Parylene copolymer material and method for improving adhesion of parylene film
Patent Information
- Application Number
- PCT/CN2025/114593
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-03-25
- Filing Date
- 2025-08-14
- Publication Date
- 2026-10-01
Smart Images
Figure CN2025114593_01102026_PF_FP_ABST
Abstract
Description
A Pyrelin copolymer material and a method for improving the adhesion of Pyrelin films Technical Field
[0001] This invention relates to the field of perylene materials technology, and in particular to a perylene copolymer material and a method for improving the adhesion of perylene films. Background Technology
[0002] Perelin C is a polymeric thin film material prepared by chemical vapor deposition (CVD) and features excellent formability, a smooth surface, and no pores. Due to its outstanding biocompatibility and hydrolysis resistance, this thin film material became the first perelin derivative to be recognized as having the highest biocompatibility level among plastic materials, and is widely used in the field of bio-MEMS (see: Noh HS, Huang Y, Hesketh P J. Sensors and Actuators B: Chemical, 2004, 102(1):78-85).
[0003] Despite the excellent performance of phenelin films, their unique molecular structure and low surface energy, resulting from CVD deposition on substrate surfaces, lead to poor natural adhesion between phenelin films and common substrates (see: Charmet J, Bitterli J, Sereda O, et al. Journal of Microelectromechanical Systems, 2013, 22(4): 855-864). This insufficient adhesion significantly limits the lifespan of phenelin films in certain applications requiring long-term stability and high reliability. Detachment or interfacial failure between the film and substrate can severely impact the overall performance of related products or applications (see: Ortigoza-Diaz J, Scholten K, Meng E. Journal of Microelectromechanical Systems, 2018, 27(5): 874-885).
[0004] Currently, a common strategy to improve the adhesion of phenelzine films is to use adhesives. These adhesives are usually surface-active materials, such as silane coupling agents and ionomer adhesives, which significantly improve adhesion by forming chemical bonds between the phenelzine film and various substrates (such as silicon-based substrates). However, this method has certain limitations: because the chemical properties and physical behavior of the adhesive may be incompatible with the phenelzine film, it may adversely affect the film's temperature resistance, corrosion resistance, and other properties (see: Hassler C, Von Metzen RP, Ruther P, Stieglitz T. Journal of Biomedical Materials Research Part B: Applied Biomaterials, 2010, 93(1):266-74).
[0005] Therefore, there is an urgent need to provide a method to improve the adhesion of Pyrelin films to silicon-based substrates, thereby overcoming the shortcomings of existing methods and providing a new technical approach to improve film performance. Summary of the Invention
[0006] To address the aforementioned technical problems, this invention provides a phenelzine copolymer material and a method for improving the adhesion of phenelzine films. This invention aims to overcome the inherent defects of traditional methods in improving the adhesion of phenelzine films. The invention prepares films by copolymerizing common phenelzine monomers with phenelzine H monomers. This method can significantly improve the adhesion of phenelzine films to silicon-based substrates while maintaining the uniformity and surface smoothness of the films.
[0007] This invention is achieved through the following technical solution:
[0008] The first objective of this invention is to provide a perylene copolymer material, the structure of which is shown below:
[0009] R1, R2, R3, and R4 are each independently selected from one of the following groups: hydrogen atom, halogen, amino, nitro, ester, aldehyde, methoxy, ethoxy, cyano, trifluoromethyl, ethynyl, vinyl, and saturated alkyl; wherein m≧1 and n≧1.
[0010] The second objective of this invention is to provide a method for preparing a phenelzine copolymer, comprising the following steps:
[0011] The conventional phenelzine monomer and phenelzine H monomer were prepared by chemical vapor deposition copolymerization.
[0012] The conventional pyrene monomer is selected from one or more of pyrene N monomer, pyrene C monomer, pyrene D monomer, pyrene F monomer, and pyrene HT monomer.
[0013] In one embodiment of the present invention, the mass ratio of the conventional pyreline monomer to the pyreline H monomer is 0-3:1-3.
[0014] In one embodiment of the present invention, the pyreline H monomer is prepared by the following method:
[0015] (1) Mix p-xylene ring dimer with catalyst in organic solvent, add liquid bromine dropwise, heat and reflux to react, separate solid and liquid after reaction, recrystallize the obtained solid phase to obtain brominated p-xylene;
[0016] (2) The obtained bromo-p-xylene was stirred thoroughly with diethyl ether and cooled; n-butyllithium was added dropwise and then the mixture was heated to room temperature and stirred, and then cooled down; N,N-dimethylformamide was added and the mixture was heated to room temperature and stirred to obtain the pyrene H monomer;
[0017] The catalyst is iron powder; the organic solvent is selected from dichloromethane.
[0018] A third objective of this invention is to provide the application of the said phenelin copolymer in the preparation of phenelin films.
[0019] The fourth objective of this invention is to provide a method for improving the adhesion of a paraben film, comprising the following steps:
[0020] S1. Place the pre-cleaned substrate into the deposition chamber and set aside.
[0021] S2. Mix the conventional type of pyrelin monomer to be plated with the pyrelin H monomer and place it in the evaporation chamber; the conventional type of pyrelin monomer is selected from one or more of the following: pyrelin N monomer, pyrelin C monomer, pyrelin D monomer, pyrelin F monomer and pyrelin HT monomer.
[0022] S3. Under vacuum conditions of -10Pa to -0.5Pa, conventional pyrelin monomer and pyrelin H monomer in the evaporation chamber are evaporated, pyrolyzed in a cracking furnace, and deposited on the substrate in the deposition chamber to form a pyrelin film.
[0023] In one embodiment of the present invention, in step S1, the substrate is a silicon-based substrate; the silicon-based substrate is selected from one or more of silicon wafers, glass sheets and PDMS.
[0024] In one embodiment of the present invention, in step S2, the mass ratio of the conventional type of pyreline monomer to the pyreline H monomer is 0-3:1-3.
[0025] In one embodiment of the present invention, in step S3, the evaporation temperature is 80°C to 200°C.
[0026] In one embodiment of the present invention, in step S3, the pyrolysis temperature is 600°C to 680°C.
[0027] This invention reveals that the phenelzine H monomer (containing a formyl substituent on its benzene ring) possesses excellent adhesion properties. By copolymerizing phenelzine H with other common phenelzine monomers, the adhesion between phenelzine films and silicon-based substrates can be significantly improved, thereby overcoming the shortcomings of existing methods and providing a novel technical approach to enhancing film performance.
[0028] The technical solution of the present invention has the following advantages compared with the prior art:
[0029] 1. This invention significantly improves the adhesion of Piriton film through copolymerization. The copolymerized film still retains the excellent properties of Piriton materials, such as no pinholes, good shape retention, and uniformity.
[0030] 2. This invention significantly improves film adhesion through copolymerization, greatly enhancing the adhesion between Piriton and the substrate.
[0031] 3. The method of significantly improving film adhesion through copolymerization in this invention is simple to operate and does not require complex pretreatment of the substrate or coating with coupling agent.
[0032] 4. The copolymerization ratio and the type of initial phenelzine can be adjusted in this invention, which greatly improves the adhesion of the film through copolymerization, and has a wide range of applications. Attached Figure Description
[0033] To make the content of this invention easier to understand, the invention will be further described in detail below with reference to specific embodiments and accompanying drawings, wherein...
[0034] Figure 1 is a diagram showing the adhesion strength between the perylene and the silicon wafer in this invention;
[0035] Figure 2 is an electron microscope image of the phenelzine thin film in this invention; where A is a planar view and B is an interface view. Detailed Implementation
[0036] The present invention will be further described below with reference to the accompanying drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. However, the embodiments described are not intended to limit the present invention.
[0037] This invention provides a phenelzine copolymer material and a method for improving the adhesion of phenelzine films. The method for improving the adhesion of phenelzine films is based on phenelzine H monomer raw materials and conventional phenelzine raw materials, and is prepared by chemical deposition copolymerization. This method significantly improves the adhesion of the phenelzine material while maintaining film uniformity and surface smoothness. The film adhesion on various silicon-containing substrates is significantly improved. Specifically, it includes the following steps:
[0038] S1. Place the pre-cleaned substrate into the deposition chamber and set aside.
[0039] S2. Mix the conventional type of pyrelin monomer to be plated with the pyrelin H monomer and place them in the evaporation chamber; the conventional type of pyrelin monomer is selected from one or more of the following: pyrelin N monomer, pyrelin C monomer, pyrelin D monomer, pyrelin F monomer, and pyrelin HT monomer.
[0040] S3. Under vacuum conditions of -10Pa to -0.5Pa, conventional pyrelin monomer and pyrelin H monomer in the evaporation chamber are evaporated, pyrolyzed in a cracking furnace, and deposited on the substrate in the deposition chamber to form a pyrelin film.
[0041] Preferably, in step S1, the pre-cleaning specifically involves: soaking the substrate in acetone or ethanol and performing ultrasonic cleaning, then rinsing it with deionized water, and finally drying it for later use.
[0042] Preferably, in step S2, the conventional pyreline monomer is selected from one or more of pyreline N monomer, pyreline C monomer, pyreline D monomer, pyreline F monomer and pyreline HT monomer; the mass ratio of the conventional pyreline monomer to the pyreline H monomer is 0-3:1-3.
[0043] Preferably, in step S3, the evaporation temperature is controlled between 80°C and 200°C. The pyrolysis temperature is controlled between 600°C and 680°C. The deposition chamber temperature is controlled at 30°C. The vacuum degree is -10Pa to -0.5Pa.
[0044] Unless otherwise specified, the experimental methods used in the following examples are conventional methods, and the materials and reagents used are commercially available.
[0045] In the embodiments of this invention, both the Piriton C monomer and the Piriton F monomer were purchased from Suzhou Kerry Nanotechnology Co., Ltd.
[0046] Table 1
[0047] Example 1
[0048] This embodiment provides a method for preparing phenelzine H monomer, the specific steps of which are as follows:
[0049] (1) Synthesis of p-xylene bromide: p-xylene cyclodisomer (41.6 g, 20.0 mmol) and iron powder (1.2 g, 21.43 mmol) were added to a reaction flask, followed by 600 mL of dichloromethane solvent. 24 mL of liquid bromine was slowly added dropwise at room temperature. After the addition was complete, the mixture was heated to reflux and reacted for 24 h. The reaction was quenched with saturated sodium sulfite solution. After the red color of the solution disappeared, the layers were separated, the organic layer was removed, filtered, and the solid was collected. The crude product was recrystallized from ethanol to obtain a white solid p-xylene bromide (30.66 g, 8.36 mmol, yield 42%).
[0050] Synthesis of Pyrelin H monomer: 10.0 g (2.73 mmol) of the prepared p-bromoxylene was added to 700 mL of ultradry diethyl ether. After thorough stirring, the mixture was cooled to 0 °C, and 65.0 mL (81.20 mmol) of n-butyllithium solvent was slowly added dropwise using a syringe. The mixture was slowly brought to room temperature and stirred for 6 h. At 0 °C, 40.0 mL (516.0 mmol) of ultradry N,N-dimethylformamide was added. The mixture was slowly brought to room temperature and stirred for 3 h. The reaction mixture was quenched with 30 mL of 6N hydrochloric acid and diluted with 50 mL of distilled water, then extracted with dichloromethane (2 × 100 mL). The resulting organic layer was washed with saturated sodium bicarbonate solution (2 × 100 mL) and saturated brine (2 × 100 mL). After drying with anhydrous magnesium sulfate, the solvent was evaporated under reduced pressure to obtain a pale yellow crude product. The crude product was recrystallized with toluene to obtain a white solid pyreline H monomer (6.2 g, 23.50 mmol, yield 86.0%).
[0051] Example 2
[0052] This embodiment provides a method for improving the adhesion of a paraben film, the specific steps of which are as follows:
[0053] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0054] Pyrelin C monomer and pyrelin H monomer were weighed at a mass ratio of 3:1. After thoroughly mixing the weighed pyrelin C monomer and pyrelin H monomer, the mixture was placed in an evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the pyrelin C monomer and pyrelin H monomer evaporated, the mixture underwent a chemical reaction within the pyrolysis furnace. Subsequently, at room temperature, a thin film was deposited on the silicon wafer surface in the deposition chamber to form a pyrelin coating.
[0055] Example 3
[0056] This embodiment provides a method for improving the adhesion of a paraben film, the specific steps of which are as follows:
[0057] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0058] Pyrelin C monomer and pyrelin H monomer were weighed in a 1:1 mass ratio and thoroughly mixed before being placed in an evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the pyrelin C and H monomers evaporated, the mixture underwent a chemical reaction within the pyrolysis furnace, subsequently depositing a thin film on the silicon wafer surface in the deposition chamber at room temperature, thus obtaining a pyrelin coating.
[0059] Example 4
[0060] This embodiment provides a method for improving the adhesion of a paraben film, the specific steps of which are as follows:
[0061] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0062] Pyrelin C monomer and Pyrelin H monomer were weighed at a mass ratio of 1:3. After thoroughly mixing the weighed Pyrelin C monomer and Pyrelin H monomer, the mixture was placed in an evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the Pyrelin C monomer and Pyrelin H monomer evaporated, the mixture underwent a chemical reaction within the pyrolysis furnace. Subsequently, at room temperature, a thin film was deposited on the silicon wafer surface in the deposition chamber to form a Pyrelin coating.
[0063] Example 5
[0064] This embodiment provides a method for improving the adhesion of a paraben film, the specific steps of which are as follows:
[0065] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0066] A certain mass of pyrelin H monomer was weighed, the same as the total mass of pyrelin C and pyrelin H monomers in Example 2; the pyrelin H monomer was placed in the evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the pyrelin H monomer evaporated, the monomer underwent pyrolysis in the pyrolysis furnace, and subsequently, at room temperature, a thin film was deposited on the silicon wafer surface in the deposition chamber to form a pyrelin coating.
[0067] Example 6
[0068] This embodiment provides a method for improving the adhesion of a paraben film, the specific steps of which are as follows:
[0069] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0070] Pyrelin F monomer and Pyrelin H monomer were weighed at a mass ratio of 1:3. After thoroughly mixing the weighed Pyrelin F monomer and Pyrelin H monomer, the mixture was placed in an evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the Pyrelin F monomer and Pyrelin H monomer evaporated, the mixture underwent a chemical reaction within the pyrolysis furnace. Subsequently, at room temperature, a thin film was deposited on the silicon wafer surface in the deposition chamber to form a Pyrelin coating.
[0071] Example 7
[0072] This embodiment provides a method for improving the adhesion of a paraben film, the specific steps of which are as follows:
[0073] The glass slides are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0074] Pyrelin C monomer and Pyrelin H monomer were weighed at a mass ratio of 3:1. After thoroughly mixing the weighed Pyrelin C monomer and Pyrelin H monomer, the mixture was placed in an evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the Pyrelin C monomer and Pyrelin H monomer evaporated, the mixture underwent a chemical reaction within the pyrolysis furnace. Subsequently, at room temperature, a thin film was deposited on the surface of a glass slide in the deposition chamber to form a Pyrelin coating.
[0075] Comparative Example 1
[0076] This comparative example provides a method for preparing a phenelin thin film, the specific steps of which are as follows:
[0077] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0078] A certain mass of pyrelin C monomer was weighed, the same as the total mass of pyrelin C and pyrelin H monomers in Example 2; the pyrelin C monomer was placed in the evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the pyrelin C monomer evaporated, the monomer underwent pyrolysis in the pyrolysis furnace, and subsequently, at room temperature, a thin film was deposited on the surface of the silicon wafer substrate in the deposition chamber to form a pyrelin coating.
[0079] Comparative Example 2
[0080] This comparative example provides a method for preparing a phenelin thin film, the specific steps of which are as follows:
[0081] The silicon wafers are soaked in acetone and ultrasonically cleaned, then rinsed with deionized water and finally dried for later use.
[0082] A certain mass of pyrelin F monomer was weighed, the same as the total mass of pyrelin C and pyrelin H monomers in Example 2; the pyrelin F monomer was placed in the evaporation chamber. Under a vacuum of -4.0 Pa, the pyrolysis furnace was heated to 680°C, while the evaporation chamber was simultaneously heated to 160°C. After the pyrelin F monomer evaporated, the monomer underwent pyrolysis in the pyrolysis furnace, and subsequently, at room temperature, a thin film was deposited on the surface of the silicon wafer substrate in the deposition chamber to form a pyrelin coating.
[0083] Performance Characterization
[0084] (1) The adhesion strength of the P-silicon wafer was measured by scratch test. Taking Comparative Example 1 as a reference, as shown in Figure 1, at the inflection point in the depth and scratch distance graph, the film cracked and peeled off. The corresponding load cell size (also known as critical load cell) is the adhesion force between the film and the substrate, which is 2.03 mN.
[0085] The adhesion of the Piriton coatings obtained in the above embodiments and comparative examples was tested, and the results are shown in Table 1:
[0086] Table 1
[0087] As shown in Table 1, compared with the Piriton C monomer coating of Comparative Example 1, the adhesion of the Piriton coating in this embodiment of the invention is improved by 11.7-17 times, which is a significant improvement. Therefore, this invention has good application prospects in improving the adhesion of Piriton films.
[0088] (2) Figure 2 is an electron microscope image of the pyrelin film prepared in Example 3 of the present invention. As can be seen from the figure, the pyrelin film prepared in the present invention retains the excellent characteristics of pyrelin-like materials, such as no pinholes, good shape retention, and uniformity.
[0089] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.
Claims
1. A perylene copolymer material, characterized in that, The structure of the Perylene copolymer is shown below: R1, R2, R3, and R4 are each independently selected from one of the following groups: hydrogen atom, halogen, amino, nitro, ester, aldehyde, methoxy, ethoxy, cyano, trifluoromethyl, ethynyl, vinyl, and saturated alkyl; wherein m≧1 and n≧1.
2. The method for preparing the perelene copolymer material according to claim 1, characterized in that, Includes the following steps: The conventional phenelzine monomer and phenelzine H monomer were prepared by chemical vapor deposition copolymerization. The conventional pyrene monomer is selected from one or more of pyrene N monomer, pyrene C monomer, pyrene D monomer, pyrene F monomer, and pyrene HT monomer.
3. The preparation method according to claim 1, characterized in that, The mass ratio of the conventional type of pyrelin monomer to the pyrelin H monomer is 0-3:1-3.
4. The preparation method according to claim 1, characterized in that, The pyrene H monomer was prepared by the following method: (1) Mix p-xylene ring dimer with catalyst in organic solvent, add liquid bromine dropwise, heat and reflux to react, separate solid and liquid after reaction, recrystallize the obtained solid phase to obtain brominated p-xylene; (2) The obtained brominated p-xylene was stirred thoroughly with diethyl ether and cooled; n-butyllithium was added dropwise and then stirred at room temperature and cooled down; N,N-dimethylformamide was added and stirred at room temperature to obtain the pyrene H monomer.
5. The application of the phenelzine copolymer material according to claim 1 in the preparation of phenelzine films.
6. A method for improving the adhesion of a paraben film, characterized in that, Includes the following steps: S1. Place the pre-cleaned substrate into the deposition chamber and set aside. S2. Mix the conventional type of pyrelin monomer to be plated with the pyrelin H monomer and place it in the evaporation chamber; the conventional type of pyrelin monomer is selected from one or more of the following: pyrelin N monomer, pyrelin C monomer, pyrelin D monomer, pyrelin F monomer and pyrelin HT monomer. S3. Under vacuum conditions of -10Pa to -0.5Pa, conventional pyrelin monomer and pyrelin H monomer in the evaporation chamber are evaporated, pyrolyzed in a cracking furnace, and deposited on the substrate in the deposition chamber to form a pyrelin film.
7. The method according to claim 6, characterized in that, In step S1, the substrate is a silicon-based substrate; the silicon-based substrate is selected from one or more of silicon wafers, glass sheets, and PDMS.
8. The method according to claim 6, characterized in that, In step S2, the mass ratio of the conventional type of pyreline monomer to the pyreline H monomer is 0-3:1-3.
9. The method according to claim 6, characterized in that, In step S3, the evaporation temperature is 80℃~200℃.
10. The method according to claim 6, characterized in that, In step S3, the pyrolysis temperature is 600℃~680℃.