
A device comprising the two-dimensional polymer nanosheet according to claim 1 .
20. The method of claim 19,
wherein the device is a transistor, sensor, imaging agent, light emitting diode, photovoltaic cell, or conductive display.

Images