KR102545566B1 - 2-dimensional polymer nanosheet and width, length, and height tunable method of preparing the same - Google Patents

Abstract

Semiconducting two-dimensional (2D) nanomaterials prepared by self-assembly of conjugated polymers are promising materials for optoelectronic applications. However, there have been no examples of 2D nanosheets in which length and aspect ratio are simultaneously controlled through self-assembly. The present application successfully prepared a uniform semiconductor 2D sheet by blending and heating a conjugated poly(cyclopentenylenevinylene) homopolymer and its block copolymer. Using this as a 2D seed, homopolymers were added as unomers to achieve living crystallization driven self-assembly (CDSA). Interestingly, unlike typical 2D CDSA examples that show radial growth, the homopolymer only assembles in one direction. Due to this uniaxial growth, the length of 2D nanosheets can be precisely tuned with a narrow dispersion according to the unimer-to-seed ratio. In addition, we studied the growth kinetics of living 2D CDSA and confirmed the primary kinetics. In addition, the present inventors fabricated several 2D block comic cells (BCMs) including penta-BCMs by a one-shot method.

Description

Two-dimensional polymer nanosheet and its width, length, and height controllable 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 controlling its width, length, and height.

2-dimensional (2D) organic nanostructures based on soft materials, especially conjugated 2D materials such as graphene, have potential applications as electron transport platforms due to their unique characteristics based on ultra-thin and flat shapes. has been noticed Self-assembly of semi-crystalline polymers is one of the efficient bottom-up approaches to synthesize these synthetic 2D nanostructures, and so far, such as PFS, PLLA, PCL, and PE, which have a unique two-dimensional crystal arrangement By self-assembly of a block copolymer (BCP) containing a semi-crystalline polymer and a solubilizing shell block, 2D nanostructures of various shapes such as rectangle, hexagon, diamond, and square have been successfully synthesized. P3HT, PPV, and PF, which are semi-crystalline conjugated polymers, have also been utilized as conjugated 2D materials with various potential applications such as sensors, imaging agents, light emitting diodes, and photovoltaic cells.

Controlling the shape and size of the structure is essential for higher applicability of these 2D polymer materials, and accordingly, strategies for diversifying the shape of nanostructures as well as size and shape control strategies 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 have been developed. It was utilized for the synthesis of uniform 2D nanostructures. However, unlike self-assembly of inorganic or organic planar molecules, conventional polymer self-assembly grows radially by forming a lamellae arrangement through chain-folding of crystalline polymers. Therefore, detailed control of each length other than the aspect ratio of the 2D nanostructure is limited. In addition, in the case of conjugated 2D materials, there is a limitation that irregular aggregation occurs because the strong π-π (pi-pi) interaction of the conjugated polymer lowers the solubility of the 2D nanostructure. In order to solve this problem, so far, conductive 2D polymer nanostructures have been synthesized from the self-assembly of BCP by introducing a soluble shell block to the conjugated core block, and even these have been synthesized with aspect ratio and width controlled by changing the concentration or solvent composition, and seeds It was difficult to fine-tune the length through the introduction of the growth method.

Overall, various 2D nanostructures have been successfully formed through high-level control, but on the other hand, 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 new 2D nanostructures through various polymer designs. Recently, growth kinetic studies based on living CDSA of PFS-b-PDMS BCP have been reported in earnest for the one-dimensional crystallization process. It has a chain conformational effect and is inevitably different from analogous living polymerization or single molecule assembly growth kinetics. On the other hand, self-assembly of homopolymers, which are easy to synthesize, is the simplest method for forming nanostructures and is a suitable tool for 2D growth kinetics. Recently, a 2D self-assembly strategy of homopolymers introducing charged-groups was developed led by Manners group, and it was revealed that the shape of 2D nanostructures was determined by the relative difference in growth rate with respect to the crystallographic direction. Growth kinetics have not yet been studied.

Republic of Korea Patent Publication No. 10-2013-0036856.

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

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

A first aspect of the present application is a block copolymer represented by Formula 1 or Formula 2 below; And a two-dimensional polymer nanosheet comprising a homopolymer represented by Formula 3 below is provided:

[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 from 20 to 70;

n and p are each independently an integer from 5 to 70;

q is an integer from 5 to 70;

In a second aspect of the present application, (a) obtaining a two-dimensional seed by mixing a block copolymer represented by Formula 1 or Formula 2 below and a homopolymer represented by Formula 3 below; and (b) obtaining a two-dimensional polymer nanosheet by adding a homopolymer represented by Chemical Formula 3 to the two-dimensional seed to obtain a two-dimensional polymer nanosheet. 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 from 20 to 70;

n and p are each independently an integer from 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, a blend strategy was used to successfully form uniform semiconductor 2D nanosheets without stacking. By adding the homopolymer as the unomer to the initial 2D seed formed by the above manufacturing method, a living 2D CDSA by a seed-growth mechanism was possible. Interestingly, the homopolymers were uniaxially assembled on the 2D seeds to form sharp edges 2D nanorectangles with controlled length and area. Kinetic studies of the uniaxial growth of 2D assemblies based on real-time imaging of living CDSA confirmed that they follow a first-order rate law that exactly follows the living polymerization-like kinetics. In addition, complex and height-varied block comicelle (BCM) structures were successfully formed 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, the length of the finally formed 2D nanosheet can be adjusted according to the U/S (unimer to seed) ratio of the unimers. Finally, depending on the molecular weight of the unomer, block comicelles of various heights may be formed.

1A is a TEM image of a uniform 2D seed produced by heating and maturing P1 ₅₀ -b-P2 ₂₂ and P2 ₂₂ homopolymers in a 2:1 mixing ratio (numbers in the image are average width (W _n ), length (L _n ) and dispersion), and Fig. 1b shows the HR- The FFT pattern obtained from the TEM image, and Fig. 1c is a schematic diagram of the 2D seed and its proposed detailed structure, showing its crystalline array and the observed crystal growth rate. 1d is an AFM image of a 2D seed, and FIG. 1e shows a height profile along a white line in the AFM image.
According to an embodiment of the present disclosure, FIG. 2A shows TEM images of 2D rectangles of controlled length and area with U/S ratios of 2, 3, 5, 10, and 15, respectively [numbers in the image represent average area (A _n )]. and the degree of dispersion], and FIGS. 2B and 2C are plots showing the linear dependence of the area (An) and average length (Ln) in the (010) direction as a function of the U/S ratio, respectively, demonstrating 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. AFM images and a 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 versus 14.4 nm of the original 2D seed), Fig. 2f is uniaxial along the (010) direction. Schematic diagram of living 2D CDSA through (uniaxial) seed-growth. The fabricated 2D rectangular 2D schematic is based on the interdigitating slip-stack packing model of P2 homopolymer with a simplified structure in the ab plane. to be
3A and 3B are plots showing the length (L _n ) of a 2D rectangle over time at various U/S ratios from 2 to 15 (monitored for 3 weeks) and the first order It is a plot showing the initial reaction rate versus the unimer concentration [U] confirming the kinetics. Figures 3c and 3d show an Eyring plot of the rate constant k' extracted from seed-growth experiments at various temperatures and Ln (L _final - L from the primary growth of various unomers with different DPs at 25 ° C, respectively. (time)) versus time.
In an embodiment of the present application, Figure 4a is a scheme for a method for manufacturing a composite 2D BCM by the 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. 4B, 4C, and 4D are TEM images, electron density profiles, and 2D and 3D height AFM images of penta-BCMs, respectively, showing clear differences between the two types of penta-BCMs prepared by the sequential addition. 4e is a scheme for preparing one 2D BCM by one-shot adding two unimers, and FIG. 4f is a TEM image and electron density of penta-BCM obtained by one-shot living CDSA. is the profile [numbers in the image indicate mean length (L _n ) and degree of dispersion].
5 is a schematic diagram of a method for adjusting the width of a 2D nanosheet according to the addition of a co-solvent, according to an embodiment of the present disclosure.
6A to 6G are TEM images of 2D nanosheets having variously controlled lengths and widths, respectively, according to an embodiment of the present disclosure.
7A to 7L are AFM images and profiles of 2D nanosheets having variously controlled lengths and widths, respectively, according to an embodiment of the present disclosure.
8a to 8e show, in an embodiment of the present application, DLS analysis, UV-vis absorption analysis, change in width and length according to the ratio of the co-solvent, and according to the ratio of the co-solvent for the structure of each 2D nanosheet. It is the result of analyzing the change in aspect ratio according to the change in area and the ratio of the co-solvent.
9a to 9e are TEM images of 2D nanosheets obtained by adjusting the length of each 2D seed having a width of 910 nm from 1.9 μm to 4.2 μm according to the U/S ratio in one embodiment of the present application. 9f and 9g show U/S of 2D nanosheets obtained by adjusting the length from 1.9 μm to 4.2 μm according to the U/S ratio for a 2D seed having a width of 910 nm, respectively, in an embodiment of the present application. It is a plot showing the change of L _n in the (010) direction according to the S ratio after aging for 67 hours, or after aging for 45 hours and 67 hours.
10A to 10E are TEM images of 2D nanosheets obtained by adjusting the length of each 2D seed having a width of 850 nm from 3.3 μm to 5.3 μm according to the U/S ratio in one embodiment of the present application. In addition, FIG. 10f shows the U/S ratio of 2D nanosheets obtained by adjusting the length to 3.3 μm to 5.3 μm according to the U/S ratio for each 2D seed having a width of 850 nm in one embodiment of the present application. It is a plot showing the change of L _n in the (010) direction according to
11a to 11c are TEM images of 2D nanosheets obtained by adjusting the length of a 2D seed having a width of 650 nm from 5.1 μm to 8.0 μm according to the U/S ratio, respectively, in an embodiment of the present application; It is a plot showing the change of L _n in the (010) direction according to the U/S ratio. FIG. 11d shows the U/S ratio of 2D nanosheets obtained by adjusting the length from 5.1 μm to 8.0 μm according to the U/S ratio for each 2D seed having a width of 650 nm in an embodiment of the present application. It is a plot showing the change of L _n in the (010) direction and the change of W _n in the (100) direction.
12a to 12e are TEM images of 2D nanosheets obtained by adjusting the length of each 2D seed having a width of 510 nm from 1.7 μm to 4.9 μm according to the U/S ratio in one embodiment of the present application. In addition, FIG. 12f shows the U/S ratio of 2D nanosheets obtained by adjusting the length from 1.7 μm to 4.9 μm according to the U/S ratio for each 2D seed having a width of 510 nm in one embodiment of the present application. It is a plot showing the change of L _n in the (010) direction according to
13 is a schematic diagram illustrating a 2D nanosheet whose length is additionally adjusted based on a 2D seed whose width and length are adjusted, according to an embodiment of the present disclosure.

Hereinafter, with reference to the accompanying drawings, embodiments and embodiments of the present application will be described in detail so that those skilled in the art can easily practice the present invention. However, the present disclosure may be embodied in many different forms and is not limited to the implementations 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" to another part, this includes not only the case of being "directly connected" but also the case of being "electrically connected" with another element in between. do.

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

Throughout the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

As used herein, the terms "about," "substantially," and the like are used at or approximating that number when manufacturing and material tolerances inherent in the stated meaning are given, and are intended to assist in the understanding of this disclosure. Accurate or absolute figures are used to prevent undue exploitation by unscrupulous infringers of the stated disclosure.

The term "step of" or "step of" used throughout the present specification does not mean "step for".

Throughout this specification, the term "combination(s) of these" 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 including 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 ethyl group, octyl group, 2,2,4-trimethylpentyl group, nonyl group, decyl group, undecyl group, dodecyl group, and isomers thereof, and the like, 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 is a block copolymer represented by Formula 1 or Formula 2 below; And a two-dimensional polymer nanosheet comprising a homopolymer represented by Formula 3 below is provided:

[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 of 20 to 70, n and p are each independently an integer of 5 to 70, and q is an integer of 5 to 70.

In one embodiment of the present application, R ¹ and R ³ are each independently substituted or unsubstituted, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, 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, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, an n- It may be a 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 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 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, -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 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 It may be 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 is limited thereto. It may not be.

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 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. 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 It may be 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.

In a second aspect of the present application, (a) obtaining a two-dimensional seed by mixing a block copolymer represented by Formula 1 or Formula 2 below and a homopolymer represented by Formula 3 below; and (b) obtaining a two-dimensional polymer nanosheet by adding a homopolymer represented by Chemical Formula 3 to the two-dimensional seed to obtain a two-dimensional polymer nanosheet. 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 of 20 to 70, n and p are each independently an integer of 5 to 70, and q is an integer of 5 to 70.

Detailed descriptions of portions overlapping with the first aspect of the present application have been omitted, but the description of the first aspect of the present application can be equally applied even if the description 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), the width of the 2-dimensional seed may be adjusted by adding a second solvent different from the first solvent. Here, the first solvent is at least one selected from chloroform, dichloromethane, and tetrahydrofuran, and the second solvent is methyl chloride, dichloromethane (DCM; or methylene chloride, methylene chloride, MC), chloroform , tetrahydrofuran, toluene, chlorobenzene, dichlorobenzene, and ortho-dichlorobenzene may be at least one selected from, 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 2-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 unimers 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 unimers to be added. Here, a block comichel may be formed by adding the unomer having two or more different degrees of polymerization, but may not be limited thereto. For example, a penta-block comichel may be formed by adding the unomer having two different degrees of polymerization.

In one embodiment of the present application, the two or more unomers 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, seed-growth of one type of unimers occurs preferentially, so that one-shot block comichel formation is possible.

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

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

Detailed descriptions of portions overlapping with the first and second aspects of the present application have been omitted, but the contents described for the first and second aspects of the present application will be applied equally even if the description is omitted in the third aspect of the present application. can

In one embodiment of the present application, if the device uses electrical/thermal conductivity and/or fluorescence, the two-dimensional polymer nanosheet of the present application may be included and/or applied without limitation.

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

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

[Example]

1. Common materials and polymers

Without further reference, all reagents were purchased 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 third generation (G3) catalyst was prepared according to previously published methods.

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 a magnetic bar. The vial was purged three 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, the Ar (g) purged G3 catalyst was dissolved in 50 μL THF, 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 into methanol at room temperature. The purple solid obtained was filtered and dried in vacuo. Conversion of the monomers was calculated from the ¹ H NMR spectrum of the remaining crude mixture.

(2) P1 ₅₀ - b -P2 ₂₂ and P2 ₂₂ Preparation of a blend 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 in a ratio of 2:1 (or 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. In detail, samples for TEM and AFM imaging were prepared by spin-coating a drop (about 0.05 mL) of the above 2D seed colloidal solution onto a carbon-coated copper grid (for TEM imaging) or freshly cleaved mica (for AFM imaging). (rotation speed = 3,000 rpm for 30 seconds).

(4) P2 _n Manufacturing of length-adjustable 2D rectangles through living 2D CDSA of unimers

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) in 10 g/L chloroform was added to the 2D seed solution. -to-seed (U/S) mass ratio was added. The samples were then aged at X°C (variable temperature).

(5) Growth kinetics of living 2D CDSA

To study the growth kinetics of the 2D assembly in the solution phase, we monitored the living 2D assembly according to the aging time after adding the unimomer solution to the seed solution. For each nanostructure, the distribution 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, at least 30 randomly selected individuals were processed to determine mean values across data sets. All particles in each image were counted to reduce subjectivity.

3. Results and discussion

(1) The idea of this study

In previous studies, the present inventors reported that conjugated PCPV homopolymers containing fluorene and bulky substituents were successfully self-assembled by their uniform orthorhombic crystalline arrays. For example, P2 ₂₂ homopolymer (M _n = 9.01 kDa, Ð = 1.13) assembles into a 2D rectangle directly in chloroform, but no control over the structure was possible due to its low solubility. _{In addition, the present inventors have a BCP microstructure (BCP, P1 50 - b -P2 22, P1 50 - b} -P2 _22, M _n = 38.6 kDa, Ð = 1.10). This modification stabilizes the P2 crystalline block, enabling precise control of the width and length through the living CDSA, but this method has a limitation in that only 1D nanofibers are produced. Based on previous studies, the present inventors 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 the solution phase. To achieve this co-assembly, we 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) was heated at 50°C for 1 hour heating conditions to obtain 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 are uniform with a very narrow length and area dispersion (<1.02) of 790.7 nm (± 104.8) width ( W _n ), 456.7 nm (± 39.6) length ( L _n ) and 0.36 It has an average area value of (±0.063) ν m ² . It was confirmed through cryogenic TEM imaging by freezing a low concentration of 0.05 g/L in chloroform that the 2D self-assembly occurred in solution rather than 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 the blend of the 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 direction 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 implies that the P1 shell block from the BCP occupies the upper and lower ends of the 2D seed, thereby resulting in a conventional P2 single assembly. It suppresses the frequently observed problem of multiple stacking and makes the 2D seed colloidally stable. This direction also affected the height of the 2D seed 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 conventional 2D rectangles from P2 homopolymer only without additional P1 shell block (Figs. 1d and 1e).

(3) Area (length) control 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. 2D seed (A _n of 0.32 (± 0.059) μm ² ) in 0.03 g/L chloroform at various unimer-to-seed (U/S) mass ratios from 2 to 15, low molecular weight P2 ₁₀ in 10 g/L chloroform (Unimer, M _n = 5.0 kDa, Ð = 1.15) solution was added. After optimization, P2 ₁₀ successfully performed CDSA to form a uniform 2D rectangle, and its area increased 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 portion of the 2D seed appears darker, easily distinguishable from the newly formed 2D sheet derived from P2 ₁₀ unimers (Fig. 2a). Surprisingly, unlike other 2D seeds (platelets) that grew radially (both distal and lateral) to the seed, the 2D rectangles of the P2 ₁₀ unimers only grew in one direction along the (010) plane of the 2D seed. . Due to the uniaxial growth, it was possible to control the L _n (010) of the 2D rectangle from 1.5 μm to 8.8 μm while maintaining the width (W _n ) in the (100) direction (Fig. 2c). Low-magnification TEM images showed that the length dispersion was 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 gradually increased from 454 nm to 4.9 μm in chloroform solution as the U/S ratio increased (Fig. 1d). By AFM analysis, the height of the 2D rectangle in the (001) direction is also due to the higher degree of polymerization (DP) of the P2 block relative to the seed for the 2D seed and newly formed 2D sheet (about 14.4 ± 0.4 nm, respectively). 7.8 ± 0.6 nm) (Fig. 2e). In order 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 influenced by thermodynamics, we , the orientation of the orthorhombic crystal lattice of P2 homopolymer was closely investigated (Fig. 2f). The (010) plane is occupied by the rigid fluorene moiety of the P2 chain and probably has a much higher surface energy compared to the (100) plane exposing neohexyl groups. Thus, during the elongation process, these distinct crystallographic planes of the 2D seed allow the P2 unimers to crystallize kinetically in the direction of higher surface energy, leading to preferential crystallization of the unimers along the (010) direction. can do. Similarly, in our previous studies, 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 having distinct crystalline surfaces. In addition, the P2 chain containing a trans alkene exclusively appeared to show a fully extended conformation without chain folding in the 2D array, thereby maximizing the selective assembly of unimers 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, these uniaxial-living 2D CDSAs are excellent systems for conducting kinetic studies of 2D assemblies in solution. Through real-time monitoring using TEM analysis, as shown in Figure 3a, the present inventors added P2 ₁₀ homopolymer at various U/S ratios under the aforementioned conditions (0.03 g/L seed in chloroform solution at -13 °C). and a growth kinetics study was performed by measuring the increase in length. As expected, the higher the U/S ratio and unimomer [U] ₀ concentration, the faster the elongation. Interestingly, the plot of Ln growth versus time was in excellent agreement with the first-order kinetic function of [U] ₀ , with R ² values greater than 0.991, similar to conventional living polymerizations (Table 2, Entries 1-5 ). The rate constant (k') was also consistent within the experimental error regardless of the U/S ratio. Using the alternation method, the response order of [U] calculated from the initial rate by analyzing the increase in L _n in the initial phase was 0.964 (±0.085) (Fig. 3b). The first-order kinetics of the living 2D CDSA of the P2 homopolymer were further confirmed. This is an interesting result, as previous studies on living 1D CDSAs of P1- b -P2 or PFS BCPs showed significant deviations in first-order kinetics. The main difference of the current 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 shape effect due to the absence of shell blocks. Finally, P2, which does not undergo chain folding, directly forms crystalline arrays, making our 2D CDSAs akin to ideal crystallization, which is akin to living supramolecular polymerization of small organic molecules such as porphyrin derivatives.

To investigate the effect of temperature on CDSA, the rate was measured again at four different 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. From these values, an Eyring plot was generated to determine the activation enthalpy and entropy for the seed-growth process, which are negative values of -31.7 kJ/mol and -384 J/Kmol, respectively, resulting in faster growth at lower temperatures. (Table 2, entries 6-9, Fig. 3c). In addition, another kinetic study was performed using 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 with 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 the initial rate constant k′ (Table 2, entries 10-12, FIG. 3d). The growth of P2 ₁₅ 20 times faster than P2 ₁₀ may be due to the higher crystallinity of P2 ₁₅ . Similar to the previous report for P2, the average height of the new 2D sheet increased from 7.8 nm to 10.4 nm depending on the DP of P2. Using the longer P2 unimers, it was possible to perform living 2D CDSA at 25 °C with various U/S ratios from 1 to 10, ranging from 0.64 μm to 5.5 μm for P2 ₁₃ and 0.80 μm to 0.80 μm for P2 ₁₅ . A tunable L _n of each fabricated 2D rectangle of 3.3 μm was provided.

entry Unimer (kDa) ripening temperature
(℃) U/S ratio k' (h ^-One ) Error (h ^-One ) R ² One 5.0 -13 2 6.5ⅹ10 ^-3 6.1ⅹ10 ^-4 0.991 2 3 5.1ⅹ10 ^-3 4.0ⅹ10 ^-4 0.993 3 5 4.9ⅹ10 ^-3 4.2ⅹ10 ^-4 0.991 4 10 5.4ⅹ10 ^-3 4.6ⅹ10 ^-5 0.995 5 15 4.4ⅹ10 ^-3 2.5ⅹ10 ^-5 0.997 6 5.0 0 10 3.0ⅹ10 ^-3 8.4ⅹ10 ^-5 0.999 7 -10 3.8ⅹ10 ^-3 1.4ⅹ10 ^-4 0.999 8 -20 7.3ⅹ10 ^-3 2.2ⅹ10 ^-4 0.999 9 -25 1.1ⅹ10 ^-2 2.7ⅹ10 ^-4 0.999 10 5.0 25 10 1.3ⅹ10 ^-4 4.3ⅹ10 ^-5 0.999 11 5.6 1.5ⅹ10 ^-3 5.9ⅹ10 ^-5 0.999 12 6.1 2.5ⅹ10 ^-3 1.4ⅹ10 ^-4 0.999

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

Interestingly, uniaxial living 2D CDSAs can be fabricated into more complex multi-block comicelles (BCMs) through serial seed-growth from various P2 unimers. Similar to block copolymerization via living polymerization, sequential addition of P2 ₁₀ and P2 ₁₅ provided penta-BCM with controlled length and height along the (010) direction (unimer in 10 g/L chloroform, 3 of U/S ratio, [2D seed] = 0.03 g/L in chloroform, Fig. 4a). By changing the order of addition, two types of symmetric penta-BCM, A(P2 ₁₅ )-B(P 2 ₁₀ )-S (seed)-BA and BASAB, were produced with uniform length and narrow dispersion (Fig. 4b). Since the A block of P2 ₁₅ appears darker than the B block of P2 ₁₀ due to its 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 simpler but more difficult one-shot BCM by simultaneously adding two P2 unimers to a 2D seed with each U/S ratio of 3 at 25 °C. Since the more crystalline P2 ₁₅ grew much faster than the P2 ₁₀ , the longer P2 ₁₅ preferentially assembles into 2D seeds. Then, when the temperature was lowered to 0 °C, the self-assembly of the shorter P2 ₁₀ was initiated through a seed-growth mechanism to form the same BASAB penta-BCM prepared by sequential addition (Fig. 4e). These results provide an excellent example of these novel strategies that can be used to construct complex nanostructures based on a deep understanding of 2D assembly processes.

Because 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 unimers, indicating that the longer P2 emits more intense light. In addition, videos of micellar solutions recorded by confocal laser scanning microscopy (CLSM) show sustained 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 enable control of the width further from the successful preparation of the 2D nanosheet having a controlled length. In particular, when THF or chloroform was added as a co-solvent in a simple heating and aging method in a dichloromethane (DCM) solution of one example of PCPV homopolymers containing fluorene and bulky substituents in previous studies , at 18 different content ratios, it was observed that the aspect ratio was controlled. 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. It was inferred that it was caused by .

Accordingly, the present inventors used the linear dependence of the aspect ratio of the nanosheets due to the cosolvent effect in order to achieve the production of 2D nanosheets in which the width and length are simultaneously controlled using the blend, and a simple heating method followed by cosolvent addition and aging was used. In this respect, various conditions were screened by changing the co-solvent % and concentration in the above method for producing uniform single-layer 2D seeds.

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

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

With the obtained uniform 2D seeds whose widths are controlled, the present inventors performed CDSA through seed growth with additionally controlled lengths to provide an environment in which the widths and lengths are simultaneously controlled. 2D seeds whose widths were adjusted according to the volume ratio (indicated as "SMC") of 0%, 10%, 20%, and 30% of the co-solvent DCM added during seed formation were used, and the U/S ratio was adjusted. Accordingly, 2D nanosheets with controlled lengths were prepared by selectively growing in the (010) direction. Additionally, in order to increase the length control speed, the present inventors controlled the length of the nanosheet by adding a co-solvent DCM (indicated as “CMC”) during the CDSA process through seed growth. In this case, the volume % of DCM is was set at 50%. In the conditions of each experiment, the conditions other than the volume ratio of SMC and the U / S ratio 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 regardless of CMC 50%, and the length increased linearly with the U/S ratio. First, the length control of the 2D seed of 0% SMC with a width of 970 nm was successful from 1,890 nm to 4,160 nm (FIGS. 9a to 9g). The length control of the 850 nm wide 2D seed was successful from 3,300 nm to 5,300 nm (Figs. 10a to 10f). The length control of the 650 nm wide 2D seed was successful from 5,100 nm to 8,000 nm (Figs. 11a to 11d). Finally, the length control of the 2D seed with 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 generating 2D nanosheets with both width and length controlled through length-controlled CDSA of 2D seeds with controlled width.

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

4. Conclusion

In conclusion, we have successfully fabricated the formation of uniform semiconductor 2D rectangles with sharp corners from semi-crystalline conjugated homopolymers by a uniaxial seed-growth approach. This intriguing directionally-selective assembly allows control of the length of 2D rectangles with narrow dispersion via 2D CDSA for the first time. Using uniaxial growth from these homopolymers, 2D growth kinetics studies have shown that homopolymer self-assembly follows idealized first-order kinetics similar to living polymerization. These results indicate that the polymer self-assembly follows an ideal crystallization since the morphological effects of shell block or backbone chain folding are removed. Finally, 2D CDSA fabricated several complex but well-controlled penta-BCMs using different sizes of P2. Ultimately, we succeeded in one-shot BCM formation based on our understanding of growth kinetics, which provided an excellent guideline for optimizing self-assembly conditions. These precisely controlled, homogeneous fluorescent 2D nanostructures have great potential for optoelectronic applications.

The above description of the present application is for illustrative purposes, and those skilled in the art 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, the embodiments described above should be understood as illustrative in all respects and not limiting. For example, each component described as a single type may be implemented in a distributed manner, and similarly, 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 detailed description above, and all changes or modifications derived from the meaning and scope of the claims and equivalent concepts thereof should be construed as being included in the scope of the present application. .

Claims (20)

a block copolymer represented by Formula 1 or Formula 2 below; and
Homopolymer represented by the following formula (3)
Two-dimensional polymer nanosheets containing:
[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 from 20 to 70;
n and p are each independently an integer from 5 to 70;
q is an integer from 5 to 70;
According to claim 1,
R ¹ and R ³ are each independently a substituted or unsubstituted methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, an iso-butyl group, a 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 A practical, two-dimensional polymer nanosheet.
According to 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 methylbutyl group, a two-dimensional polymer nanosheet.
According to claim 1,
-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, a two-dimensional polymer nanosheet.
According to claim 1,
The width (100) of the two-dimensional polymer nanosheet is from 100 nm to 10 μm, the two-dimensional polymer nanosheet.
According to claim 1,
The length (010) of the two-dimensional polymer nanosheet is from 500 nm to 20 μm, the two-dimensional polymer nanosheet.
According to claim 1,
The height of the two-dimensional polymer nanosheet is from 1 nm to 500 nm, the two-dimensional polymer nanosheet.
According to claim 1,
The two-dimensional polymer nanosheet has conductivity and / or fluorescence, the two-dimensional polymer nanosheet.
(a) obtaining a two-dimensional seed by mixing a block copolymer represented by Formula 1 or Formula 2 below and a homopolymer represented by Formula 3 below; and
(b) obtaining a two-dimensional polymer nanosheet by adding a unomer containing a homopolymer represented by Formula 3 below 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 from 20 to 70;
n and p are each independently an integer from 5 to 70;
q is an integer from 5 to 70;
According to claim 9,
In (a), the two-dimensional seed is formed by co-assembly of the block copolymer and the homopolymer, the method for producing a two-dimensional polymer nanosheet.
According to claim 9,
In (b), the two-dimensional polymer nanosheet is a method of producing a two-dimensional polymer nanosheet that is formed by seed-growth.
According to claim 11,
The seed-growth is a method for producing a two-dimensional polymer nanosheet that is a primary reaction.
According to 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 adjust the width of the two-dimensional seed, a method for producing a two-dimensional polymer nanosheet.
According to 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.
According to claim 9,
In (b), to adjust the length of the two-dimensional polymer nanosheet according to the mass ratio of the unomer to the seed, a method for producing a two-dimensional polymer nanosheet.
According to claim 9,
In (b), to adjust the height of the two-dimensional polymer nanosheet according to the degree of polymerization of the unimers to be added, a method for producing a two-dimensional polymer nanosheet.
17. The method of claim 16,
A method for producing a two-dimensional polymer nanosheet, wherein a block comichel is formed by adding the unomers having two or more different degrees of polymerization.
According to claim 9,
A method for producing a two-dimensional polymer nanosheet, further comprising a heating step and/or aging step in (a) and/or (b).
A device comprising the two-dimensional polymer nanosheet according to any one of claims 1 to 8.
According to claim 19,
Wherein the device is a transistor, sensor, imaging agent, light emitting diode, photovoltaic cell, or conductive display.

Images