Microwave assembly chip cleaning agent based on double solvents and preparation method thereof

Abstract

This application relates to the field of microelectronic cleaning technology, and discloses a microwave component chip cleaning agent based on a dual-solvent method and its preparation method. The cleaning agent is composed of a polar phase consisting of diethylene glycol butyl ether, N-methylpyrrolidone, and benzotriazole; a non-polar phase consisting of decafluoropentane, methoxynonfluorobutane, and isopropanol; and a fluorinated block polyether modified trisiloxane stabilizer, which is then constructed into a stable microemulsion system through high shear. The preparation method of the cleaning agent includes separate preparation of the polar mother liquor and cyclic preparation of the non-polar mixed liquor, and the addition of the stabilizer under strictly controlled temperature conditions for high-shear continuous emulsification and degassing at a reduced rate. This invention achieves deep emptying of residual dirt in micron-sized extremely narrow slits by inducing a thermodynamic phase change in low-boiling-point components through the penetration of the microemulsion into confined spaces, and utilizes the phase change energy generated by local vaporization expansion to squeeze out the dirt, thus significantly improving the component cleaning and emptying rate and ensuring the electrical performance of the underlying layer.

Description

Technical Field

[0001] This invention relates to the field of microelectronic cleaning technology, specifically to a dual-solvent microwave component chip cleaning agent and its preparation method. Background Technology

[0002] The assembly structure of microwave component chips is usually quite compact. After the component mounting and soldering process, a mixture of solidified rosin resin, activated metal ions and grease will inevitably remain in the extremely narrow gaps at the micrometer level on the bottom and around the chip.

[0003] Conventional single-phase polar cleaning agents primarily rely on the principle of "like dissolves like" to remove organic and inorganic contaminants. However, due to the high surface tension of polar solvents, they encounter strong capillary resistance when facing the confined spaces of microwave components, which are only tens of micrometers in size, making it difficult for the cleaning agent to effectively penetrate deep into the narrow crevices. Even if some polar solvents can penetrate and dissolve the contaminants, the lack of outward mass transfer causes the waste liquid carrying contaminants to remain in the crevices, leading to secondary precipitation of the contaminants after solvent evaporation and leaving long-term electrochemical corrosion risks. On the other hand, pure non-polar fluorinated solvents have low surface tension and a certain degree of permeability, allowing them to enter fine pores. However, their chemical dissolution ability for cured cross-linked resins and free metal ions is weak, making it impossible to fundamentally remove contaminants adhering to the substrate surface.

[0004] To compensate for the shortcomings of conventional cleaning agents in terms of mass transfer and decontamination capabilities in narrow slits, existing processes often require the introduction of high-power ultrasonic waves for auxiliary cleaning. Microwave components are typically filled with gold wire bonding structures with diameters of only tens of micrometers. When the localized high-pressure shock waves generated by ultrasonic cavitation directly act on the roots of these fine grains and solder joints, they can easily cause mechanical damage or breakage of the bonding points, thereby reducing the mechanical reliability and yield of the device. Existing cleaning methods struggle to simultaneously achieve deep decontamination in micrometer-level extremely narrow slits and protect the fragile structure of the component without introducing strong external mechanical forces. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a microwave component chip cleaning agent based on dual solvents and its preparation method. The aim is to solve the problems that conventional cleaning agents have difficulty overcoming capillary resistance to penetrate extremely narrow slits for effective decontamination and evacuation, and that excessive reliance on high-power ultrasonic-assisted cleaning can easily damage the fragile bonding structure inside the device.

[0006] To achieve the above objectives, the present invention provides the following technical solution:

[0007] In a first aspect, the present invention provides a microwave component chip cleaning agent based on dual solvents, employing the following technical solution:

[0008] The dual-solvent microwave component chip cleaning agent is made from the following components in parts by weight:

[0009] Diethylene glycol butyl ether 127.5–175 parts; N-methylpyrrolidone 15–62.5 parts; benzotriazole 4–12.5 parts; 1,1,1,2,2,3,4,5,5,5-decafluoropentane 448.8–630 parts; 1-methoxynonafluorobutane 168–261.8 parts; isopropanol 23.85–42 parts; fluorinated block polyether modified trisiloxane stabilizer 2–10 parts.

[0010] The microwave component chip cleaning agent based on dual solvents is constructed into a microemulsion system through high-shear emulsification. When the microemulsion system enters the micron-level confined space, the internal thermodynamic phase transition of 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 1-methoxynonafluorobutane occurs. The phase change energy is generated through local high-frequency vaporization expansion, which is used to squeeze out the diethylene glycol butyl ether and N-methylpyrrolidone to dissolve and remove the dirt.

[0011] By adopting the above technical solution, the polar phase is composed of diethylene glycol butyl ether, N-methylpyrrolidone and benzotriazole, and the non-polar phase is composed of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1-methoxynonafluorobutane and isopropanol. Furthermore, a fluorinated block polyether modified trisiloxane stabilizer is added to this system, enabling the cleaning agent system to penetrate into extremely narrow confined spaces and provide in-situ venting kinetic energy.

[0012] Specifically, the evacuation mechanism of the cleaning agent of the present invention is as follows:

[0013] In the initial cleaning stage, the polar phase component utilizes its strong intramolecular polar groups to dissolve and peel off the cured rosin and activated ions from the substrate surface, while the non-polar phase component provides extremely low surface tension. Fluorinated block polyether-modified trisiloxane stabilizers exert interfacial activity, emulsifying and combining the immiscible polar and non-polar phases to form a nanoscale microemulsion system with the polar phase as the continuous phase and the non-polar phase as the dispersed phase. This system overcomes capillary resistance and rapidly penetrates into the micron-sized chip slits. Once the microemulsion system enters the slits, the temperature of the chip itself or the ultrasonic cleaning temperature is transferred to the interior of the microemulsion system, causing the low-boiling-point fluoroalkanes (i.e., 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 1-methoxynonafluorobutane) in the dispersed droplet state to reach the phase transition critical point, transforming from liquid to gas phase.

[0014] During this phase transition, the volume of the nonpolar phase droplets expands rapidly, causing the droplets to rupture and generating local high-frequency vaporization shock waves. This phase transition energy acts directly on the peripheral polar continuous phase, providing fluid shear force from the inside out, forcing the polar phase, which has dissolved a large amount of dirt, to detach from the pore structure and flow into the external circulation, thus physically cutting off the path of dirt reflux and secondary precipitation.

[0015] Preferably, the fluorinated block polyether modified trisiloxane stabilizer is prepared by the following steps:

[0016] In a reactor equipped with a reflux condenser, a mechanical stirrer, and a nitrogen protection device, toluene and 1,1,3,3,5,5-hexamethyltrisiloxane were added. Under nitrogen protection, the mechanical stirrer was turned on and the temperature was increased to form an initial mixture. Allyl polyethylene glycol was mixed with 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene to obtain a monomer mixture to be added dropwise. Isopropanol chloroplatinate solution was added to the reactor as a catalyst, and the monomer mixture to be added dropwise at a set rate to carry out a hydrosilylation reaction. After the addition was completed, the temperature was increased to carry out a ripening reaction until the characteristic absorption peak of the Si-H bond in the infrared spectrum completely disappeared, and a reaction solution was obtained. The reaction solution was subjected to vacuum distillation to remove toluene solvent and unreacted monomer volatiles, and then cooled to obtain a fluorinated block polyether modified trisiloxane stabilizer.

[0017] By employing the above technical solution, this invention utilizes a hydrosilylation reaction with a specific chain segment structure to construct an amphiphilic molecular topology with bidirectional affinity. Under the catalysis of chloroplatinic acid, the active Si-H bonds at both ends of 1,1,3,3,5,5-hexamethyltrisiloxane undergo addition reactions with allyl polyethylene glycol and fluorinated olefins, respectively, containing terminal double bonds.

[0018] During the reaction, hydrophilic polyethylene glycol segments and hydrophobic and lipophilic perfluorocarbon chains are grafted onto both ends of the siloxane backbone, respectively. In the preparation of the cleaning agent microemulsion, the hydrophilic segments are distributed in the polar mother liquor network, and the perfluorocarbon chains are bound to the surface of the fluorinated nonpolar phase microdroplets, effectively reducing the interfacial tension between the two phases and maintaining the static thermodynamic stability of the microdroplets before the phase transition.

[0019] Preferably, the specific process parameters for preparing the fluorinated block polyether modified trisiloxane stabilizer are as follows:

[0020] Based on molar amounts, 1,1,3,3,5,5-hexamethyltrisiloxane provides a total of 0.1 mol of Si-H bonds, allyl polyethylene glycol provides 0.04–0.08 mol, and 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene provides 0.025–0.065 mol; the hydrosilylation reaction temperature is 75℃–80℃, the rate of addition of the monomer mixture is 1–2 drops / second, and the addition process lasts for 2–3 hours; the aging reaction temperature is 85℃–90℃, and the aging reaction time is 5–6 hours.

[0021] By adopting the above technical solution, the material ratio and reaction temperature control parameters are further controlled to ensure that the total molar amount of terminal double bonds is slightly excessive, thereby ensuring that the Si-H bonds are completely consumed and avoiding residual active free hydrogen-containing siloxanes from affecting the long-term storage safety of the final product.

[0022] Preferably, the total mass ratio of the polar phase component to the non-polar phase component is 1:3 to 1:5.6; the dual-solvent microwave component chip cleaning agent is made from the following components in parts by weight: 160 parts diethylene glycol butyl ether; 36 parts N-methylpyrrolidone; 4 parts benzotriazole; 556.5 parts 1,1,1,2,2,3,4,5,5,5-decafluoropentane; 214.65 parts 1-methoxynonafluorobutane; 23.85 parts isopropanol; and 5 parts fluorinated block polyether modified trisiloxane stabilizer.

[0023] By adopting the above technical solution and limiting the specific dosage of each component, while ensuring that the polarity of rosin and ionic fouling maintains sufficient dissolution capacity, sufficient fluorinated hydrocarbon content is provided to induce phase change expansion kinetic energy, thereby maximizing the deep venting rate.

[0024] Secondly, the present invention provides a method for preparing a microwave component chip cleaning agent based on a dual-solvent approach, employing the following technical solution:

[0025] The preparation method of the microwave component chip cleaning agent based on dual solvents includes the following steps:

[0026] In a reaction vessel equipped with a cooling jacket, diethylene glycol butyl ether and N-methylpyrrolidone were added, and stirring was started. Then benzotriazole was added and stirring was continued until the benzotriazole was completely dissolved to obtain a polar mother liquor.

[0027] In a closed mixing tank, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1-methoxynonafluorobutane and isopropanol are pumped in sequentially, and the internal circulation pump is turned on to circulate and mix, so as to obtain a non-polar mixture.

[0028] Fluorine-containing block polyether modified trisiloxane stabilizer is added to the polar mother liquor, the stirring speed is increased to disperse the fluorine-containing block polyether modified trisiloxane stabilizer, and then a cooling medium is introduced into the jacket of the reactor to cool down the material in the reactor, thus obtaining a cooled polar mother liquor containing stabilizer.

[0029] Start the high-shear emulsifier at the bottom of the reactor and pump the non-polar mixture into the reactor through the feed pipe. Maintain the emulsification process under temperature control to obtain a microemulsion mixture.

[0030] The high-shear emulsifier was turned off, the stirrer was kept on, and the stirring speed was reduced under temperature control to remove microbubbles, thus obtaining a microwave component chip cleaning agent based on dual solvents.

[0031] By adopting the above technical solution, the stepwise dissolution combined with temperature-controlled high-shear emulsification process prevents flocculation or stratification during the mixing of the two phases. In specific operation, a polar mother liquor is first prepared separately to dissolve the solid benzotriazole. Then, a stabilizer is added to fully extend the molecular chains. Subsequently, the non-polar phase is pumped in from below the liquid surface through the feed pipe. At this time, the hydrodynamic shear force generated by the high-shear rotor disperses the non-polar phase fluid into micro-droplets, thereby forming a stable microemulsion.

[0032] Preferably, in the step of obtaining the polar mother liquor: the anchor stirrer is turned on at 20℃~30℃, the stirrer speed is set to 50~80rpm, and stirring is continued for 20~40 minutes. In the step of obtaining the non-polar mixture: the internal circulation pump is turned on, and the mixture is circulated for 15~30 minutes. In the step of obtaining the cooled polar mother liquor containing stabilizer: the stirring speed is increased to 100~150rpm and the mixture is dispersed for 10~20 minutes; chilled brine is introduced into the jacket of the reactor to lower the temperature of the material inside the reactor to 10℃~15℃. In the step of obtaining the microemulsion mixture: the temperature inside the reactor is maintained not exceeding 15℃~20℃; the speed of the high-shear emulsifier is set to 1200~1500rpm; the non-polar mixture is pumped submerged into the reactor at a flow rate of 10~20L / min, and the emulsification process is maintained for 15~25 minutes. In the step of preparing a microwave component chip cleaning agent based on dual solvents: the stirrer speed is reduced to 50-80 rpm, and the mixture is stirred at 10℃-15℃ for 20-30 minutes.

[0033] By adopting the above technical solution, the ineffective vaporization and volatilization of low-boiling-point substances (such as 1,1,1,2,2,3,4,5,5,5-decafluoropentane) caused by high shear friction heat generation can be effectively suppressed, thus preserving the total amount of effective phase change energy storage medium in the finished product. In addition, the removal of emulsion-entrained gases through end-of-line degassing treatment improves the shelf-life stability of the cleaning agent.

[0034] This invention provides a microwave component chip cleaning agent based on a dual-solvent method and its preparation method. It has the following beneficial effects:

[0035] 1. This invention utilizes a polar phase composed of diethylene glycol butyl ether, N-methylpyrrolidone, and benzotriazole to dissolve and peel off dirt from the substrate surface. Then, non-polar phases with low surface tension, such as 1,1,1,2,2,3,4,5,5,5-decafluoropentane and 1-methoxynonafluorobutane, penetrate into the micron-scale confined space. Under heated conditions, this induces a thermodynamic phase transition in the non-polar phase droplets within the microemulsion system. The local phase change energy generated by the rapid vaporization and expansion of the droplets provides an inward-to-outward physical shear force, forcing the dissolved dirt polar phase to overcome capillary resistance and detach from the pore structure to the outside. This improves the deep air evacuation rate of the extremely narrow slits in the microwave component and cuts off the path of dirt reflux and secondary precipitation.

[0036] 2. This invention uses a specifically prepared fluorinated block polyether-modified trisiloxane as a stabilizer. A bidirectional amphiphilic molecular structure with bidirectional affinity is constructed by grafting hydrophilic polyethylene glycol fragments and hydrophobic and lipophilic perfluorocarbon chains to both ends of 1,1,3,3,5,5-hexamethyltrisiloxane. This structure reduces the interfacial tension between the polar mother liquor and the fluorinated nonpolar phase droplets, allowing the highly immiscible two-phase fluids to combine and form a nanoscale microemulsion system, maintaining the static thermodynamic stability required for the dispersed droplets to undergo a phase transition before entering a confined space.

[0037] 3. The preparation method of this invention employs a stepwise emulsification process involving separate preparation of the polar mother liquor and pumping in the non-polar phase liquid. Combined with high-shear conditions controlled at 10°C to 20°C, this suppresses the ineffective vaporization and volatilization of low-boiling-point fluoroalkanes caused by high-speed rotor frictional heat generation, thus locking in the total amount of effective phase change working fluid in the finished cleaning agent. The degassing treatment by reducing the stirring speed at the end removes gases entrained during emulsification, preventing two-phase stratification and flocculation, and improving the long-term shelf-life stability of the cleaning agent product. Attached Figure Description

[0038] Figure 1 This is a comparison chart of the slit mass transfer kinetics test results of Embodiments 1-5 and some comparative examples of the present invention; wherein, Figure 1 (a) is a bar chart showing the final slit clearance rate of Examples 1-5 and their corresponding proportions. Figure 1 (b) is a time-series line graph of slit mass transfer kinetics for Example 1, Comparative Example 1, Comparative Example 4 and Comparative Example 5;

[0039] Figure 2 This is a comparison chart of the system stability test results of the embodiments and comparative examples of the present invention under long-term boiling cycle; wherein, Figure 2 (a) is a time-series bar chart showing the retention rate of fluorine components in each group during the long-term cycling process. Figure 2 (b) is a scatter plot of the closed-cup flash point of the residual liquid in each group after 168 hours of long-acting circulation;

[0040] Figure 3 This is a comparison chart of the overall cleaning performance and ion residue test results of the embodiments and comparative examples of the present invention; wherein, Figure 3 (a) is a bar chart showing the overall removal rate of mixed pollutants for each group. Figure 3 (b) Line graph showing the equivalent NaCl ion residue on the substrate surface after cleaning for each group;

[0041] Figure 4 This is a comparison chart of the gold wire bonding tensile strength and compatibility test results of sensitive substrates in the embodiments and comparative examples of the present invention; wherein, Figure 4 (a) is a biaxial bar chart showing the average tensile strength and bonding failure rate of gold wires after cleaning in each group. Figure 4 (b) is a bar chart showing the surface roughness changes of gallium arsenide substrates in each group after long-term immersion. Detailed Implementation

[0042] The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0043] Preparation Examples 1-4:

[0044] Preparation Example 1:

[0045] This preparation example provides a fluorinated block polyether modified trisiloxane stabilizer C1, comprising the following steps:

[0046] In a reactor equipped with a reflux condenser, a mechanical stirrer, and a nitrogen protection device, add 100g of toluene and 10.4g of 1,1,3,3,5,5-hexamethyltrisiloxane (0.05mol, providing a total of 0.1mol of Si-H bonds), start stirring under nitrogen protection and heat to 80℃;

[0047] 24.0 g (0.06 mol) of allyl polyethylene glycol and 15.6 g (0.045 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene were mixed evenly to obtain the monomer mixture to be added dropwise.

[0048] 0.5 g of isopropanol chloroplatinate solution with a platinum mass fraction of 20 ppm was added to the reactor as a catalyst, and then the monomer mixture to be added was added dropwise at a rate of 2 drops / second for 2 hours.

[0049] After the addition is complete, the temperature of the reactor is raised to 85°C for a aging reaction for 5 hours, until a sample is taken to detect the 2120 cm⁻¹ infrared spectrum. -1 The characteristic absorption peaks of the Si-H bonds at that location completely disappeared;

[0050] The reaction solution was transferred to a vacuum distillation apparatus and subjected to vacuum distillation for 2 hours at an absolute pressure of 0.01 MPa and a temperature of 110 °C to remove toluene solvent and unreacted fluorinated monomers and other low-boiling-point volatiles. After cooling to room temperature, a pale yellow transparent liquid was obtained, thus preparing fluorinated block polyether modified trisiloxane stabilizer C1.

[0051] Preparation Example 2:

[0052] This preparation example provides a fluorinated block polyether modified trisiloxane stabilizer C2, comprising the following steps:

[0053] In a reactor equipped with a reflux condenser, a mechanical stirrer, and a nitrogen protection device, 100 g of toluene and 10.4 g (0.05 mol, providing 0.1 mol of total Si-H bonds) of 1,1,3,3,5,5-hexamethyltrisiloxane were added. The mixture was stirred and heated to 80 °C under nitrogen protection. 16.0 g (0.04 mol) of allyl polyethylene glycol and 22.5 g (0.065 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene were mixed evenly to obtain the monomer mixture to be added dropwise.

[0054] 0.5 g of isopropanol chloroplatinate solution with a platinum mass fraction of 20 ppm was added to the reactor as a catalyst, and then the monomer mixture to be added was added dropwise at a rate of 2 drops / second for 2 hours.

[0055] After the addition is complete, the temperature of the reactor is raised to 85°C for a aging reaction for 5 hours, until a sample is taken to detect the 2120 cm⁻¹ infrared spectrum. -1 The characteristic absorption peaks of the Si-H bonds at that location completely disappeared;

[0056] The reaction solution was transferred to a vacuum distillation apparatus and subjected to vacuum distillation for 2 hours at an absolute pressure of 0.01 MPa and a temperature of 110 °C to remove toluene solvent and unreacted fluorinated monomers and other low-boiling-point volatiles. After cooling to room temperature, a pale yellow transparent liquid was obtained, and fluorinated block polyether modified trisiloxane stabilizer C2 was prepared.

[0057] Preparation Example 3:

[0058] This preparation example provides a fluorinated block polyether modified trisiloxane stabilizer C3, comprising the following steps:

[0059] In a reactor equipped with a reflux condenser, a mechanical stirrer, and a nitrogen protection device, 100 g of toluene and 10.4 g (0.05 mol, providing 0.1 mol of total Si-H bonds) of 1,1,3,3,5,5-hexamethyltrisiloxane were added. The mixture was stirred and heated to 80 °C under nitrogen protection. 32.0 g (0.08 mol) of allyl polyethylene glycol and 8.7 g (0.025 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene were mixed evenly to obtain the monomer mixture to be added dropwise.

[0060] 0.5 g of isopropanol chloroplatinate solution with a platinum mass fraction of 20 ppm was added to the reactor as a catalyst, and then the monomer mixture to be added was added dropwise at a rate of 2 drops / second for 2 hours.

[0061] After the addition is complete, the temperature of the reactor is raised to 85°C for a aging reaction for 5 hours, until a sample is taken to detect the 2120 cm⁻¹ infrared spectrum. -1 The characteristic absorption peaks of the Si-H bonds at that location completely disappeared;

[0062] The reaction solution was transferred to a vacuum distillation apparatus and subjected to vacuum distillation for 2 hours at an absolute pressure of 0.01 MPa and a temperature of 110 °C to remove toluene solvent and unreacted fluorinated monomers and other low-boiling-point volatiles. After cooling to room temperature, a pale yellow transparent liquid was obtained, and fluorinated block polyether modified trisiloxane stabilizer C3 was prepared.

[0063] Preparation Example 4:

[0064] This preparation example provides a fluorinated block polyether modified trisiloxane stabilizer C4, comprising the following steps:

[0065] In a reactor equipped with a reflux condenser, a mechanical stirrer, and a nitrogen protection device, add 100g of toluene and 10.4g of 1,1,3,3,5,5-hexamethyltrisiloxane (0.05mol, providing a total of 0.1mol of Si-H bonds), start stirring under nitrogen protection and heat to 75°C;

[0066] 24.0 g (0.06 mol) of allyl polyethylene glycol and 15.6 g (0.045 mol) of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene were mixed evenly to obtain the monomer mixture to be added dropwise.

[0067] 0.5 g of a 20 ppm platinum isopropanol chloroplatinate solution was added to the reactor as a catalyst. The monomer mixture to be added was then added dropwise at a rate of 1 drop / second for 3 hours. After the addition was complete, the reactor temperature was raised to 90°C for a aging reaction for 6 hours, until a sample was taken and the infrared spectrum at 2120 cm⁻¹ was detected.-1 The characteristic absorption peaks of the Si-H bonds at that location completely disappeared;

[0068] The reaction solution was transferred to a vacuum distillation apparatus and subjected to vacuum distillation for 2 hours at an absolute pressure of 0.01 MPa and a temperature of 110 °C to remove toluene solvent and unreacted fluorinated monomers and other low-boiling-point volatiles. After cooling to room temperature, a pale yellow transparent liquid was obtained, thus preparing the fluorinated block polyether modified trisiloxane stabilizer C4.

[0069] Examples 1-5:

[0070] Example 1:

[0071] This embodiment provides a microwave component chip cleaning agent based on dual solvents and its preparation method, including the following steps:

[0072] S1. In a reaction vessel equipped with a cooling jacket, add 160g of diethylene glycol butyl ether and 36g of N-methylpyrrolidone, turn on the anchor stirrer and set the speed to 60rpm, then add 4g of benzotriazole, and continue stirring at 25°C for 30 minutes until the solid is completely dissolved to obtain a homogeneous polar mother liquor.

[0073] S2. In a sealed stainless steel mixing tank, pump in 556.5g of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 214.65g of 1-methoxynonafluorobutane, and 23.85g of isopropanol in sequence. Turn on the internal circulation pump and circulate and mix at room temperature for 20 minutes to obtain a homogeneous nonpolar mixture.

[0074] S3. Take out 5g of stabilizer C1 prepared in Example 1 and add it to the polar mother liquor. Increase the stirring speed to 120rpm and disperse for 15 minutes. Then, pass the frozen brine into the jacket of the reactor to lower the temperature of the material in the reactor to 15°C and obtain the cooled polar mother liquor containing the stabilizer.

[0075] S4. Under the condition of maintaining the temperature inside the reactor not exceeding 20℃, start the high shear emulsifier at the bottom of the reactor and set the speed to 1200 rpm. Pump the non-polar mixture into the reactor at a flow rate of 15 L / min through the submersible feed pipe. After the feeding is completed, maintain the high shear state and emulsify continuously for 20 minutes to obtain a microemulsion mixture.

[0076] S5. Turn off the high-shear emulsifier, keep the anchor stirrer on and reduce the speed to 60 rpm, and stir slowly at 15°C for 20 minutes to remove microbubbles entrained during the emulsification process, thus obtaining the microwave component chip cleaning agent.

[0077] Example 2:

[0078] This embodiment provides a microwave component chip cleaning agent based on dual solvents and its preparation method, including the following steps:

[0079] S1. In a reaction vessel equipped with a cooling jacket, add 175g of diethylene glycol butyl ether and 62.5g of N-methylpyrrolidone, turn on the anchor stirrer and set the speed to 60rpm, then add 12.5g of benzotriazole, and continue stirring at 25°C for 30 minutes until the solid is completely dissolved to obtain a homogeneous polar mother liquor.

[0080] S2. In a sealed stainless steel mixing tank, pump in 448.8g of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 261.8g of 1-methoxynonafluorobutane, and 37.4g of isopropanol in sequence. Turn on the internal circulation pump and circulate and mix at room temperature for 20 minutes to obtain a homogeneous nonpolar mixture.

[0081] S3. Take 2g of stabilizer C2 prepared in Example 2 and add it to the polar mother liquor. Increase the stirring speed to 120rpm and disperse for 15 minutes. Then, pass the frozen brine into the jacket of the reactor to lower the temperature of the material in the reactor to 15°C and obtain the cooled polar mother liquor containing the stabilizer.

[0082] S4. Under the condition of maintaining the temperature inside the reactor not exceeding 20℃, start the high shear emulsifier at the bottom of the reactor and set the speed to 1200 rpm. Pump the non-polar mixture into the reactor at a flow rate of 15 L / min through the submersible feed pipe. After the feeding is completed, maintain the high shear state and emulsify continuously for 20 minutes to obtain a microemulsion mixture.

[0083] S5. Turn off the high-shear emulsifier, keep the anchor stirrer on and reduce the speed to 60 rpm, and stir slowly at 15°C for 20 minutes to remove microbubbles entrained during the emulsification process, thus obtaining the microwave component chip cleaning agent.

[0084] Example 3:

[0085] This embodiment provides a microwave component chip cleaning agent based on dual solvents and its preparation method, including the following steps:

[0086] S1. In a reaction vessel equipped with a cooling jacket, add 127.5g of diethylene glycol butyl ether and 15g of N-methylpyrrolidone, turn on the anchor stirrer and set the speed to 60rpm, then add 7.5g of benzotriazole, and continue stirring at 25°C for 30 minutes until the solid is completely dissolved to obtain a homogeneous polar mother liquor.

[0087] S2. In a sealed stainless steel mixing tank, pump in 630g of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 168g of 1-methoxynonafluorobutane and 42g of isopropanol in sequence, turn on the internal circulation pump, and circulate and mix at room temperature for 20 minutes to obtain a homogeneous nonpolar mixture.

[0088] S3. Take 10g of stabilizer C3 prepared in Preparation Example 3 and add it to the polar mother liquor. Increase the stirring speed to 120rpm and disperse for 15 minutes. Then, introduce frozen brine into the jacket of the reactor to lower the temperature of the material in the reactor to 15°C and obtain a cooled polar mother liquor containing stabilizer.

[0089] S4. Under the condition of maintaining the temperature inside the reactor not exceeding 20℃, start the high shear emulsifier at the bottom of the reactor and set the speed to 1200 rpm. Pump the non-polar mixture into the reactor at a flow rate of 15 L / min through the submersible feed pipe. After the feeding is completed, maintain the high shear state and emulsify continuously for 20 minutes to obtain a microemulsion mixture.

[0090] S5. Turn off the high-shear emulsifier, keep the anchor stirrer on and reduce the speed to 60 rpm, and stir slowly at 15°C for 20 minutes to remove microbubbles entrained during the emulsification process, thus obtaining the microwave component chip cleaning agent.

[0091] Example 4:

[0092] This embodiment provides a microwave component chip cleaning agent based on dual solvents and its preparation method, including the following steps:

[0093] S1. In a reaction vessel equipped with a cooling jacket, add 160g of diethylene glycol butyl ether and 36g of N-methylpyrrolidone, turn on the anchor stirrer and set the speed to 60rpm, then add 4g of benzotriazole, and continue stirring at 25°C for 30 minutes until the solid is completely dissolved to obtain a homogeneous polar mother liquor.

[0094] S2. In a sealed stainless steel mixing tank, pump in 556.5g of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 214.65g of 1-methoxynonafluorobutane, and 23.85g of isopropanol in sequence. Turn on the internal circulation pump and circulate and mix at room temperature for 20 minutes to obtain a homogeneous nonpolar mixture.

[0095] S3. Take out 5g of stabilizer C4 prepared in Preparation Example 4 and add it to the polar mother liquor. Increase the stirring speed to 120rpm and disperse for 15 minutes. Then, pass the frozen brine into the jacket of the reactor to lower the temperature of the material in the reactor to 10°C and obtain the cooled polar mother liquor containing the stabilizer.

[0096] S4. Under the condition of maintaining the temperature inside the reactor not exceeding 15℃, start the high shear emulsifier at the bottom of the reactor and set the speed to 1200 rpm. Pump the non-polar mixture into the reactor at a flow rate of 10 L / min through the submersible feed pipe. After the feeding is completed, maintain the high shear state and emulsify continuously for 25 minutes to obtain a microemulsion mixture.

[0097] S5. Turn off the high-shear emulsifier, keep the anchor stirrer on and reduce the speed to 50 rpm, and stir slowly at 10°C for 30 minutes to remove microbubbles entrained during the emulsification process, thus obtaining the microwave component chip cleaning agent.

[0098] Example 5:

[0099] This embodiment provides a microwave component chip cleaning agent based on dual solvents and its preparation method, including the following steps:

[0100] S1. In a reaction vessel equipped with a cooling jacket, add 160g of diethylene glycol butyl ether and 36g of N-methylpyrrolidone, turn on the anchor stirrer and set the speed to 60rpm, then add 4g of benzotriazole, and continue stirring at 25°C for 30 minutes until the solid is completely dissolved to obtain a homogeneous polar mother liquor.

[0101] S2. In a sealed stainless steel mixing tank, pump in 556.5g of 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 214.65g of 1-methoxynonafluorobutane, and 23.85g of isopropanol in sequence. Turn on the internal circulation pump and circulate and mix at room temperature for 20 minutes to obtain a homogeneous nonpolar mixture.

[0102] S3. Take out 5g of stabilizer C1 prepared in Example 1 and add it to the polar mother liquor. Increase the stirring speed to 120rpm and disperse for 15 minutes. Then, pass the frozen brine into the jacket of the reactor to lower the temperature of the material in the reactor to 15°C and obtain the cooled polar mother liquor containing the stabilizer.

[0103] S4. Under the condition of maintaining the temperature inside the reactor not exceeding 20℃, start the high shear emulsifier at the bottom of the reactor and set the speed to 1500 rpm. Pump the non-polar mixture into the reactor at a flow rate of 20 L / min through the submersible feed pipe. After the feeding is completed, maintain the high shear state and emulsify continuously for 15 minutes to obtain a microemulsion mixture.

[0104] S5. Turn off the high-shear emulsifier, keep the anchor stirrer on and reduce the speed to 80 rpm, and stir slowly at 15°C for 20 minutes to remove microbubbles entrained during the emulsification process, thus obtaining the microwave component chip cleaning agent.

[0105] Comparative Examples 1-5:

[0106] Comparative Example 1:

[0107] Compared with Example 1, the difference is that the stabilizer C1 obtained in Preparation Example 1 was not added, the pre-dispersion process in step S3 was omitted, and the polar mother liquor obtained in step S1 was directly mixed with the non-polar mixture obtained in step S2 and then subjected to high-shear emulsification. All other aspects are the same.

[0108] Comparative Example 2:

[0109] Compared with Example 1, the difference lies in the type of stabilizer. In step S3, stabilizer C1 is replaced by an equal mass of commercially available conventional nonionic surfactant fatty alcohol polyoxyethylene ether. All other aspects are the same.

[0110] Comparative Example 3:

[0111] Compared with Example 1, the difference is that N-methylpyrrolidone was not added, and in step S1, the entire mass of this component was replaced with diethylene glycol butyl ether, while the rest were the same.

[0112] Comparative Example 4:

[0113] Compared with Example 1, the difference is that no polar mother liquor components and stabilizer C1 were added, steps S1 and S3 were omitted, and the non-polar mixture obtained in step S2 was used as the cleaning agent alone. All other aspects are the same.

[0114] Comparative Example 5:

[0115] Compared with Example 1, the difference lies in the change of the shear environment of the preparation process. The high-shear emulsifier homogenization process in step S4 is cancelled. Instead, an anchor mixer is used to mix the mixture at a speed of 60 rpm for 20 minutes. All other aspects are the same.

[0116] Test Examples 1-4:

[0117] Test Example 1:

[0118] This test case mainly conducts physical simulation tests on the mass transfer kinetics (slit emptying time) and cleaning thoroughness (final slit emptying rate) of the cleaning agents prepared in Examples 1-5 and Comparative Examples 1, 4, and 5 under extremely narrow gaps, in order to verify the actual effectiveness of the thermodynamic self-driven micropump effect.

[0119] The experimental testing process is as follows:

[0120] 1. A parallel quartz glass plate with a surface roughness Ra of 0.1μm is selected. A polyimide gasket with a thickness of 30μm is sandwiched between the two glass plates to control the spacing. The external part is fixed by applying uniform pressure through a miniature stainless steel clamp to make an ultra-narrow slit test piece that simulates the bottom mounting structure of microwave component chips.

[0121] 2. Using a microsyringe with an extremely fine needle, inject 50 mg of standard rosin-based flux into the slit of the test piece. This flux system contains 20% natural rosin and 80% isopropanol solvent by mass. Place the test piece filled with liquid into an 85°C vacuum drying oven and bake for 2 hours to allow the isopropanol solvent to completely evaporate and form a dense and solidified flux residue film deep within the slit. After cooling to room temperature, accurately weigh the initial total mass M1 of the test piece with the solidified flux using an analytical balance with an accuracy of 0.1 mg, and simultaneously record the reference mass M0 of the empty test piece before flux injection.

[0122] 3. Pour the cleaning agents obtained in Examples 1 to 5, as well as Comparative Examples 1, 4 and 5, into jacketed beakers equipped with constant temperature water bath jackets, start the circulating water bath, and control the internal liquid temperature of each cleaning agent system to be constant at 45°C.

[0123] 4. Suspend the test piece with cured flux vertically on the metal wire of a high-precision dynamic microbalance, and lower the suspension to quickly and completely immerse it in the constant-temperature cleaning agent. Connect the balance's data acquisition port to the back-end workstation to continuously record the change in the suspended mass of the test piece in the liquid at a sampling frequency of 1Hz. When the range of mass fluctuation within 60 consecutive seconds is less than 0.2mg, it is determined that the mass transfer and dissolution process within the slit has reached thermodynamic equilibrium. Record the total time t consumed at this point, which is defined as the slit emptying time.

[0124] 5. After the test piece reaches dissolution equilibrium, slowly remove it from the cleaning agent and dry it in a vacuum oven at 60℃ for 1 hour to remove residual cleaning agent solvent from the surface and slits. After cooling, weigh its final total mass M2. Calculate the final slit clearance rate using R=(M1-M2) / (M1-M0)×100%. Each test group is performed in parallel three times, and the arithmetic mean is taken as the final evaluation data for that group.

[0125] Table 1. Slit emptying dynamics test data of Examples 1-5 and some comparative examples

[0126] Group Slit emptying time (s) Final slit evacuation rate (%) Example 1 126.5 96.3 Example 2 141.8 93.7 Example 3 118.2 97.5 Example 4 133.4 94.8 Example 5 114.7 98.4 Comparative Example 1 342.1 51.6 Comparative Example 4 77.3 14.5 Comparative Example 5 425.8 63.2

[0127] Combining the data in Table 1 and Figure 1 (Comparison of slit mass transfer kinetics test results between Examples 1-5 and some comparative examples) A ​​comprehensive analysis is performed. This figure visually demonstrates the significant differences in mass transfer efficiency and cleaning thoroughness of cleaning agents in extremely narrow enclosed spaces under different formulations and process conditions.

[0128] Figure 1(b) in the figure is a time-series line graph of slit mass transfer kinetics for Examples 1, 1, 4, and 5. The vertical axis corresponds to the dynamic change in the slit evacuation rate. This sub-graph, combined with the data in Table 1, shows that in a constant-temperature immersion environment of 45°C, the systems of the examples exhibit extremely high time efficiency and decontamination capacity, with the final evacuation rate consistently above 93%, and the time to reach equilibrium controlled within 150 seconds. During the experiment, it was observed that when the systems of the examples came into contact with the inside of the slit, the low-boiling-point fluorinated solvent components rapidly vaporized deep within the gap. The resulting microbubbles, during their outward escape phase, forced the polar solvent carrying dissolved contaminants out of the slit. This thermodynamic phase change-driven liquid exchange efficiency is far higher than that of conventional static molecular diffusion relying on concentration gradients. In contrast, although Comparative Example 4 completed the physical penetration and vaporization cycle extremely quickly in just 77.3 seconds thanks to the extremely low surface tension of the pure fluorine solvent, its chemical dissolving power on the cured flux resin was almost zero. After reaching its peak in a very short time, the curve stopped at 14.5%, only washing away the loose residue at the edge.

[0129] Figure 1 Figure (a) shows the final slit evacuation rate of Examples 1-5 and their corresponding comparative examples. The gray bars in the figure represent the percentage of the final slit evacuation rate for each group. This sub-figure clearly shows that the introduction of the specially formulated interfacial stabilizer and the high-shear process at the front end play a decisive role in the final cleaning effect. In Comparative Example 1, due to the absence of an interfacial stabilizer, severe macroscopic stratification occurred between the polar and non-polar phases within the slit. The kinetic energy of the bubbles generated by boiling could not be effectively transferred to the high-viscosity polar mother liquor, resulting in a large amount of dirt being trapped deep within the slit and unable to be discharged, causing the evacuation rate to plummet to 51.6%.

[0130] Comparative Example 5 retained the complete chemical formula but eliminated the high-shear homogenization process. The system relied solely on conventional stirring to form an unstable emulsion with large droplets. These large droplets encountered severe capillary resistance when attempting to enter the 30μm slit, making it difficult to activate the micro-pump effect across the entire region, resulting in a final air evacuation rate of only 63.2%. The bar charts for Examples 1 to 5 consistently showed extremely high heights, confirming that the present invention, through the synergy of emulsification and stabilizers, achieves a perfect coupling of soft and hard polarity synergy and phase change energy at the microscale, which helps to overcome the technical bottleneck of cleaning the bottom blind zone of microwave components.

[0131] Test Example 2:

[0132] This test case mainly focuses on the system stability test of the cleaning agents prepared in Examples 1-5 and Comparative Examples 1 and 2 under long-term boiling cycle. The retention rate of fluorinated solvent components and the change of system flash point are monitored to verify the role of this scheme in preventing ratio drift.

[0133] The experimental testing process is as follows:

[0134] 1. In a simulated standard single-tank vapor phase cleaning machine with a condensate recovery pipeline, 5.0 kg of fresh cleaning agent samples prepared in Examples 1-5 and Comparative Examples 1 and 2 were injected as initial working solutions.

[0135] 2. Activate the bottom heating device of the cleaning machine and set the heating temperature to 50℃ to keep the cleaning agent system in a continuous state of slight boiling and condensation reflux. The equipment will operate continuously for 168 hours under standard atmospheric pressure without adding any fresh cleaning solution to the tank during this period to simulate a high-intensity continuous industrial cleaning environment.

[0136] 3. At the three time points of 0 hours (initial state), 72 hours and 168 hours of equipment operation, 20 mL of liquid sample is drawn from below the liquid surface in the middle of the boiling tank, placed in a sealed glass sampling bottle and cooled to room temperature for testing.

[0137] 4. Quantitative analysis of components was performed on samples at different time points using a gas chromatograph equipped with a thermal conductivity detector (TCD). The total mass percentage of the nonpolar fluorine phase (B phase) in the system was calculated using the standard curve method, and the mass retention rates of fluorine components at 72 hours and 168 hours were calculated based on the initial concentration at 0 hours.

[0138] 5. Take samples collected at the 168-hour mark and test the flash point of the residual liquid using a closed-cup flash point analyzer according to the standard closed-cup method. If no flash ignition occurs after heating to 90℃, record it as >90℃; if a clear flash point is detected, record the specific temperature value. This data is used to assess whether there are any safety hazards due to the accumulation of flammable polar solvents in the cleaning agent after long-term use. Each test is repeated three times, and the arithmetic mean is taken.

[0139] Table 2. Long-term cycling stability test data of Examples 1-5 and some comparative examples

[0140] Group Fluorine component retention rate (%) after 72 hours Fluorine component retention rate (%) after 168 h Flash point of residual liquid in the 168-hour system (°C) Example 1 98.2 96.1 >90 Example 2 97.4 94.8 >90 Example 3 98.6 96.7 >90 Example 4 97.9 95.3 >90 Example 5 98.8 97.2 >90 Comparative Example 1 68.3 42.5 61.4 Comparative Example 2 75.1 54.6 67.2

[0141] Combining the data in Table 2 and Figure 2 A comprehensive analysis was conducted. This figure reflects the differences in the physical anchoring ability of different formulation systems to low-boiling-point fluorinated solvents and the resulting differences in thermodynamic stability under the harsh physical environment of continuous heating and reflux.

[0142] Figure 2(a) in the figure is a time-series bar chart of fluorine component retention rate for each group during the long-term cycling process. This sub-chart, combined with the data in Table 2, shows that after 168 hours of continuous boiling, Examples 1 to 5 still maintained a non-polar fluorine component retention rate of over 94%. Experimental studies observed that the fluorinated block polyether modified trisiloxane stabilizer formed a dynamic molecular barrier film at the gas-liquid interface. The perfluoroalkyl segments of the stabilizer molecule generate intermolecular forces with the underlying fluorinated solvent, while its polyether segments intertwine with the polar solvent. This microstructure helps reduce the escape rate of fluorinated solvent molecules.

[0143] The systems in the examples did not undergo significant phase separation during prolonged thermodynamic cycling, which is beneficial for maintaining the designed ratio balance of the cleaning agent throughout its lifespan. In contrast, Comparative Example 1 did not add any interfacial stabilizers, and the polar and non-polar solvents were in a simple mechanical mixing state. The low-boiling-point fluorinated solvent evaporated in large quantities during the initial heating phase and was difficult to completely capture and recover by the condenser, resulting in a sharp decrease in its 168-hour retention rate to 42.5%. Comparative Example 2 introduced a conventional fatty alcohol polyoxyethylene ether surfactant, but due to the lack of a fluorinated segment that matches the fluorinated solvent, the interfacial anchoring effect was weak, and the retention rate was only 54.6%, failing to play a substantial role in inhibiting drift.

[0144] Figure 2 (b) is a scatter plot of the closed-cup flash point of the residual liquid in each group after 168 hours of long-term circulation, with the vertical axis corresponding to the flash ignition temperature of the system. The flash point of the cleaning agent is directly related to the fire safety margin in industrial production. Since fluorinated solvents are non-flammable, they usually act as a safety barrier to mask the flammability of polar mother liquor. As can be seen from the data, Examples 1 to 5 successfully suppressed the excessive loss of fluorine components, and the flame retardant barrier in the system was maintained, with the residual liquids not exhibiting flash ignition characteristics within the test upper limit of 90°C. However, in Comparative Examples 1 and 2, due to the large amount of fluorine component volatilization, the concentration of flammable polar solvents such as diethylene glycol butyl ether and N-methylpyrrolidone in the remaining liquid was relatively enriched. This ratio drift directly caused the residual liquids of Comparative Examples 1 and 2 to ignite at 61.4°C and 67.2°C, respectively. This phenomenon shows that the phase stabilization strategy adopted in the examples not only helps to maintain the consistency of cleaning performance, but also ensures operational safety during long-term application.

[0145] Test Example 3:

[0146] This test case mainly evaluates the comprehensive cleaning rate and residual amount of ionic contaminants of the cleaning agents prepared in Examples 1-5 and Comparative Examples 1, 3, and 4, in order to verify the removal efficiency of the soft and hard polarity synergistic cleaning mode for complex contaminants and the safety of the surface electrical properties after cleaning.

[0147] The experimental testing process is as follows:

[0148] 1. An alumina ceramic substrate with dimensions of 50mm×50mm×1mm was selected as the test carrier for simulating microwave components. 0.2g of mixed contaminants was uniformly coated on the substrate surface. The contaminants were prepared by mixing no-clean flux, thermal grease and industrial rust-preventive oil in a mass ratio of 3:1:1 to simulate the complex soft and hard composite contamination conditions in the production site.

[0149] 2. Place the substrate coated with contaminants into a constant temperature oven at 120℃ and bake for 1 hour to promote the evaporation of some organic solvents and cause the resin to undergo a certain degree of cross-linking and curing. After cooling to room temperature, weigh its initial total mass using an analytical balance with an accuracy of 0.1 mg.

[0150] 3. Inject each group of cleaning agents into the ultrasonic cleaning tank separately. Turn off the ultrasonic generator and use only the heating function to maintain the liquid temperature at 45°C. Immerse the substrate vertically in the cleaning agent and let it stand for 5 minutes without applying any mechanical force. After removing the substrate, rinse it briefly with isopropanol to remove residual liquid from the surface. Then place it in an 80°C oven to dry for 30 minutes. After cooling, weigh the final mass and calculate the overall contaminant removal rate.

[0151] 4. Ion contamination testing was conducted according to IPC-TM-6502.3.25 standard. The cleaned and dried substrate was placed in the test chamber of the ion contamination tester, which contained a mixture of isopropanol and deionized water at a volume ratio of 75:25. The testing system circulated and extracted residual ions from the substrate surface, while monitoring the conductivity of the solution in real time. After the test, the instrument automatically converted the conductivity data into the equivalent sodium chloride (NaCl) residue per unit area, expressed in μg / cm². 2 Each experiment tested three substrates in parallel, and the results were averaged.

[0152] Table 3. Overall cleaning performance and ion residue test data of Examples 1-5 and some comparative examples

[0153] Group Overall pollutant removal rate (%) <![CDATA[Equivalent NaCl ion residue amount (μg / cm 2 )]]> Example 1 96.8 0.42 Example 2 95.3 0.51 Example 3 97.4 0.38 Example 4 96.1 0.45 Example 5 98.2 0.33 Comparative Example 1 71.5 2.68 Comparative Example 3 80.2 1.95 Comparative Example 4 32.6 5.84

[0154] Combining the data in Table 3 and Figure 3 A comprehensive analysis was conducted. This figure reflects the differences in macroscopic detergency and microscopic ion removal capabilities of cleaning agents with different component structures when facing complex contaminants containing resins, greases, and metal salts.

[0155] Figure 3(a) in the figure is a bar chart showing the overall removal rate of mixed contaminants for each group. Combined with the data in Table 3, the overall contaminant removal rates for Examples 1 to 5 all reached over 95%. During the test, it was found that the polar and non-polar phases in the cleaning agent formed a uniform microenvironment under the bridging of the stabilizer. The non-polar fluorinated solvent preferentially penetrated and dissolved low-polarity substances such as anti-rust oil and thermal grease on the substrate surface, opening a channel for the polar phase to contact the cured flux resin at the bottom layer. The organic solvent in the polar phase then swelled and peeled off the resin structure; this synergistic effect facilitated the comprehensive coverage and removal of complex contaminants. Comparative Example 3 removed N-methylpyrrolidone from the polar mother liquor, reducing the system's solubility parameter matching degree for the cured crosslinked resin, resulting in some hard dirt residue and a removal rate reduced to 80.2%. Comparative Example 4 used only pure fluorinated solvents, exhibiting significant solubility selectivity when facing mixed dirt, almost unable to remove rosin resin and ionic salts, with a removal rate of only 32.6%.

[0156] Figure 3 (b) in the figure shows a line graph of the equivalent NaCl ion residue on the substrate surface after cleaning for each group. This indicator is commonly used to assess the potential leakage or electrochemical migration risk after component cleaning, and the industry-standard safety requirement is generally below 1.56 μg / cm³. 2 Data shows that the residual ion levels in all example groups were controlled at 0.55 μg / cm³. 2 The following demonstrates that the polar phase can effectively encapsulate and remove metal-activated ions in the microemulsion system. In Comparative Example 1, the lack of a stabilizer led to macroscopic stratification of the two phases, preventing the polar solvent from uniformly contacting the substrate surface. This resulted in uneven ion cleaning in certain areas, with the residual concentration increasing to 2.68 μg / cm³. 2 This exceeds the conventional safety threshold. In Comparative Example 4, ion exchange and dissolution were performed in a non-polar medium, and a concentration as high as 5.84 μg / cm³ was measured. 2 Severe ion residues were observed. These results indicate that maintaining a balanced configuration of the system's hard and soft polarities, as well as the microscopic uniformity of the phase states, helps to improve apparent cleanliness while ensuring the reliability of the underlying electrical performance.

[0157] Test Example 4:

[0158] This test case mainly tests the gold wire bonding pull force and compatibility with sensitive substrates of the cleaning agents prepared in Examples 1-5 and Comparative Examples 1, 4, and 5, in order to verify the non-destructive protection of the micron-level fragile structure and semiconductor substrate inside the microwave component without relying on strong ultrasonic assistance.

[0159] The experimental testing process is as follows:

[0160] 1. Gallium arsenide bare chips with pre-deposited metal pads on their surface were selected as the substrate. Gold wire ball bonding with a wire diameter of 25 μm was performed on the surface using an automated wire bonding machine to fabricate a simulated microwave component test unit. A measured amount of no-clean flux was applied to the bonding points and the substrate surface, and the mixture was placed in a 150°C oven for 1 hour to cure and form tightly adhered aged dirt.

[0161] 2. The initial surface roughness (Ra1) of the uncoated area of ​​each gallium arsenide substrate was measured and recorded in advance using a laser confocal microscope, with the measurement accuracy set to the nanometer level.

[0162] 3. Add each group of cleaning agents to an immersion cleaning tank equipped with a constant temperature heating function, and maintain the temperature at 45℃. Suspend and completely immerse the cured test unit in the cleaning tank, maintaining static boiling cleaning for 15 minutes. To compare the effect of physical shear force on the device, in addition to the static cleaning group, Comparative Example 5 added an extra group with 40kHz operation and a power density of 0.5W / cm². 2 An ultrasonic cleaning unit (referred to as Comparative Example 5 - Ultrasonic Unit) was used to compensate for the insufficient cleaning power of the conventional emulsification system. After cleaning, all test units were removed, rinsed with isopropanol, and dried with nitrogen at room temperature.

[0163] 4. A microelectronic push-pull force tester was used to perform pull-out failure tests on the cleaned gold wires. The test hook pulled the gold wire vertically upward at a constant speed of 0.5 mm / s, and the ultimate tensile force (unit: g) at the point of breakage or detachment of each gold wire was recorded. 50 gold wires were randomly selected from each test unit for testing, and the average tensile force and the failure rate of solder joint detachment or root breakage were statistically analyzed (failure rate = number of abnormal breaks / total number of tests × 100%).

[0164] 5. The test unit that has completed the tensile test is re-immersed in the corresponding cleaning agent at 50°C for a 72-hour extreme immersion test. After removal and drying, the surface roughness (Ra2) of the same area of ​​the substrate is measured again, and the roughness change value ΔRa is calculated (ΔRa=Ra2-Ra1, unit: nm). This data is used to evaluate whether there is chemical corrosion of sensitive semiconductor materials by the polar phase system of the cleaning agent under long-term contact.

[0165] Table 4. Test data on gold wire bonding tensile strength and substrate compatibility of Examples 1-5 and some comparative examples.

[0166] Group Average gold wire tensile strength (g) Bond failure rate (%) Substrate roughness variation ΔRa (nm) Example 1 9.12 1.8 1.25 Example 2 8.85 2.1 1.48 Example 3 9.34 1.4 1.12 Example 4 8.97 2.5 1.63 Example 5 9.41 1.2 0.95 Comparative Example 1 9.05 2.0 4.82 Comparative Example 4 9.52 1.0 0.21 Comparative Example 5 - Static 8.91 2.2 1.84 Comparative Example 5 - Ultrasound 5.36 18.6 2.15

[0167] Combining the data in Table 4 and Figure 4 A comprehensive analysis was conducted. This figure objectively presents the mechanical integrity of the internal micro-interconnection structure of the microwave component and the surface chemical stability of the semiconductor substrate under the influence of different cleaning media and energy fields.

[0168] Figure 4 (a) in the figure shows the biaxial bar graph of the average pull force and bonding failure rate of the gold wires after cleaning for each group. Combined with the data in Table 4, in Examples 1 to 5, under the static boiling cleaning mode, the average pull force of the gold wires remained above 8.8g, and the bonding failure rate was controlled within 3%. This mechanical performance is basically consistent with the untreated standard reference. The study found that the system in the examples utilizes the thermodynamic phase change energy induced by the microemulsion structure in a confined space to gently and effectively peel off the cured resin adhering to the root of the solder joint. This cleaning method, combining chemical penetration and micro-thermodynamics, avoids fatigue damage to the gold wire grain structure caused by macroscopic physical shear force, helping to ensure the mechanical strength of fragile bonding points.

[0169] In contrast, Comparative Example 5 suffered from poor static cleaning force due to uneven emulsification. After introducing conventional ultrasonic assistance (Comparative Example 5 – Ultrasonic), the localized high-pressure shock wave generated by cavitation directly acted on the 25μm fine gold wire, causing the average tensile force to plummet to 5.36g, and the bonding failure rate to be as high as 18.6%. This indicates that traditional ultrasonic-enhanced cleaning methods have a high risk of mechanical damage, while the self-driven micropump mechanism of this solution is beneficial for achieving the same or even better cleaning effect in the absence of ultrasonic treatment.

[0170] Figure 4 (b) in the figure shows a bar chart of the surface roughness changes of gallium arsenide substrates in each group after long-term immersion. A slight increase in surface roughness usually indicates that the polar solvent or additives in the cleaning agent have caused slight dissolution or corrosion of the substrate. Data shows that after 72 hours of extreme immersion, the roughness increment ΔRa in the example groups was less than 1.7 nm, and no obvious lattice peeling or oxide spots were observed under an electron microscope. This is attributed to the inert buffering effect of the fluorine-based solvent phase in the system. The fluorine-containing block stabilizer adsorbs on the solid substrate surface to form a dynamic hydrophobic and oleophobic film, blocking the continuous attack of strongly soluble molecules (such as N-methylpyrrolidone) in the polar phase on the gallium arsenide grain boundaries, which helps maintain the initial smoothness of the sensitive substrate.

[0171] Comparative Example 1, by removing the interfacial phase stabilizer, resulted in a high concentration of polar mother liquor being directly and prolongedly exposed to the substrate surface, causing localized micro-erosion and increasing the roughness change to 4.82 nm. Comparative Example 4 used a pure non-polar fluorine solvent; due to its extremely high chemical inertness, the roughness change was only 0.21 nm, but combined with previous comprehensive decontamination data, its cleaning ability has significant shortcomings. The above tests demonstrate that this invention, through interfacial phase control, ensures strong dissolution of organic contaminants while also maintaining excellent compatibility with semiconductor materials.

Claims

1. A microwave component chip cleaning agent based on dual solvents, characterized in that, It is made from the following components in parts by weight: 127.5–175 parts of diethylene glycol butyl ether; 15–62.5 parts of N-methylpyrrolidone; Benzotriazole 4–12.5 parts; 1,1,1,2,2,3,4,5,5,5-Decafluoropentane 448.8~630 parts; 1-Methoxynonfluorobutane, 168–261.8 parts; Isopropanol 23.85–42 parts; Fluorine-containing block polyether modified trisiloxane stabilizer, 2-10 parts; The cleaning agent is emulsified into a microemulsion system through high shear emulsification. When the microemulsion system enters a micron-level confined space, a thermodynamic phase change occurs in the internal low-boiling-point components, squeezing out the dirt dissolved and stripped by the polar components.

2. The microwave component chip cleaning agent based on dual solvents according to claim 1, characterized in that, The fluorinated block polyether modified trisiloxane stabilizer is prepared by the following steps: In a reactor equipped with a reflux condenser, a mechanical stirrer, and a nitrogen protection device, toluene and 1,1,3,3,5,5-hexamethyltrisiloxane are added. Stirring is started and the temperature is raised under nitrogen protection to form an initial mixture. Allyl polyethylene glycol was mixed evenly with 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecylfluoro-1-octene to obtain the monomer mixture to be added. A solution of isopropanol chloroplatinate was added to the reaction vessel as a catalyst, and the mixture of monomers to be added was added dropwise at a uniform rate to carry out a hydrosilylation reaction. After the addition is complete, the temperature is raised to carry out the ripening reaction until the characteristic absorption peak of Si-H bond in the infrared spectrum completely disappears, and the reaction solution is obtained. The reaction solution was subjected to vacuum distillation to remove low-boiling-point volatiles, and then cooled to room temperature to obtain the fluorinated block polyether modified trisiloxane stabilizer.

3. The microwave component chip cleaning agent based on dual solvents according to claim 2, characterized in that, The specific process parameters for preparing the fluorinated block polyether modified trisiloxane stabilizer are as follows: In molar amounts, the total amount of Si-H bonds provided by the 1,1,3,3,5,5-hexamethyltrisiloxane is 0.1 mol, the allyl polyethylene glycol is 0.04 to 0.08 mol, and the 3,3,4,4,5,5,6,6,7,7,8,8,8-tetrafluoro-1-octene is 0.025 to 0.065 mol; The hydrosilylation reaction was carried out at a temperature of 75°C to 80°C, and the dropwise addition process lasted for 2 to 3 hours. The ripening reaction is carried out at a temperature of 85℃ to 90℃ for 5 to 6 hours.

4. The microwave component chip cleaning agent based on dual solvents according to claim 1, characterized in that, It is made from the following components in parts by weight: 160 parts of diethylene glycol butyl ether; 36 parts of N-methylpyrrolidone; 4 parts of benzotriazole; 1,1,1,2,2,3,4,5,5,5-Decafluoropentane 556.5 parts; 214.65 parts of 1-methoxynonafluorobutane; Isopropanol 23.85 parts; Five parts of fluorinated block polyether modified trisiloxane stabilizer.

5. A method for preparing a microwave component chip cleaning agent based on dual solvents, characterized in that, The preparation of the dual-solvent-based microwave component chip cleaning agent according to any one of claims 1-4 comprises the following steps: In a reaction vessel equipped with a cooling jacket, diethylene glycol butyl ether and N-methylpyrrolidone were added, and stirring was started. Then benzotriazole was added, and stirring was continued until the solid was completely dissolved, resulting in a homogeneous polar mother liquor. In a closed mixing tank, 1,1,1,2,2,3,4,5,5,5-decafluoropentane, 1-methoxynonafluorobutane and isopropanol are pumped in sequentially, and the internal circulation pump is turned on to circulate and mix, so as to obtain a homogeneous nonpolar mixture. Fluorine-containing block polyether modified trisiloxane stabilizer is added to the polar mother liquor, the stirring speed is increased to disperse it, and then a cooling medium is introduced into the jacket of the reactor to cool down the material in the reactor, thereby obtaining a cooled polar mother liquor containing stabilizer. Under temperature control, the high-shear emulsifier at the bottom of the reactor is started, and the non-polar mixture is uniformly pumped into the reactor through the feed pipe. After the feeding is completed, the high-shear state is maintained for continuous emulsification to obtain a microemulsion mixture. Turn off the high-shear emulsifier, keep the agitator on, and reduce the agitation speed under controlled temperature conditions to remove microbubbles and obtain the cleaning agent.

6. The preparation method of the microwave component chip cleaning agent based on dual solvents according to claim 5, characterized in that, In the step of obtaining the polar mother liquor: Turn on the anchor stirrer at 20℃~30℃, set the speed to 50~80rpm, and stir continuously for 20~40 minutes until the solid is completely dissolved.

7. The preparation method of the microwave component chip cleaning agent based on dual solvents according to claim 5, characterized in that, In the step of obtaining the nonpolar mixture: Turn on the internal circulation pump at room temperature and circulate the mixture for 15 to 30 minutes.

8. The preparation method of the microwave component chip cleaning agent based on dual solvents according to claim 5, characterized in that, In the step of obtaining the cooling polar mother liquor containing the stabilizer: Increase the stirring speed to 100-150 rpm and disperse for 10-20 minutes; introduce chilled brine into the jacket of the reactor to lower the temperature of the material inside the reactor to 10-15℃.

9. The preparation method of the microwave component chip cleaning agent based on dual solvents according to claim 5, characterized in that, The specific method for obtaining the microemulsion mixture is as follows: Maintain the temperature inside the reactor at no more than 15℃~20℃; start the high-shear emulsifier with a speed set to 1200~1500rpm; pump the non-polar mixture into the reactor uniformly at a flow rate of 10~20L / min, and maintain high-shear state for continuous emulsification for 15~25 minutes.

10. The preparation method of the microwave component chip cleaning agent based on dual solvents according to claim 5, characterized in that, In the step of preparing the cleaning agent: Reduce the stirring speed to 50-80 rpm and stir at 10-15℃ for 20-30 minutes.

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