Co-based organically coordinated nanoparticles and method for producing the same, photoresist composition and use thereof

Abstract

The present invention relates to Co-based organic coordination nanoparticles, a method for preparing the same, a photoresist composition and its use. The Co-based organic coordination nanoparticles provided by the present invention are represented by the general formula Co m R n Q x M y N z where Co is one of two types of ions, divalent Co and trivalent Co, R is selected from a benzoic acid group or a m-methylbenzoic acid group, Q can be selected from imidazole and its derivatives, M is a carboxylic acid, and N is water of crystallization, and the Co-based organically coordinated nanoparticle crystal size is 1 nm to 5 nm. The nanoparticles can be placed in a photoresist composition and exposed to electron beams or mid-ultraviolet, deep-ultraviolet, or extreme-ultraviolet radiation and developed to obtain patterns with high resolution, high sensitivity, and low line roughness. The Co-based organically coordinated nanoparticles and photoresist compositions provided by the present invention have greater potential for application in the field of EUV lithography.

Description

[Technical Field]

[0001] The present invention relates to the technical field of photoresists, and in particular to Co-based organically coordinated nanoparticles and their preparation method, photoresist compositions and their use. [Background technology]

[0002] Photoresist refers to a corrosion-resistant thin film material whose solubility changes when exposed to ultraviolet, electron beam, particle beam, extreme ultraviolet (EUV), or soft x-ray radiation. With the continuous advancement of semiconductor technology and the development of Moore's Law, semiconductor manufacturing processes are correspondingly shrinking, placing greater demands on the reduction of processing feature sizes. To meet more advanced semiconductor manufacturing processes and achieve smaller feature sizes, lithography technology is also constantly evolving, from I-line, G-line, deep ultraviolet (DUV), 193 nm, and immersion 193 nm to extreme ultraviolet lithography and electron beam lithography, among other microfabrication methods. After photoresist film is exposed and developed to form a lithographic pattern, it is then dry- or wet-etched. While the portions of the substrate not covered by the photoresist film are directly etched, the surface of the substrate covered by the photoresist film is protected by the photoresist film and is not etched. Etching resistance is an extremely important evaluation index for photoresists. Excellent etching resistance can ensure that the photoresist protects the substrate surface from damage during the etching process, and can effectively simplify the etching process, greatly improving the yield of etched products.

[0003] Traditional photoresists have complex components, including the photoresist resin itself, photosensitizers, leveling agents, stabilizers, dispersants, thickeners, and solvents. This makes production processes complicated and places strict demands on control of formulation and purity. Traditional photoresists are mostly high-molecular-weight polymers containing numerous functional additives. Their complex composition results in a wide size distribution of photoresists, with components of various sizes, some of which reach 10-20 nm. This makes it difficult to control the size of photoresist patterns and can lead to numerous defects. Furthermore, the application range of traditional photoresists is significantly affected by the wavelength of the light source, requiring different photoresists for different light sources. Currently, metal oxide photoresists are a hot research topic, and they have become a viable option for ultrafine pattern exposure using EUV or electron beams. Zn-based nanoorganic ligand photoresists are a metal oxide organic ligand system previously investigated by the applicant, and their lithography performance has been verified. Co and Zn are close to each other in the periodic table and have certain similarities in their properties, making them suitable for use as photoresists. However, no Co-based nanoorganic ligand photoresists have been reported to date. The present inventors conducted further research into this material system and synthesized a Co-based nanoorganic photoresist composition with improved lithography performance. Summary of the Invention [Problem to be solved by the invention]

[0004] The present invention addresses the problems of large edge roughness and low pattern resolution in patterns obtained by lithography using conventional photoresists. It provides novel Co-based organic coordination nanoparticles and a method for producing the same, as well as a photoresist composition containing the Co-based organic coordination nanoparticles and use thereof. [Means for solving the problem]

[0005] [Produced metal-organic nanoparticles] The present invention relates to a compound having the general formula Com R n Q x M y N z The present invention provides Co-based organic coordination nanoparticles, wherein: Co is a divalent Co ion and a trivalent Co ion, m, n, and x are all greater than 0, and y and z are equal to or greater than 0; JPEG2025528818000002.jpg25170Q can be selected from imidazole and its derivatives; M is a carboxylic acid; N is water of crystallization, Furthermore, the size of the Co-based organically coordinated nanoparticle crystals is 1 nm to 5 nm. Furthermore, Co-based organic coordination nanoparticles have the following properties: Co 12 (C6H5COO) 12 (CH3C2N2H3) 12 (CH3COO) 18 (H2O)6, or It may also have the structure Co2(C7H7COO)4(CH3C2N2H3)2.

[0006] [Method for producing metal-organic coordination nanoparticles] Co2(C7H7COO)4(CH3C2N2H3)2 nanoparticles are produced by the following method. Add m-methylbenzoic acid or benzoic acid and cobalt acetate to a flask, add an organic solvent to dissolve the m-methylbenzoic acid or benzoic acid and cobalt acetate, then add 1-methylimidazole, continue stirring under a constant temperature condition, and perform rotary evaporation under a constant vapor pressure to obtain the product.

[0007] Furthermore, the molar ratio of the m-methylbenzoic acid or benzoic acid plus cobalt acetate ranges from 1:2 to 2:1, and the molar ratio of the m-methylbenzoic acid or benzoic acid, cobalt acetate, and 1-methylimidazole ranges from 1:1:(1 to 3).

[0008] The organic solvent is any one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2 propanol, tetrahydrofuran, methanol, ethanol, and propanol.

[0009] The stirring temperature is controlled to 25 to 125°C, preferably 30 to 100°C, more preferably 30 to 80°C, the pressure range of the rotary evaporation is controlled to 70 to 140mBar, preferably 70 to 120mBar, more preferably 80 to 100mBar, and simultaneously the temperature of the rotary evaporation is controlled to 30 to 45°C, preferably 30 to 40°C.

[0010] [Metal-organic coordination nanoparticle photoresist] The present invention further provides a photoresist composition comprising the Co-based organically coordinated nanoparticles.

[0011] The photoresist composition also includes a photoinitiator and an organic dispersion solvent, the photoinitiator preferably comprising 0.5 wt% to 10 wt% of the composition, and the nanoparticles preferably comprising 3 wt% to 20 wt% of the composition.

[0012] Further, the photoinitiator is any one or more selected from N-hydroxynaphthalimide triflate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid.

[0013] Furthermore, the organic dispersion solvent is any one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. The solvent is preferably ethyl acetate.

[0014] [Method for patterning metal-organic coordination nanoparticle photoresist] The present invention also provides a method for forming a lithography pattern using the above-mentioned photoresist composition, which comprises applying the photoresist composition dropwise onto a substrate by spin coating and heating the photoresist composition on a hot plate, exposing the photoresist composition to electron beams or mid-ultraviolet, deep-ultraviolet or extreme-ultraviolet radiation, and developing the photoresist composition with a developer.

[0015] Furthermore, the spin coating rotation speed is set to 1500 to 2500 rpm, the heating temperature of the hot plate is controlled to 50 to 80° C., and the heating time is controlled to 40 to 120 seconds.

[0016] Furthermore, the exposure dose is 50 mJ / cm 2 ~500mJ / cm 2 Preferably, the exposure dose is 150 mJ / cm 2 ~300mJ / cm 2 Let's say.

[0017] Furthermore, the development time can be selected from 3 to 10 seconds, and is preferably 3 seconds, 5 seconds, or 7 seconds.

[0018] Furthermore, the developer is any one or a mixture of a plurality of substances selected from decalin, tetralin, indene, indane, quinoline, 1-methylnaphthalene, toluene, ortho-xylene, meta-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature is room temperature or 20°C to 50°C.

[0019] The thickness of the pre-film layer after removing the organic dispersion solvent can be 10 nm to 100 nm, specifically, 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or 90 nm to 100 nm.

[0020] The substrate can be selected from a silicon plate, and other substrates that are insoluble in developer can be selected according to actual needs.

[0021] Furthermore, the nanoparticles are used in the photoresist field, especially in electron beam, mid-ultraviolet, deep ultraviolet, and extreme ultraviolet photoresists. As for the mask, the deep ultraviolet and longer wavelength light sources are transmissive masks, the extreme ultraviolet light is a reflective mask, and the electron beam is exposed according to a pattern set by software. [Effects of the Invention]

[0022] Compared with the prior art, the technical solution of the present invention has the following advantages: The Co-based organic coordination nanoparticles obtained by the present invention have a special structure that interacts with a photoinitiator under light irradiation conditions, changing the polarity of the material and causing aggregation, resulting in a change in the solubility of the Co-based organic coordination nanoparticles before and after light irradiation. Due to these properties, using these Co-based organic coordination nanoparticles as a photoresist component can create differences in the solubility of the exposed and shaded portions of the photoresist in the developer. The exposed portions aggregate in the developer and reduce their solubility, while the shaded portions do not aggregate and dissolve in the developer. This allows the unexposed areas to be removed after development, resulting in a pattern of the desired shape. Using the Co-based organic coordination nanoparticles of the present invention as a photoresist component can achieve superior lithography performance, such as high resolution, high sensitivity, and low line roughness. [Brief explanation of the drawings]

[0023] [Figure 1] FIG. 1 is a chart showing the DLS particle size test results of the purple viscous liquids prepared in Examples 1 and 14 of the present invention. The curve on the left is the test result of Example 1, and the curve on the right is the test result of Example 14. [Figure 2A] FIG. 2A is a diagram showing the chemical structure of the crystal produced in Example 1 of the present invention. [Figure 2B] FIG. 2B is a chemical structure diagram of the crystals produced in Example 14 of the present invention. [Figure 3]FIG. 3 is a chart showing the infrared absorption spectra of the crystals produced in Examples 1 and 14 of the present invention. [Figure 4-15] 4 to 15 show exposure patterns corresponding to Examples 2 to 13 of the present invention, respectively. [Figure 16-27] 16 to 27 show exposure patterns corresponding to Examples 15 to 26 of the present invention, respectively. [Figure 28] FIG. 28 shows an exposure pattern according to a 27th embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0024] To facilitate an understanding of the present invention, the present invention will now be described more fully hereinafter with reference to the associated drawings. Preferred embodiments of the present invention are illustrated in the drawings. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein. Rather, the purpose of providing these embodiments is to provide a more thorough and complete understanding of the present disclosure.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. In this specification, the terms used to describe the present invention are intended to describe specific embodiments and are not intended to limit the present invention.

[0026] The present invention relates to a compound having the general formula Co m R n Q x M y N z The present invention provides Co-based organic coordination nanoparticles. Here, Co is a divalent Co ion and a trivalent Co ion. JPEG2025528818000003.jpg25170Q can be selected from imidazole and its derivatives; M is a carboxylic acid and N is water of crystallization.

[0027] Furthermore, the size of the Co-based organically coordinated nanoparticle crystals is 1 nm to 5 nm.

[0028] m, n, and x are all greater than 0, y and z are 0 or greater, and further, 2≦m≦12, 4≦n≦12, 2≦x≦12, 0≦y≦18, and 0≦z≦6; Furthermore, Co-based organic coordination nanoparticles have the following properties: Co 12 (C6H5OO) 12 (CH3C2N2H3) 12 (CH3COO) 18 (H2O)6, It may also have the structure Co2(C7H7COO)4(CH3C2N2H3)2.

[0029] The Co-based organic coordination nanoparticles obtained by the present invention have a special structure that interacts with a photoinitiator under light irradiation conditions, changing the polarity of the material and causing aggregation, resulting in a change in the solubility of the Co-based organic coordination nanoparticles before and after light irradiation. Due to these properties, using these Co-based organic coordination nanoparticles as a photoresist component can create differences in the solubility of the exposed and shaded portions of the photoresist in the developer. The exposed portions aggregate in the developer and reduce their solubility, while the shaded portions do not aggregate and dissolve in the developer. This allows the unexposed areas to be removed after development, resulting in a pattern of the desired shape. Using the Co-based organic coordination nanoparticles of the present invention as a photoresist component can achieve superior lithography performance, such as high resolution, high sensitivity, and low line roughness.

[0030] Co2(C7H7COO)4(CH3C2N2H3)2 nanoparticles are prepared by the following method: Add m-methylbenzoic acid or benzoic acid and cobalt acetate to a flask, add an organic solvent to dissolve the m-methylbenzoic acid or benzoic acid and cobalt acetate, then add 1-methylimidazole, continue stirring under a constant temperature condition, and perform rotary evaporation under a constant vapor pressure to obtain the product.

[0031] Furthermore, the molar ratio of the m-methylbenzoic acid or benzoic acid to cobalt acetate is in the range of 1:2 to 2:1, and the molar ratio of the m-methylbenzoic acid or benzoic acid, cobalt acetate, and 1-methylimidazole is in the range of 1:1:(1 to 3), The organic solvent is any one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2 propanol, tetrahydrofuran, methanol, ethanol, and propanol.

[0032] The stirring temperature is controlled to 25 to 125°C, preferably 30 to 100°C, more preferably 30 to 80°C, the pressure range of the rotary evaporation is controlled to 70 to 140mBar, preferably 70 to 120mBar, more preferably 80 to 100mBar, and simultaneously the temperature of the rotary evaporation is controlled to 30 to 45°C, preferably 30 to 40°C.

[0033] The present invention further provides a photoresist composition containing the Co-based organic coordination nanoparticles, which also contains a photoinitiator and an organic dispersion solvent, the photoinitiator preferably accounting for 0.5 wt% to 10 wt% of the composition, and the nanoparticles preferably accounting for 3 wt% to 20 wt% of the composition.

[0034] Further, the photoinitiator is any one or more selected from N-hydroxynaphthalimide triflate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid.

[0035] Furthermore, the organic dispersion solvent is any one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. The solvent is preferably ethyl acetate.

[0036] The present invention also provides a method for forming a lithography pattern using the above-mentioned photoresist composition, which comprises applying the photoresist composition dropwise onto a substrate by spin coating and heating the photoresist composition on a hot plate, exposing the photoresist composition to electron beams or mid-ultraviolet, deep-ultraviolet or extreme-ultraviolet radiation, and developing the photoresist composition with a developer.

[0037] Furthermore, the spin coating rotation speed is set to 1500 to 2500 rpm, the heating temperature of the hot plate is controlled to 50 to 80° C., and the heating time is controlled to 40 to 120 seconds.

[0038] Furthermore, the exposure dose is 50 mJ / cm 2 ~500mJ / cm 2 Preferably, the exposure dose is 150 mJ / cm 2 ~300mJ / cm 2 Let's say.

[0039] Furthermore, the development time can be selected from 3 to 10 seconds, and is preferably 3 seconds, 5 seconds, or 7 seconds. Furthermore, the developer is any one or a mixture of a plurality of substances selected from decalin, tetralin, indene, indane, quinoline, 1-methylnaphthalene, toluene, ortho-xylene, meta-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature is room temperature or 20°C to 50°C.

[0040] The thickness of the pre-film layer after removing the organic dispersion solvent can be 10 nm to 100 nm, specifically, 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or 90 nm to 100 nm.

[0041] The substrate can be selected from a silicon plate, and other substrates that are insoluble in developer can be selected according to actual needs.

[0042] Furthermore, the nanoparticles are used in the photoresist field, especially in electron beam, mid-ultraviolet, deep ultraviolet, and extreme ultraviolet photoresists. As for the mask, the deep ultraviolet and longer wavelength light sources are transmissive masks, the extreme ultraviolet light is a reflective mask, and the electron beam is exposed according to a pattern set by software.

[0043] Example 1 4.88 g (40 mmol) of benzoic acid and 4.98 g (20 mmol) of cobalt acetate were added to a 100 mL flask, followed by 45 mL of tetrahydrofuran. 1.67–2.30 g (20–28 mmol) of 1-methylimidazole were added and the mixture was stirred and heated at 25–125°C for 24 hours. The product was rotary evaporated at 70–140 mBar and 30–45°C for 20–40 minutes to obtain a purple viscous liquid. DLS particle size analysis was performed on the resulting product. The results are shown in the left curve of Figure 1. The produced system is found to be nanoparticles (average particle size 3.1 nm). Furthermore, by leaving the liquid at rest at low temperature, crystals were obtained. Infrared absorption spectroscopy of these crystals was performed, and the test results shown in Figure 3 were obtained. 3130 cm -1 This absorption peak is the absorption peak of the aromatic ring after bonding, which is the same as the infrared absorption peak of free benzoic acid at 3000-3100 cm. -1This is because the benzoic acid group is located between the benzoic acid group and the Co-based organic ligand structure, and corresponds to the stretching vibration of the unsaturated =CH of the benzene ring of the benzoic acid group. In other words, a small shift in the absorption peak position of the benzoic acid occurs in the synthesized Co-based organic ligand structure material, which indicates that the benzoic acid group is bonded to the molecular structure of the metal organic compound. When the molecular structure was analyzed in combination with the results of nuclear magnetic resonance analysis, it was found that the Co 12 (C6H5OO) 12 (CH3C2N2H3) 12 (CH3COO) 18 The resulting compound (H2O)6 was shown in Figure 2A. The molecular structure is a polynuclear complex containing 12 Co rings and benzoic acid, N-methylimidazole, and acetate as ligands. Except for N-methylimidazole, the remaining ligands are all bridged around the Co rings and bonded to the periphery. It can be seen that the material produced by the method of this example is a metal-organic ligand nanoparticle.

[0044] Examples 2 to 4 The solution (5.0 wt%) prepared in Example 1 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 50°C for 1 minute. The photoresist film was then coated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2 The resulting line patterns with half-pitches of 9.04 μm, 10.01 μm, and 10.62 μm were obtained by developing the exposed film using mesitylene for 3 s, 5 s, and 7 s, respectively, as shown in Figures 4, 5, and 6, respectively.

[0045] Examples 5 to 7 The solution (5.0 wt%) prepared in Example 1 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 60°C for 1 minute. The photoresist film was then coated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm.2 The resulting line patterns with half-pitches of 9.48 μm, 9.74 μm, and 9.92 μm were obtained by exposure at a dose of 1000 μm and development using mesitylene for 3 s, 5 s, and 7 s, respectively, as shown in Figures 7, 8, and 9, respectively.

[0046] Examples 8 to 10 The solution (5.0 wt%) prepared in Example 1 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 70°C for 1 minute. The photoresist film was then coated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2 The resulting line patterns were exposed at a dose of 9.48 μm, 10.62 μm, and 10.62 μm, respectively, and developed using mesitylene as a developer for 3 s, 5 s, and 7 s, as shown in Figures 10, 11, and 12, respectively.

[0047] Examples 11 to 13 The solution (5.0 wt%) prepared in Example 1 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 80°C for 1 minute. The photoresist film was then coated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2 and developed using mesitylene as a developer for 3 seconds, 5 seconds, and 7 seconds, respectively, to obtain line exposure patterns with half-pitches of 9.04 μm, 10.01 μm, and 11.06 μm, as shown in Figures 13, 14, and 15, respectively.

[0048] Example 14 5.44 g (40 mmol) of m-methylbenzoic acid and 4.98 g (20 mmol) of cobalt acetate were added to a 100 mL flask, followed by 45 mL of tetrahydrofuran. 1.67–2.30 g (20–28 mmol) of 1-methylimidazole were added and the mixture was stirred and heated at 25–125°C for 24 hours. The product was rotary evaporated at 70–140 mBar and 30–45°C for 20–40 minutes to obtain a purple viscous liquid. DLS particle size analysis was performed on the product. The results are shown in the right curve of Figure 1. The produced system was found to be nanoparticles (average particle size 4.3 nm). Furthermore, by leaving the liquid at rest at low temperature, crystals were obtained. Infrared absorption spectroscopy of these crystals yielded the results shown in Figure 3. 2922 cm -1 and 3130 cm -1 It can be seen that there is one absorption peak in each of the three. -1 In addition to the benzene ring unsaturated =CH stretching vibration absorption peak corresponding to the benzoic acid group, -1 There is an additional alkyl group C—H peak below. The infrared absorption spectrum of the product produced in this example also has corresponding absorption peaks near these two positions, with a small shift, indicating that the m-methylbenzoic acid group is bonded to the molecular structure of the metal-organic compound. The material produced by the method of this example is a metal-organic ligand nanoparticle. Its molecular structure is Co2(C7H7COO)4(CH3C2N2H3)2, as shown in Figure 2B.

[0049] Examples 15 to 17 The solution (5.0 wt%) prepared in Example 14 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 50°C for 1 minute. The photoresist film was then irradiated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2The resulting line patterns with a half-pitch of 1 μm were obtained by exposure at a dose of 1 μm and development using mesitylene for 3 s, 5 s, and 7 s, respectively, as shown in Figures 16, 17, and 18, respectively.

[0050] Examples 18 to 20 The solution (5.0 wt%) prepared in Example 14 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 60°C for 1 minute. The photoresist film was then irradiated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2 The resulting line patterns with a half-pitch of 1 μm were obtained by exposure at a dose of 1 μm, followed by development using mesitylene for 3 s, 5 s, and 7 s, respectively, as shown in Figures 19, 20, and 21, respectively.

[0051] Examples 21 to 23 The solution (5.0 wt%) prepared in Example 14 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 70°C for 1 minute. The photoresist film was then coated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2 The resulting line patterns with a half-pitch of 1 μm were obtained by exposure at a dose of 1 μm, followed by development using mesitylene for 3 s, 5 s, and 7 s, respectively, as shown in Figures 22, 23, and 24, respectively.

[0052] Examples 24 to 26 The solution (5.0 wt%) prepared in Example 14 was mixed with 0.5 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 80°C for 1 minute. The photoresist film was then coated with a 254 nm ultraviolet mercury lamp at 150 mJ / cm. 2 The resulting line patterns with a half-pitch of 1 μm were obtained by exposure at a dose of 1 μm, followed by development using mesitylene for 3 s, 5 s, and 7 s, respectively, as shown in Figures 25, 26, and 27, respectively.

[0053] Example 27 The solution (3.5 wt%) prepared in Example 14 was mixed with 10 wt% PAG-1 (N-hydroxynaphthalimide triflate), and the solvent was propylene glycol monoethyl ether acetate. The mixture was spin-coated onto a silicon wafer at a rotation speed of 2000 rpm and then heated on a hot plate at 60°C for 1 minute. EBL exposure was performed at 850 μC / cm. 2 The test was performed at a dose of 1.0 A and a line intensity of 1.0 to 3.0 A. Mesitylene was used as the developer, and the development time was 9 seconds, resulting in a line with a half-pitch of 100 nm, as shown in FIG.

[0054] In summary, the present invention provides various effective nanoparticles and corresponding compositions that have been verified to have good lithography performance under structural and mid-UV and electron beam lithography (EBL) conditions, thereby achieving better lithography performance such as high resolution, high sensitivity, and low line roughness.

Claims

1. Co-based organic coordination nanoparticles, The general composition formula is Co ｍ R ｎ Q ｘ M ｙ N ｚ where Co is two types of ions, divalent Co and trivalent Co, m, n, and x are all greater than 0, and y and z are 0 or greater; Q can be selected from imidazole and its derivatives; M is a carboxylic acid; N is water of crystallization, The Co-based organic coordination nanoparticles are characterized in that the size of the Co-based organic coordination nanoparticle crystals is 1 nm to 5 nm.

2. The structure of the nanoparticles is Co １２ (C ６ H ５ COO) １２ (CH ３ C ２ N ２ H ３ ) １２ (CH ３ COO) １８ (H ２ O) ６ or Co ２ (C ７ H ７ COO) ４ (CH ３ C ２ N ２ H ３ ) ２ 2. The Co-based organic coordination nanoparticle according to claim 1, wherein:

3. The method for producing the Co-based organic coordination nanoparticles according to claim 1 or 2, specifically, A method for producing Co-based organically coordinated nanoparticles, comprising the steps of: adding m-methylbenzoic acid or benzoic acid and cobalt acetate to a flask; adding an organic solvent to dissolve the m-methylbenzoic acid or benzoic acid and the cobalt acetate; then adding 1-methylimidazole; continuing to stir under a constant temperature condition; and rotary evaporating under a constant vapor pressure to obtain a product.

4. The method for producing Co-based organic coordination nanoparticles according to claim 3, wherein the molar ratio of m-methylbenzoic acid or benzoic acid to cobalt acetate is in the range of 0.5 to 2, and the molar ratio of m-methylbenzoic acid or benzoic acid:cobalt acetate:1-methylimidazole is in the range of 1:1:(1 to 3).

5. 4. The method for producing Co-based organic coordination nanoparticles according to claim 3, wherein the organic solvent is one or more selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2-propanol, tetrahydrofuran, methanol, ethanol, and propanol.

6. The method for producing Co-based organically coordinated nanoparticles according to claim 3, characterized in that the stirring temperature is controlled to 25 to 125°C, the pressure range of rotary evaporation is controlled to 70 to 140 mBar, and the temperature of rotary evaporation is controlled to 30 to 45°C.

7. 1. A photoresist composition comprising: A photoresist composition comprising the Co-based organic coordination nanoparticles of claim 1 or 2, a photoinitiator, and an organic dispersion solvent, wherein the photoinitiator accounts for 0.5 wt % to 10 wt % of the composition, and the nanoparticles account for 3 wt % to 20 wt % of the composition.

8. 8. The photoresist composition of claim 7, wherein the photoinitiator is one or more selected from the group consisting of N-hydroxynaphthalimide triflate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid.

9. 8. The photoresist composition of claim 7, wherein the organic dispersion solvent is at least one selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

10. 1. A method for forming a lithographic pattern, comprising: The photoresist composition according to any one of claims 7 to 9 is applied dropwise onto a substrate by spin coating, and heated on a hot plate. The photoresist composition is then exposed to an electron beam or medium ultraviolet, deep ultraviolet, or extreme ultraviolet, and developed with a developer. The spin coating rotation speed is 1500 to 2500 rpm, the hot plate heating temperature is controlled to 50 to 80°C, the heating time is controlled to 40 to 120 s, and the exposure dose is 50 mJ / cm. ２ ~500 mJ / cm ２ and a development time of 3 to 10 seconds.

11. 11. The method of claim 10, wherein the developer is one or a mixture of two or more selected from the group consisting of decalin, tetralin, indene, indane, quinoline, 1-methylnaphthalene, toluene, ortho-xylene, meta-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature h is room temperature or 20°C to 50°C.

12. 11. The method for forming a lithography pattern according to claim 10, wherein the thickness of the pre-deposition layer after removing the organic dispersion solvent can be 10 nm to 100 nm.

13. 3. Use of the Co-based organic coordination nanoparticles according to claim 1 or 2, 3. The use of the Co-based organic coordination nanoparticles according to claim 1 or 2, wherein the Co-based organic coordination nanoparticles are mainly used in electron beam, mid-ultraviolet, deep-ultraviolet or extreme-ultraviolet photoresists.

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