ZN-BASED ORGANIC COORDINATION NANOPARTICLES AND PREPARATION METHOD THEREFOR, PHOTORESIST COMPOSITION, AND USE THEREOF

Abstract

The present invention relates to a Zn-based organic coordination nanoparticles and a preparation method therefor, a photoresist composition, and use thereof. Zinc acetate, m-methylbenzoic acid and a nitrogen-containing organic ligand are mixed and stirred in an organic solvent, and are then subjected to a post-treatment to obtain a Zn-based organic coordination nanoparticles having a chemical general formula of [Zn.sub.mX.sub.n(CH.sub.3COO).sub.tY.sub.pH.sub.q].sub.r, wherein X is m-methylbenzoate; CH.sub.3COO represents acetate; Y is the nitrogen-containing organic ligand; r is the degree of polymerization; m, n, p, q, n and r are each independently selected from any integer of 1-20; and t is selected from any integer of 0-20. In the present invention, the Zn-based organic coordination nanoparticles are used as a film-forming agent of a photoresist, and compared with an existing photoresists, the prepared photoresist has lithographie properties of a high resolution, a high sensitivity and a low line roughness.

Claims

1. A Zn-based organic coordination nanoparticle, having a chemical formula of [Zn.sub.mX.sub.n(CH.sub.3COO).sub.tY.sub.pH.sub.q].sub.r, wherein X is m-methylbenzoic acid, CH.sub.3COO represents acetate, Y is a nitrogen-containing organic ligand, r is a degree of polymerization, each of m, n, p, q, n and r is independently selected from any integer from 1 to 20, and t is selected from any integer from 0 to 20.

2. The nanoparticle according to claim 1, wherein Y is any one or more selected from organic fatty amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, and amides and their derivatives.

3. The nanoparticle according to claim 1, wherein Y is selected from diethylamine, piperidine, diisopropylethylamine, and tetrahydropyrrole.

4. The nanoparticle according to claim 1, wherein each of m, n, p, q, n and r is independently an integer between 1-10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10, and t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.

5. The nanoparticle according to claim 1, wherein the size of the Zn-based organic coordination nanoparticle crystal is from 1 nm to 4 nm.

6. The nanoparticle according to claim 1, wherein the Zn-based organic coordination nanoparticle has a structural formula of: Zn.sub.2(CH.sub.3C.sub.6H.sub.4COO).sub.5(C.sub.4H.sub.11N)H, wherein C.sub.4H.sub.11N is diethylamine, and CH.sub.3C.sub.6H.sub.4COO is m-methylbenzoate; or Zn.sub.4(CH.sub.3C.sub.6H.sub.4COO).sub.6(CH.sub.3COO).sub.6(C.sub.4H.sub.9N).sub.4H.sub.4, wherein C.sub.4H.sub.9N is tetrahydropyrrole; or Zn.sub.3(CH.sub.3C.sub.6H.sub.4COO).sub.7(CH.sub.3COO)(C.sub.5H.sub.11N).sub.2H.sub.2, wherein C.sub.5H.sub.11N is piperidine; or Zn.sub.2(CH.sub.3C.sub.6H.sub.4COO).sub.5(C.sub.8H.sub.19N)H, wherein C.sub.8H.sub.19N is diisopropylethylamine.

7. A method for preparing a nanoparticle according to claim 1, comprising: mixing and stirring zinc acetate, m-methylbenzoic acid and a nitrogen-containing organic ligand in an organic solvent; and post-treating the mixture to obtain the nanoparticle, wherein the molar ratio of zinc acetate: m-methylbenzoic acid and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

8. A photoresist composition, comprising the nanoparticle according to claim 1.

9. The photoresist composition according to claim 8, further comprising a photoacid agent and an organic dispersing solvent, wherein the photoacid makes up 5 wt %-10 wt % of the composition, and the nanoparticle makes up 3 wt %-20 wt % of the composition.

10. The photoresist composition according to claim 9, wherein the photoacid agent is any one or more selected from N-hydroxynaphthaleneimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalene disulfonic acid, tert-butylphenyl iodonium perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.

11. The photoresist composition according to claim 9, wherein the organic dispersing solvent is any one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol and propanol.

12. A lithography method, comprising: using the photoresist composition according to claim 9; dripping the photoresist composition onto a substrate; rotating and heating the substrate, and then exposing the substrate with an electron beam, Mid-Ultra-Violet, Deep-Ultra-Violet or Extreme Ultra-Violet; and developing the substrate with a developing agent.

13. The lithography method according to claim 12, wherein the exposure dose of Mid-Ultra-Violet, Deep-Ultra-Violet or Extreme Ultra-Violet is 50 mJ/cm.sup.2500 mJ/cm.sup.2, and the exposure dose of electron beam is 50 C/cm.sup.2500 C/cm.sup.2.

14. The lithography method according to claim 12, wherein the a developing agent is any one selected from decalin, tetralin, indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane and cyclohexane, or any mixture thereof; and the developing temperature is room temperature, or 20 C.50 C.

15. Use of the nanoparticles according to claim 1, in the field of photoresist, including photoresists for electron beam, Mid-Ultra-Violet, Deep-Ultra-Violet or Extreme Ultra-Violet.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0043] FIG. 1 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticle according to Example 1 of the present invention.

[0044] FIG. 2A is a Hydrogen-1 Nuclear Magnetic Resonance (.sup.1H NMR) Spectrum of the Zn-based organic coordination nanoparticle and raw materials according to Example 1 of the present invention.

[0045] FIG. 2B is an infrared spectrum of the Zn-based organic coordination nanoparticle according to Example 1 of the present invention.

[0046] FIG. 3 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticle according to Example 2 of the present invention.

[0047] FIG. 4A is a Hydrogen-1 Nuclear Magnetic Resonance Spectrum of the Zn-based organic coordination nanoparticle and raw materials according to Example 2 of the present invention.

[0048] FIG. 4B is an infrared spectrum of the Zn-based organic coordination nanoparticle according to Example 2 of the present invention.

[0049] FIG. 5 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticle according to Example 3 of the present invention.

[0050] FIG. 6A is a Hydrogen-1 Nuclear Magnetic Resonance Spectrum of the Zn-based organic coordination nanoparticle and raw materials according to Example 3 of the present invention.

[0051] FIG. 6B is an infrared spectrum of the Zn-based organic coordination nanoparticle according to Example 3 of the present invention.

[0052] FIG. 7 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticle according to Example 4 of the present invention.

[0053] FIG. 8A is a Hydrogen-1 Nuclear Magnetic Resonance Spectrum of the Zn-based organic coordination nanoparticle and raw materials according to Example 4 of the present invention.

[0054] FIG. 8B is an infrared spectrum of the Zn-based organic coordination nanoparticle according to Example 4 of the present invention.

[0055] FIG. 9A and FIG. 9B are the images of the exposed samples of the Zn-based organic coordination nanoparticle according to Example 1 of the present invention under Deep-Ultra-Violet of 254 nm and under electron beam.

[0056] FIG. 10A and FIG. 10B are the images of the exposed samples of the Zn-based organic coordination nanoparticle according to Example 2 of the present invention under Deep-Ultra-Violet of 254 nm and under electron beam.

[0057] FIG. 11A and FIG. 11B are the images of the exposed samples of the Zn-based organic coordination nanoparticle according to Example 3 of the present invention under Deep-Ultra-Violet of 254 nm and under electron beam.

[0058] FIG. 12A and FIG. 12B are the images of the exposed samples of the Zn-based organic coordination nanoparticle according to Example 4 of the present invention under Deep-Ultra-Violet of 254 nm and under electron beam.

[0059] FIG. 13 shows the difference in Extreme Ultra-Violet exposure performance of Example 1 of the present invention when it is first synthesized and after being left for two months.

[0060] FIG. 14 shows the difference in Extreme Ultra-Violet exposure performance of Comparative Example 1 of the present invention when it is first synthesized and after being left for two months.

[0061] FIG. 15 shows the difference in exposure performance of Comparative Example 2 of the present invention when it is first synthesized and after being left for two months.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Example 1

[0062] 0.02 mol of zinc acetate, 0.04 mol of m-methylbenzoic acid, 0.03 mol of organic amine diisopropylethylamine and 45 mL of the solvent ethyl acetate were mixed and stirred evenly. The mixture was stirred at 65 C. for 8 h, was rotated and evaporated with a rotary evaporator at 50 C. for 30 minutes, and then was evacuated in a vacuum oven at 65 C. for 5 hours to obtain the synthesized product of Example 1. After analysis, the nanoparticle obtained in Example 1 comprised Zn.sub.2(CH.sub.3CH.sub.4COO).sub.5(C.sub.8H.sub.19N)H. The .sup.1H NMR (600 MHz, DMSO-d6) of the nanoparticle is 7.77-7.75 (m), 7.75-7.70 (m), 7.31-7.26 (m), 3.29-3.21 (m), 2.73 (q), 2.34 (s), 1.87 (s), 1.08 (d). The particle size, the .sup.1H NMR Spectrum and Infrared Spectrum of the raw materials used and the obtained nanoparticle were characterized, as shown in FIG. 1, FIG. 2A and FIG. 2B. According to the NMR detection results: after the photoresist nanoparticle of Example 1 was synthesized, each of the monomers were coordinated respectively and peak shifts occurred. The peaks in the diisopropylethylamine structure shifted from 0.94, 2.42 and 2.96 to 1.08, 2.73 and 3.24 respectively; the peak of the methyl group in zinc acetate shifted from 1.82 to 1.87; the peak of the methyl group in m-methylbenzoic acid shifted from 2.37 to 2.34, and the benzene ring peak also shifted from 7.39, 7.44 and 7.76 to 7.29, 7.73 and 7.76. It can be seen from FIG. 2B that the peaks at 1630 cm.sup.1, 1558 cm.sup.1 and 1370 cm.sup.1 correspond to the symmetric and asymmetric stretching of COO in the carboxyl group. At 820 cm.sup.1-650 cm.sup.1 is the bending vibration peak of CH in the aromatic ring of m-methylbenzoic acid. The vibration signals of the benzene ring skeleton are observed at 1600 cm.sup.1 and 1500 cm.sup.1-1450 cm.sup.1. The peak at 621 cm.sup.1 is attributed to the stretching vibration of the ZnO bond.

Example 2

[0063] Different from Example 1, diethylamine was selected as the organic amine in Example 2, and the rest was the same as in Example 1 to obtain the synthesized product of Example 2. After analysis, the obtained nanoparticle comprised Zn.sub.2(CH.sub.3C.sub.6H.sub.4COO).sub.5(C.sub.4H.sub.11N)H. The particle size and the .sup.1H NMR Spectrum of the raw materials used and the obtained nanoparticle were characterized, particularly as shown in FIG. 3, FIG. 4A and FIG, 4B. According to the NMR detection results: .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.74 (d), 7.71 (dt), 7.30-7.22 (m), 2.86 (q), 2.33 (s,), 1.83 (s), 1.14 (t). After the photoresist nanoparticle of Example 2 was synthesized, each of the monomers was coordinated respectively and peak shifts occurred. The peaks in the diethylamine structure shifted from 0.98 and 2.50 to 1.14 and 2.86 respectively; the peak of the methyl group in zinc acetate shifted from 1.82 to 1.83; the peak of the methyl group in m-methylbenzoic acid shifted from 2.37 to 2.33, the peaks of the benzene ring also shifted from 7.39, 7.44 and 7.76 to 7.25, 7.71 and 7.74. It can be seen from FIG. 4B that the peaks at 1630 cm.sup.1, 1558 cm.sup.1 and 1370 cm.sup.1 correspond to the symmetric and asymmetric stretching of COO in the carboxyl group. At 820 cm.sup.1-650 cm.sup.1 is the bending vibration peak of CH in the aromatic ring of m-methylbenzoic acid. The vibration signals of the benzene ring skeleton are observed at 1600 cm.sup.1 and 1500 cm.sup.1-1450 cm.sup.1. The peak at 621 cm.sup.1 is attributed to the stretching vibration of the ZnO bond.

Example 3

[0064] Different from Example 1, piperidine was selected as the organic amine in Example 3, and the rest was the same as in Example 1 to obtain the synthesized product of Example 3. After analysis, the obtained nanoparticle comprised Zn.sub.3(CH.sub.3C.sub.6H.sub.4COO).sub.7(CH.sub.3COO)(C.sub.5H.sub.11N).sub.2H.sub.2. The particle size and .sup.1H NMR Spectrum of the raw materials used and the obtained nanoparticle were characterized, particularly as shown in FIG. 5 and FIG. 6A and FIG. 6B. According to the NMR detection results: .sup.1H NMR (400 MHz, DMSO-d.sub.6) 7.77-7.74 (m), 7.75-7.70 (m), 7.29-7.23 (m), 2.96 (t, J=5.5 Hz), 2.33 (s), 1.85 (s), 1.63-1.54 (m), 1.53 (s). After the photoresist nanoparticle of Example 3 was synthesized, each of the monomers was coordinated respectively, and peak shifts occurred. The peaks in the piperidine structure shifted from 1.35, 1.43 and 2.58 to 1.53, 1.59 and 2.96 respectively; the peak of the methyl group in zinc acetate shifted from 1.82 to 1.85; the peak of the methyl group in m-methylbenzoic acid shifted from 2.37 to 2.33, and the peak of the benzene ring also shifted from 7.39, 7.44 and 7.76 to 7.26, 7.73 and 7.75. It can be seen from FIG. 6B that the peaks at 1630 cm.sup.1, 1558 cm.sup.1 and 1370 cm.sup.1 correspond to the symmetric and asymmetric stretching of COO in the carboxyl group. At 820 cm.sup.1-650 cm.sup.1 is the bending vibration peak of CH in the aromatic ring of m-methylbenzoic acid. The vibration signals of the benzene ring skeleton are observed at 1600 cm.sup.1 and 1500 cm.sup.1-1450 cm.sup.1. The peak at 621 cm.sup.1 is attributed to the stretching vibration of the ZnO bond.

Example 4

[0065] Different from Example 1, tetrahydropyrrole was selected as the organic amine in Example 4, and the rest was the same as in Example 1 to obtain the synthesized product of Example 4. After analysis, the obtained nanoparticle comprised Zn.sub.4(CH.sub.3C.sub.6H.sub.4COO).sub.6(CH.sub.3COO).sub.6(C.sub.4H.sub.9N).sub.4H. The particle size and .sup.1H NMR Spectrum of the raw materials used and the obtained nanoparticle were characterized, particularly as shown in FIG. 7, FIG. 8A and FIG. 8B. According to the NMR detection results: .sup.1H NMR (600 MHz, DMSO-d.sub.6) 7.75 (dd), 7.72 (ddd), 7.32-7.24 (m), 3.03 (d), 2.34 (s), 1.85 (s), 1.75 (q). Each of the monomers was coordinated respectively, and peak shifts occurred. The peaks in the tetrahydropyrrole structure shifted from 1.54 and 2.66 to 1.75 and 3.03 respectively; the peak of the methyl group in zinc acetate shifted from 1.82 to 1.85; the peak of the methyl group in m-methylbenzoic acid shifted from 2.37 to 2.34, the peaks of the benzene ring also shifted from 7.39, 7.44 and 7.76 to 7.27, 7.72 and 7.75. It can be seen from FIG. 8B that the peaks at 1630 cm.sup.1, 1558 cm.sup.1 and 1370 cm.sup.1 correspond to the symmetric and asymmetric stretching of COO in the carboxyl group. At 820 cm.sup.1-650 cm.sup.1 is the bending vibration peak of CH in the aromatic ring of m-methylbenzoic acid. The vibration signals of the benzene ring skeleton are observed at 1600 cm.sup.1 and 1500 cm.sup.1-1450 cm.sup.1. The peak at 621 cm.sup.1 is attributed to the stretching vibration of the ZnO bond.

Example 5

[0066] The nanoparticle in Example 1 was dissolved with propylene glycol methyl ether acetate, the mass ratio of the nanoparticle in the composition was controlled to 5%, and then the photoacid N-hydroxynaphthalimide trifluoromethanesulfonic acid was added thereto, the mass of the photoacid made up 10% of the composition, the composition was stirred for 5 minutes until all the composition was dissolved completely to obtain a photoresist mixture solution.

[0067] The photoresist mixture solution was filtered twice with a filter head, then the silicon wafer was placed on a coater, the photoresist was dripped onto the silicon wafer, the rotational speed was set to 2000 r/min, and the silicon wafer was rotated for 1 minute. Then, the silicon wafer was heated on a hot plate at 80 C. for 1 minute. The exposure was performed under electron beam, Mid-Ultra-Violet, Deep Ultra-Violet, or Extreme Ultra-Violet. After exposure, the silicon wafer was developed with decahydronaphthalene for 10 s-40 s, and was blown dry with nitrogen.

[0068] The obtained test patterns were shown in FIG. 9A and FIG. 9B. FIG. 9A shew that clear exposure patterns were obtained by the synthesized product of Example 1 under the conditions of Mid-Ultra-Violet (150 mJ/cm.sup.2) and electron beam (150 C/cm.sup.2) (FIG. 9B).

Example 6-9

[0069] The nanoparticles obtained in Examples 2-4 were subjected to the lithography test, respectively, and the obtained patterns were shown in FIGS. 10A-12B. FIG. 10A and FIG. 10B shew the exposure patterns of the photoresist comprising the nanoparticle synthesized in Example 2 under the conditions of Mid-Ultra-Violet (150 mJ/cm.sup.2) and electron beam (150 C/cm.sup.2, 50 nm), respectively. FIG. 11A and FIG. 11B were the exposure patterns of the photoresist comprising the nanoparticle synthesized in Example 3 under the conditions of Mid-Ultra-Violet (150 mJ/cm.sup.2) and electron beam (270 C/cm.sup.2, 50 nm), respectively. FIG. 12A and FIG. 12B were the exposure patterns of the photoresist comprising the nanoparticle synthesized in Example 4 under the conditions of Mid-Ultra-Violet (150 mJ/cm.sup.2) and electron beam (120 C/cm.sup.2, 50 nm), respectively.

Comparative Example 1

[0070] For the preparation method in Example 1, m-methylbenzoic acid was replaced with benzoic acid to obtain a nanoparticle. The rest is the same as Example 1.

Comparative Example 2

[0071] The organic amine in the preparation method in Example 1 was replaced with triethylamine to obtain a nanoparticle. The rest is the same as Example 1.

Example 10

[0072] For Example 1 and Comparative Examples 1 and 2, exposure was performed under EUV (with exposure condition 200 mJ/cm.sup.2), and the exposure patterns as shown in FIGS. 13-15 were obtained after 2 months. From the patterns, it can be seen that, when the nanoparticle of Example 1 was just synthesized: the lines were not bridged, the contrast was good; and two months later, the lines were not bridged basically, and the contrast was good.

[0073] When the nanoparticle of Comparative Example 1 was just synthesized: the lines were not bridged basically, and the contrast was good; and two months later, the lines were bridged, and the contrast was slightly worse. When the nanoparticles of Comparative Example 2 were just synthesized: the lines were bridged, the contrast was slightly worse; and two months later, the lines were severely adhered, there were more fractures, and the contrast was worse. It can be seen that the nanoparticles in this application are better in stability than those of Comparative Examples 1-2.

[0074] In view of above, the present invention obtains four effective nanoparticles, verifies their particle size distributions and good lithography performances under the conditions of Deep-Ultra-Violet lithography at a wavelength of 254 nm and electron beam lithography, which can achieve better lithography performance such as high resolution, high sensitivity, and low line roughness, and proves that m-methylbenzoic acid as a ligand can improve the stability of nanoparticles in lithography.