Quantum optical microcavity device based on fluorocarboxylic acid hydrophobic modification and preparation method thereof

Abstract

The invention discloses a quantum optical microcavity device based on fluorocarboxylic acid hydrophobic modification and a preparation method thereof, and relates to the field of organic chemistry and optical engineering. The hydrophobic fluorinated organic carboxylic acid self-assembled monomolecular layer is formed on the surface of the silicon dioxide quantum optical microcavity through chemical reaction between a solution prepared from one or more fluorinated organic carboxylic acid molecules of C3F7COOH, C5F11COOH, C7F15COOH, C9F19COOH or C11F23COOH and an interface of the whispering gallery mode silicon dioxide quantum optical microcavity. Compared with a surface hydrophobic quantum optical microcavity formed by a fluorinated organosilane self-assembled monomolecular layer, the density of molecules formed by fluorinated organic carboxylic acid on the surface of the quantum optical microcavity is larger, and the surface hydrophobic performance of the echo wall mode quantum optical microcavity can be more effectively improved.

Description

Technical Field

[0001] This application relates to the fields of organic chemistry and optical engineering, specifically to a quantum optical microcavity device based on hydrophobic modification of fluorinated carboxylic acids and its fabrication method. Background Technology

[0002] Whispering-gallery mode optical wall devices are resonant devices that localize optical field intensity to a microscale. By confining the optical field to a ring-shaped boundary, continuous total emission of light occurs within the cavity. When the optical path length of the beam around the cavity is matched to an integer multiple of the wavelength, the system generates optical resonance with a high quality factor. Therefore, whispering-gallery mode quantum optical microcavities can effectively modulate broadband pump light, resulting in self-coherent enhancement of the pump light during resonant propagation and ultimately generating an optical frequency comb output. The comb tooth frequency is located in the optical band, while its repetition frequency can extend from the 50 MHz microwave band to the 10 THz terahertz band, thus establishing an interrelationship between light waves, microwaves, and terahertz waves. Therefore, whispering-gallery mode quantum optical microcavities have promising prospects.

[0003] Among microcavity materials, silica is widely used due to its inherent low optical loss and mature fabrication process. However, since silica whispering-gallery mode microcavities are typically exposed to air, the surface hydroxyl groups readily adsorb water molecules from the air, leading to a decrease in the optical stability of silica-based whispering-gallery mode quantum optical microcavity devices. To suppress water adsorption on the surface of silica whispering-gallery mode microcavities and improve device environmental stability, hydrophobic modification of the silica quantum optical microcavity surface is an effective approach. One current effective solution is surface modification based on self-assembled monolayers; however, the molar ratio of the active head groups of the fluorinated organosilane molecules reacting with the hydroxyl groups on the silica quantum optical microcavity surface is 1:3, resulting in a low surface coverage density of the fluorinated organosilanes. Therefore, there is a need to develop a high-coverage-density self-assembled monolayer modified whispering-gallery mode silica quantum optical microcavity device. Summary of the Invention

[0004] To address the problems existing in the prior art, this application provides a quantum optical microcavity device based on hydrophobic modification of fluorinated carboxylic acids and its preparation method. Through the interfacial chemical reaction between the fluorinated organic carboxylic acid solution and the whispering-gallery mode silica quantum optical microcavity, a hydrophobic self-assembled monolayer is formed on the surface of the silica quantum optical microcavity, thus solving the problem of low coverage density of hydrophobic molecules on the surface of the silica quantum optical microcavity.

[0005] To achieve the above objectives, this application provides the following technical solution: This application provides a quantum optical microcavity device based on hydrophobic modification of fluorinated carboxylic acids, comprising: Whispering-gallery mode quantum optical microcavity; A fluorinated organic carboxylic acid monolayer is attached to the surface of the whispering-gallery mode quantum optical microcavity via a chemical reaction, and the fluorinated organic carboxylic acid monolayer inhibits water adsorption on the surface of the whispering-gallery mode quantum optical microcavity. Fluorinated organic carboxylic acids are C3F7COOH and C5F7COOH. 11 COOH, C7F 15 COOH, C9F 19 COOH or C 11 F 23 One or more of COOH.

[0006] In some embodiments, the surface material of the whispering-gallery mode quantum optical microcavity is an inorganic silicon oxide compound.

[0007] In some embodiments, the structure of the whispering-gallery mode quantum optical microcavity includes microsphere, microdisk, microwedge, microring, microbottle, or microbubble.

[0008] This application also provides a method for fabricating a quantum optical microcavity device based on hydrophobic modification with fluorinated carboxylic acids, comprising: S1: Prepare the whispering-gallery mode quantum optical microcavity, clean it, and perform surface treatment; S2: Mix the fluorinated organic carboxylic acid with an organic solvent to prepare a fluorinated organic carboxylic acid solution; S3: Immerse the whispering-gallery mode quantum optical microcavity in the fluorinated organic carboxylic acid solution for a chemical reaction, and after cleaning and drying, obtain a quantum optical microcavity device based on hydrophobic modification of fluorinated carboxylic acid.

[0009] In some embodiments, the method for fabricating the whispering-gallery mode quantum optical microcavity in step S1 includes micro / nano fabrication or thermal melting.

[0010] In some embodiments, in step S1, oxygen plasma surface treatment is used, with a treatment power of 80~120W and a treatment time of 5~30min.

[0011] In some embodiments, in step S2, the organic solvent is one or more of toluene, ethanol, acetone, dichloromethane, and ethyl acetate.

[0012] In some embodiments, in step S2, the solute concentration in the fluorinated organic carboxylic acid solution is 10. -3 ~1.0mol / L.

[0013] In some embodiments, in step S3, the chemical reaction is carried out at a temperature of 20~100°C for a reaction time of 0.5~36h.

[0014] In some embodiments, in step S3, the cleaning method includes rinsing or ultrasonic cleaning using one or more of deionized water, ethanol, or acetone.

[0015] This application has the following beneficial effects: This application utilizes fluorinated organic carboxylic acids to surface-modify silica whispering-gallery mode quantum optical microcavity devices, forming a hydrophobic self-assembled monolayer on the silica quantum optical microcavity surface. The carboxyl groups of the fluorinated organic carboxylic acid react with the hydroxyl groups of the carbon dioxide quantum optical microcavity in a 1:1 molar ratio, significantly increasing the coverage density of hydrophobic molecules on the silica quantum optical wall surface. This effectively enhances the hydrophobic properties of the device and strengthens its optical stability. Attached Figure Description

[0016] Various other advantages and benefits will become apparent to those skilled in the art upon reading the following detailed description of preferred embodiments. The accompanying drawings are for illustrative purposes only and are not intended to limit the scope of this application. Furthermore, the same reference numerals denote the same parts throughout the drawings. In the drawings: Figure 1 This is a schematic diagram illustrating the mechanism of the chemical reaction between fluorinated organic carboxylic acid molecules and the surface of a silicon dioxide quantum optical microcavity in this application; Figure 2 This is a schematic diagram showing the connection between fluorinated organic carboxylic acid molecules and the surface of a whispering-gallery mode quantum optical microcavity in this application via chemical bonds; Figure 3 This is a comparative schematic diagram showing the formation of self-assembled monolayers on the surface of a silicon dioxide quantum optical microcavity by fluorinated organic carboxylic acid molecules and fluorinated organosilane molecules in this application. Detailed Implementation

[0017] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0018] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0019] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0020] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0021] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0022] Unless otherwise specified, the technical solutions described in this invention are conventional solutions in the art; unless otherwise stated, the raw materials and reagents used in the following embodiments are commercially available products, or can be prepared by conventional methods in the art. The technical solutions provided by this invention are described in detail below with reference to embodiments, but they should not be construed as limiting the scope of protection of this invention.

[0023] This application provides a quantum optical microcavity device based on hydrophobic modification of fluorinated carboxylic acids, comprising: Whispering-gallery mode quantum optical microcavity; A fluorinated organic carboxylic acid monolayer is attached to the surface of a whispering-gallery mode quantum optical microcavity via a chemical reaction. The fluorinated organic carboxylic acid monolayer is connected to the surface of the whispering-gallery mode quantum optical microcavity through chemical bonds, such as... Figure 2 As shown, a monolayer of fluorinated organic carboxylic acids suppresses water adsorption on the surface of a whispering-gallery mode quantum optical microcavity.

[0024] Fluorinated organic carboxylic acids are C3F7COOH and C5F7COOH. 11 COOH, C7F 15 COOH, C9F 19 COOH or C 11 F 23 One or more of COOH. The surface material of the whispering-gallery mode quantum optical microcavity is an inorganic silicon oxide compound, while the whispering-gallery mode quantum optical microcavity is a silicon dioxide quantum optical microcavity. The chemical reaction mechanism between the above-mentioned fluorinated organic carboxylic acids and the surface of the quantum optical microcavity is as follows: Figure 1As shown. The structures of whispering-gallery mode quantum optical microcavities include microspheres, microdisks, microwedges, microrings, microbottles, or microbubbles.

[0025] In existing technologies, when fluorinated organosilanes react with the hydroxyl groups on the surface of silica quantum optical microcavities, the molar ratio of the active head groups of the fluorinated organosilane molecules to the hydroxyl groups on the silica surface is typically 1:3, and sometimes even lower. This results in insufficient hydrophobic modification and limited hydrophobic or antifouling properties. This application uses fluorinated organocarboxylic acids to hydrophobically modify the surface of the quantum optical microcavities. When the carboxyl groups of the fluorinated organocarboxylic acids react with the hydroxyl groups on the silica quantum optical microcavities, the molar ratio is 1:1, forming an intermediate transition state. At this point, proton transfer occurs between the carboxyl groups and the hydroxyl groups on the silica surface, and the transition state undergoes a dehydration reaction. Ultimately, the fluorinated organocarboxylic acid molecules are connected to the silica quantum optical microcavity surface through chemical bonds, resulting in more thorough hydrophobic modification. This significantly increases the coverage density of hydrophobic molecules on the silica quantum optical microcavity surface, effectively improving the hydrophobic performance of the device and enhancing its optical stability.

[0026] Example 1 This embodiment provides a method for fabricating an optical microcavity device based on hydrophobic modification of C3F7COOH, wherein C3F7COOH is perfluorobutyric acid with a relative molecular mass of 214.0388 g / mol and the structural formula is: .

[0027] The specific steps are as follows: (1) A carbon dioxide laser with an output wavelength of 1550 nm was used to melt fiber tapers to sinter silica microspheres with a diameter of 50 μm; (2) Transfer the glass slide containing at least one silica microsphere obtained in step (1) into a beaker, and clean it with deionized water, ethanol and acetone in sequence for 5 min with ultrasonic cleaning. After heating, dry it with high pressure nitrogen. (3) Transfer the glass slide containing at least one silica microsphere obtained in step (2) into a plasma cleaner, set the power to 90W, set the processing time to 12min, introduce oxygen at an appropriate flow rate and start the processing, and remove the glass slide from the plasma cleaner after the processing is completed. (4) Weigh 0.54g of C3F7COOH into a 50mL beaker, add 5mL of ethyl acetate, stir thoroughly to form a solution with a concentration of 1mol / L, and pour an appropriate volume of the solution into a glass petri dish; (5) Immerse the glass slide containing at least one silica microsphere obtained in step (3) in the glass culture dish containing the C3F7COOH ethyl acetate solution obtained in step (4), place the glass culture dish in an oven, set the temperature to 45°C, maintain the constant temperature for 30 hours, cool to room temperature and take it out. (6) Use ethanol to rinse and clean the glass slide carrying at least one silica microsphere obtained in step (5), and then place it in a vacuum drying oven to dry it, so as to obtain a C3F7COOH modified silica surface hydrophobic microsphere cavity device.

[0028] Example 2 This embodiment provides a C5F 11 A method for fabricating hydrophobic microsphere cavity devices on COOH-modified silica surfaces, wherein C5F 11 COOH perfluorohexanoic acid, with a relative molecular mass of 314.0544 g / mol, has the following structural formula: .

[0029] The specific steps are as follows: (1) A carbon dioxide laser with an output wavelength of 1550 nm was used to melt fiber tapers to sinter silica microspheres with a diameter of 50 μm; (2) Transfer the glass slide containing at least one silica microsphere obtained in step (1) into a beaker, and clean it with deionized water, ethanol and acetone in sequence for 5 min with ultrasonic cleaning. After heating, dry it with high pressure nitrogen. (3) Transfer the glass slide containing at least one silica microsphere obtained in step (2) into a plasma cleaner, set the power to 90W, set the processing time to 12min, introduce oxygen at an appropriate flow rate and start the processing, and remove the glass slide from the plasma cleaner after the processing is completed. (4) Weigh 0.79g of C5F 11 Add COOH to a 50mL beaker, add 5mL of ethyl acetate, stir thoroughly to form a 1mol / L solution, and pour an appropriate volume of the solution into a glass petri dish. (5) Immerse the glass slide containing at least one silica microsphere obtained in step (3) in the glass culture dish containing the C5F11COOH ethyl acetate solution obtained in step (4), place the glass culture dish in an oven, set the temperature to 45°C, maintain the constant temperature for 30 hours, cool to room temperature and take it out. (6) Rinse the glass slide containing at least one silica microsphere obtained in step (5) with ethanol, and then place it in a vacuum drying oven to dry, to obtain C5F. 11 Hydrophobic microsphere cavity devices with COOH-modified silica surfaces.

[0030] Example 3 This embodiment provides a C7F 15 A method for fabricating hydrophobic microsphere cavity devices on COOH-modified silica surfaces, wherein C7F 15 COOH is perfluorooctanoic acid, with a relative molecular mass of 414.0700 g / mol, and its structural formula is: .

[0031] The specific steps are as follows: (1) A carbon dioxide laser with an output wavelength of 1550 nm was used to melt fiber tapers to sinter silica microspheres with a diameter of 50 μm; (2) Transfer the glass slide containing at least one silica microsphere obtained in step (1) into a beaker, and clean it with deionized water, ethanol and acetone in sequence for 5 min with ultrasonic cleaning. After heating, dry it with high pressure nitrogen. (3) Transfer the glass slide containing at least one silica microsphere obtained in step (2) into a plasma cleaner, set the power to 90W, set the processing time to 12min, introduce oxygen at an appropriate flow rate and start the processing, and remove the glass slide from the plasma cleaner after the processing is completed. (4) Weigh 1.04g of C7F 15 Add COOH to a 50mL beaker, add 5mL of ethyl acetate, stir thoroughly to form a 1mol / L solution, and pour an appropriate volume of the solution into a glass petri dish. (5) Place the glass slide containing at least one silica microsphere obtained in step (3) into the slide containing C7F obtained in step (4). 15 Immerse the glass petri dishes in ethyl COOH solution, place the glass petri dishes in an oven, set the temperature to 45℃, maintain the constant temperature for 30 hours, then cool to room temperature and remove them; (6) Rinse the glass slide containing at least one silica microsphere obtained in step (5) with ethanol, and then place it in a vacuum drying oven to dry, to obtain C7F. 15 Hydrophobic microsphere cavity devices with COOH-modified silica surfaces.

[0032] Example 4 This embodiment provides a C9F 19 A method for fabricating hydrophobic microsphere cavity devices on COOH-modified silica surfaces, wherein C9F 19 COOH is perfluorodecanoic acid, with a relative molecular mass of 514.0857 g / mol, and its structural formula is: .

[0033] The specific steps are as follows: (1) A carbon dioxide laser with an output wavelength of 1550 nm was used to melt fiber tapers to sinter silica microspheres with a diameter of 50 μm; (2) Transfer the glass slide containing at least one silica microsphere obtained in step (1) into a beaker, and clean it with deionized water, ethanol and acetone in sequence for 5 min with ultrasonic cleaning. After heating, dry it with high pressure nitrogen. (3) Transfer the glass slide containing at least one silica microsphere obtained in step (2) into a plasma cleaner, set the power to 90W, set the processing time to 12min, introduce oxygen at an appropriate flow rate and start the processing, and remove the glass slide from the plasma cleaner after the processing is completed. (4) Weigh 1.29g of C9F 19 Add COOH to a 50mL beaker, add 5mL of ethyl acetate, stir thoroughly to form a 1mol / L solution, and pour an appropriate volume of the solution into a glass petri dish. (5) Place the glass slide containing at least one silica microsphere obtained in step (3) into the slide containing C9F obtained in step (4). 19 Immerse the glass petri dishes in ethyl COOH solution, place the glass petri dishes in an oven, set the temperature to 45℃, maintain the constant temperature for 30 hours, then cool to room temperature and remove them; (6) Rinse the glass slide containing at least one silica microsphere obtained in step (5) with ethanol, and then place it in a vacuum drying oven to dry it to obtain C9F. 19 Hydrophobic microsphere cavity devices with COOH-modified silica surfaces.

[0034] Example 5 This embodiment provides a C 11 F 23 A method for fabricating hydrophobic microsphere cavity devices on COOH-modified silica surfaces, wherein C 11 F 23 COOH is perfluorododecanoic acid, with a relative molecular mass of 614.1013 g / mol, and its structural formula is: .

[0035] The specific steps are as follows: (1) A carbon dioxide laser with an output wavelength of 1550 nm was used to melt fiber tapers to sinter silica microspheres with a diameter of 50 μm; (2) Transfer the glass slide containing at least one silica microsphere obtained in step (1) into a beaker, and clean it with deionized water, ethanol and acetone in sequence for 5 min with ultrasonic cleaning. After heating, dry it with high pressure nitrogen. (3) Transfer the glass slide containing at least one silica microsphere obtained in step (2) into a plasma cleaner, set the power to 90W, set the processing time to 12min, introduce oxygen at an appropriate flow rate and start the processing, and remove the glass slide from the plasma cleaner after the processing is completed. (4) Weigh 1.54g C 11 F 23Add COOH to a 50mL beaker, add 5mL of ethyl acetate, stir thoroughly to form a 0.5mol / L solution, and pour an appropriate volume of the solution into a glass petri dish; (5) Place the glass slide containing at least one silica microsphere obtained in step (3) into the slide containing C obtained in step (4). 11 F 23 Immerse the glass petri dishes in ethyl COOH solution, place the glass petri dishes in an oven, set the temperature to 45℃, maintain the constant temperature for 30 hours, then cool to room temperature and remove them; (6) Rinse the glass slide containing at least one silica microsphere obtained in step (5) with ethanol, then place it in a vacuum drying oven to dry, and obtain C. 11 F 23 Hydrophobic microsphere cavity devices with COOH-modified silica surfaces.

[0036] like Figure 3 As shown, traditional hydrophobic modification of the silica quantum optical microcavity surface is based on self-assembled monolayer surface modification. When the active head groups of fluorinated organosilane molecules react with the hydroxyl groups on the silica quantum optical microcavity surface in a molar ratio of 1:3, the surface coverage density of the fluorinated organosilanes is relatively low. In this application, a hydrophobic self-assembled monolayer is formed on the silica surface through an interfacial chemical reaction between a fluorinated organocarboxylic acid solution and the silica quantum optical microcavity. The molar ratio of the carboxyl groups of the fluorinated organocarboxylic acid to the hydroxyl groups on the silica quantum optical microcavity surface is 1:1, significantly increasing the coverage of hydrophobic molecules on the silica quantum optical microcavity surface, effectively improving the hydrophobic performance of the device, and enhancing the optical stability of the quantum optical microcavity device.

[0037] Those skilled in the art will understand that the steps, measures, and solutions in the various operations, methods, and processes discussed in this application can be alternated, modified, combined, or deleted. Furthermore, other steps, measures, and solutions in the various operations, methods, and processes discussed in this application can also be alternated, modified, rearranged, decomposed, combined, or deleted. Furthermore, steps, measures, and solutions in the prior art that are similar to those disclosed in this application can also be alternated, modified, rearranged, decomposed, combined, or deleted.

[0038] The above description is only a partial embodiment of this application. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of this application, and these improvements and modifications should also be considered within the scope of protection of this application.

Claims

1. A quantum optical microcavity device based on hydrophobic modification of fluorocarboxylic acids, characterized in that, The application relates to a quantum optical microcavity device based on fluorocarboxylic acid hydrophobic modification. The quantum optical microcavity device comprises: an echo wall mode quantum optical microcavity; a fluorinated organic carboxylic acid monolayer attached to the surface of the echo wall mode quantum optical microcavity through a chemical reaction, wherein the fluorinated organic carboxylic acid monolayer inhibits water adsorption on the surface of the echo wall mode quantum optical microcavity; and a surface material of the echo wall mode quantum optical microcavity is an inorganic silicon oxide compound. The structure of the echo wall mode quantum optical microcavity comprises a microsphere type, a microdisk type, a micro-wedge type, a micro-ring type, a micro-bottle type or a micro-bubble type. fluoroorganic carboxylic acids are one or more of C3F7COOH, C5F 11 COOH, C7F 15 COOH, C9F 19 COOH or C 11 F 23 COOH.

2. The quantum optical microcavity device based on hydrophobic modification with fluorocarboxylic acid according to claim 1, characterized in that, The application further relates to a preparation method of the quantum optical microcavity device based on fluorocarboxylic acid hydrophobic modification.

3. The quantum optical microcavity device based on hydrophobic modification with fluorocarboxylic acid according to claim 1, characterized in that, The preparation method comprises the following steps: S1, preparing the echo wall mode quantum optical microcavity, cleaning and performing surface treatment; S2, mixing the fluorinated organic carboxylic acid with an organic solvent to prepare a fluorinated organic carboxylic acid solution; and S3, immersing the echo wall mode quantum optical microcavity in the fluorinated organic carboxylic acid solution to perform a chemical reaction, and then cleaning and drying to obtain the quantum optical microcavity device based on fluorocarboxylic acid hydrophobic modification.

4. Process for the production of quantum optical microcavity devices based on hydrophobic modification of fluorocarboxylic acids according to any one of claims 1 to 3, characterized in that, In the step S1, the method for preparing the echo wall mode quantum optical microcavity comprises micro-nano processing or hot melt processing. In the step S1, an oxygen plasma surface treatment is adopted, the treatment power is 80-120 W, and the treatment time is 5-30 min. In the step S2, the organic solvent is one or more of toluene, ethanol, acetone, dichloromethane and ethyl acetate. In the step S3, the chemical reaction is performed at a temperature of 20-100 DEG C, and the reaction time is 0.5-36 h.

5. The method for producing a quantum optical microcavity device based on hydrophobic modification with a fluorocarboxylic acid according to claim 4, characterized by, In the step S3, the cleaning method comprises flushing or ultrasonic cleaning by using one or more of deionized water, ethanol or acetone.

6. The method for producing a quantum optical microcavity device based on a fluorocarboxylic hydrophobic modifier according to claim 4, characterized by, ​ 7. The method for producing a quantum optical microcavity device based on a fluorocarboxylic hydrophobic modifier according to claim 4, characterized by, ​ 8. The method for producing a quantum optical microcavity device based on a fluorocarboxylic hydrophobic modifier according to claim 4, characterized by, The solute concentration in the fluorinated organic carboxylic acid solution is 10 -3 1.0 mol / L.

9. The method for producing a quantum optical microcavity device based on hydrophobic modification with a fluorocarboxylic acid according to claim 4, characterized by, ​ 10. The method for producing a quantum optical microcavity device based on a fluorocarboxylic hydrophobic modifier according to claim 4, characterized by, ​

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