Fluorine-containing compound, coolant containing fluorine-containing compound and application of fluorine-containing compound

文档序号：372955 发布日期：2021-12-10 浏览：47次中文

阅读说明：本技术 一种含氟化合物、包含其的冷却剂及用途 (Fluorine-containing compound, coolant containing fluorine-containing compound and application of fluorine-containing compound ) 是由曾一铮刘星米欣于 2021-09-30 设计创作，主要内容包括：本发明涉及一种含氟化合物、包含其的冷却剂及用途。所述冷却剂,包含本发明所述的含氟化合物,且所述冷却剂的沸程为120～140℃,适合于半导体最高制程温度在70～90℃的制程单元。本申请提供的含氟化合物倾点和沸点合适,流动性、导热系数和比热都适合用作半导体制程的冷却剂成分,且温室效应潜能值和臭氧破坏潜能值较低,对环境破坏小。(The invention relates to a fluorine-containing compound, a coolant containing the fluorine-containing compound and application of the fluorine-containing compound. The coolant contains the fluorine-containing compound, has a boiling range of 120-140 ℃, and is suitable for a processing unit with the highest processing temperature of a semiconductor being 70-90 ℃. The fluorine-containing compound provided by the application has proper pour point and boiling point, and the fluidity, the thermal conductivity coefficient and the specific heat are all suitable for being used as the coolant components in the semiconductor manufacturing process, and the fluorine-containing compound has lower greenhouse effect potential and ozone destruction potential and has small environmental damage.)

1. A fluorochemical compound, wherein said fluorochemical compound has the structure:

2. a process for the preparation of a fluorochemical according to claim 1, said process comprising the steps of:

(1) adding H into hexafluoropropylene at-30-50 deg.c in methanol water solution₂O₂Carrying out nucleophilic oxidation reaction with KOH to obtain perfluoroepoxypropane;

(2) adding the perfluoroepoxypropane obtained in the step (1) into an aprotic solvent, and adding an alkali metal fluoride as a catalyst to obtain an oligomer with one end of acyl fluoride;

(3) adding the oligomer with one end of acyl fluoride obtained in the step (2) into an alkali solution for hydrolysis, and heating to remove carbon dioxide to obtain a hydrogen-containing fluorooxa straight-chain alkane mixture;

(4) distilling the mixture of the hydrogen-containing fluorooxa straight-chain alkane obtained in the step (3) to leave a fraction with a boiling point of 124-126 ℃ to obtain the fluorine-containing compound of claim 1;

preferably, after the fraction with the boiling point of 124-126 ℃ is left in the step (4), drying the fraction;

preferably, said drying treatment comprises adding a drying agent to said fraction.

3. A coolant, characterized in that the coolant comprises the fluorine-containing compound according to claim 1, or the coolant comprises the fluorine-containing compound produced by the production method according to claim 2;

the coolant further comprises 20 wt% or less of a linear oxaalkane auxiliary grafted with a perfluoro-substituted alkane group, the linear oxadecane auxiliary grafted with a hydrogen atom, the hydrogen atom, and the hydrogen atom;

the boiling range of the coolant is 120-140 ℃.

4. The coolant according to claim 3, wherein the coolant comprises 80 wt% or more of the fluorine-containing compound according to claim 1, 17 to 19 wt% of a linear oxaalkane auxiliary having at least one hydrogen atom grafted with a perfluoro-substituted alkane group; the linear oxaalkane assistant grafted with the perfluoro-substituted alkane group and containing at least one hydrogen atom is trioxadecane grafted with the perfluoro-substituted alkane group and containing at least one hydrogen atom, and the linear oxaalkane assistant grafted with the perfluoro-substituted alkane group and containing at least one hydrogen atom is used in a mass ratio of 1: 0.9-1: 1.1.

5. The coolant according to claim 3 or 4, wherein the linear oxaalkane having at least one hydrogen atom grafted with a perfluoro-substituted alkane group has 1 to 2 hydrogen atoms in the molecule;

further preferably, the linear oxaalkane containing at least one hydrogen atom grafted with a perfluoro-substituted alkane group is 2-hydro-perfluoro-5, 8-dimethyl-3, 6, 9-trioxadecane and 2-hydro-perfluoro-5, 8-dimethyl-3, 6, 9-trioxadecane in a mass ratio of 1:0.9 to 1: 1.1.

6. The coolant of any one of claims 3 to 5, further comprising 0.02 to 0.07 wt% of a nanofluid;

preferably, the nanofluid comprises a silane coupling agent modified fumed silica;

preferably, the silane coupling agent includes at least one of hexamethyldisilazane, hexamethylvinyl silazane, or a combination of at least two thereof.

7. The coolant according to any one of claims 3 to 6, wherein the coolant further comprises less than 10 wt% of 2-hydro-perfluoro-oxatetradecane grafted with an alkyl group, preferably 1 to 3 wt% of 2-hydro-perfluoro-5, 8, 11-trimethyl-3, 6,9, 12-tetraoxatetradecane.

8. The coolant according to any one of claims 3 to 7, wherein the coolant comprises the following components in percentage by weight:

preferably, the coolant comprises the following components in percentage by weight:

9. use of the coolant according to any one of claims 3 to 8 as a coolant for etching substrates in semiconductor processing;

preferably, in the semiconductor manufacturing process, the heat of the etching substrate is taken away by helium, the helium carrying the heat exchanges heat with a coolant to cool the etching substrate, and the coolant after heat exchange is circularly refrigerated;

preferably, the highest temperature of the etching substrate in the semiconductor manufacturing process is less than or equal to 90 ℃.

10. A semiconductor processing device, characterized in that, a helium input pipeline for introducing helium into the space of the processing unit and a helium output pipeline for circulating the gas in the space of the processing unit are arranged in the processing unit with the highest processing temperature below 90 ℃, the helium input pipeline and the helium output pipeline are communicated to form a helium circulating pipeline outside the processing unit, the helium circulating pipeline passes through the inside of a cooling liquid circulating pipeline and is used for exchanging heat between the helium in the pipeline and the cooling liquid in the cooling liquid circulating pipeline, and the cooling agent according to any one of claims 3 to 8 is filled in the cooling liquid circulating pipeline.

Technical Field

The invention belongs to the field of cooling, and particularly relates to a fluorine-containing compound, a coolant containing the fluorine-containing compound and application of the fluorine-containing compound.

Background

The semiconductor process includes wafer making, chip making and post-packaging, and the chip making includes the steps of oxide layer growth, patterning, etching, cleaning and stoving, film growth, ion implantation, etc. In the patterning process, steps of coating photoresist, exposing, developing, baking and the like are generally included; in the etching step, removing the patterned specific region, including plasma etching and the like; the film growth mode comprises metal deposition, copper process deposition, chemical vapor deposition, physical deposition and the like; ion implantation is generally used to create PN junctions and improve conductivity between the collector and emitter of the transistor.

In the whole semiconductor manufacturing process, the temperature of the manufacturing process is greatly changed, especially for the etching and film growth stages, the temperature of a chip to be processed is high, and the chip needs to be cooled, while different processing units have different processing temperatures, the boiling range of the coolant is too high, which can provide enough cooling effect, but causes damage to the environment, and the boiling range of the coolant is too low, which cannot provide enough cooling effect.

There is a need in the art to develop a coolant that can be used at a specific process temperature for a semiconductor process, that can provide a sufficient cooling effect, and that is environmentally friendly.

Disclosure of Invention

In view of the deficiencies of the prior art, it is an object of the present invention to provide a fluorochemical compound having the structure:

the fluorine-containing compound contains a small amount of hydrogen atoms, greatly reduces GWP (greenhouse potential) and ODP (ozone destruction potential), and simultaneously maintains good liquid fluidity, high thermal conductivity and high specific heat.

The second object of the present invention is to provide a method for preparing a fluorine-containing compound according to the first object, comprising the steps of:

(1) in methanol aqueous solution at-30-50 deg.C (such as-35 deg.C, -40 deg.C, -45 deg.C) to hexafluoroPropylene with (30% strength) H₂O₂Carrying out nucleophilic oxidation reaction with KOH to obtain perfluoroepoxypropane;

(2) adding the perfluoroepoxypropane obtained in the step (1) into an aprotic solvent, and adding an alkali metal fluoride as a catalyst to obtain an oligomer with one end of acyl fluoride;

(4) distilling the mixture of the hydrogen-containing fluoro oxa straight-chain alkane obtained in the step (3) and reserving a fraction with the boiling range of 124-126 ℃ to obtain the fluorine-containing compound which is one of the purposes.

Preferably, in the step (4), after a fraction with a boiling point of 124-126 ℃ is left, drying treatment is carried out on the fraction.

Preferably, said drying treatment comprises adding a drying agent to said fraction.

The desiccant is exemplified by water-absorbent silica gel.

The method for preparing the fluorine-containing compound described herein is only one of the methods for preparing the fluorine-containing compound, and those skilled in the art can synthesize or isolate the fluorine-containing compound described herein by other means.

The third object of the present invention is to provide a coolant containing the fluorine-containing compound according to the first object or the fluorine-containing compound produced by the production method according to the second object; the coolant further comprises 20 wt% or less of a linear oxaalkane auxiliary grafted with a perfluoro-substituted alkane group, the linear oxadecane auxiliary grafted with a hydrogen atom, the hydrogen atom, and the hydrogen atom; the boiling range of the coolant is 120-140 ℃ (such as 122-134 ℃, 125-137 ℃, 127-135 ℃ and the like).

The boiling range of the coolant is 120-140 ℃, and the coolant is suitable for cooling a semiconductor process with the highest working temperature below 90 ℃ (such as 60 ℃, 70 ℃, 80 ℃, 85 ℃ and the like). In addition, the coolant has low GWP (greenhouse potential) and ODP (ozone destruction potential), so when the coolant is used for cooling the semiconductor process with the highest process temperature of lower than 70 ℃, the coolant has little damage to the environment. In other words, the coolant of the present invention can be used in semiconductor processes with a maximum process temperature below 90 ℃.

Preferably, the coolant comprises more than 80 wt% of the fluorine-containing compound, 17-19 wt% of a linear oxaalkane auxiliary agent which at least contains one hydrogen atom and is grafted with a perfluoro-substituted alkane group; the linear oxaalkane assistant grafted with the perfluoro-substituted alkane group and containing at least one hydrogen atom is trioxadecane grafted with the perfluoro-substituted alkane group and containing at least one hydrogen atom, and the linear oxaalkane assistant grafted with the perfluoro-substituted alkane group and containing at least one hydrogen atom is used in a mass ratio of 1: 0.9-1: 1.1.

The fluorine-containing compound with the compound chain length of 12 (trioxadecane grafted with perfluoro-substituted alkane groups and at least containing one hydrogen atom) has a similar structure with the fluorine-containing compound with the compound chain length of 10 (trioxadecane grafted with perfluoro-substituted alkane groups and at least containing one hydrogen atom), has good compatibility and can increase the boiling range span, and on the other hand, the fluorine-containing alkane with the compound chain length of 10 (trioxadecane grafted with perfluoro-substituted alkane groups and at least containing one hydrogen atom) can reduce the freezing point, so that the coolant still keeps good fluidity and the cooling efficiency of the coolant is improved when the coolant is cooled to (-20 to-30 ℃).

The content of the fluorine-containing alkane with the chain length of 10 is too high, the lower limit of the boiling range is lower than 120 ℃, the content of the fluorine-containing alkane with the chain length of 10 is too low, and the fluidity is poor when the coolant is cooled; the content of the fluorine-containing alkane with the chain length of 12 is too high, the fluidity of the cooling agent is poor, the content of the fluorine-containing alkane with the chain length of 12 is too low, and the lower limit of the boiling range is lower than 120 ℃.

Preferably, the linear oxaalkane molecule grafted with the perfluoro-substituted alkane group, which contains at least one hydrogen atom, contains 1-2 hydrogen atoms.

Too much hydrogen atom content, easy decomposition of the compound and unstable coolant; the composition does not contain hydrogen atoms, and has great damage to the environment and high GWP.

A trioxadecane structure containing one hydrogen atom grafted with a perfluoro-substituted alkane group of the formula(2-hydro-perfluoro-5, 8-dimethyl-3, 6, 9-trioxadecane); the mixture of trioxadecanes containing one hydrogen atom grafted with a perfluoro-substituted alkane group is(2-hydro-perfluoro-5, 8-dimethyl-3, 6, 9-trioxadecane).

Further preferably, the linear oxaalkane containing at least one hydrogen atom grafted with a perfluoro-substituted alkane group is 2-hydro-perfluoro-5, 8-dimethyl-3, 6, 9-trioxadecane and 2-hydro-perfluoro-5, 8-dimethyl-3, 6, 9-trioxadecane in a mass ratio of 1:0.9 to 1: 1.1.

Preferably, the coolant further comprises 0.02-0.07 wt% of nanofluid.

The nanometer fluid can improve the heat conductivity of the coolant and improve the cooling efficiency, and the nanometer fluid can not volatilize and can not cause the increase of GWP value.

Preferably, the nanofluid comprises a silane coupling agent modified fumed silica.

Preferably, the silane coupling agent includes at least one of hexamethyldisilazane, hexamethylvinyl silazane, or a combination of at least two thereof.

The thermal conductivity of the cooling liquid can be enhanced by adding fumed silica to the cooling liquid. However, the fumed silica particles tend to aggregate together, creating nano-fluid destabilization, thereby losing the effect of increasing the thermal conductivity of the coolant. In the application, the fumed silica is modified by the silane coupling agent, a steric hindrance stabilizing effect is formed around the nano particles, namely, the spatial isolation is formed, the contact among the particles is avoided, and meanwhile, the modified nano fluid is hydrophobic and is easier to disperse in the cooling liquid, so that the purpose of stable dispersion of the nano fluid is achieved, and the thermal conductivity of the cooling liquid is enhanced.

Preferably, the coolant further comprises less than 10 wt% of 2-hydro-perfluoro-oxatetradecane grafted with an alkyl group, preferably 1 to 3 wt% of 2-hydro-perfluoro-5, 8, 11-trimethyl-3, 6,9, 12-tetraoxatetradecane.

The 2-hydrogen-perfluoro-5, 8, 11-trimethyl-3, 6,9, 12-tetraoxatetradecane has the structure

Preferably, the coolant comprises the following components in percentage by weight:

preferably, the coolant comprises the following components in percentage by weight:

it is a fourth object of the present invention to provide a use of the coolant according to the third object as a coolant for etching a substrate in a semiconductor process.

Preferably, in the semiconductor manufacturing process, the heat of the etching substrate is taken away by helium, the helium carrying the heat exchanges heat with a coolant to cool the etching substrate, and the coolant after heat exchange is circularly refrigerated;

preferably, the highest temperature of the substrate etched in the semiconductor process is less than or equal to 90 ℃ (e.g., 60 ℃, 65 ℃, 70 ℃, 80 ℃, 85 ℃, etc.).

The fifth purpose of the present application is to provide a semiconductor processing apparatus, the highest process temperature of the semiconductor processing apparatus is provided with a helium input pipeline for introducing helium into the space of the processing unit and a helium output pipeline for circulating the gas in the space of the processing unit out in the processing unit below 90 ℃, the helium input pipeline and the helium output pipeline are in the external communication of the processing unit to form a helium circulation pipeline, the helium circulation pipeline passes through the inside of the cooling liquid circulation pipeline and is used for exchanging heat between the helium in the pipeline and the cooling liquid in the cooling liquid circulation pipeline, and the cooling agent is filled in the cooling liquid circulation pipeline for the second purpose.

The semiconductor processing platform of the invention includes but is not limited to a stepper (brand such as Nikon, Canon, SML, etc.), Ion Implanter Ion implantation machine (brand such as Nissin Elec, etc. of Nixin), CVD machine (brand such as application material AMAT, Novellus, etc.), D/E dry etching (brand such as east electronic TEL, AMAT, Lam, Hitachi, etc.), IC Tester test (brand such as Edwadada Advantest, Terada Teradyna, etc.), Prober (brand such as TEL, Tokyo precision Tokyo Seimitsu, etc.), Handler (brand such as Advantest, DeltaDelta Design, etc.).

Compared with the prior art, the method has the following beneficial effects:

the fluorine-containing compound provided by the application has proper boiling point and pour point, and is suitable for being used as a coolant component in a semiconductor manufacturing process, and the GWP (greenhouse potential value) and the ODP (ozone destruction potential value) are low, so that the environment is slightly damaged.

In addition, the coolant prepared based on the fluorine-containing compound is suitable for a processing unit with the highest processing temperature of a semiconductor being 70-90 ℃, and has low environmental damage.

Drawings

FIG. 1 is a drawing ofMass spectrogram of (1);

FIG. 2 isMass spectrogram of (1);

FIG. 3 is a drawing showingMass spectrogram of (1);

FIG. 4 is a drawing showingMass spectrum of (2).

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are commercially available.

Preparation example 1

A fluorine-containing compound is providedThe preparation method comprises the following steps:

(1) adding 30% concentration H to 100mL of hexafluoropropylene in a methanol aqueous solution at a volume ratio of 1:1 at-40 deg.C₂O₂Nucleophilic oxidation with KOH, said H₂O₂The mol ratio of the obtained product to KOH is 1:1, and perfluoroepoxypropane is obtained;

(2) adding the perfluoroepoxypropane obtained in the step (1) into 100mL of a diethylene glycol dimethyl ether solvent, and adding 0.02mol of cesium fluoride as a catalyst to obtain an oligomer with one end of acyl fluoride;

(3) adding the oligomer with one end of acyl fluoride obtained in the step (2) into a 1mol/L KOH solution (the addition amount is 1.05 mol parts based on potassium hydroxide) for hydrolysis, and heating to 80-100 ℃ to remove carbon dioxide to obtain a hydrogen-containing fluorooxa straight-chain alkane mixture;

(4) and (3) distilling the hydrogen-containing fluorooxa straight-chain alkane mixture obtained in the step (3), reserving components with a boiling range of 124-126 ℃, adding silica gel for water absorption into the fraction to obtain the fluorine-containing compound of one purpose, and determining the purity to be 98% by gas chromatography-mass spectrometry.

Mass spectrum: the test conditions were: the GC-MSD (Agilent 5977E) is adopted for characterization, the conditions are that the molecular weight scanning range is 10-1000, the ion source temperature is 230 ℃, the quadrupole temperature is 150 ℃, and the characterization result is shown in figure 1.

Preparation example 2

Compound (I)Andcan be prepared by the following method:

(4) distilling the hydrogen-containing fluorooxa straight-chain alkane mixture obtained in the step (3), reserving components with a boiling range of 101-103 ℃, and performing water absorption treatment on the components through silica gel to obtain the hydrogen-containing fluorooxa straight-chain alkane mixtureThe purity is 95 percent; reserving components with the boiling range of 152-154 ℃, and performing water absorption treatment on the components through silica gel to obtain the productThe purity is 97%; reserving components with a boiling range of 183-185 ℃, and performing water absorption treatment on the components through silica gel to obtain the active silicon dioxideThe purity is 95%.

Mass spectrum: the test conditions were: the method is characterized by adopting GC-MSD (Agilent 5977E) under the conditions that the molecular weight scanning range is 10-1000, the ion source temperature is 230 ℃, and the quadrupole temperature is 150 ℃;

the test results are shown in FIG. 2;

the test results are shown in FIG. 3;

the test results are shown in FIG. 4.

Preparation example 3

Preparation of modified fumed silica:

and (3) enabling the fumed silica to be in a fluidized state, introducing nitrogen carrying hexamethylvinyl silazane (maintaining the partial pressure of the hexamethylvinyl silazane at 4-6kPa) into a chamber where the fluidized fumed silica is located, carrying out modification treatment on the fumed silica for 25min, and collecting a product, namely the modified fumed silica.

Example 1