Semiconductor photolithography temperature compensation plate and preparation method thereof

Abstract

The application discloses a kind of semiconductor photoetch temperature compensation plate and preparation method thereof, it is related to semiconductor device manufacturing technical field.The method includes first to aluminium nitride micro powder is successively carried out temperature-controlled oxidation passivation, yttrium oxide sintering aid coating, silicon dioxide bridging layer coating and coupling functionalization processing, and modified aluminium nitride heat-conducting reinforcing filler is prepared;β-lithium feldspar micro powder is successively carried out dilute phosphoric acid activation, aluminum phosphate diffusion barrier coating, silicon dioxide sealing layer coating and coupling functionalization processing, and modified β-lithium feldspar negative expansion compensation filler is prepared.Melted quartz micro powder, the above two kinds of modified fillers and zinc borate micro powder and sodium carboxymethyl cellulose are mixed, after wet ball milling, spray granulation, vacuum hot-pressing sintering, controlled-rate cooling annealing and precision machining, temperature compensation plate is obtained.The application realizes the synergistic optimization of thermal conductivity and thermal expansion coefficient by low-temperature sintering and dispersion regulation while maintaining low expansion, and constructs efficient heat-conducting network.

Description

Technical Field

[0001] This invention relates to the field of semiconductor device manufacturing technology, specifically to a semiconductor photolithography temperature compensation plate and its preparation method. Background Technology

[0002] As integrated circuit manufacturing processes continue to advance towards higher integration and smaller linewidths, the performance requirements for temperature compensation plates in lithography equipment are becoming increasingly stringent. As a core structural component of the wafer stage and mask stage in a lithography machine, the temperature compensation plate functions to maintain a high degree of geometric stability of the supported components during exposure, thereby ensuring nanometer-level overlay and imaging accuracy. However, current mainstream temperature compensation plate materials generally face the following technical bottlenecks: On the one hand, materials with ultra-low coefficients of thermal expansion (such as microcrystalline glass and fused silica) have extremely low intrinsic thermal conductivity, typically only 1.0–1.5 W / (m·K). Under high energy density exposure conditions (especially EUV lithography), local heat on the plate surface cannot be quickly conducted away, and the resulting in-plane temperature gradient will cause local thermal distortion, seriously affecting image quality. On the other hand, although high thermal conductivity ceramic materials (such as aluminum nitride and silicon carbide) have excellent thermal conductivity, their coefficients of thermal expansion are much higher than near zero, making it difficult to meet the stringent requirements of advanced processes for maintaining sub-nanometer dimensional stability of temperature compensation plates under temperature fluctuations of ±0.001K. How to simultaneously achieve high thermal conductivity and near-zero coefficient of thermal expansion in the same material system is a key problem that urgently needs to be solved in the field of semiconductor lithography temperature compensation plate technology. Summary of the Invention

[0003] The purpose of this invention is to provide a semiconductor photolithography temperature compensation plate and its preparation method to solve the technical problems mentioned in the background art.

[0004] To achieve the above objectives, the present invention provides the following technical solution: A method for fabricating a semiconductor photolithography temperature compensation plate includes the following steps: 1) Aluminum nitride micro powder was subjected to temperature-controlled oxidation passivation treatment, yttrium oxide sintering aid sol coating treatment, tetraethyl orthosilicate sol-gel silica bridging layer coating treatment and KH-560 coupling functionalization treatment in sequence to obtain modified aluminum nitride thermally conductive filler. 2) The β-lithium nepheline microcrystalline powder was subjected to dilute phosphoric acid surface activation treatment, aluminum phosphate diffusion barrier layer sol-gel coating treatment, tetraethyl orthosilicate silica sealing layer coating treatment and KH-560 coupling functionalization treatment in sequence to obtain modified β-lithium nepheline negative expansion compensation filler. 3) The fused silica micro powder, the modified aluminum nitride thermally conductive enhanced filler, the modified β-lithium nepheline negative expansion compensating filler, zinc borate micro powder and sodium carboxymethyl cellulose are mixed and then subjected to wet ball milling, spray drying granulation, vacuum hot pressing sintering, controlled cooling, annealing, precision grinding and chemical mechanical polishing to obtain a semiconductor photolithography temperature compensation board.

[0005] This invention modifies aluminum nitride micropowder to construct a highly efficient continuous heat transfer network within a fused silica matrix. The mechanism by which it improves the thermal conductivity of the temperature compensation plate lies in: aluminum nitride itself possesses extremely high phonon thermal conductivity, making it an ideal carrier for constructing heat conduction pathways; temperature-controlled oxidation passivation treatment forms a dense aluminum oxide passivation shell of controllable thickness on the surface of the aluminum nitride particles, effectively preventing water molecules from eroding and hydrolyzing the aluminum nitride lattice during subsequent wet processing, fundamentally ensuring the integrity of the high thermal conductivity crystal structure of aluminum nitride; the yttrium oxide sintering aid nano-coating forms a local eutectic liquid phase at the interface between the aluminum nitride particles and the fused silica matrix during subsequent hot-pressing sintering. This liquid phase, driven by sintering pressure, fully... The wetted and filled interfacial gaps, and solidified into a dense glassy bonding layer after cooling, eliminated interfacial pores and microcracks between particles and the matrix, significantly reducing phonon scattering loss at heterogeneous interfaces. The amorphous silica bridging layer prepared by the sol-gel method has homogeneous chemical bonding characteristics with the fused silica matrix, enabling aluminum nitride particles to achieve seamless transition connection with the matrix through a Si-O-Si covalent bond network, further eliminating interfacial acoustic impedance mismatch. The outermost grafted KH-560 coupling agent promotes the uniform dispersion of modified aluminum nitride particles in the slurry during wet ball milling, ensuring that the thermally conductive filler forms a uniformly interwoven three-dimensional continuous thermally conductive pathway network in the sintered body rather than isolated hot spots with local agglomeration. The synergistic effect of the aforementioned temperature-controlled passivation, sintering aid coating, homogeneous bridging, and coupling dispersion interfacial structures enables high thermal conductivity aluminum nitride particles to form a continuous and interconnected phonon transport network in a low thermal conductivity molten quartz matrix with good dispersion and dense interfacial bonding, which significantly improves the overall thermal conductivity of the temperature compensation plate.

[0006] This invention constructs a thermal expansion compensation system by introducing β-lithium nepheline negative expansion microcrystalline filler with multi-level surface protection into a fused silica matrix. The mechanism by which this system reduces the thermal expansion coefficient of the temperature compensation plate lies in the unique filled quartz-derived crystal structure of β-lithium nepheline. Its Al / Si oxygen tetrahedral framework exhibits significant contraction along the c-axis direction due to intensified vibration of lithium ions along the c-axis channel as temperature increases, macroscopically manifesting as a strong negative thermal expansion effect. It is one of the best-known thermally stable negative expansion ceramic materials. By introducing it into a fused silica matrix with micro-positive expansion in a specific ratio, the volume contraction of the negative expansion phase during heating precisely offsets the positive expansion components of the matrix and the aluminum nitride thermally conductive filler, thus controlling the overall thermal expansion coefficient of the composite system to near zero. The process involves several key elements: First, the dilute phosphoric acid activation treatment introduces phosphate and hydroxyl active sites on the surface of β-lithium nepheline microcrystals, providing a chemical anchoring basis for subsequent coatings. Second, the aluminum phosphate diffusion barrier layer is the core protective structure. The dense network structure composed of phosphorus-oxygen tetrahedra in the AlPO4 amorphous layer exhibits extremely low lithium-ion mobility, effectively preventing the outward diffusion and loss of lithium ions from the β-lithium nepheline lattice during high-temperature sintering, thus preserving the structural integrity and negative expansion characteristics of the β-lithium nepheline crystal. Third, the outer silica sealing layer provides homogeneous chemical bonding with the fused silica matrix, ensuring efficient mechanical transfer between the negative expansion filler and the matrix. This allows the volume shrinkage of β-lithium nepheline to be effectively transferred to the surrounding matrix through the rigid interface, achieving macroscopic expansion compensation.

[0007] Preferably, in step 1), the conditions for the temperature-controlled oxidation passivation treatment are: heating to 600-700℃ at a rate of 2℃ / min and holding for 2-4 hours in a dry air atmosphere.

[0008] Preferably, in step 1), the conditions for the yttrium oxide sintering aid sol-gel coating treatment are as follows: yttrium nitrate hexahydrate is dissolved in anhydrous ethanol to prepare a 0.1–0.3 mol / L yttrium salt solution; aluminum nitrate powder is added, and the pH is adjusted to 8.5–9.5 with 2 mol / L ammonia water to achieve the desired yttrium content. 3+ The in-situ precipitate forms a Y(OH)3 coating, which is then calcined at 500–600 °C for 2 hours under a nitrogen atmosphere to transform into a Y2O3 coating.

[0009] Preferably, in step 2), the β-lithium nepheline microcrystalline powder is obtained by ball milling and heat treatment of lithium carbonate, alumina and silicon dioxide in a molar ratio of 1:1:2.

[0010] Preferably, in step 2), the concentration of the dilute phosphoric acid solution used in the dilute phosphoric acid surface activation treatment is 0.5 to 1.5 wt%.

[0011] Preferably, in step 2), the conditions for the sol-gel coating treatment of the aluminum phosphate diffusion barrier layer are as follows: aluminum dihydrogen phosphate is dissolved in deionized water to prepare a solution of 0.05-0.15 mol / L, β-lithium nepheline powder is added, and the solution is evaporated and concentrated at 80°C. After vacuum drying at 60°C, the solution is calcined to form an AlPO4 amorphous diffusion barrier layer.

[0012] Preferably, in step 2), the calcination temperature of the silica sealing layer during the tetraethyl orthosilicate silica sealing layer coating process is 450–550°C.

[0013] Preferably, in step 3), based on 100 parts by weight of fused silica micro powder, the modified aluminum nitride thermal conductivity enhancing filler is 15-25 parts, the modified β-lithium nepheline negative expansion compensating filler is 10-20 parts, the zinc borate micro powder is 1.0-3.0 parts, and the sodium carboxymethyl cellulose is 0.3-1.0 parts.

[0014] The Y₂O₃ sintering aid layer on the surface of the modified aluminum nitride filler needs to be sintered at a relatively high temperature to form a sufficient liquid phase to wet and fill the interfacial gaps and achieve densification. However, this sintering temperature is close to the critical temperature for lithium ion activation and migration in the β-lithium nepheline lattice. This creates a contradiction in the required sintering temperature: if a higher sintering temperature is used to meet the densification requirements of aluminum nitride, even with the application of an aluminum phosphate diffusion barrier layer, some lithium ions will still diffuse outward into the fused silica matrix through the microscopic defect sites of the barrier layer under long-term high-temperature and high-pressure conditions. This leads to local lattice distortion or even phase decomposition of the β-lithium nepheline crystal due to lithium deficiency, weakening its negative expansion compensation effect. On the other hand, lithium ions diffuse into the matrix, causing the partially fused silica to transform into a lithium silicate glass phase. The thermal expansion coefficient of this phase is much higher than that of pure fused silica, which in turn worsens the thermal expansion performance of the matrix. Conversely, if the sintering temperature is lowered to protect the β-lithium nepheline crystals, the Y2O3 sintering aid cannot form a sufficient liquid phase, and the interfacial gaps between the aluminum nitride particles and the fused silica matrix cannot be effectively wetted and filled, leaving a large number of interfacial pores and microcracks. These interfacial defects constitute a high thermal resistance barrier for phonon transmission, causing a large number of breaks in the thermal conductivity network. As a result, the high thermal conductivity advantage of modified aluminum nitride cannot be effectively transferred to the matrix, and the actual thermal conductivity of the plate is far lower than the theoretical expected value. To address this technical problem, this invention introduces zinc borate micropowder and sodium carboxymethyl cellulose (CMC) into the technical solution. Zinc borate begins to soften at 600–700°C, forming a low-melting-point boron-zinc glassy liquid phase. This liquid phase can wet and fill the interfacial gaps between aluminum nitride particles and the matrix at temperatures far below the lithium-ion activation and migration temperature, producing a synergistic sintering aid effect with the Y2O3 sintering aid. This allows the system to achieve sufficient densification at a lower sintering temperature, significantly shortening the material's residence time in the high-temperature range and effectively suppressing the lithium-ion diffusion rate from a kinetic perspective. The carboxyl functional groups of sodium carboxymethyl cellulose uniformly coat the surfaces of the two types of modified filler particles through electrostatic adsorption, effectively preventing differential sedimentation and stratification of high-density aluminum nitride particles and low-density β-lithium nepheline particles due to density differences during slurry preparation and spray drying. This ensures the uniform distribution of the two types of fillers in the granulated powder and green body. CMC is completely thermally decomposed and burned off below 400°C during the sintering heating process, leaving no carbon impurities in the sintered body. The synergistic effect of the two additives enables the thermally conductive network constructed by modified aluminum nitride and the negative expansion compensation system constructed by modified β-nepheline to achieve full densification and uniform interpenetration at a lower sintering temperature, while maximizing the preservation of the crystal structure integrity of β-nepheline, thus achieving synergistic optimization of the thermal conductivity and thermal expansion coefficient of the temperature compensation plate.

[0015] Preferably, in step 3), the conditions for vacuum hot pressing sintering are as follows: first, the temperature is raised to 400°C at 5°C / min and held for 30 min to thermally decompose and burn off the sodium carboxymethyl cellulose; then, the temperature is raised to 900-1050°C at 5°C / min and held at 20 MPa for 2-4 h; after sintering, the temperature is lowered to room temperature at a controlled rate of 2°C / min.

[0016] A semiconductor photolithography temperature compensation plate is prepared by the above method.

[0017] Compared with the prior art, the beneficial effects of the present invention are: 1. By constructing a continuous and dense phonon transport network between aluminum nitride particles and fused silica matrix through multi-level interface modification, the interface defects and phonon scattering are effectively eliminated, and the thermal conductivity of the temperature compensation plate is greatly improved. 2. Introduce surface-protected β-lithium nepheline negative expansion filler, and use its volume shrinkage to precisely offset the positive expansion of the matrix, thereby controlling the thermal expansion coefficient of the plate to near zero. 3. By leveraging the low-temperature liquid-phase sintering aid of zinc borate and the uniform dispersion effect of sodium carboxymethyl cellulose, densification is achieved at a lower sintering temperature, while preserving the β-lithium nepheline structure. This allows the high thermal conductivity network and the negative expansion compensation system to work together efficiently, achieving optimal synergy between thermal conductivity and thermal expansion coefficient. Attached Figure Description

[0018] Figure 1 This is a low-magnification SEM image of the surface of the semiconductor photolithography temperature compensation plate prepared in Example 4 of the present invention; Figure 2 This is a magnified SEM image of the surface of the semiconductor photolithography temperature compensation plate prepared in Example 4 of the present invention. Figure 3 This is a high-magnification SEM image of the surface of the semiconductor photolithography temperature compensation plate prepared in Example 4 of the present invention. Detailed Implementation

[0019] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only a part of the embodiments of the present invention, and not all of them. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention. Example 1

[0020] A method for fabricating a semiconductor photolithography temperature compensation plate includes the following steps: 1) Weigh 50g of aluminum nitride micro powder (particle size 10μm, purity 99.5%, oxygen content ≤0.5wt%) using an electronic balance and spread it evenly on the bottom of a clean alumina crucible (spreading thickness not exceeding 10mm). Place the crucible in a muffle furnace and heat it to 650℃ at a rate of 2℃ / min. Keep it at this temperature for 3h in a dry air atmosphere. After natural cooling, remove the crucible and ultrasonically clean it three times with 300mL of anhydrous ethanol. Dry it for 6h at 80℃ and a vacuum of -0.08MPa. Pass it through a 300-mesh standard sieve to obtain AlN-O powder.

[0021] A 0.25 mol / L yttrium salt solution was prepared by dissolving yttrium nitrate hexahydrate (Y(NO3)3·6H2O) in 150 mL of anhydrous ethanol. 30 g of AlN-O powder was weighed and added to the yttrium salt solution. After stirring at 300 rpm for 30 min, 2 mol / L ammonia was added dropwise to adjust the pH to 9.0, and the reaction was continued for 2 h. The powder was washed three times by centrifugation with anhydrous ethanol, dried under vacuum at 60 °C for 8 h, and then calcined in a tube furnace under a nitrogen atmosphere at a rate of 5 °C / min to 550 °C for 2 h to obtain Y2O3@Al2O3@AlN powder.

[0022] 12.5 mL of TEOS was added to 250 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred at 30 °C for 1 h to hydrolyze and obtain silica sol. 25 g of Y₂O₃@Al₂O₃@AlN powder was added to the silica sol and stirred at 400 rpm for 4 h. The pH was then adjusted to 8.5 with 2 mol / L ammonia and stirred for 1 h. The mixture was washed four times with anhydrous ethanol by centrifugation, dried under vacuum at 70 °C for 8 h, and then calcined at 500 °C for 2 h under a nitrogen atmosphere to obtain SiO₂@Y₂O₃@Al₂O₃@AlN powder.

[0023] 0.75 g of KH-560 was added to a mixed solvent of 90 mL anhydrous ethanol and 10 mL deionized water. The pH was adjusted to 4.5 with glacial acetic acid, and the mixture was stirred and hydrolyzed at 30 °C for 1 h. 25 g of SiO2@Y2O3@Al2O3@AlN powder was added to the hydrolysate, and the mixture was stirred and refluxed at 75 °C for 3 h. The mixture was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified aluminum nitride thermally conductive filler.

[0024] 2) Weigh out 0.1 mol of Li₂CO₃, 0.1 mol of α-Al₂O₃, and 0.2 mol of SiO₂ in a planetary ball mill at 300 rpm for 12 h using anhydrous ethanol as the medium. After drying, heat the mixture to 1200 °C in a muffle furnace at 5 °C / min and hold for 6 h. After natural cooling, crush and grind the mixture in a planetary ball mill to a D50 ≈ 5 μm, and pass it through a 500-mesh sieve to obtain β-LiAlSiO₄ microcrystalline powder.

[0025] 20g of β-LiAlSiO4 microcrystalline powder was weighed and added to 200mL of 1.2wt% dilute phosphoric acid solution, and stirred at 45℃ for 1.5h. The powder was washed with deionized water by centrifugation until pH≥6.0, and then vacuum dried at 60℃ for 6h to obtain activated micropowder. Al(H2PO4)3 was then dissolved in 200mL of deionized water to prepare a 0.12mol / L solution. The activated powder was added to the solution and stirred at 300rpm for 30min. The solution was evaporated and concentrated at 80℃ to a viscous state, and then vacuum dried at 60℃ for 12h. The powder was then heated to 500℃ at 2℃ / min and held for 2h in a muffle furnace, and passed through a 400-mesh sieve to obtain AlPO4@β-LiAlSiO4 powder.

[0026] 7.5 mL of TEOS was added to 150 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h to obtain silica sol. 20 g of AlPO4@β-LiAlSiO4 powder was added to the silica sol, and the mixture was stirred at 400 rpm for 4 h. The pH was adjusted to 8.5 with 2 mol / L ammonia water, and the mixture was stirred for 1 h. The mixture was centrifuged and washed four times, vacuum dried at 70 °C for 8 h, and calcined at 500 °C for 2 h under nitrogen protection. Then, 0.60 g of KH-560 was added to 90 mL of anhydrous ethanol and 10 mL of deionized water, and the pH was adjusted to 4.5 with glacial acetic acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h. The powder was added to the hydrolysate and refluxed at 75 °C for 3 h. The mixture was centrifuged and washed three times, vacuum dried at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified β-lithium nepheline negative expansion compensating filler.

[0027] 3) Weigh 100g of fused silica micro powder, 23g of modified aluminum nitride thermally conductive reinforcing filler, 18g of modified β-lithium nepheline negative expansion compensating filler, 2.5g of zinc borate micro powder, and 0.8g of sodium carboxymethyl cellulose. Add deionized water to control the solid content to 50wt%. Wet ball mill the mixture at 200rpm for 10h in a planetary ball mill. After spray drying and granulation (inlet 220℃ / outlet 110℃), the slurry is loaded into a 6mm graphite mold and heated to 400℃ at 5℃ / min in a vacuum hot-pressing sintering furnace. Hold for 30min to remove the binder, then heat to 1000℃ at 5℃ / min and apply a pressure of 20MPa for 3h (vacuum degree ≤10Pa). Cool to room temperature at a controlled rate of 2℃ / min. Anneal at 600℃ for 6h to eliminate residual stress. After double-sided precision grinding and chemical mechanical polishing to a surface shape accuracy PV≤0.5μm and a surface roughness Ra≤0.05μm, and then cleaning with ultrapure water, a semiconductor photolithography temperature compensation plate is obtained. Example 2

[0028] A method for fabricating a semiconductor photolithography temperature compensation plate includes the following steps: 1) Weigh 50g of aluminum nitride micro powder (particle size 10μm, purity 99.5%, oxygen content ≤0.5wt%) using an electronic balance and spread it evenly on the bottom of a clean alumina crucible (spreading thickness not exceeding 10mm). Place the crucible in a muffle furnace and heat it to 650℃ at a rate of 2℃ / min. Keep it at this temperature for 3h in a dry air atmosphere. After natural cooling, remove the crucible and ultrasonically clean it three times with 300mL of anhydrous ethanol. Dry it for 6h at 80℃ and a vacuum of -0.08MPa. Pass it through a 300-mesh standard sieve to obtain AlN-O powder.

[0029] A 0.15 mol / L yttrium salt solution was prepared by dissolving yttrium nitrate hexahydrate (Y(NO3)3·6H2O) in 150 mL of anhydrous ethanol. 30 g of AlN-O powder was weighed and added to the yttrium salt solution. After stirring at 300 rpm for 30 min, 2 mol / L ammonia was added dropwise to adjust the pH to 9.0, and the reaction was continued for 2 h. The powder was washed three times by centrifugation with anhydrous ethanol, dried under vacuum at 60 °C for 8 h, and then calcined in a tube furnace under a nitrogen atmosphere at a rate of 5 °C / min to 550 °C for 2 h to obtain Y2O3@Al2O3@AlN powder.

[0030] 12.5 mL of TEOS was added to 250 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred at 30 °C for 1 h to hydrolyze and obtain silica sol. 25 g of Y₂O₃@Al₂O₃@AlN powder was added to the silica sol and stirred at 400 rpm for 4 h. The pH was then adjusted to 8.5 with 2 mol / L ammonia and stirred for 1 h. The mixture was washed four times with anhydrous ethanol by centrifugation, dried under vacuum at 70 °C for 8 h, and then calcined at 500 °C for 2 h under a nitrogen atmosphere to obtain SiO₂@Y₂O₃@Al₂O₃@AlN powder.

[0031] 0.75 g of KH-560 was added to a mixed solvent of 90 mL anhydrous ethanol and 10 mL deionized water. The pH was adjusted to 4.5 with glacial acetic acid, and the mixture was stirred and hydrolyzed at 30 °C for 1 h. 25 g of SiO2@Y2O3@Al2O3@AlN powder was added to the hydrolysate, and the mixture was stirred and refluxed at 75 °C for 3 h. The mixture was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified aluminum nitride thermally conductive filler.

[0032] 2) Weigh out 0.1 mol of Li₂CO₃, 0.1 mol of α-Al₂O₃, and 0.2 mol of SiO₂ in a planetary ball mill at 300 rpm for 12 h using anhydrous ethanol as the medium. After drying, heat the mixture to 1200 °C in a muffle furnace at 5 °C / min and hold for 6 h. After natural cooling, crush and grind the mixture in a planetary ball mill to a D50 ≈ 5 μm, and pass it through a 500-mesh sieve to obtain β-LiAlSiO₄ microcrystalline powder.

[0033] 20g of β-LiAlSiO4 microcrystalline powder was weighed and added to 200mL of 0.8wt% dilute phosphoric acid solution, and stirred at 45℃ for 1.5h. The powder was washed with deionized water by centrifugation until pH≥6.0, and then vacuum dried at 60℃ for 6h to obtain activated micropowder. Al(H2PO4)3 was then dissolved in 200mL of deionized water to prepare a 0.08mol / L solution. The activated powder was added to the solution and stirred at 300rpm for 30min. The solution was evaporated and concentrated at 80℃ to a viscous state, and then vacuum dried at 60℃ for 12h. The powder was then heated to 500℃ at 2℃ / min and held for 2h in a muffle furnace, and passed through a 400-mesh sieve to obtain AlPO4@β-LiAlSiO4 powder.

[0034] 7.5 mL of TEOS was added to 150 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h to obtain silica sol. 20 g of AlPO4@β-LiAlSiO4 powder was added to the silica sol, and the mixture was stirred at 400 rpm for 4 h. The pH was adjusted to 8.5 with 2 mol / L ammonia water, and the mixture was stirred for 1 h. The mixture was centrifuged and washed four times, vacuum dried at 70 °C for 8 h, and calcined at 500 °C for 2 h under nitrogen protection. Then, 0.60 g of KH-560 was added to 90 mL of anhydrous ethanol and 10 mL of deionized water, and the pH was adjusted to 4.5 with glacial acetic acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h. The powder was added to the hydrolysate and refluxed at 75 °C for 3 h. The mixture was centrifuged and washed three times, vacuum dried at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified β-lithium nepheline negative expansion compensating filler.

[0035] 3) Weigh 100g of fused silica micro powder, 18g of modified aluminum nitride thermally conductive reinforcing filler, 12g of modified β-lithium nepheline negative expansion compensating filler, 1.5g of zinc borate micro powder, and 0.5g of sodium carboxymethyl cellulose. Add deionized water to control the solid content to 50wt%. Wet ball mill the mixture at 200rpm for 10h in a planetary ball mill. After spray drying and granulation (inlet 220℃ / outlet 110℃), the slurry is loaded into a 6mm graphite mold and heated to 400℃ at 5℃ / min in a vacuum hot-pressing sintering furnace. Hold for 30min to remove the binder, then heat to 1000℃ at 5℃ / min and apply a pressure of 20MPa for 3h (vacuum degree ≤10Pa). Cool to room temperature at a controlled rate of 2℃ / min. Anneal at 600℃ for 6h to eliminate residual stress. After double-sided precision grinding and chemical mechanical polishing to a surface shape accuracy PV≤0.5μm and a surface roughness Ra≤0.05μm, and then cleaning with ultrapure water, a semiconductor photolithography temperature compensation plate is obtained. Example 3

[0036] A method for fabricating a semiconductor photolithography temperature compensation plate includes the following steps: 1) Weigh 50g of aluminum nitride micro powder (particle size 10μm, purity 99.5%, oxygen content ≤0.5wt%) using an electronic balance and spread it evenly on the bottom of a clean alumina crucible (spreading thickness not exceeding 10mm). Place the crucible in a muffle furnace and heat it to 650℃ at a rate of 2℃ / min. Keep it at this temperature for 3h in a dry air atmosphere. After natural cooling, remove the crucible and ultrasonically clean it three times with 300mL of anhydrous ethanol. Dry it for 6h at 80℃ and a vacuum of -0.08MPa. Pass it through a 300-mesh standard sieve to obtain AlN-O powder.

[0037] Yttrium nitrate hexahydrate (Y(NO3)3·6H2O) was dissolved in 150 mL of anhydrous ethanol to prepare a 0.2 mol / L yttrium salt solution. 30 g of AlN-O powder was weighed and added to the yttrium salt solution. After stirring at 300 rpm for 30 min, 2 mol / L ammonia was added dropwise to adjust the pH to 9.0, and the reaction was continued for 2 h. The powder was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 60 °C for 8 h, and then calcined in a tube furnace under a nitrogen atmosphere at a rate of 5 °C / min to 550 °C for 2 h to obtain Y2O3@Al2O3@AlN powder.

[0038] 12.5 mL of TEOS was added to 250 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred at 30 °C for 1 h to hydrolyze and obtain silica sol. 25 g of Y₂O₃@Al₂O₃@AlN powder was added to the silica sol and stirred at 400 rpm for 4 h. The pH was then adjusted to 8.5 with 2 mol / L ammonia and stirred for 1 h. The mixture was washed four times with anhydrous ethanol by centrifugation, dried under vacuum at 70 °C for 8 h, and then calcined at 500 °C for 2 h under a nitrogen atmosphere to obtain SiO₂@Y₂O₃@Al₂O₃@AlN powder.

[0039] 0.75 g of KH-560 was added to a mixed solvent of 90 mL anhydrous ethanol and 10 mL deionized water. The pH was adjusted to 4.5 with glacial acetic acid, and the mixture was stirred and hydrolyzed at 30 °C for 1 h. 25 g of SiO2@Y2O3@Al2O3@AlN powder was added to the hydrolysate, and the mixture was stirred and refluxed at 75 °C for 3 h. The mixture was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified aluminum nitride thermally conductive filler.

[0040] 2) Weigh out 0.1 mol of Li₂CO₃, 0.1 mol of α-Al₂O₃, and 0.2 mol of SiO₂ in a planetary ball mill at 300 rpm for 12 h using anhydrous ethanol as the medium. After drying, heat the mixture to 1200 °C in a muffle furnace at 5 °C / min and hold for 6 h. After natural cooling, crush and grind the mixture in a planetary ball mill to a D50 ≈ 5 μm, and pass it through a 500-mesh sieve to obtain β-LiAlSiO₄ microcrystalline powder.

[0041] 20g of β-LiAlSiO4 microcrystalline powder was weighed and added to 200mL of 1.0wt% dilute phosphoric acid solution, and stirred at 45℃ for 1.5h. The powder was washed with deionized water by centrifugation until pH≥6.0, and then vacuum dried at 60℃ for 6h to obtain activated micropowder. Al(H2PO4)3 was then dissolved in 200mL of deionized water to prepare a 0.1mol / L solution. The activated powder was added to the solution and stirred at 300rpm for 30min. The solution was evaporated and concentrated at 80℃ to a viscous state, and then vacuum dried at 60℃ for 12h. The powder was then heated to 500℃ at 2℃ / min and held for 2h in a muffle furnace, and passed through a 400-mesh sieve to obtain AlPO4@β-LiAlSiO4 powder.

[0042] 7.5 mL of TEOS was added to 150 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h to obtain silica sol. 20 g of AlPO4@β-LiAlSiO4 powder was added to the silica sol, and the mixture was stirred at 400 rpm for 4 h. The pH was adjusted to 8.5 with 2 mol / L ammonia water, and the mixture was stirred for 1 h. The mixture was centrifuged and washed four times, vacuum dried at 70 °C for 8 h, and calcined at 500 °C for 2 h under nitrogen protection. Then, 0.60 g of KH-560 was added to 90 mL of anhydrous ethanol and 10 mL of deionized water, and the pH was adjusted to 4.5 with glacial acetic acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h. The powder was added to the hydrolysate and refluxed at 75 °C for 3 h. The mixture was centrifuged and washed three times, vacuum dried at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified β-lithium nepheline negative expansion compensating filler.

[0043] 3) Weigh 100g of fused silica micro powder, 20g of modified aluminum nitride thermally conductive reinforcing filler, 15g of modified β-lithium nepheline negative expansion compensating filler, 2g of zinc borate micro powder, and 0.6g of sodium carboxymethyl cellulose. Add deionized water to control the solid content to 50wt%. Wet ball mill the mixture at 200rpm for 10h in a planetary ball mill. After spray drying and granulation (inlet 220℃ / outlet 110℃), the slurry is loaded into a 6mm graphite mold and heated to 400℃ at 5℃ / min in a vacuum hot-pressing sintering furnace. Hold for 30min to remove the binder, then heat to 1000℃ at 5℃ / min and apply a pressure of 20MPa for 3h (vacuum degree ≤10Pa). Cool to room temperature at a controlled rate of 2℃ / min. Anneal at 600℃ for 6h to eliminate residual stress. After double-sided precision grinding and chemical mechanical polishing to a surface shape accuracy PV≤0.5μm and a surface roughness Ra≤0.05μm, and then cleaning with ultrapure water, a semiconductor photolithography temperature compensation plate is obtained. Example 4

[0044] A method for fabricating a semiconductor photolithography temperature compensation plate includes the following steps: 1) Weigh 50g of aluminum nitride micro powder (particle size 10μm, purity 99.5%, oxygen content ≤0.5wt%) using an electronic balance and spread it evenly on the bottom of a clean alumina crucible (spreading thickness not exceeding 10mm). Place the crucible in a muffle furnace and heat it to 700℃ at a rate of 2℃ / min. Keep it at this temperature for 4h in a dry air atmosphere. After natural cooling, remove the crucible and ultrasonically clean it three times with 300mL of anhydrous ethanol. Dry it at 80℃ and vacuum degree -0.08MPa for 6h. Pass it through a 300-mesh standard sieve to obtain AlN-O powder.

[0045] Yttrium nitrate hexahydrate (Y(NO3)3·6H2O) was dissolved in 150 mL of anhydrous ethanol to prepare a 0.3 mol / L yttrium salt solution. 30 g of AlN-O powder was weighed and added to the yttrium salt solution. After stirring at 300 rpm for 30 min, 2 mol / L ammonia was added dropwise to adjust the pH to 9.5, and the reaction was continued for 2 h. The powder was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 60 °C for 8 h, and then calcined in a tube furnace under a nitrogen atmosphere at a rate of 5 °C / min to 600 °C for 2 h to obtain Y2O3@Al2O3@AlN powder.

[0046] 12.5 mL of TEOS was added to 250 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred at 30 °C for 1 h to hydrolyze and obtain silica sol. 25 g of Y₂O₃@Al₂O₃@AlN powder was added to the silica sol and stirred at 400 rpm for 4 h. The pH was then adjusted to 8.5 with 2 mol / L ammonia and stirred for 1 h. The mixture was washed four times with anhydrous ethanol by centrifugation, dried under vacuum at 70 °C for 8 h, and then calcined at 500 °C for 2 h under a nitrogen atmosphere to obtain SiO₂@Y₂O₃@Al₂O₃@AlN powder.

[0047] 0.75 g of KH-560 was added to a mixed solvent of 90 mL anhydrous ethanol and 10 mL deionized water. The pH was adjusted to 4.5 with glacial acetic acid, and the mixture was stirred and hydrolyzed at 30 °C for 1 h. 25 g of SiO2@Y2O3@Al2O3@AlN powder was added to the hydrolysate, and the mixture was stirred and refluxed at 75 °C for 3 h. The mixture was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified aluminum nitride thermally conductive filler.

[0048] 2) Weigh out 0.1 mol of Li₂CO₃, 0.1 mol of α-Al₂O₃, and 0.2 mol of SiO₂ in a planetary ball mill at 300 rpm for 12 h using anhydrous ethanol as the medium. After drying, heat the mixture to 1200 °C in a muffle furnace at 5 °C / min and hold for 6 h. After natural cooling, crush and grind the mixture in a planetary ball mill to a D50 ≈ 5 μm, and pass it through a 500-mesh sieve to obtain β-LiAlSiO₄ microcrystalline powder.

[0049] 20g of β-LiAlSiO4 microcrystalline powder was weighed and added to 200mL of 1.5wt% dilute phosphoric acid solution, and stirred at 45℃ for 1.5h. The powder was washed with deionized water by centrifugation until pH≥6.0, and then vacuum dried at 60℃ for 6h to obtain activated micropowder. Al(H2PO4)3 was then dissolved in 200mL of deionized water to prepare a 0.15mol / L solution. The activated powder was added to the solution and stirred at 300rpm for 30min. The solution was evaporated and concentrated at 80℃ to a viscous state, and then vacuum dried at 60℃ for 12h. The powder was then heated to 500℃ in a muffle furnace at 2℃ / min and held for 2h. The powder was then passed through a 400-mesh sieve to obtain AlPO4@β-LiAlSiO4 powder.

[0050] 7.5 mL of TEOS was added to 150 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h to obtain silica sol. 20 g of AlPO4@β-LiAlSiO4 powder was added to the silica sol, and the mixture was stirred at 400 rpm for 4 h. The pH was adjusted to 8.5 with 2 mol / L ammonia water, and the mixture was stirred for 1 h. The mixture was centrifuged and washed four times, vacuum dried at 70 °C for 8 h, and calcined at 550 °C for 2 h under nitrogen protection. Then, 0.60 g of KH-560 was added to 90 mL of anhydrous ethanol and 10 mL of deionized water, and the pH was adjusted to 4.5 with glacial acetic acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h. The powder was added to the hydrolysate and refluxed at 75 °C for 3 h, centrifuged and washed three times, vacuum dried at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified β-lithium nepheline negative expansion compensating filler.

[0051] Weigh 100g of fused silica micropowder, 25g of modified aluminum nitride thermally conductive reinforcing filler, 20g of modified β-lithium nepheline negative expansion compensating filler, 3g of zinc borate micropowder, and 1g of sodium carboxymethyl cellulose. Add deionized water to control the solid content to 50wt%, and wet ball mill at 200rpm for 10h in a planetary ball mill. After spray drying and granulation (inlet 220℃ / outlet 110℃), the slurry is loaded into a 6mm graphite mold and heated to 400℃ at 5℃ / min in a vacuum hot-pressing sintering furnace, held for 30min to remove the binder, then heated to 1050℃ at 5℃ / min and held under 20MPa pressure for 4h (vacuum degree ≤10Pa). Cool to room temperature at a controlled rate of 2℃ / min. Anneal at 600℃ for 6h to eliminate residual stress. After double-sided precision grinding and chemical mechanical polishing to a surface shape accuracy PV≤0.5μm and a surface roughness Ra≤0.05μm, and then cleaning with ultrapure water, a semiconductor photolithography temperature compensation plate is obtained.

[0052] like Figure 1 The image shown is a low-magnification SEM (scanning electron microscope) image of the surface of the semiconductor photolithography temperature compensation plate prepared in Example 4 of this invention. Figure 2 The image shown is a magnified SEM image of the surface of the semiconductor photolithography temperature compensation plate prepared in Example 4 of this invention. Figure 3 This is a high-magnification SEM image of the surface of the semiconductor photolithography temperature compensation plate prepared in Example 4 of the present invention. It can be observed that the surface of the semiconductor photolithography temperature compensation plate exhibits a flat and smooth morphology. Example 5

[0053] A method for fabricating a semiconductor photolithography temperature compensation plate includes the following steps: 1) Weigh 50g of aluminum nitride micro powder (particle size 10μm, purity 99.5%, oxygen content ≤0.5wt%) using an electronic balance and spread it evenly on the bottom of a clean alumina crucible (spreading thickness not exceeding 10mm). Place the crucible in a muffle furnace and heat it to 600℃ at a rate of 2℃ / min. Keep it at this temperature for 2h in a dry air atmosphere. After natural cooling, remove the crucible and ultrasonically clean it three times with 300mL of anhydrous ethanol. Dry it at 80℃ and vacuum degree -0.08MPa for 6h. Pass it through a 300-mesh standard sieve to obtain AlN-O powder.

[0054] Yttrium nitrate hexahydrate (Y(NO3)3·6H2O) was dissolved in 150 mL of anhydrous ethanol to prepare a 0.1 mol / L yttrium salt solution. 30 g of AlN-O powder was weighed and added to the yttrium salt solution. After stirring at 300 rpm for 30 min, 2 mol / L ammonia was added dropwise to adjust the pH to 8.5, and the reaction was continued for 2 h. The powder was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 60 °C for 8 h, and then calcined in a tube furnace under a nitrogen atmosphere at a rate of 5 °C / min to 500 °C for 2 h to obtain Y2O3@Al2O3@AlN powder.

[0055] 12.5 mL of TEOS was added to 250 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred at 30 °C for 1 h to hydrolyze and obtain silica sol. 25 g of Y₂O₃@Al₂O₃@AlN powder was added to the silica sol and stirred at 400 rpm for 4 h. The pH was then adjusted to 8.5 with 2 mol / L ammonia and stirred for 1 h. The mixture was washed four times with anhydrous ethanol by centrifugation, dried under vacuum at 70 °C for 8 h, and then calcined at 500 °C for 2 h under a nitrogen atmosphere to obtain SiO₂@Y₂O₃@Al₂O₃@AlN powder.

[0056] 0.75 g of KH-560 was added to a mixed solvent of 90 mL anhydrous ethanol and 10 mL deionized water. The pH was adjusted to 4.5 with glacial acetic acid, and the mixture was stirred and hydrolyzed at 30 °C for 1 h. 25 g of SiO2@Y2O3@Al2O3@AlN powder was added to the hydrolysate, and the mixture was stirred and refluxed at 75 °C for 3 h. The mixture was washed three times with anhydrous ethanol by centrifugation, dried under vacuum at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified aluminum nitride thermally conductive filler.

[0057] 2) Weigh out 0.1 mol of Li₂CO₃, 0.1 mol of α-Al₂O₃, and 0.2 mol of SiO₂ in a planetary ball mill at 300 rpm for 12 h using anhydrous ethanol as the medium. After drying, heat the mixture to 1200 °C in a muffle furnace at 5 °C / min and hold for 6 h. After natural cooling, crush and grind the mixture in a planetary ball mill to a D50 ≈ 5 μm, and pass it through a 500-mesh sieve to obtain β-LiAlSiO₄ microcrystalline powder.

[0058] 20g of β-LiAlSiO4 microcrystalline powder was weighed and added to 200mL of 0.5wt% dilute phosphoric acid solution, and stirred at 45℃ for 1.5h. The powder was washed with deionized water by centrifugation until pH≥6.0, and then vacuum dried at 60℃ for 6h to obtain activated micropowder. Al(H2PO4)3 was then dissolved in 200mL of deionized water to prepare a 0.05mol / L solution. The activated powder was added to the solution and stirred at 300rpm for 30min. The solution was evaporated and concentrated at 80℃ to a viscous state, and then vacuum dried at 60℃ for 12h. The powder was then heated to 500℃ at 2℃ / min and held for 2h in a muffle furnace, and passed through a 400-mesh sieve to obtain AlPO4@β-LiAlSiO4 powder.

[0059] 7.5 mL of TEOS was added to 150 mL of anhydrous ethanol, and the pH was adjusted to 2.5 with 0.1 mol / L hydrochloric acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h to obtain silica sol. 20 g of AlPO4@β-LiAlSiO4 powder was added to the silica sol, and the mixture was stirred at 400 rpm for 4 h. The pH was adjusted to 8.5 with 2 mol / L ammonia water, and the mixture was stirred for 1 h. The mixture was centrifuged and washed four times, vacuum dried at 70 °C for 8 h, and calcined at 450 °C for 2 h under nitrogen protection. Then, 0.60 g of KH-560 was added to 90 mL of anhydrous ethanol and 10 mL of deionized water, and the pH was adjusted to 4.5 with glacial acetic acid. The mixture was stirred and hydrolyzed at 30 °C for 1 h. The powder was added to the hydrolysate and refluxed at 75 °C for 3 h. The mixture was centrifuged and washed three times, vacuum dried at 85 °C for 6 h, and passed through a 400-mesh sieve to obtain the modified β-lithium nepheline negative expansion compensating filler.

[0060] 3) Weigh 100g of fused silica micro powder, 15g of modified aluminum nitride thermally conductive reinforcing filler, 10g of modified β-lithium nepheline negative expansion compensating filler, 1g of zinc borate micro powder, and 0.3g of sodium carboxymethyl cellulose. Add deionized water to control the solid content to 50wt%. Wet ball mill the mixture at 200rpm for 10h in a planetary ball mill. After spray drying and granulation (inlet 220℃ / outlet 110℃), the slurry is loaded into a 6mm graphite mold and heated to 400℃ at 5℃ / min in a vacuum hot-pressing sintering furnace. Hold for 30min to remove the binder, then heat to 900℃ at 5℃ / min and apply 20MPa pressure for 2h (vacuum degree ≤10Pa). Cool to room temperature at a controlled rate of 2℃ / min. Anneal at 600℃ for 6h to eliminate residual stress. After double-sided precision grinding and chemical mechanical polishing to a surface shape accuracy PV≤0.5μm and a surface roughness Ra≤0.05μm, and then cleaning with ultrapure water, a semiconductor photolithography temperature compensation plate is obtained.

[0061] Comparative Example 1: The difference from Example 4 is that the modified aluminum nitride thermal conductivity enhancing filler in step 3) is replaced with ordinary aluminum nitride micro powder, and the modified β-lithium nepheline negative expansion compensating filler is replaced with β-LiAlSiO4 microcrystalline powder.

[0062] Comparative Example 2: The difference from Example 4 is that no modified aluminum nitride thermally conductive filler is added in step 3).

[0063] Comparative Example 3: The difference from Example 4 is that the modified β-lithium nepheline negative expansion compensation filler is not added in step 3).

[0064] Comparative Example 4: The difference from Example 4 is that zinc borate powder and sodium carboxymethyl cellulose are not added in step 3).

[0065] Comparative Example 5: The difference from Example 4 is that zinc borate powder is not added in step 3).

[0066] Comparative Example 6: The difference from Example 4 is that sodium carboxymethyl cellulose is not added in step 3).

[0067] Performance testing: (1) Thermal conductivity test: The thermal conductivity of the temperature compensation plate was tested using the laser flash method. The temperature compensation plates prepared in each embodiment and comparative example were processed into circular samples with a diameter of 12.7 mm and a thickness of 2 mm. A layer of graphite coating was uniformly sprayed on both sides of the sample to improve the surface absorption rate of laser and the emissivity of infrared radiation. A laser thermal conductivity meter was used to irradiate the lower surface of the sample with a xenon lamp pulse flash under a constant temperature of 25℃. The temperature rise curve of the upper surface of the sample was recorded by an infrared detector. The thermal diffusivity α was calculated by fitting the Cape-Lehman model. At the same time, the specific heat capacity cp of the sample was measured at 25℃ using a differential scanning calorimeter, and the bulk density ρ of the sample was measured using the Archimedes displacement method. The thermal conductivity was calculated according to the formula λ=α×cp×ρ. The average value of 3 parallel samples in each group of tests was taken.

[0068] (2) Thermal expansion coefficient test: The linear thermal expansion coefficient of the temperature compensation plate was tested using a high-precision pusher-type thermal expansion meter. Each sample was processed into a cuboid rod with a length of 25 mm and a cross-section of 4 mm × 4 mm. The thermal expansion meter was used to heat the sample from room temperature to 200 °C at a heating rate of 2 °C / min under a high-purity nitrogen protective atmosphere. The expansion curve of the sample length as a function of temperature was recorded. The average linear thermal expansion coefficient (CTE) in the temperature range of 20–100 °C was taken. The average value of 3 parallel samples in each group was taken.

[0069] (3) Bulk density and apparent porosity test: The bulk density and apparent porosity of the temperature compensation plate were tested using the Archimedes displacement method. Each sample was processed into a block sample of approximately 10 mm × 10 mm × 5 mm. The sample was first dried at 110 °C to constant weight, and the dry weight m1 was weighed using an analytical balance. Then, the sample was placed in a vacuum desiccator and evacuated to -0.095 MPa, and then immersed in deionized water for 2 hours to fully fill the open pores with water. The suspended weight m2 in the water and the weight m3 after wiping the saturated surface dry were weighed. The bulk density was calculated according to the formula ρ = m1 / (m3-m2) × ρwater, and the apparent porosity was calculated according to the formula P = (m3-m1) / (m3-m2) × 100%. The average value of 5 parallel samples in each group was taken.

[0070] (4) Three-point bending strength test: The bending strength of the temperature compensation plate was tested using the three-point bending method. Each specimen was precisely machined into a rectangular bar with a length of 25 mm, a width of 4 mm, and a thickness of 3 mm. The machined surface was finely ground with 1200# diamond sandpaper and chamfered. A universal testing machine was used, according to configuration B of ASTM C1161-2018 standard, with a span of 20 mm and a loading rate of 0.5 mm / min, to conduct a three-point bending test under ambient temperature and atmospheric conditions. The strength was determined according to the formula σ. f =3FL / (2bh 2 Calculate the flexural strength, where F is the fracture load, L is the span, b is the specimen width, and h is the specimen thickness. Each test group shall take the average value of no less than 5 valid specimens.

[0071] (5) Surface roughness test: The surface roughness of the temperature compensation plate after chemical mechanical polishing was tested using a non-contact white light interferometry method. A three-dimensional optical surface profilometer was used with a 50× objective lens (field of view 0.14mm×0.11mm). Five non-overlapping measurement areas were randomly selected on the polished surface of each sample. The arithmetic mean roughness Ra value of each area was measured and recorded. The average value of the five measurement areas was taken as the surface roughness test result of the sample.

[0072] Table 1: Performance Test Results of Examples and Comparative Examples

[0073] Note: CTE units are ×10 -7 / ℃, which is 0.1ppm / ℃; a positive value indicates positive expansion, and a negative value indicates negative expansion.

[0074] Compared to Example 4, Comparative Example 1 used unmodified ordinary aluminum nitride micropowder and unmodified β-LiAlSiO4 microcrystalline powder to replace the modified filler, resulting in a significant decrease in thermal conductivity from 10.5 W / (m·K) to 3.5 W / (m·K) and CTE from 0.8 × 10⁻⁶. -7 / ℃ rose sharply to 18.5×10 -7 At ℃, the apparent porosity increased from 0.06% to 1.45%, and the three-point bending strength decreased from 162 MPa to 68 MPa. This is because untreated aluminum nitride undergoes severe hydrolysis during wet ball milling and sol-coating, resulting in the destruction of the high thermal conductivity crystal structure. Furthermore, the NH3 generated by hydrolysis forms a large number of pore defects in the sintered body. At the same time, the unprotected β-lithium nepheline undergoes a large outward diffusion and loss of lithium ions during high-temperature sintering, causing irreversible phase decomposition of the crystal structure and complete loss of negative expansion compensation function. Moreover, the lithium ions diffused into the matrix cause the locally fused quartz to transform into a highly expandable lithium silicate glass phase, which in turn worsens the thermal expansion performance of the matrix.

[0075] Compared to Example 4, Comparative Example 2, without the addition of modified aluminum nitride thermal conductivity enhancer filler, showed a sharp drop in thermal conductivity from 10.5 W / (m·K) to 1.6 W / (m·K), approaching the intrinsic thermal conductivity level of pure fused silica. This indicates that modified aluminum nitride is the core functional component for constructing an efficient thermal conductivity network, and its absence results in the loss of the system's high thermal conductivity advantage. Simultaneously, the CTE showed an increase to -2.8 × 10⁻⁶. -7 The negative value of / ℃ is due to the lack of positive expansion contribution from aluminum nitride filler, which leads to the negative expansion effect of β-lithium nepheline overcompensating for the micro-positive expansion of the fused silica matrix. As a result, the system exhibits negative expansion overall, deviating from the near-zero target.

[0076] Compared to Example 4, Comparative Example 3, without the addition of modified β-lithium nepheline negative expansion compensating filler, still maintained a high thermal conductivity (9.8 W / (m·K)), but the CTE decreased from 0.8 × 10⁻⁶. -7 / ℃ rose sharply to 12.5×10 -7 / ℃ (i.e., 1.25ppm / ℃), which is far from the near-zero level. This is because the system lacks a negative expansion phase to offset the positive expansion components of the fused silica matrix and aluminum nitride thermally conductive filler. The thermal expansion coefficient of the temperature compensation plate is entirely determined by the combined effect of the matrix and the positive expansion filler, and thermal expansion compensation cannot be achieved.

[0077] Compared to Example 4, Comparative Example 4, without the addition of zinc borate micron powder and sodium carboxymethyl cellulose, showed a decrease in thermal conductivity from 10.5 W / (m·K) to 4.8 W / (m·K), and a decrease in CTE from 0.8 × 10⁻⁶. -7 / ℃ rose to 8.2×10 -7 At ℃, the apparent porosity increased sharply from 0.06% to 0.95%, and the three-point bending strength decreased from 162MPa to 82MPa. This is because, on the one hand, the synergistic sintering effect of the low-melting-point boron-zinc glass phase liquid phase formed by zinc borate at 600-700℃ and the Y2O3 sintering aid was lacking, resulting in insufficient densification of the system at 1050℃ and a large amount of residual interfacial gaps. At the same time, in order to pursue densification, it was necessary to extend the high-temperature holding time, which aggravated the diffusion of lithium ions through the micro-defect sites of the aluminum phosphate barrier layer. On the other hand, the dispersion and stabilization effect of CMC was lacking, and the high-density aluminum nitride particles and low-density β-lithium nepheline particles underwent severe differential sedimentation and stratification during slurry preparation and spray drying due to density differences. The two types of fillers were distributed very unevenly in the sintered body, and the thermal conductivity network and negative expansion compensation system both failed.

[0078] Compared to Example 4, Comparative Example 5, without the addition of zinc borate powder, showed a decrease in thermal conductivity to 5.5 W / (m·K) and an increase in CTE to 6.5 × 10⁻⁶. -7 At 1050℃, the apparent porosity increased to 0.68%, and the three-point bending strength decreased to 95 MPa. This is because the lack of low-temperature liquid-phase sintering aid from zinc borate meant that the system relied solely on Y2O3 as a sintering aid. Under sintering conditions of 1050℃, the degree of interfacial densification was insufficient, leaving a large number of interfacial pores and microcracks between the aluminum nitride particles and the matrix, forming a high thermal resistance barrier for phonon transmission. At the same time, insufficient densification forced a longer high-temperature holding time, which exacerbated the diffusion and loss of lithium ions and weakened the negative expansion compensation effect of β-lithium nepheline.

[0079] Compared to Example 4, Comparative Example 6, without the addition of sodium carboxymethyl cellulose, showed a decrease in thermal conductivity to 7.8 W / (m·K) and a reduction in CTE from 0.8 × 10⁻⁶. -7 / ℃ rose to 3.8×10 -7At ℃, the surface roughness Ra increased from 0.028 μm to 0.045 μm. Although zinc borate still provided some low-temperature sintering assistance to maintain the apparent porosity at a low level (0.18%), the lack of CMC dispersion stabilization led to differential sedimentation and stratification of the two types of modified fillers with different densities in the slurry and granulated powder: aluminum nitride thermally conductive filler locally agglomerated to form isolated hot spots rather than continuous three-dimensional thermal conductive pathways, reducing the effectiveness of the thermal conductive network; the uneven distribution of β-lithium nepheline negative expansion filler resulted in significant differences in the thermal expansion compensation effect in different areas of the plate, which was macroscopically manifested as CTE deviating from the near-zero level, and the inhomogeneity of the microstructure led to an increase in surface roughness after polishing.

[0080] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the essence and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for fabricating a semiconductor photolithography temperature compensation plate, characterized in that, Includes the following steps: 1) Aluminum nitride micro powder was subjected to temperature-controlled oxidation passivation treatment, yttrium oxide sintering aid sol coating treatment, tetraethyl orthosilicate sol-gel silica bridging layer coating treatment and KH-560 coupling functionalization treatment in sequence to obtain modified aluminum nitride thermally conductive filler. 2) The β-lithium nepheline microcrystalline powder was subjected to dilute phosphoric acid surface activation treatment, aluminum phosphate diffusion barrier layer sol-gel coating treatment, tetraethyl orthosilicate silica sealing layer coating treatment and KH-560 coupling functionalization treatment in sequence to obtain modified β-lithium nepheline negative expansion compensation filler. 3) The fused silica micro powder, the modified aluminum nitride thermally conductive enhanced filler, the modified β-lithium nepheline negative expansion compensating filler, zinc borate micro powder and sodium carboxymethyl cellulose are mixed and then subjected to wet ball milling, spray drying granulation, vacuum hot pressing sintering, controlled cooling, annealing, precision grinding and chemical mechanical polishing to obtain a semiconductor photolithography temperature compensation board.

2. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 1), the conditions for the temperature-controlled oxidation passivation treatment are: heating to 600-700℃ at a rate of 2℃ / min and holding for 2-4 hours in a dry air atmosphere.

3. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 1), the conditions for the yttrium oxide sintering aid sol-gel coating treatment are as follows: yttrium nitrate hexahydrate is dissolved in anhydrous ethanol to prepare a 0.1–0.3 mol / L yttrium salt solution; aluminum nitrate powder is added, and the pH is adjusted to 8.5–9.5 with 2 mol / L ammonia water. 3+ The in-situ precipitate forms a Y(OH)3 coating, which is then calcined at 500–600 °C for 2 hours under a nitrogen atmosphere to transform into a Y2O3 coating.

4. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 2), the β-lithium nepheline microcrystalline powder is obtained by ball milling and heat treatment of lithium carbonate, alumina and silicon dioxide in a molar ratio of 1:1:

2.

5. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 2), the concentration of the dilute phosphoric acid solution used in the dilute phosphoric acid surface activation treatment is 0.5 to 1.5 wt%.

6. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 2), the conditions for the sol-gel coating treatment of the aluminum phosphate diffusion barrier layer are as follows: aluminum dihydrogen phosphate is dissolved in deionized water to prepare a solution of 0.05-0.15 mol / L, β-lithium nepheline powder is added, and the solution is evaporated and concentrated at 80°C. After vacuum drying at 60°C, the solution is calcined to form an AlPO4 amorphous diffusion barrier layer.

7. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 2), the calcination temperature of the silica sealing layer during the tetraethyl orthosilicate silica sealing layer coating process is 450-550℃.

8. The method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 3), based on 100 parts of fused silica micro powder, the modified aluminum nitride thermal conductivity enhancing filler is 15-25 parts, the modified β-lithium nepheline negative expansion compensating filler is 10-20 parts, the zinc borate micro powder is 1.0-3.0 parts, and the sodium carboxymethyl cellulose is 0.3-1.0 parts.

9. A method for preparing a semiconductor photolithography temperature compensation plate according to claim 1, characterized in that, In step 3), the conditions for vacuum hot pressing sintering are as follows: first, the temperature is raised to 400℃ at 5℃ / min and held for 30min to thermally decompose and burn off the sodium carboxymethyl cellulose; then, the temperature is raised to 900-1050℃ at 5℃ / min and held at 20MPa pressure for 2-4h; after sintering, the temperature is lowered to room temperature at a controlled rate of 2℃ / min.

10. A semiconductor photolithography temperature compensation plate, characterized in that, It is prepared by the method described in any one of claims 1 to 9 above.

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