阅读说明：本技术 一种用于半导体芯片固体蜡清洗的组合物 (Composition for cleaning semiconductor chip solid wax ) 是由 刘小勇 李丛香 邱小真 房龙翔 叶鑫煌 肖小江 刘文生 黄晓莉 张梦雪 于 2021-09-10 设计创作，主要内容包括：本发明属于表面活性剂技术领域,具体涉及一种用于半导体芯片固体蜡清洗的组合物,包括阴离子松香基磷酸酯钠盐聚醚表面活性剂,高效渗透剂,乳化剂,螯合剂,有机助剂和高纯水。本发明通过阴离子松香基磷酸酯钠盐聚醚表面活性剂与高效渗透剂和乳化剂混配,可以使固体蜡溶胀、破裂脱离芯片表面,并快速乳化溶解,解决了市面上溶剂型产品存在的环保和安全问题,且易清洗无残留。(The invention belongs to the technical field of surfactants, and particularly relates to a composition for cleaning solid wax of a semiconductor chip. According to the invention, the anionic rosin-based phosphate sodium salt polyether surfactant, the high-efficiency penetrating agent and the emulsifier are mixed, so that the solid wax can be swelled, broken and separated from the surface of the chip, and is quickly emulsified and dissolved, the problems of environmental protection and safety of solvent type products on the market are solved, and the solvent type products are easy to clean and have no residue.)

1. A composition for solid wax cleaning of semiconductor chips, characterized by: the composition comprises the following components in percentage by mass, wherein the sum of the mass percentages is 100%: 9-12% of anionic rosin-based phosphate sodium salt polyether surfactant, 0.5-2% of high-efficiency penetrating agent, 0.1-5% of emulsifier, 0.1-1% of chelating agent, 1-5% of organic auxiliary agent and the balance of high-purity water.

2. The composition of claim 1, wherein the composition comprises: the anionic rosin-based phosphate sodium salt polyether surfactant is selected from the following structures:

at least one of surfactants, wherein n is an integer between 0 and 6 and m is an integer between 2 and 6.

3. The composition for cleaning the solid wax of the semiconductor chip according to claim 2, wherein: the preparation method of the anionic rosin-based phosphate sodium salt polyether surfactant comprises the following steps:

1) synthesizing rosin acyl chloride:

placing phosphorus trichloride and trichloromethane into a dry three-neck flask, preparing a magnetic stirrer, a condenser and a charging funnel, dropwise adding a trichloromethane solution dissolved with abietic acid into the three-neck flask, stirring, reacting the mixture at 65 ℃ for 3 hours, cooling to room temperature, and then carrying out reduced pressure distillation to obtain viscous light liquid rosin acyl chloride;

2) and (3) synthesizing rosin ester:

placing a diol compound into a three-neck flask, preparing a magnetic stirrer, a condenser and an addition funnel, then dropwise adding a trichloromethane solution dissolved with rosin acyl chloride into the three-neck flask, stirring the reaction mixture at room temperature for 1 hour, then heating and refluxing for 2 hours, and removing the solvent in a reduced pressure distillation mode to obtain viscous liquid rosin ester;

3) synthesizing rosin-based phosphate ester:

dissolving rosin ester in chloroform, placing the chloroform in a reaction flask, heating and refluxing the chloroform by using a magnetic stirrer, dropwise adding PPA (polyphosphoric acid) into the reaction flask, stirring and heating the mixture until the mixture is refluxed for 4-6 hours, washing redundant PPA by using distilled water, removing the solvent by reduced pressure distillation, and drying to obtain yellow viscous liquid rosin-based phosphate;

4) synthesizing rosin-based phosphate polyether:

dissolving rosin-based phosphate into trichloromethane, placing the trichloromethane into a three-neck flask provided with a stirring and refluxing device, adding triethylene diamine, dripping polyether into a system, reacting for 3 hours at a constant temperature of 80 ℃, and after the reaction is finished, carrying out reduced pressure distillation to obtain colorless transparent liquid, namely rosin-based phosphate polyether;

5) synthesizing an anionic rosin-based phosphate sodium salt polyether surfactant:

and (3) carrying out saponification reaction on the rosin-based phosphate polyether and sodium hydroxide, and substituting hydrogen of hydroxyl by sodium ions to obtain the anionic rosin-based phosphate sodium salt polyether surfactant.

4. The composition of claim 1, wherein the composition comprises: the high-efficiency penetrant is at least one of JFC, JFC-1, JFC-2, JFC-E, JFC-M, fast T, OEP-70, AEP and low-foam penetrant SF.

5. The composition of claim 1, wherein the composition comprises: the emulsifier is at least one of E-1003, E-1006, MOA-5, MOA-7, L64, E1310, E1308, peregal O, NPE-105, NPE-108, Tween 20, Tween 60 and Tween 80.

6. The composition of claim 1, wherein the composition comprises: the organic auxiliary agent is any one or more of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether.

7. The composition of claim 1, wherein the composition comprises: the chelating agent is one or more of ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, tetrasodium ethylenediamine tetraacetic acid, citric acid, sodium citrate, glucose, sodium gluconate, sodium tripolyphosphate and 18-crown-6.

8. The composition of claim 1, wherein the composition comprises: the high-purity water is deionized water, and the conductivity of the high-purity water at 25 ℃ is not lower than 18 MOmega.

9. The method for preparing the composition for cleaning the solid wax of the semiconductor chip according to claim 1, wherein the composition comprises: firstly adding anionic rosin-based phosphate sodium salt polyether surfactant, efficient penetrant and emulsifier into high-purity water, then adding organic auxiliary agent, forming a uniform system at the stirring speed of 200rpm, and then adding chelating agent while stirring to finally obtain a uniform, stable, clear and transparent solution.

Technical Field

The invention belongs to the technical field of surfactants, and particularly relates to a chemical preparation used in the field of semiconductors, which is used for cleaning semiconductor chip solid wax.

Background

Before the semiconductor chip packaging test, one surface of the functional area needs to be coated with solid wax, and the functional area is fixed on a grinding disc under the pressure, so that the exposed surface of the chip is ground and polished. And after grinding and polishing, cleaning by using a solid wax cleaning agent to recover the intrinsic functional surface of the chip. The solid wax used in the industry at present contains long-chain fatty acids, rosin and modified rosin derivatives as main components.

The solid wax cleaning agent on the market mostly adopts solvent oil containing aromatic derivatives, and because the aromatic derivatives and rosin derivatives have more similar structures, the cleaning effect on the rosin derivatives can be enhanced except the dissolving effect of hydrocarbon on paraffin, but the cleaning of subsequent chemicals is needed, so that the purpose of thoroughly cleaning dirt can be achieved. Patent CN 109679790A discloses a cleaning agent for bonding wax of semiconductor chip, which adopts C8 hydrocarbon solvent or C9 hydrocarbon solvent 5-10%, C10 hydrocarbon solvent, C11 hydrocarbon solvent or C12 hydrocarbon solvent 50-70%, C13 hydrocarbon solvent or C14 hydrocarbon solvent 5-10%, dipropylene glycol dimethyl ether 20-30%, all components are mutually matched to dissolve solid wax. The solvent type solid wax cleaning agent has the problems of complex cleaning process, low efficiency, irritant odor of solvent oil compounds, harm to human bodies, flammability and explosiveness, potential safety hazard, difficulty in treating waste liquid, increase of use cost and the like. The water-based solid wax cleaning agent is adopted, and the anionic rosin-based phosphate ester sodium salt polyether surfactant, the high-efficiency penetrating agent and the emulsifier are mixed, so that the solid wax can be swelled, broken and separated from the surface of the chip, and is quickly emulsified and dissolved, the problems of environmental protection and safety of solvent type products on the market are solved, and the cleaning agent is easy to clean and has no residue.

Disclosure of Invention

The invention mainly solves the technical problem of providing the composition for cleaning the solid wax of the semiconductor chip, and the composition can enable the solid wax to swell, break and separate from the surface of the chip and quickly emulsify and dissolve by mixing the anionic rosin-based phosphate sodium salt polyether surfactant, the high-efficiency penetrating agent and the emulsifying agent, solves the problems of environmental protection and safety of solvent type products on the market, and is easy to clean and free of residues.

In order to solve the above problems, the present invention is implemented by the following technical solutions.

The composition for cleaning the semiconductor chip solid wax comprises the following components in percentage by mass, wherein the sum of the mass percentages is 100%: 9-12% of anionic rosin-based phosphate sodium salt polyether surfactant, 0.5-2% of high-efficiency penetrating agent, 0.1-5% of emulsifier, 0.1-1% of chelating agent, 1-5% of organic auxiliary agent and the balance of high-purity water.

The anionic rosin-based phosphate sodium salt polyether surfactant is selected from the following structures:

at least one of surfactants, wherein n is an integer between 0 and 6 and m is an integer between 2 and 6.

The preparation method of the anionic rosin-based phosphate sodium salt polyether surfactant comprises the following steps:

1) synthesis of rosin acyl chloride 2:

phosphorus trichloride and chloroform were placed in a dry three-necked round bottom flask equipped with a magnetic stirrer, condenser and addition funnel. The chloroform solution dissolved with abietic acid 1 was added dropwise to a three-necked flask and stirred. The mixture was reacted at 65 ℃ for 3 hours, cooled to room temperature, and then distilled under reduced pressure. A viscous light liquid rosin acid chloride 2 was obtained.

2) Synthesis of rosin ester 4:

diol compound 3 was placed in a three-necked round bottom flask equipped with a magnetic stirrer, condenser, and addition funnel. Then, a chloroform solution containing rosin acid chloride 2 dissolved therein was added dropwise to the three-necked flask, and the reaction mixture was stirred at room temperature for 1 hour and then heated under reflux for 2 hours. The solvent was removed by distillation under reduced pressure. A viscous liquid rosin ester 4 was obtained.

Wherein n is an integer between 0 and 6.

3) Synthesis of rosin-based phosphate 5:

rosin ester 4 was dissolved in chloroform and placed in a reaction flask, heated with a magnetic stirrer and refluxed. PPA polyphosphate was added dropwise to the reaction flask. The mixture was then heated to reflux with stirring for 4-6 hours. Then, the excess PPA was washed with distilled water, the solvent was removed by distillation under reduced pressure, and dried to obtain a yellow viscous liquid, rosinyl phosphate 5.

Wherein n is an integer between 0 and 6.

4) Synthesizing rosin-based phosphate polyether 7:

dissolving rosin-based phosphate 5 in chloroform, placing the solution in a three-neck flask provided with a stirring and refluxing device, adding triethylene diamine, dropwise adding polyether 6 into the system, and reacting for 3 hours at the constant temperature of 80 ℃. After the reaction is finished, carrying out reduced pressure distillation to obtain colorless transparent liquid, namely the rosin-based phosphate polyether 7.

5) Synthesis of anionic rosin-based phosphate sodium salt polyether surfactant 8:

and (3) performing saponification reaction on the rosin-based phosphate polyether 7 and sodium hydroxide according to the ratio of 1:1, and substituting hydrogen of hydroxyl by sodium ions to obtain the anionic rosin-based phosphate sodium salt polyether surfactant 8.

The rosin group in the anionic rosin-based phosphate sodium salt polyether surfactant is similar to and compatible with the structure of wax, and can dissolve various components in the wax; the alkyl acid ester structure has low surface tension, is combined with wax, has strong permeability, is environment-friendly and is easy to degrade; the phosphate structure has excellent emulsibility, and wax can be emulsified to form water-soluble emulsion; the polyether chain can adjust the hydrophilic and lipophilic properties of the surfactant, so that the activity of the surfactant is improved, and the hydrophilic and lipophilic properties of the surfactant are adjusted by adjusting the EO amount in the polyether chain, so that the lipophilic end can more easily react with the solid wax, and the cleaning speed and the cleaning effect of the solid wax are improved.

The high-efficiency penetrant is at least one of JFC, JFC-1, JFC-2, JFC-E, JFC-M, fast T, OEP-70, AEP and low-foam penetrant SF.

The emulsifier is at least one of E-1003, E-1006, MOA-5, MOA-7, L64, E1310, E1308, peregal O, NPE-105, NPE-108, Tween 20, Tween 60 and Tween 80.

The organic auxiliary agent is any one or more of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether.

The chelating agent is one or more of ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, tetrasodium ethylenediamine tetraacetic acid, citric acid, sodium citrate, glucose, sodium gluconate, sodium tripolyphosphate and 18-crown-6.

The high-purity water is deionized water, and the conductivity of the high-purity water at 25 ℃ is not lower than 18 MOmega.

The preparation method of the composition comprises the following steps: firstly adding anionic rosin-based phosphate sodium salt polyether surfactant, efficient penetrant and emulsifier into high-purity water, then adding organic auxiliary agent, forming a uniform system at the stirring speed of 200rpm, and then adding chelating agent while stirring to finally obtain a uniform, stable, clear and transparent solution.

The invention has the following remarkable advantages:

by adding anionic rosin-based phosphate sodium salt polyether surfactant, rosin groups in the surfactant are similar to and dissolved in the structure of the wax, so that various components in the wax can be dissolved; the alkyl acid ester structure has low surface tension, is combined with wax, has strong permeability, is environment-friendly and is easy to degrade; the phosphate structure has excellent emulsibility, and wax can be emulsified to form water-soluble emulsion; the polyether chain can adjust the hydrophilic and lipophilic properties of the surfactant, so that the activity of the surfactant is improved, and the hydrophilic and lipophilic properties of the surfactant are adjusted by adjusting the EO amount in the polyether chain, so that the lipophilic end can more easily react with the solid wax, and the cleaning speed and the cleaning effect of the solid wax are improved. The components in the composition are matched with each other, so that the solid wax on the semiconductor chip can swell and break to separate from the surface of the chip, and is quickly emulsified and dissolved, the problems of complex cleaning process, low efficiency, environmental protection and safety existing in solvent type products on the market are solved, and meanwhile, the composition is non-toxic and non-corrosive, has small smell, does not pollute the environment, and has the characteristics of low foam, easy rinsing and the like.

Detailed Description

The composition for cleaning the semiconductor chip solid wax comprises the following components in percentage by mass, wherein the sum of the mass percentages is 100%: 9-12% of anionic rosin-based phosphate sodium salt polyether surfactant, 0.5-2% of high-efficiency penetrating agent, 0.1-5% of emulsifier, 0.1-1% of chelating agent, 1-5% of organic auxiliary agent and the balance of high-purity water.

The anionic rosin-based phosphate sodium salt polyether surfactant is selected from the following structures:

at least one of surfactants, wherein n is an integer between 0 and 6 and m is an integer between 2 and 6.

The preparation method of the anionic rosin-based phosphate sodium salt polyether surfactant comprises the following steps:

1) synthesis of rosin acyl chloride 2:

phosphorus trichloride (0.01mol) and chloroform (20mL) were placed in a dry 250mL three-necked round bottom flask equipped with a magnetic stirrer, condenser and addition funnel. A chloroform (100mL) solution containing abietic acid 1(0.01mol) was added dropwise to a 250mL three-necked flask and stirred. The mixture was reacted at 65 ℃ for 3 hours, cooled to room temperature, and then distilled under reduced pressure. Viscous light liquid rosin acyl chloride 2 was obtained in yield: 92.5 percent.

2) Synthesis of rosin ester 4:

diol compound 3(0.01mol) was placed in a 250ml three necked round bottom flask equipped with a magnetic stirrer, condenser and addition funnel. Then 100ml of HCl solution containing rosin acyl chloride 2(0.01mol)₃Added dropwise to a three-necked flask, and the reaction mixture was stirred at room temperature for 1 hour and then heated under reflux for 2 hours. The solvent was removed by distillation under reduced pressure. A viscous liquid rosin ester 4 was obtained in a yield of 90.2%.

Wherein n is an integer between 0 and 6.

3) Synthesis of rosin-based phosphate 5:

rosin ester compound 4(0.01mol) was dissolved in 100mL of chloroform and placed in a 250mL reaction flask, heated with a magnetic stirrer and refluxed. Polyphosphoric acid (PPA 0.01mol) was added dropwise to a 250mL reaction flask. The mixture was then heated to reflux with stirring for 4-6 hours. Then, the excess PPA was washed with distilled water, the solvent was removed by distillation under reduced pressure, and dried to obtain a yellow viscous liquid, rosinyl phosphate 5, with a yield of 82.8%.

Wherein n is an integer between 0 and 6.

4) Synthesizing rosin-based phosphate polyether 7:

rosin phosphate 5(0.01mol) is dissolved in 100mL of chloroform and placed in a three-neck flask with a stirring and refluxing device, triethylene diamine is added, polyether 6 is dripped into the system, and the reaction is carried out for 3 hours at the constant temperature of 80 ℃. After the reaction is finished, carrying out reduced pressure distillation to obtain colorless transparent liquid, namely the rosin-based phosphate polyether 7, wherein the yield is 88%.

5) Synthesis of anionic rosin-based phosphate sodium salt polyether surfactant 8:

rosin-based phosphate ester polyether 7 and sodium hydroxide are subjected to saponification reaction in a ratio of 1:1, and hydrogen of hydroxyl is replaced by sodium ions to obtain the anionic rosin-based phosphate ester sodium salt polyether surfactant 8, wherein the yield is 85%.

The characterization data for compound 8 when n is 2 and m is 4 for the anionic rosin-based phosphate sodium salt polyether surfactant used is as follows:

¹H NMR(300MHz，DMSO-d6),δ:0.86(d,6H,CH3),1.19-1.44(m,CH2,2H),1.27(m,1H,CH),1.27(s,3H,CH3),1.38-1.63(m,2H,CH2),1.43-1.53(m,2H,CH2),1.61(t,2H,CH2),1.70(t,2H,CH2),1.76(m,1H,CH),1.76-2.01(m,2H,CH2),1.90(m,1H,CH),1.94-2.19(m,2H,CH2),2.32-2.48(m,2H,CH2),2.38(m,1H,CH),3.40(s,3H,CH3),3.52(m,14H,CH2),3.55(t,2H,CH2),3.72(t,2H,CH2),4.04(m,2H,CH2),4.06(t,2H,CH2),4.20(m,2H,CH2),5.50(s 1H,＝CH),5.75(s,1H,＝CH).

¹³C NMR(125MHz，DMSO-d6),δ:20,21.9,24.7,25.8,26.0,26.3,28.1,30.7,34.8,37.5,43.1,43.5,59.3,65.5,66.1,70,70.1,70.4,71.6,122.4,135.5,146,177.9.

HRMS Calculation C34H59O11P (M + H)⁺674.79, found 674.45.

The corresponding yield in the above reaction process is that in the preparation of n-2, m-4, compound 8.

The rosin group in the anionic rosin-based phosphate sodium salt polyether surfactant is similar to and compatible with the structure of wax, and can dissolve various components in the wax; the alkyl acid ester structure has low surface tension, is combined with wax, has strong permeability, is environment-friendly and is easy to degrade; the phosphate structure has excellent emulsibility, and wax can be emulsified to form water-soluble emulsion; the polyether chain can adjust the hydrophilic and lipophilic properties of the surfactant, and the activity of the surfactant is improved.

The high-efficiency penetrant is at least one of JFC, JFC-1, JFC-2, JFC-E, JFC-M, fast T, OEP-70, AEP and low-foam penetrant SF.

The emulsifier is at least one of E-1003, E-1006, MOA-5, MOA-7, L64, E1310, E1308, peregal O, NPE-105, NPE-108, Tween 20, Tween 60 and Tween 80.

The organic auxiliary agent is any one or more of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, ethylene glycol, propylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether and propylene glycol monobutyl ether.

The chelating agent is one or more of ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, tetrasodium ethylenediamine tetraacetic acid, citric acid, sodium citrate, glucose, sodium gluconate, sodium tripolyphosphate and 18-crown-6.

The high-purity water is deionized water, and the conductivity of the high-purity water at 25 ℃ is not lower than 18 MOmega.

The preparation method of the composition comprises the following steps: firstly adding anionic rosin-based phosphate sodium salt polyether surfactant, efficient penetrant and emulsifier into high-purity water, then adding organic auxiliary agent, forming a uniform system at the stirring speed of 200rpm, and then adding chelating agent while stirring to finally obtain a uniform, stable, clear and transparent solution.

In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.

Detergent compositions of different compositions were formulated according to the formulations in table 1.

TABLE 1 Components and their contents in different cleaning agent compositions

The chips coated with the solid wax were respectively immersed in the cleaning agent compositions prepared in examples 1 to 4 and comparative examples 1 to 5, cleaned at a set operating temperature for a set operating time, taken out, cleaned with deionized water, and blown dry with nitrogen. The operating conditions and results are shown in Table 2.

TABLE 2 cleaning Effect of different cleaning agent compositions on solid wax on chip

As can be seen from the combination of tables 1-2, the cleaning agent combination of the invention can effectively remove the solid wax on the chip within the set temperature and time, and obtain a solution with uniform dissolution, and is easy to rinse without residue.

Compared with example 1, comparative example 1 does not contain anionic rosin-based phosphate disodium salt gemini surfactant, the wax on the surface of the chip cannot be cleaned at the operating temperature and within the operating time, and a large amount of solid wax remains.

Compared with example 1, comparative example 2 contains no high efficiency penetrant, most of the solid wax is cleaned up at the operation temperature and time, and a small amount of the solid wax remains on the surface of the chip.

In comparison with example 1, comparative example 3 contains no emulsifier, and the solid wax comes off the surface of the chip at the operating temperature and time without completely emulsifying and dissolving.

In comparison with example 1, comparative example 4 contains no chelating agent, and the solid wax was peeled off from the chip surface and a small amount of the solid wax was back-adhered to the chip surface at the operating temperature and time.

Compared with the example 1, the comparative example 5 does not contain organic additives, and the solid falls off and dissolves in the operation temperature and time, so that oil stains are left on the surface of the chip.

As can be shown by the above example 1 and comparative examples 1-5, the anionic rosinyl phosphate disodium salt gemini surfactant, the penetrating agent and the emulsifying agent interact with each other to peel off and emulsify and dissolve the solid wax on the surface of the chip, the organic auxiliary agent has the function of assisting cleaning, the chelating agent has the functions of resisting static electricity and preventing dirt from being sticky back, and each component is not necessary.

The above embodiments describe the present invention in detail, but they are only examples and do not limit the scope of the invention. All equivalent modifications and substitutions made by the present specification are within the scope of the present invention and are included in the patent protection scope of the present invention.