TGV glass substrate with directionally arranged high-precision aperture and high depth-diameter ratio microchannels and preparation method of TGV glass substrate

Abstract

The invention discloses a TGV glass substrate with directionally arranged high-precision aperture and high aspect ratio microchannels and a preparation method thereof. Template preparation: depositing a template material on the surface of the substrate, and then forming a template pattern on the surface of the substrate by using photoresist through photoetching, developing and etching technologies; glass powder preparation: melting glass, carrying out water quenching on the glass in a molten state, and then carrying out ball milling on the crushed glass particles to obtain the glass powder; glass powder filling: filling glass powder into the gaps of the template; glass forming: sintering and annealing the obtained template; glass treatment: grinding and cleaning the formed glass; and forming micro-channels: etching the glass by using an etching solution, and cleaning to obtain the TGV glass substrate with directionally arranged micro-channels with high precision aperture and high depth-diameter ratio. The problems that in an existing TGV glass substrate preparation method, microchannel arrangement is difficult to accurately control, the preparation process is complex, and the cost is high are solved.

Description

Technical Field

[0001] The present invention relates to the technical field of glass, and particularly relates to an oriented arrangement high-precision aperture and high aspect ratio microchannel TGV glass substrate and a preparation method thereof. Background Art

[0002] With the rapid development of semiconductor technology, packaging technology has increasingly become more refined and integrated. In this context, as a core material in semiconductor packaging, the performance of the glass substrate directly determines the performance and long-term reliability of the final device. A high-performance glass substrate not only needs to have excellent electrical insulation performance, thermal stability, and mechanical strength, but also should be able to adapt to various complex processing technologies.

[0003] In recent years, glass substrates with oriented microchannels (Through-Glass Vias, TGV) have received extensive attention due to their unique structure and excellent performance. By forming vertical microchannels in the glass, this substrate realizes the interconnection between the upper and lower layer circuits, greatly improving the packaging density and signal transmission efficiency. In the fields of high-end chips, radio frequency devices, optoelectronic devices, etc., TGV glass substrates have shown great application potential.

[0004] Although TGV glass substrates have many advantages, the existing preparation methods face many challenges. These challenges not only limit the further application of TGV glass substrates, but also increase their production cost and difficulty. For example: the current mainstream TGV technology uses direct hole-forming processes such as laser-induced etching and plasma dry etching, and has the following problems:

[0005] 1) High energy consumption: When using a CO 2 laser for etching, the power usually needs to exceed 500W, which results in a large amount of energy consumption.

[0006] 2) High cost: High energy consumption and complex equipment requirements make the production cost of TGV glass substrates remain high.

[0007] 3) Low efficiency: The existing etching process is slow, which is not conducive to large-scale and efficient production.

[0008] 4) Sidewall roughness: Rough pore walls are easily formed during the etching process, which will affect the subsequent metallization quality and thus affect the performance of the device.

[0009] 5) Aspect ratio limitation: Limited by the etching technology, the aspect ratio of the microchannels is difficult to reach the ideal state, which limits the application of TGV glass substrates in higher density packaging.

[0010] 6) Poor pore diameter consistency: Due to the high difficulty of process control, the pore diameter consistency of the microchannels is poor, which will have an adverse impact on subsequent processing and device performance.

[0011] Therefore, it is of great practical significance to develop a preparation method of TGV glass substrate that is efficient, low-cost and capable of precisely controlling the size and arrangement direction of microchannels. Summary of the Invention

[0012] The technical problem to be solved by the present invention is: to overcome the deficiencies of the prior art and provide a TGV glass substrate with high-precision pore diameter and high aspect ratio microchannels arranged in a direction and a preparation method thereof, so as to solve the problems of difficult precise control of microchannel arrangement, complex preparation process and high cost in the existing TGV glass substrate preparation method.

[0013] The technical solution of the present invention is as follows:

[0014] On the one hand, the present invention provides a preparation method of a TGV glass substrate with high-precision pore diameter and high aspect ratio microchannels arranged in a direction, including the following steps:

[0015] S1 Template preparation: Deposit template material on the surface of the substrate, and then use photoresist to form a template pattern on the surface of the substrate through photolithography, development and etching techniques;

[0016] S2 Glass powder preparation: Melt the glass, quench the molten glass with water, use the rapid cooling effect of water to quickly cool and break the glass into small particles, and then ball-mill the broken glass particles. Through the impact and grinding of the grinding balls in the ball mill, the glass particles are further refined into glass powder with the required particle size;

[0017] S3 Glass powder filling: Fill the glass powder into the voids of the template obtained in step S1;

[0018] S4 Glass forming: Sinter and anneal the template obtained in step S3;

[0019] S5 Glass treatment: Grind and clean the formed glass;

[0020] S6 Microchannel formation: Etch the glass with an etching solution, and after cleaning, obtain a TGV glass substrate with high-precision pore diameter and high aspect ratio microchannels arranged in a direction.

[0021] Preferably, in step S1, the substrate is made of alumina ceramic, tungsten rhenium alloy or molybdenum titanium alloy; the alumina ceramic is successively subjected to isostatic pressing and grinding. When isostatic pressing, the pressure is 150 - 250 MPa, the pressure holding time is 10 - 20 min, the grinding particle size is 1 - 5 μm, the grinding pressure is 0.1 - 0.3 MPa, and the grinding time is 2 - 5 h; the surface roughness Ra of the treated alumina ceramic ≤ 0.05 μm; the tungsten rhenium alloy is successively subjected to electrical discharge machining and polishing. The pulse width of the electrical discharge machining is 10 - 50 μs, the pulse interval is 50 - 100 μs, the peak current is 5 - 20 A, the abrasive particle size used for polishing is 0.1 - 1 μm, the polishing pressure is 0.05 - 0.1 MPa, and the polishing time is 1 - 3 h; the surface roughness Ra of the treated tungsten rhenium alloy ≤ 0.02 μm; the molybdenum titanium alloy is successively subjected to rolling, forging and grinding. The rolling temperature is 1000 - 1200 °C, the rolling force is 1000 - 2000 kN, the number of rolling passes is 5 - 10 times, the forging temperature is 1100 - 1300 °C, the forging ratio is 3 - 5, the grinding particle size is 2 - 5 μm, the grinding pressure is 0.05 - 0.2 MPa, and the grinding time is 1 - 2 h; the surface roughness Ra of the treated molybdenum titanium alloy ≤ 0.05 μm.

[0022] The alumina ceramic substrate used in the present invention has characteristics such as high hardness, high melting point and good chemical stability, and its softening point is usually above 2000 °C. The melting point of tungsten is as high as 3422 °C, which is one of the metals with the highest melting points, and its softening point is also much higher than 1200 °C. The melting point of molybdenum is 2623 °C, the softening point is above 1200 °C, and it has good high-temperature strength and electrical conductivity.

[0023] Preferably, in step S1, the template material is cylindrical, including a core layer and an outer layer. The core layer is a scandium-stabilized zirconia (Sc 2 O 3 -ZrO 2 ) layer, and the outer layer is a yttrium aluminum nitride (Y 2 O 3 -AlN) layer; the thickness of the scandium-stabilized zirconia layer is 70 - 73 μm, and the thickness of the yttrium aluminum nitride layer is 2 - 5 μm. Utilizing the characteristics of the Sc 2 O 3 -ZrO 2 layer such as high melting point, good high-temperature mechanical properties and a thermal expansion coefficient matching that of the glass matrix, it ensures good bonding with the glass substrate at high temperatures and stable self-structure; the Y 2 O 3 -AlN layer, as a barrier layer, can prevent the diffusion of glass components and play a certain protective role.

[0024] Preferably, a template material is deposited on the surface of the substrate by chemical vapor deposition or physical vapor deposition. When using chemical vapor deposition, the process conditions are as follows: when depositing the scandium-stabilized zirconia layer, the deposition temperature is 600 - 800 °C, the Sc source gas flow rate is 5 - 10 sccm, and the Zr source gas flow rate is 10 - 20 sccm; when depositing the yttrium aluminum nitride layer, the deposition temperature is 700 - 800 °C, the Y source gas flow rate is 3 - 5 sccm, and the Al source gas flow rate is 8 - 12 sccm; during the template preparation process, after the deposition of the scandium-stabilized zirconia layer, photoresist coating, photolithography, development, and etching are carried out to form the core layer, then photoresist stripping is performed, followed by the deposition of the yttrium aluminum nitride layer, and then photoresist coating, photolithography, development, and etching are carried out again to form the template; among them, ultraviolet lithography is used for photolithography, the exposure time is 10 - 30 s, and the exposure energy is 100 - 300 mJ / cm 2 , the development time is 1 - 3 min, reactive ion etching (RIE) is used for etching, and the etching gas is CF 4 and O 2 mixed gas, the CF 4 flow rate is 20 - 50 sccm, the O 2 flow rate is 5 - 10 sccm, and the etching power is 100 - 200 W; physical vapor deposition uses magnetron sputtering.

[0025] Preferably, in step S2, the melting temperature is 1200 - 1500 °C, and the particle size of the obtained glass powder is 300 - 500 nm.

[0026] Preferably, in step S3, an ultrasonic vibration filling device is used to fill the glass powder into the voids of the template, the vibration frequency is 20 - 40 kHz, and the amplitude is 5 - 20 μm; filling is carried out in a vacuum environment, the vacuum degree ≤ 10 -3 Pa, the filling pressure is 0.05 - 0.2 MPa, the filling time is 30 - 60 min, and the template pore filling rate ≥ 98%; the humidity of the glass powder is controlled ≤ 0.1%.

[0027] Preferably, in step S4, during sintering, nitrogen protection is carried out throughout, and the oxygen content ≤ 10 ppm; in the first stage, it is heated to 400 - 500 °C at a rate of 3 - 7 °C / min and held for 1 - 3 h; in the second stage, it is heated to 700 - 800 °C at a rate of 2 - 5 °C / min and held for 0.5 - 2 h; in the third stage, it is heated to 900 - 1000 °C at a rate of 1 - 3 °C / min and held for 2 - 4 h; during sintering in the third stage, an isostatic pressure of 1 - 3 MPa is applied; during annealing, when the temperature is above the glass transition temperature (T g ), it is cooled at a rate of 4 - 6 °C / min, and when the temperature drops below the glass transition temperature (T g ), it is cooled at a rate of 1 - 3 °C / min; and at the glass transition temperature (T g) Keep warm for 20 - 40 min.

[0028] Preferably, in step S5, during grinding, use a diamond grinding wheel with a particle size of #2000 for grinding, and the grinding pressure is 0.1 - 0.3 MPa; the grinding fluid is an SiO 2 alkaline suspension with a pH of 9 - 10, and the flow rate is 3 - 7 L / min; the target thickness of grinding is 0.2 ± 0.02 mm, and the surface roughness Ra ≤ 0.01 μm; during cleaning, use deionized water and isopropyl alcohol for ultrasonic cleaning alternately, the temperature during cleaning is 30 - 50 °C, and the ultrasonic power is 150 - 250 W; then perform argon plasma cleaning, with a power of 200 - 400 W and a time of 3 - 7 min.

[0029] Preferably, in step S6, the etching solution is a mixed aqueous solution of nitric acid and hydrogen peroxide, the concentration of nitric acid is 30 - 50 wt.%, the concentration of hydrogen peroxide is 10 - 20 wt.%, the temperature of the etching solution is 30 - 50 °C, and the etching time is 1 - 3 h; the flow rate of the etching solution is 0.5 - 1 m / s to improve the etching uniformity.

[0030] In the etching solution of the present invention, nitric acid has strong oxidizing properties, and hydrogen peroxide is also a strong oxidizing agent. The chemical environment formed after the two are mixed can cause Sc 2 O 3 -ZrO 2 and Y 2 O 3 -AlN to undergo an oxidation reaction to generate ions or compounds that are soluble in the solution, thereby realizing the etching of the template material.

[0031] On the other hand, the present invention provides a TGV glass substrate with high-precision apertures and high aspect ratio microchannels arranged in a directional manner prepared by the above method for preparing a TGV glass substrate with high-precision apertures and high aspect ratio microchannels arranged in a directional manner.

[0032] Compared with the prior art, the present invention has the following beneficial effects:

[0033] 1. The method for preparing a TGV glass substrate with high-precision apertures and high aspect ratio microchannels arranged in a directional manner of the present invention realizes the directional arrangement of microchannels in the TGV glass substrate, high-precision apertures and high aspect ratio, and improves the consistency and stability of signal transmission.

[0034] 2. The method for preparing a TGV glass substrate with high-precision apertures and high aspect ratio microchannels arranged in a directional manner of the present invention has a simple preparation process and low cost, provides a strong guarantee for large-scale production, and brings huge economic benefits and market competitiveness to the semiconductor industry.

[0035] 3. The preparation method of the directionally arranged high-precision aperture and high aspect ratio microchannel TGV glass substrate of the present invention has good compatibility and can be combined with existing semiconductor manufacturing processes. This means that the application of the new method can be achieved without large-scale transformation of the existing production line or investment in new equipment. This compatibility not only reduces the cost and risk of technology upgrading but also speeds up the popularization of new technologies. By closely integrating with existing processes, the present invention will bring more efficient and flexible manufacturing solutions to the semiconductor industry. Detailed implementation manners

[0036] In order to enable those skilled in the art to better understand the technical solutions in the present invention, the following will clearly and completely describe the technical solutions of the present invention in conjunction with the embodiments of the present invention.

[0037] Example 1

[0038] The preparation method of the directionally arranged high-precision aperture and high aspect ratio microchannel TGV glass substrate in this embodiment includes the following steps:

[0039] S1 Template preparation

[0040] S11 Substrate: Alumina ceramic is used as the substrate. First, isostatic pressing is carried out with an isostatic pressing pressure of 200 MPa and a pressure holding time of 15 min; then grinding treatment is carried out with a grinding particle size of 3 μm, a grinding pressure of 0.2 MPa, and a grinding time of 3 h to obtain an alumina ceramic substrate with a surface roughness Ra = 0.03 μm.

[0041] S12 Template material deposition: The low-pressure chemical vapor deposition (LPCVD) method is used to deposit a cylindrical template material, including a Sc 2 O 3 -ZrO 2 core layer and a Y 2 O 3 -AlN outer layer. First, the Sc 2 O 3 -ZrO 2 layer is deposited at a deposition temperature of 700 °C, with a Sc source gas flow rate of 8 sccm and a Zr source gas flow rate of 15 sccm. The deposition time is controlled so that the thickness of the Sc 2 O 3 -ZrO 2 layer reaches about 72 μm. Subsequently, the Y 2 O 3 -AlN layer is deposited at a deposition temperature of 750 °C, with a Y source gas flow rate of 4 sccm, an Al source gas flow rate of 10 sccm, and the N source gas flow rate adjusted according to the reaction equilibrium. The deposition time is controlled so that the Y 2 O 3The thickness of the -AlN layer reaches about 3 μm. During the template preparation process, after the deposition of the Sc 2 O 3 -ZrO 2 layer, photoresist coating, photolithography, development, and etching are carried out to form the core layer, then photoresist stripping is performed, and then the Y 2 O 3 -AlN layer is deposited, and then photoresist coating, photolithography, development, and etching are carried out again to complete the template pattern fabrication. Among them, the photolithography exposure time is 20 s, the exposure energy is 200 mJ / cm 2 , the development time is 2 min, the etching is carried out by reactive ion etching (RIE), and the etching gas is a mixed gas of CF 4 and O 2 . The flow rate of CF 4 is 30 sccm, the flow rate of O 2 is 8 sccm, and the etching power is 150 W.

[0042] Preparation of S2 glass powder: The alkali-free glass is heated to 1300 °C, melted for 8 h, quenched in water and then ball-milled for 40 h at a ball mill rotation speed of 300 r / min to obtain glass powder with a particle size D50 = 350 nm and a uniform particle size distribution.

[0043] Filling of S3 glass powder: Using an ultrasonic vibration filling device (ultrasonic vibration filling device ZD-2000, Shanghai Shengxi Ultrasonic Instrument Co., Ltd.), with a vibration frequency of 28 kHz, an amplitude of 12 μm, a filling pressure of 0.1 MPa, filling is carried out for 45 min in an environment with a vacuum degree of 10 -4 Pa. By adjusting the powder humidity to 0.08%, the filling rate is ensured to reach 98.5%; the filling density is monitored in real time using a laser scanning confocal microscope (LSCM) to ensure that there are no air bubbles remaining in the pores. After filling, it is lightly rolled at 0.05 MPa to eliminate the loose powder on the surface.

[0044] S4 glass forming: Sintering is carried out according to the sintering temperature curve, and the whole process is protected by nitrogen during sintering. In the first stage (debinding), it is heated to 450 °C at a rate of 5 °C / min and held for 2 h; in the second stage (pre-sintering), it is heated to 750 °C at a rate of 3 °C / min and held for 1 h; in the third stage (densification), it is heated to 950 °C at a rate of 2 °C / min and held for 3 h; at the same time, an isostatic pressure of 2 MPa is applied in the third stage. Subsequently, annealing is carried out. When the temperature is above Tg (550 °C), the cooling rate is 5 °C / min. When it cools down to 550 °C, it is held for 30 min to eliminate thermal stress. When it cools down below Tg, the cooling rate is 2 °C / min.

[0045] S5 Glass treatment: Grind using a double-sided grinder with a diamond grinding wheel (grit size #2000), a grinding pressure of 0.2 MPa, and a grinding fluid of SiO alkaline suspension (including SiO particles, sodium hydroxide, and deionized water) with a pH of 9.5 and a flow rate of 5 L / min until the thickness reaches 0.2 mm and the surface roughness Ra = 0.008 μm. After grinding, first perform ultrasonic cleaning alternately with deionized water and isopropyl alcohol at a temperature of 40°C and an ultrasonic power of 200 W; then perform argon plasma cleaning with a power of 300 W for 5 minutes. 2 alkaline suspension (including SiO 2 particles, sodium hydroxide, and deionized water), with a flow rate of 5 L / min, grind until the thickness is 0.2 mm, and the surface roughness Ra = 0.008 μm. After grinding, first use deionized water and isopropyl alcohol alternately for ultrasonic cleaning, with a cleaning temperature of 40°C and an ultrasonic power of 200 W; then perform argon plasma cleaning, with a power of 300 W and a time of 5 minutes.

[0046] S6 Microchannel formation: The etching solution is a mixed aqueous solution of HNO and H O, with a HNO concentration of 30 wt.% and a H O concentration of 10 wt.%, a flow rate of 0.8 m / s, and etch for 2 hours under stirring conditions at 40°C. After cleaning, a TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in a direction is obtained. 3 and H 2 O 2 of the mixed aqueous solution, HNO 3 concentration is 30 wt.%, H 2 O 2 concentration is 10 wt.%, flow rate is 0.8 m / s, etch for 2 hours under stirring conditions at 40°C, and after cleaning, a TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in a direction is obtained.

[0047] After SEM analysis, the pore diameter deviation of the TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in a direction prepared in this example is ±1.5%, the aspect ratio reaches 9.5:1, and the surface roughness Ra of the side wall is 45 nm.

[0048] Example 2

[0049] The preparation method of the TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in a direction in this example includes the following steps:

[0050] S1 Template preparation

[0051] S11 Substrate: Use a tungsten-rhenium alloy (containing 5 wt.% rhenium) as the substrate. First, perform electrical discharge machining with a pulse width of 30 μs, a pulse interval of 80 μs, and a peak current of 12 A; then perform polishing with an abrasive particle size of 0.5 μm, a polishing pressure of 0.08 MPa, and a polishing time of 2 hours; obtain a tungsten alloy substrate with a surface roughness Ra = 0.015 μm.

[0052] S12 Template material deposition: Deposit cylindrical template materials using physical vapor deposition (magnetron sputtering) method, including Sc O -ZrO core layer and Y O -AlN outer layer. Deposit Sc O 2 O 3 -ZrO 2 core layer and Y 2 O 3 -AlN outer layer. Deposit Sc O 2 O 3-ZrO 2 When depositing the ScO-ZrO layer, the sputtering power is 120 W, the argon gas flow rate is 25 sccm, and the vacuum degree is 6×10 -4 Pa. Control the sputtering time to make the thickness of the ScO-ZrO layer about 71 μm; when depositing the Y2O3-AlN layer, the sputtering power is 100 W, the argon gas flow rate is 25 sccm, and the vacuum degree is 6×10 2 O 3 -ZrO 2 layer about 71 μm; when depositing the Y2O3-AlN layer, the sputtering power is 100 W, the argon gas flow rate is 25 sccm, and the vacuum degree is 6×10 2 O 3 -AlN layer, the sputtering power is 100 W, the argon gas flow rate is 25 sccm, and the vacuum degree is 6×10 -4 Pa. Control the sputtering time to make the thickness of the Y2O3-AlN layer about 4 μm. During the template preparation process, after the deposition of the ScO-ZrO layer, apply photoresist, perform photolithography, develop, and etch to form the core layer, then strip the photoresist, and then deposit the Y2O3-AlN layer. After that, apply photoresist again, perform photolithography, develop, and etch to complete the template pattern making. Among them, the photolithography exposure time is 30 s, the exposure energy is 300 mJ / cm 2 O 3 -AlN layer thickness is about 4 μm. During the template preparation process, after the ScO-ZrO layer is deposited, photoresist coating, photolithography, development, and etching are carried out to form the core layer, then photoresist stripping is carried out, and then the Y2O3-AlN layer is deposited. After that, photoresist coating, photolithography, development, and etching are carried out again to complete the template pattern making. Among them, the photolithography exposure time is 30 s, the exposure energy is 300 mJ / cm 2 O 3 -ZrO 2 layer, then carry out photoresist coating, photolithography, development, and etching to form the core layer, then strip the photoresist, and then deposit the Y2O3-AlN layer. After that, carry out photoresist coating, photolithography, development, and etching again to complete the template pattern making. Among them, the photolithography exposure time is 30 s, the exposure energy is 300 mJ / cm 2 O 3 -AlN layer deposition, and then carry out photoresist coating, photolithography, development, and etching to complete the template pattern making. Among them, the photolithography exposure time is 30 s, the exposure energy is 300 mJ / cm 2 , the development time is 3 min, the etching uses reactive ion etching (RIE), and the etching gas is a mixed gas of CF 4 and O 2 The flow rate of CF 4 is 50 sccm, the flow rate of O 2 is 10 sccm, and the etching power is 200 W.

[0053] Preparation of S2 glass powder: Heat the non-alkali glass to 1400 °C, melt it for 6 h, water quench it, and then ball mill it for 35 h. The rotation speed of the ball mill is 320 r / min to obtain glass powder with a particle size D50 = 340 nm and a uniform particle size distribution.

[0054] Filling of S3 glass powder: Use an ultrasonic vibration filling device with a vibration frequency of 40 kHz, an amplitude of 20 μm, and a filling pressure of 0.2 MPa. Fill for 60 min in an environment with a vacuum degree of 10 -4 Pa. By adjusting the powder humidity to 0.06%, ensure that the filling rate reaches 98.8%; use a laser scanning confocal microscope (LSCM) to monitor the filling density in real time to ensure that there are no air bubbles remaining in the pores. After filling, gently roll it at 0.05 MPa to eliminate the loose powder on the surface.

[0055] S4 Glass forming: Sintering is carried out according to the sintering temperature curve, and nitrogen protection is maintained throughout the sintering process. In the first stage (debinding), the temperature is raised to 500 °C at a rate of 7 °C / min and held for 3 h; in the second stage (pre-sintering), the temperature is raised to 800 °C at a rate of 5 °C / min and held for 2 h; in the third stage (densification), the temperature is raised to 1000 °C at a rate of 3 °C / min and held for 4 h; meanwhile, an isostatic pressure of 3 MPa is applied in the third stage. Subsequently, annealing is carried out. When the temperature is above Tg (550 °C), the cooling rate is 6 °C / min. When the temperature drops to 550 °C, it is held for 40 min to eliminate thermal stress. When the temperature drops below Tg, the cooling rate is 3 °C / min.

[0056] S5 Glass treatment: Grinding is carried out using a double-sided grinding machine with a diamond grinding wheel (grit size #2000). The grinding pressure is 0.3 MPa, and the grinding fluid is an SiO 2 alkaline suspension (including SiO 2 particles, sodium hydroxide, and deionized water) with a flow rate of 7 L / min. Grinding is carried out until the thickness reaches 0.198 mm and the surface roughness Ra = 0.007 μm. After grinding, ultrasonic cleaning is first carried out alternately using deionized water and isopropyl alcohol. The temperature during cleaning is 50 °C, and the ultrasonic power is 250 W; subsequently, argon plasma cleaning is carried out with a power of 400 W for 3 min.

[0057] S6 Microchannel formation: The etching solution is a mixed aqueous solution of HNO 3 and H 2 O 2 . The concentration of HNO 3 is 40 wt.%, and the concentration of H 2 O 2 is 15 wt.%. The flow rate is 1 m / s. Etching is carried out for 1 h under stirring conditions at 50 °C. After cleaning, a TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in an oriented manner is obtained.

[0058] After SEM analysis, the pore diameter deviation of the TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in an oriented manner prepared in this example is ±1.8%, the aspect ratio reaches 9.2:1, and the surface roughness Ra of the side wall is 48 nm.

[0059] Example 3

[0060] The preparation method of the TGV glass substrate with high-precision pore diameter and high aspect ratio micropores arranged in an oriented manner in this example includes the following steps:

[0061] S1 Template preparation

[0062] S11 Substrate: A molybdenum-titanium alloy (containing 5 wt.% titanium) is used as the substrate. First, it undergoes rolling at a temperature of 1100 °C, with a rolling force of 1500 kN and 8 rolling passes. The forging temperature is 1200 °C, the forging ratio is 4, the grinding grit size is 3 μm, the grinding pressure is 0.15 MPa, and the grinding time is 1.5 h; a molybdenum-titanium alloy substrate with a surface roughness Ra = 0.04 μm is obtained.

[0063] S12 Template Material Deposition: The cylindrical template material, including Sc 2 O 3 -ZrO 2 core layer and Y 2 O 3 -AlN outer layer, is deposited using the LPCVD method. First, the Sc 2 O 3 -ZrO 2 layer is deposited at a temperature of 800 °C, with a Sc source gas flow rate of 10 sccm and a Zr source gas flow rate of 20 sccm. The deposition time is controlled so that the thickness of the Sc 2 O 3 -ZrO 2 layer reaches approximately 73 μm. Subsequently, the Y 2 O 3 -AlN layer is deposited at a temperature of 800 °C, with a Y source gas flow rate of 3 sccm, an Al source gas flow rate of 8 sccm, and the N source gas flow rate adjusted according to the reaction equilibrium. The deposition time is controlled so that the thickness of the Y 2 O 3 -AlN layer reaches approximately 2.5 μm. During the template preparation process, after the deposition of the Sc 2 O 3 -ZrO 2 layer, photoresist coating, photolithography, development, and etching are carried out to form the core layer, then photoresist stripping is performed, and then the Y 2 O 3 -AlN layer is deposited. After that, photoresist coating, photolithography, development, and etching are carried out again to complete the template pattern making. Among them, the photolithography exposure time is 10 s, the exposure energy is 100 mJ / cm 2 , the development time is 1 min, the etching is carried out using reactive ion etching (RIE), and the etching gas is a mixed gas of CF 4 and O 2 ; the CF 4 flow rate is 20 sccm, the O 2 flow rate is 5 sccm, and the etching power is 100 W.

[0064] Preparation of S2 glass powder: The E-glass is heated to 1500 °C, melted for 10 h, quenched in water and then ball-milled for 45 h at a ball mill rotation speed of 280 r / min to obtain glass powder with a D50 particle size of 360 nm and a uniform particle size distribution.

[0065] S3 Glass powder filling: Using an ultrasonic vibration filling device with a vibration frequency of 20 kHz, an amplitude of 5 μm, and a filling pressure of 0.05 MPa, filling is carried out for 30 min under a vacuum of 10 -4 Pa. By adjusting the powder humidity to 0.07%, the filling rate is ensured to reach 98.3%; the filling density is monitored in real time using a laser scanning confocal microscope (LSCM) to ensure that there are no air bubbles remaining in the pores. After filling, it is gently rolled at 0.05 MPa to eliminate the loose powder on the surface.

[0066] S4 Glass forming: Sintering is carried out according to the sintering temperature curve, and nitrogen protection is applied throughout the sintering process. In the first stage (debinding), the temperature is raised to 400 °C at a rate of 3 °C / min and held for 1 h; in the second stage (pre-sintering), the temperature is raised to 700 °C at a rate of 2 °C / min and held for 0.5 h; in the third stage (densification), the temperature is raised to 900 °C at a rate of 1 °C / min and held for 2 h; at the same time, an isostatic pressure of 1 MPa is applied in the third stage. Subsequently, annealing is carried out. When the temperature is above Tg (550 °C), the cooling rate is 4 °C / min. When the temperature drops to 550 °C, it is held for 20 min to eliminate thermal stress. When the temperature drops below Tg, the cooling rate is 1 °C / min.

[0067] S5 Glass treatment: Grinding is carried out using a double-sided grinder with a diamond grinding wheel (grit size #2000), a grinding pressure of 0.1 MPa, and a grinding fluid of SiO 2 alkaline suspension (including SiO 2 particles, sodium hydroxide, and deionized water) with a flow rate of 3 L / min until the thickness reaches 0.202 mm and the surface roughness Ra = 0.009 μm. After grinding, ultrasonic cleaning is first carried out alternately with deionized water and isopropyl alcohol at a temperature of 30 °C and an ultrasonic power of 150 W; subsequently, argon plasma cleaning is carried out with a power of 200 W for 7 min.

[0068] S6 Microchannel formation: The etching solution is a mixed aqueous solution of HNO 3 and H 2 O 2 with a HNO 3 concentration of 50 wt.% and a H 2 O 2 concentration of 20 wt.%, a flow rate of 1 m / s, and etching is carried out for 3 h under stirring conditions at 30 °C. After cleaning, a TGV glass substrate with a high-precision pore diameter and high aspect ratio of microchannels arranged in an oriented manner is obtained.

[0069] After SEM analysis, the pore diameter deviation of the directionally arranged high-precision pore diameter and high aspect ratio microchannel TGV glass substrate prepared in this example is ±1.6%, the aspect ratio reaches 9.8:1, and the surface roughness Ra of the side wall is 42 nm.

[0070] Comparative Example 1

[0071] The preparation method of the microchannel TGV glass substrate of Comparative Example 1 includes the following steps:

[0072] Use CO 2 The laser (with a power of 600 W) is directly used to perform laser-induced etching on the glass substrate after forming processes such as sintering and annealing to form holes. The laser beam focusing parameters are set as follows: the focal length is 100 mm, and the spot diameter is 20 μm. The etching process is carried out in a normal temperature and pressure environment without special environmental control. The etching time is adjusted according to the expected hole depth, and it takes about 10 s to etch 1 μm depth.

[0073] After SEM analysis, the pore diameter deviation of the microchannel TGV glass substrate prepared in Comparative Example 1 reaches ±8%, and the aspect ratio is only 4:1; the surface roughness Ra of the side wall is 250 nm. This is because during laser-induced etching, the distribution of laser energy on the glass surface is difficult to precisely control, resulting in poor pore diameter consistency and large deviation. At the same time, there is a large loss of laser energy during the transmission to the interior of the glass, which limits the improvement of the aspect ratio. Moreover, a heat-affected zone is generated during the laser etching process, causing local melting and re-solidification of the glass surface, resulting in an increase in the side wall roughness.

[0074] Comparative Example 2

[0075] The preparation method of the microchannel TGV glass substrate of Comparative Example 2 includes the following steps:

[0076] Use a conventional plasma dry etching equipment to etch the glass substrate to form holes. The etching gas is selected as a mixture of SF 6 and O 2 The flow rate of SF 6 is 40 sccm, and the flow rate of O 2 is 15 sccm. The etching power is 300 W, and the etching time is adjusted according to the expected hole depth, and the etching time is estimated at a rate of 1 μm / min of etching depth. During the etching process, the pressure in the equipment cavity is maintained at 10 Pa, and the electrode spacing is 20 mm.

[0077] After SEM analysis, the pore size deviation of the microchannel TGV glass substrate prepared in Comparative Example 2 is ±6%, the depth-to-width ratio is 6:1, and the surface roughness Ra of the side wall is 220 nm. This is because in plasma dry etching, the process of ion bombarding the glass surface has a certain degree of randomness, making it difficult to achieve precise control of the pore size, resulting in a relatively large pore size deviation. As the etching depth increases, the energy of ions reaching the bottom gradually weakens, and the etching efficiency decreases, limiting the increase of the depth-to-width ratio. Moreover, the physical bombardment during the etching process will cause microscopic unevenness on the glass surface, resulting in a relatively high side wall roughness.

[0078] Comparative Example 3

[0079] The difference from Example 1 is that in step S12, the deposition time is controlled to make the thickness of the Sc 2 O 3 -ZrO 2 layer reach about 75 μm, and the deposition of the Y 2 O 3 -AlN layer is not carried out.

[0080] After SEM analysis, the pore size deviation of the microchannel TGV glass substrate prepared in Comparative Example 3 is ±4%, the depth-to-width ratio is 7:1, and the surface roughness Ra of the side wall is 70 nm. This is because without the barrier of the Y 2 O 3 -AlN layer, during the process of glass powder filling, sintering and subsequent treatment, the glass components are prone to diffuse into the template material, affecting the structural stability of the template, resulting in a decrease in the control precision of the pore size and the pore wall when etching the microchannels, and further increasing the pore size deviation, reducing the depth-to-width ratio and increasing the side wall roughness.

[0081] Comparative Example 4

[0082] The difference from Example 1 is that in step S12, the Sc 2 O 3 -ZrO 2 layer is not deposited, and the deposition time is controlled to make the thickness of the Y 2 O 3 -AlN layer reach about 75 μm.

[0083] After SEM analysis, the pore size deviation of the microchannel TGV glass substrate prepared in Comparative Example 4 is ±5%, the depth-to-width ratio is 6.5:1, and the surface roughness Ra of the side wall is 80 nm. This is because Sc 2 O 3 -ZrO 2The layer has a coefficient of thermal expansion matching that of the glass substrate and good high-temperature mechanical properties. After the core layer is missing, during the high-temperature sintering and annealing processes, the thermal stress between the template and the glass does not match, and problems such as deformation and cracking are likely to occur, affecting the forming quality of the subsequent microchannels, resulting in a larger pore size deviation, a smaller aspect ratio, and an increase in the sidewall roughness.

[0084] Comparative Example 5

[0085] The difference from Example 1 is that in step S6, the etching solution is an aqueous mixed solution of HNO 3 and HF, the concentration of HNO 3 is 30 wt.%, and the concentration of HF is 10 wt.%.

[0086] After SEM analysis, the pore size deviation of the microchannel TGV glass substrate prepared in Comparative Example 5 is ±13%, the aspect ratio is 12:1, and the surface roughness Ra of the sidewall is 320 nm. This is because hydrofluoric acid will react not only with the template material but also with the glass substrate. Hydrofluoric acid will chemically react with silicon dioxide in the glass to generate gaseous silicon tetrafluoride and water. This reaction causes the glass substrate to be corroded additionally during the etching process, making it difficult to precisely control the formation process of the microchannels. On the one hand, the excessive corrosion of the glass substrate will lead to an increase in the pore size deviation; on the other hand, since the glass substrate and the template material are etched simultaneously, it is difficult to coordinate the etching rates of the two, affecting the aspect ratio of the microchannels and unable to reach the ideal state; in addition, after the surface of the glass substrate is corroded by hydrofluoric acid, microscopic unevenness will be generated, resulting in an increase in the sidewall roughness.

[0087] Through the comparison of the above examples and comparative examples, it can be seen that the preparation method of the present invention has significant advantages in controlling the pore size accuracy, improving the aspect ratio, and reducing the sidewall roughness, can effectively solve the problems existing in the prior art, and meet the high-performance requirements of advanced semiconductor packaging for TGV glass substrates.

Claims

1. A method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels, characterized in that: The following steps are involved: S1 Template preparation: Deposit template material on the substrate surface, and then use photoresist to form a template pattern on the substrate surface through photolithography, development, and etching techniques; S2 glass powder preparation: melt the glass, quench the molten glass with water, and then ball-mill the crushed glass particles to obtain glass powder; S3 glass powder filling: filling the glass powder into the gaps of the template obtained in step S1; S4 glass forming: sintering and annealing the template obtained in step S3; S5 glass processing: grinding and cleaning the formed glass; S6 Microchannel Formation: Use etching solution to etch the glass, and after cleaning, obtain a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio microchannels.

2. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels according to claim 1, characterized in that: In step S1, the substrate is made of alumina ceramic, tungsten-rhenium alloy or molybdenum-titanium alloy; the alumina ceramic is successively subjected to isostatic pressing and grinding, the pressure during isostatic pressing is 150-250MPa, the holding time is 10-20min, the grinding particle size is 1-5μm, the grinding pressure is 0.1-0.3MPa, and the grinding time is 2-5h; the surface roughness of the treated alumina ceramic Ra≤0.05μm; the tungsten-rhenium alloy is successively subjected to electrospark machining and polishing, the pulse width of the electrospark machining is 10-50μs, the pulse interval is 50-100μs, the peak current is 5-20A, and the grinding used for polishing is The particle size is 0.1-1μm, the polishing pressure is 0.05-0.1MPa, and the polishing time is 1-3h; the surface roughness of the treated tungsten-rhenium alloy is Ra≤0.02μm; the molybdenum-titanium alloy is successively subjected to rolling, forging and grinding treatment, the rolling temperature is 1000-1200℃, the rolling force is 1000-2000kN, the rolling passes are 5-10 times, the forging temperature is 1100-1300℃, the forging ratio is 3-5, the grinding particle size is 2-5μm, the grinding pressure is 0.05-0.2MPa, and the grinding time is 1-2h; the surface roughness of the treated molybdenum-titanium alloy is Ra≤0.05μm.

3. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels according to claim 1, characterized in that: In step S1, the template material is cylindrical, including a core layer and an outer layer, the core layer is a scandium-stabilized zirconia layer, and the outer layer is a yttrium aluminum nitride layer; the thickness of the scandium-stabilized zirconia layer is 70-73 μm, and the thickness of the yttrium aluminum nitride layer is 2-5 μm.

4. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels as claimed in claim 3, characterized in that: The template material is deposited on the surface of the substrate by chemical vapor deposition or physical vapor deposition. When the chemical vapor deposition method is used, the process conditions are as follows: when depositing the scandium-stabilized zirconium oxide layer, the deposition temperature is 600-800°C, the Sc source gas flow rate is 5-10sccm, and the Zr source gas flow rate is 10-20sccm; when depositing the yttrium aluminum nitride layer, the deposition temperature is 700-800°C, the Y source gas flow rate is 3-5sccm, and the Al source gas flow rate is 8-12sccm; in the template preparation process, after the scandium-stabilized zirconium oxide layer is deposited, photoresist coating, photolithography, development, and etching are performed to form a core layer, and then the photoresist is stripped, and then the yttrium aluminum nitride layer is deposited, and then the photoresist coating, photolithography, development, and etching are performed to form a template; wherein, the photolithography adopts ultraviolet lithography, the exposure time is 10-30s, and the exposure energy is 100-300mJ / cm 2 The development time is 1-3 minutes, the etching adopts reactive ion etching, the etching gas is a mixed gas of CF4 and O2, the CF4 flow rate is 20-50sccm, the O2 flow rate is 5-10sccm, and the etching power is 100-200W; the physical vapor deposition method adopts magnetron sputtering.

5. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels according to claim 1, characterized in that: In step S2, the melting temperature is 1200-1500°C, and the particle size of the obtained glass powder is 300-500nm.

6. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels as claimed in claim 1, characterized in that: In step S3, the glass powder is filled into the gaps of the template using an ultrasonic vibration filling device, with a vibration frequency of 20-40kHz and an amplitude of 5-20μm; the filling is carried out under a vacuum environment, and the vacuum degree is ≤10 -3 Pa, filling pressure is 0.05-0.2MPa, filling time is 30-60min, template pore filling rate is ≥98%; control glass powder humidity ≤0.1%.

7. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels as claimed in claim 1, characterized in that: In step S4, during sintering, nitrogen protection is used throughout the process, and the oxygen content is ≤10ppm; in the first stage, the temperature is increased to 400-500°C at 3-7°C / min and kept warm for 1-3h; in the second stage, the temperature is increased to 700-800°C at 2-5°C / min and kept warm for 0.5-2h; in the third stage, the temperature is increased to 900-1000°C at 1-3°C / min and kept warm for 2-4h; during sintering in the third stage, 1-3MPa isostatic pressure is applied; during annealing, when the temperature is above the glass transition temperature, the temperature is reduced at a rate of 4-6°C / min, and when the temperature drops below the glass transition temperature, the temperature is reduced at a rate of 1-3°C / min; and the temperature is kept warm for 20-40min at the glass transition temperature.

8. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels as claimed in claim 1, characterized in that: In step S5, during grinding, a diamond grinding wheel with a particle size of #2000 is used for grinding, and the grinding pressure is 0.1-0.3MPa; the grinding liquid is a SiO2 alkaline suspension with a pH of 9-10, and the flow rate is 3-7L / min; the target thickness of grinding is 0.2±0.02mm, and the surface roughness Ra≤0.01μm; during cleaning, deionized water and isopropanol are used alternately for ultrasonic cleaning, the cleaning temperature is 30-50°C, and the ultrasonic power is 150-250W; then argon plasma cleaning is performed, the power is 200-400W, and the time is 3-7min.

9. The method for preparing a TGV glass substrate with directional arrangement of high-precision apertures and high aspect ratio micro-channels as claimed in claim 1, characterized in that: In step S6, the etching solution is a mixed aqueous solution of nitric acid and hydrogen peroxide, the concentration of nitric acid is 30-50wt.%, the concentration of hydrogen peroxide is 10-20wt.%, the temperature of the etching solution is 30-50°C, and the etching time is 1-3h.

10. A TGV glass substrate with directional arrangement of micro-channels with high precision aperture and high aspect ratio prepared by the method for preparing a TGV glass substrate with directional arrangement of micro-channels with high precision aperture and high aspect ratio according to any one of claims 1 to 9.