METHOD OF MANUFACTURING PATTERNED SUBSTRATE

Abstract

Provided is a method of manufacturing a patterned substrate. The method may be applied to a process of manufacturing a device such as an electronic device or integrated circuit, or another use, for example, to manufacture an integrated optical system, a guidance and detection pattern of a magnetic domain memory, a flat panel display, a LCD, a thin film magnetic head or an organic light emitting diode, and used to construct a pattern on a surface to be used to manufacture a discrete tract medium such as an integrated circuit, a bit-patterned medium and/or a magnetic storage device such as a hard drive.

Claims

1. A method of manufacturing a patterned substrate, comprising: forming a polymer film including a block copolymer in which a self-assembly structure is directed on a surface of an oxygen plasma-treated substrate.

2. The method of claim 1, wherein the substrate is a metal substrate.

3. The method of claim 1, wherein the substrate includes one or more metals selected from the group consisting of gold, copper, titanium, nickel, silver, aluminum, germanium, tungsten, tin, antimony, indium, cadmium, palladium, lead and platinum, or an oxide, nitride or sulfide of the one or more metals.

4. The method of claim 1, wherein the oxygen plasma is applied with RF power of 30 to 2000 W, a process pressure of 5 to 300 mTorr and an oxygen flow rate of 20 to 100 sccm.

5. The method of claim 1, wherein the polymer film is formed in contact with the surface of the oxygen plasma-treated substrate.

6. The method of claim 1, wherein the self-assembly structure includes a vertically oriented block copolymer.

7. The method of claim 1, wherein the self-assembly structure is a lamellar structure.

8. The method of claim 1, wherein the block copolymer includes a first block and a second block different from the first block, in which the first block shows a peak at an azimuthal angle of 90 to 70 degrees or 70 to 90 degrees of a diffraction pattern of a scattering vector of 12 to 16 nm.sup.1 in a GIWAXS spectrum.

9. The method of claim 1, wherein the block copolymer includes a first block and a second block having a different chemical structure from the first block, in which the first block shows a melting transition peak or isotropic transition peak in a range of 80 to 200 C. through differential scanning calorimetry (DSC) analysis.

10. The method of claim 1, wherein the block copolymer includes a first block and a second block having a different chemical structure from the first block, in which the first block shows a peak having a full width at half maximum (FWHM) of 0.2 to 0.9 nm.sup.1 in a scattering vector (q) range of 0.5 to 10 nm.sup.1 through XRD analysis.

11. The method of claim 1, wherein the block copolymer includes a first block and a second block having a different chemical structure from the first block, in which the first block includes a side chain, and the number of chain-forming atoms (n) of the side chain and the scattering vector (q) obtained by XRD analysis performed on the first block, satisfy Equation 2:
3 to 5 nm.sup.1=nq/(2)[Equation 2] where n is the number of chain-forming atoms of the side chain, q is the smallest scattering vector (q) in which a peak is shown through XRD analysis performed on a block including the side chain, or a scattering vector (q) showing a peak having the largest peak area.

12. The method of claim 1, wherein the block copolymer includes a first block and a second block having a different chemical structure from the first block, in which the absolute value of a difference in surface energy between the first block and the second block is 10 mN/m or less.

13. The method of claim 1, wherein the block copolymer include a first block and a second block having a different chemical structure from the first block, in which the absolute value of a difference in density between the first block and the second block is 0.25 g/cm.sup.3 or more.

14. The method of claim 1, wherein the block copolymer includes a first block and a second block different from the first block, in which a volume fraction of the first block is in a range of 0.2 to 0.6, and a volume fraction of the second block is in a range of 0.4 to 0.8.

15. The method of claim 1, wherein the first block of the block copolymer includes a side chain having 8 or more chain-forming atoms.

16. The method of claim 15, wherein the first block includes a ring structure, and the side chain is substituted in the ring structure.

17. The method of claim 16, wherein the ring structure does not include a halogen atom.

18. The method of claim 15, wherein the second block of the block copolymer includes 3 or more halogen atoms.

19. The method of claim 18, wherein the second block includes a ring structure, and the halogen atom is substituted in the ring structure.

20. The method of claim 1, wherein the block copolymer includes a block having the unit represented by Formula 1: ##STR00022## where R is a hydrogen or an alkyl group, X is a single bond, an oxygen atom, a sulfur atom, S(O).sub.2, a carbonyl group, an alkylene group, an alkenylene group, an alkynylene group, C(O)X.sub.1 or X.sub.1C(O), in which X.sub.1 is an oxygen atom, a sulfur atom, S(O).sub.2, an alkylene group, an alkenylene group or an alkynylene group, and Y is a monovalent substituent including a ring structure to which the side chain having a chain-forming atom is linked.

21. The method of claim 20, wherein Y of Formula 1 is represented by Formula 2:
P-Q-Z[Formula 2] where P is an arylene group or a cycloalkylene group, Q is a single bond, an oxygen atom or NR.sub.3, in which R.sub.3 is a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, Z is the chain having three or more chain-forming atoms when P is an arylene group, or the chain having 8 or more chain-forming atoms when P is a cycloalkylene group.

22. The method of claim 21, wherein P of Formula 2 is an arylene group having 6 to 12 carbon atoms.

23. The method of claim 1, wherein the block copolymer includes a block having the unit represented by Formula 3: ##STR00023## where R is a hydrogen or an alkyl group having 1 to 4 carbon atoms, X is a single bond, an oxygen atom, C(O)O or OC(O), P is an arylene group, Q is an oxygen atom or NR.sub.3, in which R.sub.3 is a hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group or an aryl group, and Z is a linear chain having 8 or more chain-forming atoms.

24. The method of claim 1, wherein the block copolymer includes a block having the unit represented by Formula 5: ##STR00024## where B is a monovalent substituent having an aromatic structure including one or more halogen atoms.

25. The method of claim 1, further comprising: selectively removing any one block of the block copolymer, which forms a self-assembly structure.

26. The method of claim 25, further comprising: etching the substrate, after one block of the block copolymer is selectively removed.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0216] FIG. 1 shows an exemplary example of a substrate having a trench.

[0217] FIG. 2 schematically shows that a self-assembled polymer is formed in the trench of the substrate.

[0218] FIG. 3 schematically shows that any one block of the self-assembled block copolymer is selectively removed.

[0219] FIG. 4 is an image of a self-assembled polymer film formed in Example 1.

EFFECT

[0220] According to the present invention, a method of manufacturing a patterned substrate is provided. The method can be applied to a process of manufacturing devices such as an electronic device and an integrated circuit, or another use, for example, to manufacture an integrated optical system, a guidance and detection pattern of a magnetic domain memory, a flat panel display, a LCD, a thin film magnetic head or an organic light emitting diode, and used to construct a pattern on a surface to be used to manufacture a discrete tract medium such as an integrated circuit, a bit-patterned medium and/or a magnetic storage device such as a hard drive.

DETAILED DESCRIPTION OF EMBODIMENTS

[0221] Hereinafter, the present application will be described in further detail with reference to examples according to the present invention, but the scope of the present application is not limited to the following examples.

[0222] 1. NMR Analysis

[0223] NMR analysis was performed at room temperature using an NMR spectrometer including a Varian Unity Inova (500 MHz) spectrometer having a triple resonance 5 mm probe. A subject for analysis was diluted with a solvent (CDCl.sub.3) for measuring NMR at a concentration of about 10 mg/ml, and chemical shift was expressed in ppm.

[0224] <Abbreviations>

[0225] br=broad signal, s=singlet, d=doublet, dd=doublet of doublets, t=triplet, dt=doublet of triblets, q=quartet, p=quintet, m=multiplet.

[0226] 2. Gel Permeation Chromatography (GPC)

[0227] A number average molecular weight (Mn) and a distribution of molecular weight were measured by GPC. A subject for analysis such as a block copolymer or macro initiator of Example or Comparative Example was put into 5 ml vial, and diluted with tetrahydrofuran (THF) to have a concentration of about 1 mg/mL. Afterward, a standard sample for Calibration and a sample for analysis were measured after passing through a syringe filter (pore size: 0.45 m). As an analysis program, ChemStation produced by Agilent technologies was used, and an elution time for the sample was compared with a calibration curve, thereby obtaining a weight average molecular weight (Mw) and a number average molecular weight (Mn), and a ratio (Mw/Mn) was used to calculate a polydispersity index (PDI). Conditions for measuring GPC are as follows.

[0228] <Conditions for Measuring GPC>

[0229] Device: 1200 series produced by Agilent technologies

[0230] Column: Two PLgel mixed B produced by Polymer laboratories

[0231] Solvent: THF

[0232] Column temperature: 35 C.

[0233] Sample concentration: 1 mg/mL, 200 L injection

[0234] Standard sample: Polystyrene (Mp: 3900000, 723000, 316500, 52200, 31400, 7200, 3940, 485)

[0235] 3. Method for XRD Analysis

[0236] XRD analysis was performed by measuring a scattering intensity according to a scattering vector (q) by irradiating a sample with an X ray using a Pohang light source 4C beam line. As a sample, a powder-type block copolymer was obtained by purifying a synthesized block copolymer without specific pretreatment and drying the block copolymer in a vacuum oven for about one day, and put into a cell for XRD measurement. In XRD pattern analysis, an X ray having a vertical size of 0.023 mm and a horizontal size of 0.3 mm was used, and a 2D marCCD was used as a detector. A 2D diffraction pattern obtained by scattering was obtained an image. Information such as a scattering vector and a FWHM were obtained by analyzing the obtained diffraction pattern by numerical analysis method using the least square method. For the analysis, an origin program was applied, a part showing the least intensity in an XRD diffraction pattern was set as a baseline to make the intensity 0, a profile of the XRD pattern peak was fitted by Gaussian fitting, and the scattering vector and the FWHM was obtained from the fitted result. In the Gauss fitting, the R square was set to at least 0.96 or more.

[0237] 4. Measurement of Surface Energy

[0238] Surface energy was measured using a drop-shape analyzer (DSA100, KRUSS). A coating solution was prepared by diluting a material for detection (polymer) with fluorobenzene at a solid content concentration of about 2 wt %, and the prepared coating solution was applied on a silicon wafer by spin coating to have a thickness of about 50 nm and a coating area of 4 cm.sup.2 (width: 2 cm, length: 2 cm). The coating layer was dried at room temperature for about 1 hour, and then thermal-annealed at about 160 C. for about 1 hour. Deionized water having a known surface tension was dropped on the film undergoing the thermal annealing, and a mean value of five contact angles obtained by repeating measurement of contact angles five times. Likewise, diiodomethane having a known surface tension was dropped on the film undergoing the thermal annealing, and a mean value of five contact angles obtained by repeating measurement of contact angles five times. Surface energy was obtained by substituting a Strom value with respect to the surface tension of the solvent through the Owens-Wendt-Rabel-Kaelble method using the obtained mean values of the contact angles for the deionized water and diiodomethane. The value of surface energy for each block of the block copolymer was obtained by the above-described method applied to a homopolymer prepared only using a monomer for forming the block.

[0239] 5. Measurement of Volume Fraction

[0240] The volume fraction of each block of the block copolymer was calculated based on a density, measured at room temperature, and a molecular weight, measured by GPC, of the block. Here, the density was measured by a buoyancy method, and specifically, calculated based on a weight of a sample for analysis after put into a solvent (ethanol) having a known weight and density in the air.

Preparation Example 1. Synthesis of Monomer (A)

[0241] A compound of Formula A (DPM-C12) was synthesized by the following method. Hydroquinone (10.0 g, 94.2 mmol) and 1-bromododecane (23.5 g, 94.2 mmol) were put into a 250 mL flask, dissolved in 100 mL acetonitrile, treated with an excessive amount of potassium carbonate to allow a reaction at 75 C. for about 48 hours under a nitrogen condition. After the reaction, remaining potassium carbonate was filtered to remove, and the acetonitrile used in the reaction was also removed. Here, a mixed solvent of dichloromethane (DCM) and water was added to work up, and a separated organic layer was dehydrated with MgSO.sub.4. Therefore, a white solid product (4-dodecyloxyphenol; 9.8 g, 35.2 mmol) was obtained with an yield of about 37% through column chromatography using DCM.

[0242] <NMR Analysis Result>

[0243] .sup.1H-NMR (CDCl.sub.3): 6.77 (dd, 4H); 4.45 (s, 1H); 3.89 (t, 2H); 1.75 (p, 2H); 1.43 (p, 2H); 1.33-1.26 (m, 16H); 0.88 (t, 3H).

[0244] Synthesized 4-dodecyloxyphenol (9.8 g, 35.2 mmol), methacrylic acid (6.0 g, 69.7 mmol), dicyclohexylcarbodiimide (DCC;10.8 g, 52.3 mmol) and p-dimethylaminopyridine (DMAP;1.7 g, 13.9 mmol) were put into a flask, and treated with 120 mL of methylenechloride to allow a reaction at room temperature for 24 hours under nitrogen. After the reaction was completed, a salt produced in the reaction (urea salt) was removed using a filter, and remaining methylenechloride was also removed. Debris was removed through column chromatography using hexane and dichloromethane (DCM) as moving phases, and then a product thereby was recrystallized in a mixed solvent of methanol and water (1:1 mixture), thereby obtaining a white solid product (7.7 g, 22.2 mmol) with an yield of 63%.

[0245] <NMR Analysis Result>

[0246] .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.32 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.76 (p, 2H); 1.43 (p, 2H); 1.34-1.27 (m, 16H); 0.88 (t, 3H).

##STR00017##

[0247] In Formula A, R is a linear alkyl group having 12 carbon atoms.

Preparation Example 2. Synthesis of Monomer(B)

[0248] A compound of Formula B was synthesized by the method according to Preparation Example 1, except that 1-bromooctane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0249] <NMR Analysis Result>

[0250] .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.32 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.76 (p, 2H); 1.45 (p, 2H); 1.33-1.29 (m, 8H); 0.89 (t, 3H).

##STR00018##

[0251] In Formula B, R is a linear alkyl group having 8 carbon atoms.

Preparation Example 3. Synthesis of Monomer(C)

[0252] A compound of Formula C was synthesized by the method according to Preparation Example 1, except that 1-bromodecane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0253] <NMR Analysis Result>

[0254] .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.33 (dt, 1H); 5.72 (dt, 1H); 3.94 (t, 2H); 2.06 (dd, 3H); 1.77 (p, 2H); 1.45 (p, 2H); 1.34-1.28 (m, 12H); 0.89 (t, 3H).

##STR00019##

[0255] In Formula C, R is a linear alkyl group having 10 carbon atoms.

Preparation Example 4. Synthesis of Monomer(D)

[0256] A compound of Formula D was synthesized by the method according to Preparation Example 1, except that 1-bromotetradecane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0257] <NMR Analysis Result>

[0258] .sup.1H-NMR (CDCl.sub.3): 7.02 (dd, 2H); 6.89 (dd, 2H); 6.33 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.77 (p, 2H); 1.45 (p, 2H); 1.36-1.27 (m, 20H); 0.88 (t, 3H.)

##STR00020##

[0259] In Formula D, R is a linear alkyl group having 14 carbon atoms.

Preparation Example 5. Synthesis of Monomer(E)

[0260] A compound of Formula E was synthesized by the method according to Preparation Example 1, except that 1-bromohexadetane, instead of 1-bromododecane, was used. The NMR analysis result for the compound is shown below.

[0261] <NMR Analysis Result>

[0262] .sup.1H-NMR (CDCl.sub.3): 7.01 (dd, 2H); 6.88 (dd, 2H); 6.32 (dt, 1H); 5.73 (dt, 1H); 3.94 (t, 2H); 2.05 (dd, 3H); 1.77 (p, 2H); 1.45 (p, 2H); 1.36-1.26 (m, 24H); 0.89 (t, 3H)

##STR00021##

[0263] In Formula E, R is a linear alkyl group having 16 carbon atoms.

Preparation Example 6. Synthesis of Block Copolymer

[0264] 2.0 g of the monomer (A) of Preparation Example 1, 64 mg of a reversible additionfragmentation chain transfer (RAFT) reagent, cyanoisopropyldithiobenzoate, 23 mg of a radical initiator, azobisisobutyronitrile (AIBN), and 5.34 ml of benzene were put into a 10 mL Schlenk flask, and stirred at room temperature for 30 minutes under a nitrogen atmosphere to allow an RAFT polymerization reaction at 70 C. for 4 hours. After the polymerization, a reaction solution was precipitated in 250 ml of methanol as an extraction solvent, and dried through decreased pressure filtration, thereby preparing a pink macroinitiator. The yield of the macroinitiator was about 82.6 wt %, and the number average molecular weight (Mn) and distribution of molecular weight (Mw/Mn) of the macroinitiator were 9,000 and 1.16, respectively. 0.3 g of the macroinitiator, 2.7174 g of a pentafluorostyrene monomer and 1.306 ml of benzene were put into a 10 mL Schlenk flask, and stirred at room temperature for 30 minutes under a nitrogen atmosphere to allow an RAFT polymerization reaction at 115 C. for 4 hours. After the polymerization, a reaction solution was precipitated in 250 ml of methanol as an extraction solvent, and dried through decreased pressure filtration, thereby preparing a light pink block copolymer. The yield of the block copolymer was about 18 wt %, and the number average molecular weight (Mn) and distribution of molecular weight (Mw/Mn) of the block copolymer were 16,300 and 1.13, respectively. The block copolymer includes a first block derived from the monomer (A) of Preparation Example 1 and a second block derived from the pentafluorostyrene monomer.

Preparation Example 7. Synthesis of Block Copolymer

[0265] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Preparation Example 6, except that the monomer (B) of Preparation Example 2, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (B) of Preparation Example 2 and a second block derived from the pentafluorostyrene monomer.

Preparation Example 8. Synthesis of Block Copolymer

[0266] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Preparation Example 6, except that the monomer (C) of Preparation Example 3, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (C) of Preparation Example 3 and a second block derived from the pentafluorostyrene monomer.

Preparation Example 9. Synthesis of Block Copolymer

[0267] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Preparation Example 6, except that the monomer (D) of Preparation Example 4, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (D) of Preparation Example 4 and a second block derived from the pentafluorostyrene monomer.

Preparation Example 10. Synthesis of Block Copolymer

[0268] A block copolymer was prepared using a macroinitiator and a pentafluorostyrene as monomers by the method according to Preparation Example 6, except that the monomer (E) of Preparation Example 5, instead of the monomer (A) of Preparation Example 1, was used. The block copolymer includes a first block derived from the monomer (E) of Preparation Example 5 and a second block derived from the pentafluorostyrene monomer.

[0269] GPC results for the macroinitiators and the block copolymers prepared in the above Preparation Examples are summarized and listed in Table 1.

TABLE-US-00001 TABLE 1 Preparation Example 6 7 8 9 10 MI Mn 9000 9300 8500 8700 9400 PDI 1.16 1.15 1.17 1.16 1.13 BCP Mn 16300 19900 17100 17400 18900 PDI 1.13 1.20 1.19 1.17 1.17 MI: macroinitiator BCP: block copolymer Mn: number average molecular weight PDI: polydispersity index

Experiment Example 1. X-Ray Diffraction Analysis

[0270] Results for analyzing XRD patterns for the block copolymers by the above-described methods are summarized and listed in Table 2.

TABLE-US-00002 TABLE 2 Preparation Example 6 7 8 9 10 q peak value(unit: nm.sup.1) 1.96 2.41 2.15 1.83 1.72 FWHM (unit: nm.sup.1) 0.57 0.72 0.63 0.45 0.53

Experiment Example 2. Evaluation of Physical Properties of Block Copolymer

[0271] Results of evaluating properties of the block copolymers prepared in Preparation Examples 6 to 10 by the method described above are summarized and listed in Table 3.

TABLE-US-00003 TABLE 3 Preparation Example 6 7 8 9 10 First SE 30.83 31.46 27.38 26.924 27.79 block De 1 1.04 1.02 0.99 1.00 VF 0.66 0.57 0.60 0.61 0.61 Second SE 24.4 24.4 24.4 24.4 24.4 block De 1.57 1.57 1.57 1.57 1.57 VF 0.34 0.43 0.40 0.39 0.39 SE difference 6.43 7.06 2.98 2.524 3.39 De difference 0.57 0.53 0.55 0.58 0.57 Chain-forming 12 8 10 14 16 atom n/D 3.75 3.08 3.45 4.24 4.44 SE: surface energy (unit: mN/m) De: density (unit: g/cm.sup.3) VF: volume fraction SE difference: absolute value of difference in surface energy between first block and second block De difference: absolute value of difference in density between first block and second block Chain-forming atom: the number of chain-forming atoms of first block n/D: value calculated by Equation 1 (nq/(2 )) (n: the number of chain-forming atoms, q: value of scattering vector showing peak having the largest peak area in range of scattering vector from 0.5 nm.sup.1 to 10 nm.sup.1) Ref: polystyrene-polymethylmethacrylate block copolymer (first block: polystyrene block, second block: polymethylmethacrylate block)

Example 1

[0272] A polymer film was formed by treating a copper substrate with an oxygen plasma, and applying the block copolymer of Preparation Example 6 to the substrate. The oxygen plasma was applied to a surface of the copper substrate with an RF power of about 90 W, an oxygen flow rate of about 70 sccm and a process pressure of about 120 mTorr. The block copolymer of Preparation Example 6 was applied to the oxygen plasma-treated layer formed thereby without separate treatment such as formation of a neutral layer, thereby forming a polymer film. Particularly, a coating solution prepared by diluting the block copolymer with toluene at a solid content of 1.5 wt % was spin-coated, dried at room temperature for about 1 hour, and thermal-annealed at about 160 to 250 C. for about 1 hour, thereby forming a self-assembled film. An SEM image for the self-assembled film is shown in FIG. 4, which showed that a suitable self-assembly structure was formed.

Example 2

[0273] A self-assembled polymer film, which is the same as formed in Example 1, was formed, except that the block copolymer of Preparation Example 7, instead of the block copolymer of Preparation Example 6, was applied. As seen from an SEM image, it was shown that a suitable self-assembly structure is formed as described in Example 1.

Example 3

[0274] A self-assembled polymer film, which is the same as formed in Example 1, was formed, except that the block copolymer of Preparation Example 8, instead of the block copolymer of Preparation Example 6, was applied. As seen from an SEM image, it was shown that a suitable self-assembly structure is formed as described in Example 1.

Example 4

[0275] A self-assembled polymer film, which is the same as formed in Example 1, was formed, except that the block copolymer of Preparation Example 9, instead of the block copolymer of Preparation Example 6, was applied. As seen from an SEM image, it was shown that a suitable self-assembly structure is formed as described in Example 1.

Example 5

[0276] A self-assembled polymer film, which is the same as formed in Example 1, was formed, except that the block copolymer of Preparation Example 10, instead of the block copolymer of Preparation Example 6, was applied. As seen from an SEM image, it was shown that a suitable self-assembly structure is formed as described in Example 1.