Precise detection method for gas escape in spin-coated carbon material curing process
By using TPD-MS technology to precisely detect gas escape during the high-temperature curing process of spin-coated carbon materials, the problem of gas escape detection under high-temperature conditions has been solved, achieving high-precision pattern transfer and ensuring film quality.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU YARUI SEMICONDUCTOR MATERIALS CO LTD
- Filing Date
- 2026-03-18
- Publication Date
- 2026-05-05
AI Technical Summary
How to achieve precise detection of gas escape during the high-temperature curing process of spin-coated carbon materials in order to avoid film defects and process chamber contamination, and ensure the transfer quality of high aspect ratio patterns.
TPD-MS technology was used to quantitatively detect the gas escape from spin-coated carbon materials under high temperature conditions. In-situ analysis and mass spectrometry monitoring were combined with gas chromatography for gas separation and identification, so as to achieve precise characterization of the types and amounts of gases.
This improves the accuracy and reliability of detection of spin-coated carbon materials during high-temperature curing, ensures the reliability of high-precision pattern transfer, and reduces the risk of film defects and process chamber contamination.
Smart Images
Figure CN121978194A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of chemical detection technology, and more specifically to a precision detection method for gas escape during the curing process of spin-coated carbon materials. Background Technology
[0002] In semiconductor manufacturing, photolithography is a precision manufacturing technique that transfers circuit patterns designed on a photomask to a wafer for micro-patterning using photoresist or a hard mask. As integrated circuits become increasingly highly integrated and faster, pattern sizes continue to shrink. In particular, high-resolution (<56nm) patterns need to be transferred to the wafer via etching. Photoresists must be matched with ArFi (Arcade-Fit) immersion photoresist technology to achieve high-resolution pattern transfer from the photomask. However, due to the high-resolution design requirements of deep ultraviolet (DUV) photoresists, they lack sufficient etching resistance, making it difficult to meet the pattern transfer requirements for high aspect ratio patterns on the final wafer. Therefore, the industry pioneered the introduction of hard masks, which, due to their high carbon content, possess extremely strong etching resistance, thus enabling high aspect ratio patterns on the wafer.
[0003] In the early days, hard masks were typically achieved by depositing amorphous carbon onto wafers using chemical vapor deposition (CVD). While CVD can produce carbon films with high carbon content (approximately 100% C), the physical characteristics of vapor deposition easily lead to defects such as voids and seams within the trenches, resulting in poor film density. Therefore, in recent years, the industry has adopted a liquid-phase spin-coating method to prepare organic hard masks. This involves chemically synthesizing organic compounds with high carbon content (above 85% C) as spin-coated carbon onto the wafer, and then cross-linking and curing them at high temperatures to form an organic carbon-containing hard mask. Although spin-coated carbon materials can avoid the voids and slits of CVD amorphous carbon, the high-molecular organic materials used in their high-temperature curing and cross-linking process involve chemical condensation / polymerization reactions, which easily release small molecule volatiles and vaporize at high temperatures. This release of gas leads to film defects, which in turn cause pattern deformation, warping or displacement, and even the formation of micropores or pinholes. This reduces the film's density, mechanical strength and adhesion, and may also contaminate the process chamber and wafer surface, affecting the integrity of the pattern.
[0004] Therefore, how to achieve quantitative detection of gas escape from spin-coated carbon materials under high-temperature conditions is a problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0005] In view of this, the present invention provides a precise detection method for gas escape during the curing process of spin-coated carbon materials. The present invention uses TPD-MS technology to achieve quantitative detection of gas escape from spin-coated carbon materials under high-temperature conditions, ensuring the accuracy and reliability of the test data through instrumentation. The present invention solves the problem of quantitative detection of escaped gases from spin-coated carbon materials under high-temperature conditions, providing a reliable material basis and process guarantee for high-precision pattern transfer.
[0006] To achieve the above objectives, the present invention adopts the following technical solution:
[0007] A precision detection method for gas escape during the curing process of spin-coated carbon materials includes the following steps: (1) The spin-coated carbon sample is coated onto the substrate, and then the substrate is rotated and dried to form a spin-coated carbon layer; (2) The substrate containing the spin-coated carbon layer was placed on the test stage, and the gas release behavior of the sample during the heating process was analyzed in situ by TPD-MS under a helium atmosphere. The m / z ion current curve reflects the change of gas release rate with temperature / time. (3) After TPD, switch the gas flow to the adsorbate gas and expose the sample to the adsorbate gas at the set adsorption temperature (room temperature or low temperature) for 30-60 minutes to allow it to reach adsorption equilibrium. Then, switch the gas flow back to helium and start the temperature program control and mass spectrometry data acquisition (using Shimadzu QP2010 Ultra11). The system begins to heat the adsorbate gas at a uniform rate, and the mass spectrometer monitors the m / z signal intensity in real time to achieve quantitative detection of the gas.
[0008] The core principle of TPD-MS is to pre-adsorb a certain gas onto a sample, heat it at a constant rate in a vacuum environment, and simultaneously monitor the type and quantity of desorbed gases in real time using a mass spectrometer. This method is commonly used for acid-base site analysis and porous material characterization. This invention is the first to combine TPD-MS technology with the analysis of high-temperature spin-coated carbon materials, proposing a precise detection method based on TPD-MS for the gas release problem during the curing process of spin-coated carbon materials. This invention integrates real-time monitoring and quantitative analysis using TPD-MS, enabling accurate confirmation of the amount and type of gas released during the high-temperature curing process of spin-coated carbon materials. It precisely characterizes the types and amounts of gas released throughout the entire process from pre-baking (240℃) to complete curing (400℃), thereby guiding the structural design of high-performance, low-release spin-coated carbon materials.
[0009] Furthermore, the spin-coated carbon sample is composed of the following raw materials by mass fraction: 5-25% spin-coated carbon resin, 0.01-0.3% surfactant, 40-70% PGMEA, and 10-40% PGME.
[0010] Furthermore, the spin-coated carbon resin has a structure as shown in general formula 1:
[0011] General Formula 1 Wherein, AR1 and AR2 are benzene rings or naphthalene rings that may have substituents; n is 0 or 1. When n=0, AR1 and AR do not form a cross-linked structure between the aromatic rings of AR1 and AR2 via Z; when n=1, AR1 and AR2 form a cross-linked structure between the aromatic rings of AR1 and AR2 via Z. Z is a single bond or selected from any of the following structures: ; Y has the structure shown in general formula 2:
[0012] General Formula 2 In general formula 2, R1 is selected from single bonds or divalent organic groups with 1-20 carbon atoms, and R2 is selected from hydrogen atoms or monovalent organic groups with 1-20 carbon atoms.
[0013] Furthermore, the surfactant is 3M fluorocarbon surfactant FC-4430.
[0014] Furthermore, the substrate mentioned in step (1) is a 4-inch silicon wafer; The rotary heating speed is 1500 rpm, the heating temperature is 240℃, and the heating time is 60 seconds.
[0015] Furthermore, the heating process in step (2) involves heating from room temperature to 400°C at a heating rate of 10°C / min, and then maintaining the temperature at 400°C for 2 minutes.
[0016] Furthermore, the adsorbate gas mentioned in step (3) is selected from any one of NH3, CO2, CO and H2.
[0017] Furthermore, in step (3), the adsorbate gas is reheated to obtain the desorbed gas, which is then introduced into a gas chromatograph-mass spectrometer for separation and identification, thereby achieving quantitative detection of the gas.
[0018] Furthermore, the system heating method in step (3) is to heat the system from room temperature to 350-500℃ at a heating rate of 5-20℃ / min and maintain the temperature for 2 minutes.
[0019] The beneficial effects of this invention are as follows: By using precision analytical instruments such as mass spectrometers, this invention achieves online quantitative detection of gases released during the curing process of high-temperature spin-coated carbon materials. This method can directly determine the total amount of escaped gases and identify their specific chemical composition, thereby significantly improving the characterization accuracy of the gas release behavior of spin-coated carbon materials. Attached Figure Description
[0020] Figure 1 This is a graph showing the changes in the types and amounts of gas released from the product in Example 1 of the present invention as a function of temperature; Figure 2 This is a partially enlarged view showing the changes in the types and amounts of gas released from the product in Embodiment 1 of the present invention as a function of temperature; Figure 3 This is a graph showing the changes in the types and amounts of outgassing from the product of Comparative Example 1 of this invention as a function of temperature. Figure 4 This is a magnified view of the types and amounts of gas released from the product of Comparative Example 1 of the present invention as a function of temperature. Figure 5 This is a graph showing the changes in the types and amounts of outgassing from the product of Comparative Example 2 of this invention as a function of temperature. Figure 6 This is a magnified view of the types and contents of gas released from the product of Comparative Example 2 of the present invention as a function of temperature. Figure 7 Graphs showing the rate of thermal weight loss as a function of temperature for Examples 1 and Comparative Examples 1-2. Detailed Implementation
[0021] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0022] Example 1 (1) Preparation of spin-coated carbon resin 1, the structure of which is: ; The synthesis method of spin-coated carbon resin 1 is as follows: A 500 mL four-necked flask equipped with a thermometer, condenser, mechanical stirrer, and dropping funnel was immersed in an oil bath at 130°C. Under a nitrogen atmosphere, with heating and magnetic stirring on a hot plate, 50 g (0.226 mol) of N,N-diphenyl-2-butynediamine was dissolved in 131 g of propylene glycol monomethyl ether acetate (PGMEA). 3.48 g (0.0226 mol) of diethyl sulfate was added to the solution. 37.56 g (0.226 mol) of 1,4-dimethoxytoluene was added to the dropping funnel. When the reactor temperature reached 130°C, 1,4-dimethoxytoluene was added dropwise to the reactor and the reaction was allowed to proceed for more than 1.5 hours to polymerize the reactants. Upon completion of the reaction, the reaction mixture was cooled to room temperature, and then the polymerization solution was added dropwise to a 4 kg methanol solution over 3 hours. The gray product was then filtered out. The filter cake was washed with 1.5 kg of methanol each time, and the washing process was repeated twice. After filtration, the solid was dried. The final product was spin-coated carbon resin 1 (Mw: 7,650; PDI: 2.3).
[0023] (2) 10 g of spin-coated carbon resin 1 was mixed with 0.03 g of surfactant 3M fluorocarbon surfactant FC-4430, 28 g of PGMEA and 12 g of PGME to obtain a solution. The solution was filtered through a 0.22 μm nylon membrane and a 0.1 μm PTFE microporous membrane to obtain a clear filtrate, which is the spin-coated carbon composition 1.
[0024] Example 2 (1) Prepare spin-coated carbon resin 2, the structure of which is: ; The synthesis method of spin-coated carbon resin 2 is as follows: The method used was basically the same as that in Example 1, except that 50 g (0.226 mol) of N,N-diphenyl-2-butynediamine was replaced with 49.6 g (0.226 mol) of N-(but-2-yn-1-yl)-9H-carbazole. The final product was spin-coated carbon resin 2 (Mw: 7,650; PDI: 2.3).
[0025] (2) 10 g of spin-coated carbon resin 2 was mixed with 0.03 g of surfactant 3M fluorocarbon surfactant FC-4430, 28 g of PGMEA and 12 g of PGME to obtain a solution. The solution was filtered through a 0.22 μm nylon membrane and a 0.1 μm PTFE microporous membrane to obtain a clear filtrate, which is the spin-coated carbon composition 2.
[0026] Example 3 (1) Prepare spin-coated carbon resin 3, the structure of which is: ; The synthesis method of spin-coated carbon resin 3 is as follows: The method used was basically the same as that in Example 1, except that 50 g (0.226 mol) of N,N-diphenyl-2-butynediamine was replaced with 38.69 g (0.226 mol) of N-propargyl-1,4-benzoxazine. The final product was spin-coated carbon resin 3 (Mw: 6,711; PDI: 2.49).
[0027] (2) 10 g of spin-coated carbon resin 3 was mixed with 0.03 g of surfactant 3M fluorocarbon surfactant FC-4430, 28 g of PGMEA and 12 g of PGME to obtain a solution. The solution was filtered through a 0.22 μm nylon membrane and a 0.1 μm PTFE microporous membrane to obtain a clear filtrate, which is the spin-coated carbon composition 3.
[0028] Example 4 Spin-coated carbon resin 4 was prepared, and its structure is as follows: ; The synthesis method of spin-coated carbon resin 4 is as follows: the method used is basically the same as that in Example 1, except that 50 g (0.226 mol) of N,N-diphenyl-2-butynediamine is replaced with 58.16 g (0.226 mol) of N-aryl-N-propyneaniline. Spin-coated carbon resin 4 (Mw: 2,600; PDI: 1.58) is obtained.
[0029] Comparative Example 1 10 g of spin-coated carbon resin 4 was mixed with 0.15 g of crosslinking agent tetramethoxymethylglycourea, 0.1 g of N-benzyl-N,N-dimethylphenyltrifluoromethanesulfonate ammonium, 28 g of PGMEA, and 12 g of PGME to obtain a solution. This solution was filtered through a 0.22 μm nylon membrane and a 0.1 μm PTFE microporous membrane to obtain a clear filtrate, which is the spin-coated carbon composition 4.
[0030] Comparative Example 2 10 g of spin-coated carbon resin 4 was mixed with 0.15 g of crosslinking agent tetramethoxymethylglycourea, 0.1 g of p-toluenesulfonic acid, 28 g of PGMEA, and 12 g of PGME to obtain a solution. This solution was filtered through a 0.22 μm nylon membrane and a 0.1 μm PTFE microporous membrane to obtain a clear filtrate, which is the spin-coated carbon composition 5.
[0031] Test case A precision detection method for gas escape during the curing process of spin-coated carbon materials, characterized by comprising the following steps: (1) The spin-coated carbon samples of Example 1 and Comparative Examples 1-2 were coated on a 4-inch silicon wafer substrate, and then the substrate was dried by rotating at 1500 rpm and 240°C for 60 seconds to form a spin-coated carbon layer. (2) The substrate containing the spin-coated carbon layer was placed on the test stage, and the gas release behavior of the sample during the heating process was analyzed in situ by TPD-MS under a helium atmosphere. The heating process was to raise the temperature from room temperature to 400℃ at a heating rate of 10℃ / min and hold it at 400℃ for 2min to monitor the gas release of the spin-coated carbon material throughout the thermal process. The m / z ion current curve reflects the change of gas release rate with temperature / time. (3) After TPD, the gas flow was switched to the adsorbate gas. The sample was exposed to the adsorbate gas at the set adsorption temperature for 30-60 minutes to reach adsorption equilibrium. Then, the gas flow was switched back to helium, and temperature program control and mass spectrometry data acquisition were initiated (using a Shimadzu QP2010 Ultra11). The system began to reheat the adsorbate gas at a uniform rate (heating from room temperature to 400℃ at a rate of 10℃ / min, and holding at that temperature for 2 minutes) to obtain the desorbed gas. The desorbed gas was then introduced into a gas chromatograph-mass spectrometer for separation and identification. The detection results are shown in Table 1 and... Figures 1-6 As shown.
[0032] Table 1. Comparison of the types and amounts of gas released in Example 1 and Comparative Examples 1-2
[0033] The results showed that TPD-MS could accurately quantify the content and types of gases released during the heating and baking process of spin-coated carbon materials. Based on the above test data analysis, compared with the comparative example, the spin-coated carbon composition described in Example 1 exhibited a significantly reduced gas release in the temperature range commonly used for high-temperature spin-coated carbon materials, with organic gases showing the lowest release rate.
[0034] Test Example 2: Thermal stability test of spin-coated carbon composition Spin-coated carbon layers require high-temperature processing during photolithography, thus necessitating high thermal stability. Using a standard 12-inch silicon wafer as a substrate, samples with high surface flatness from Examples 1 and Comparative Examples 1-2 were spin-coated at 1500 rpm. The coated carbon layers were then baked at 240°C for 60 seconds and 400°C for 90 seconds. The resulting carbon layers were scraped off to obtain a solid. Using a thermogravimetric analyzer under nitrogen atmosphere, the temperature was increased from room temperature to 105°C at a rate of 10°C / min, held at that temperature for 10 min, and then increased to 700°C at a rate of 10°C / min to measure the weight loss rate of the spin-coated carbon layers. The test results are shown in Table 2 below. Figure 7 .
[0035] Table 2 Comparison of thermogravimetric temperatures between Example 1 and Comparative Examples 1-2
[0036] From Table 2 and Figure 7 The performance test results show that, compared with the comparative examples, the spin-coated carbon layers formed by the spin-coated carbon compositions of Examples 1-2 exhibit a 10% weight loss at temperatures above 500°C, and show a significantly reduced gas release rate below 400°C. The gas release detection results are corroborated by the thermogravimetric analysis data. Furthermore, the spin-coated carbon compositions of the examples demonstrate superior thermal stability and are less affected by thermal decomposition in subsequent high-temperature processes, thereby broadening their applicability and process compatibility in advanced semiconductor manufacturing.
[0037] This invention, based on real-time mass spectrometry (RTS) analysis, enables the monitoring of the gas release process of spin-coated carbon materials under high-temperature operating conditions. Its core principle lies in utilizing a TPD-MS coupled system to dynamically identify and quantitatively analyze various gases (such as H2O, CO2, hydrocarbons, and oxygen-containing organic compounds) released during the high-temperature baking process of spin-coated carbon materials. This technology can track gas escape behavior in real time under simulated actual operating temperature and atmosphere conditions, revealing the material's thermal stability, surface reactions, and decomposition mechanisms, providing crucial data support for the durability assessment, material optimization, and process improvement of high-temperature spin-coated carbon materials.
[0038] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention.
Claims
1. A precision detection method for gas escape during the curing process of spin-coated carbon materials, characterized in that, Includes the following steps: (1) The spin-coated carbon sample is coated onto the substrate, and then the substrate is rotated and dried to form a spin-coated carbon layer; (2) The substrate containing the spin-coated carbon layer was placed on the test stage, and the gas release behavior of the sample during the heating process was analyzed in situ using TPD-MS under a helium atmosphere; (3) After TPD, switch the gas flow to the adsorbate gas and expose the sample to the adsorbate gas for 30-60 minutes at the set adsorption temperature to allow it to reach adsorption equilibrium. Then, switch the gas flow back to helium and start the temperature program control and mass spectrometry data acquisition. The system starts to heat up to reheat the adsorbate gas, and the mass spectrometer monitors the m / z signal intensity in real time to achieve quantitative detection of the gas.
2. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 1, characterized in that, The spin-coated carbon sample is composed of the following raw materials by mass fraction: 5-25% spin-coated carbon resin, 0.01-0.3% surfactant, 40-70% PGMEA, and 10-40% PGME.
3. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 2, characterized in that, The spin-coated carbon resin has the structure shown in general formula 1: General Formula 1 Wherein, AR1 and AR2 are benzene rings or naphthalene rings that may have substituents; n is 0 or 1. When n=0, AR1 and AR do not form a cross-linked structure between the aromatic rings of AR1 and AR2 via Z; when n=1, AR1 and AR2 form a cross-linked structure between the aromatic rings of AR1 and AR2 via Z. Z is a single bond or selected from any of the following structures: ； Y has the structure shown in general formula 2: General Formula 2 In general formula 2, R1 is selected from single bonds or divalent organic groups with 1-20 carbon atoms, and R2 is selected from hydrogen atoms or monovalent organic groups with 1-20 carbon atoms.
4. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 2, characterized in that, The surfactant is 3M fluorocarbon surfactant FC-4430.
5. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 1, characterized in that, The substrate mentioned in step (1) is a silicon wafer; The rotary heating speed is 1500 rpm, the heating temperature is 240℃, and the heating time is 60 seconds.
6. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 1, characterized in that, The heating process described in step (2) is to raise the temperature from room temperature to 400°C at a heating rate of 10°C / min, and then maintain the temperature at 400°C for 2 minutes.
7. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 1, characterized in that, The adsorbate gas mentioned in step (3) is selected from any one of NH3, CO2, CO and H2.
8. The precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 1, characterized in that, In step (3), the adsorbate gas is reheated to obtain the desorbed gas, which is then introduced into a gas chromatograph-mass spectrometer for separation and identification, thereby achieving quantitative detection of the gas.
9. A precision detection method for gas escape during the curing process of spin-coated carbon materials according to claim 1 or 8, characterized in that, The system heating method described in step (3) is to raise the temperature from room temperature to 350-500℃ at a heating rate of 5-20℃ / min and keep it constant for 2min.