Detection method and detection equipment for chemical bond of bonding interface of organic material and base material

Abstract

The invention provides a detection method and detection equipment for a chemical bond of a bonding interface of an organic material and a base material, and the detection method comprises the following steps: (1) preparing the bonding interface of the organic material and the base material to obtain a test sample; (2) carrying out characterization detection on the body of the organic material, the body of the base material and the bonding interface of the organic material and the base material by utilizing a micro Raman spectrometer to obtain Raman spectrum data; (3) analyzing the Raman spectrum data to obtain the Raman spectrum signal difference between the bonding interface and the organic material body and the Raman spectrum signal difference between the bonding interface and the base material body, and confirming the chemical bond type of the bonding interface; and (4) performing Raman surface scanning imaging on the region containing the bonding interface, and detecting the distribution condition of chemical bonds in the bonding interface region. The detection method provided by the invention can be used for analyzing a chemical bond forming mechanism of interface bonding of an organic material and a base material, and can provide theoretical guidance for a chemical bonding mechanism of a polymer composite material interface.

Description

Technical Field

[0001] The invention belongs to the technical field of in-situ detection, and relates to a method and a device for detecting chemical bonds at the bonding interface between an organic material and a substrate. Background Art

[0002] Polymer composites are multiphase materials formed by physically or chemically combining a polymer matrix (such as thermosetting resins and thermoplastics) with reinforcements (such as fibers, particles, and nanofillers). These materials combine the toughness and processability of the matrix with the high strength, high modulus, or specialized properties of the reinforcement through synergistic effects. Due to their lightweight, high-strength, heat-resistant, and corrosion-resistant properties, they are widely used in aerospace, automotive, electronics, construction, energy, and biomedical fields.

[0003] With the rapid development of microelectronic packaging, semiconductor devices and composite materials technology, the interfacial bonding performance between polymers and silicon-based materials (such as silicon chips, silicon dioxide substrates, etc.) has become a key factor affecting device reliability, service life and functional stability. Chemical bonding at the interface (such as covalent bonding mediated by silane coupling agents) directly determines the mechanical strength, thermal stability and resistance to environmental aging between materials. However, the existing direct detection methods for interfacial chemical bonds still have problems such as insufficient sensitivity, destructive operations or limited analysis depth. There is an urgent need to develop new, efficient and accurate interface characterization methods.

[0004] In microelectronic packaging, polymers (such as epoxy resins, polyimides, etc.) are often used for bottom filling, passivation protection or stress buffer layers between chips and substrates. Silane coupling agents (such as KH550, KH560, etc.) are often used as interface modifiers to achieve interface enhancement through cross-linking reactions between their organic functional groups and polymers, as well as chemical bonding between siloxane groups and silicon substrates. However, if the chemical bonding is incomplete or unevenly distributed, it may lead to interface failure, causing delamination, crack propagation and other problems. Therefore, accurately detecting the type, density and distribution characteristics of interface chemical bonds is a core requirement for optimizing process parameters and improving product reliability.

[0005] Prior art also discloses technical solutions for analyzing composite material interfaces using Raman spectroscopy. For example, CN105973703A discloses a detection device and method for measuring the shear strength of composite material interfaces. This instrument uses a series of optical instruments and a load-bearing structure to test the shear strength of samples, and has the characteristics of accurate detection. CN110095449A discloses an analytical method for measuring the mechanical behavior of interfaces in metal-matrix composites. This method compares the coefficients obtained by in-situ Raman testing of reinforcements in the metal-matrix composite with the coefficients obtained by in-situ Raman testing of the reinforcements, and obtains the interfacial stress transfer efficiency in the metal-matrix composite. This method has the characteristics of good repeatability, high reliability, and simple operation. However, the test methods provided by the above two prior art technologies do not reflect the type and distribution of chemical bonds at the interface.

[0006] Since all research on pure polymers or polymer composites (such as underfill glue) must be carried out based on the interface, for example, the reliability analysis of underfill glue, interface failure and cracks and other problems mostly occur at the interface, how to characterize the bonding mechanism between organic materials and substrates has become a technical problem that needs to be solved urgently. Summary of the Invention

[0007] In view of the deficiencies in the prior art, the present invention aims to provide a method and apparatus for detecting chemical bonds at the interface between an organic material and a substrate.

[0008] The present invention provides an in-situ, non-destructive, and non-contact method for directly detecting chemical bonds at the interface between organic materials and substrates using Raman spectroscopy. This detection method can be used to analyze the chemical bond formation mechanism at the interface between organic materials and substrates, and can provide theoretical guidance for the interface chemical bonding mechanism of polymer composites (such as epoxy resin composites).

[0009] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0010] In a first aspect, the present invention provides a method for detecting chemical bonds at an interface between an organic material and a substrate, the method comprising the following steps:

[0011] (1) preparing a bonding interface between an organic material and a substrate to obtain a test sample;

[0012] (2) using a micro-Raman spectrometer to characterize and detect the bulk of the organic material, the bulk of the substrate, and the bonding interface between the organic material and the substrate to obtain Raman spectral data;

[0013] (3) analyzing the Raman spectroscopy data to obtain signal differences between the Raman spectra of the bonding interface and the bulk of the organic material and the bulk of the substrate, thereby confirming the chemical bond type of the bonding interface;

[0014] (4) Perform Raman surface scanning imaging on the area containing the bonding interface to detect the distribution of chemical bonds in the bonding interface area.

[0015] After preparing the bonding interface between the organic material and the substrate, the present invention first performs Raman spectroscopy on the bulk of the organic material, the bulk of the substrate, and the bonding interface between the two. Based on the signal difference of the Raman spectra of the bonding interface and the bulk of the organic material and the bulk of the substrate (specifically, based on the position where the new characteristic peak appears), the chemical bond type of the bonding interface can be confirmed. Then, Raman surface scanning imaging is further performed on the area containing the bonding interface, and the density and distribution of the chemical bonds in the bonding interface area can be observed (specifically, after confirming the chemical bond type of the bonding interface in the previous step, the distribution of the chemical bonds can be selected in the Raman tester to view), thereby also being able to determine whether the bonding interface is firm. The detection method provided by the present invention realizes in-situ non-destructive detection of the material interface and can provide guidance for the analysis of its interface bonding mechanism.

[0016] The following are preferred technical solutions of the present invention, but are not intended to limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved and realized.

[0017] Preferably, the organic material in step (1) comprises any one of a pure polymer and a polymer composite material.

[0018] Preferably, the pure polymer includes any one of polyolefin polymers and polystyrene polymers, or a combination of at least two of them.

[0019] Preferably, the polymer composite material includes any one of an underfill material and a thermal interface material.

[0020] Preferably, the components of the polymer composite material include resin, filler and additives.

[0021] Preferably, the resin includes any one of bisphenol F epoxy resin, bisphenol A epoxy resin, and phenolic resin, or a combination of at least two of them.

[0022] Preferably, the filler includes any one of silicon dioxide, diamond, aluminum oxide, graphene, and boron nitride, or a combination of at least two thereof.

[0023] Preferably, the auxiliary agent includes any one of a curing agent, a coupling agent, a catalyst, and an accelerator, or a combination of at least two of them.

[0024] Preferably, the curing agent includes any one of anhydride curing agents, amine curing agents, and phenolic curing agents, or a combination of at least two of them.

[0025] Preferably, the coupling agent includes any one of an organosilicon coupling agent, a silane coupling agent, and a phthalate coupling agent, or a combination of at least two of the above.

[0026] Preferably, based on the total weight of the polymer composite material as 100%, the content of the resin is 5% to 60% (for example, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, etc.), the content of the filler is 40% to 70% (for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc.), and the content of the auxiliary agent is 1% to 30% (for example, 1%, 2%, 3%, 5%, 10%, 15%, 20%, 25%, 30%, etc.).

[0027] Preferably, the substrate comprises silicon material, such as a silicon wafer.

[0028] Preferably, the laser wavelength used in the characterization test using a micro-Raman spectrometer in step (2) and the Raman surface scanning imaging test described in step (4) includes at least one of 488 nm, 514 nm, 532 nm, 633 nm, and 785 nm. Generally speaking, shorter laser wavelengths have higher energy and stronger Raman signals, but are more likely to damage the sample. Therefore, it is necessary to select an appropriate wavelength based on the different types of organic materials.

[0029] Preferably, in step (2), a micro-Raman spectrometer is used for characterization and detection, and the power of the laser is 1 mW to 25 mW, for example, 1 mW, 2 mW, 3 mW, 5 mW, 8 mW, 10 mW, 12 mW, 13 mW, 15 mW, 18 mW, 20 mW, 22 mW, 23 mW, 25 mW, etc.

[0030] Preferably, in step (2), a micro-Raman spectrometer is used for characterization and detection, and the integration time is 1s to 300s, for example, 1s, 2s, 3s, 5s, 8s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 120s, 140s, 160s, 180s, 200s, 220s, 240s, 260s, 280s, 300s, etc.

[0031] Preferably, the signal difference in step (3) includes at least one of the appearance of a new characteristic peak, a change in the intensity of the characteristic peak, a change in displacement, a change in half-peak width, and a change in relative peak intensity. Based on these signal differences, specifically, based on the location of the new characteristic peak, the type of chemical bond at the bonding interface can be determined. The new characteristic peak refers to a characteristic peak that does not appear in the bulk of the organic material or the bulk of the substrate, but appears at the bonding interface between the two.

[0032] Preferably, the area of ​​the region containing the bonding interface in step (4) is 50×80 μm to 70×120 μm, for example, 50×80 μm, 60×80 μm, 60×100 μm, 70×120 μm, etc.

[0033] Preferably, in the Raman surface scan imaging test in step (4), the laser power is 1 mW to 25 mW, for example, 1 mW, 2 mW, 3 mW, 5 mW, 8 mW, 10 mW, 12 mW, 13 mW, 15 mW, 18 mW, 20 mW, 22 mW, 23 mW, 25 mW, etc.

[0034] Preferably, in the Raman surface scan imaging test in step (4), the integration time is 1s to 300s, for example, 1s, 2s, 3s, 5s, 8s, 10s, 20s, 30s, 40s, 50s, 60s, 70s, 80s, 90s, 100s, 120s, 140s, 160s, 180s, 200s, 220s, 240s, 260s, 280s, 300s, etc.

[0035] The present invention controls the power and integration time of the laser within a specific range, thereby obtaining a clear signal without causing damage to the test sample.

[0036] In the present invention, the integration time needs to be set according to the power of the laser. Generally, the greater the laser power, the shorter the integration time.

[0037] The present invention does not specifically limit how to prepare the test sample. Taking the organic material as a polymer composite material as an example, the preparation method includes the following steps:

[0038] (1) Mixing raw materials such as resin, filler, and additives to obtain a mixed glue;

[0039] (2) After cleaning and preheating the substrate (such as a silicon wafer), the mixed glue solution is defoamed and then dispensed onto the substrate, cured, and demolded. The cured sample is inlaid with AB glue and then polished to obtain a test sample.

[0040] Preferably, the mixing in step (1) includes any one of vacuum high-speed mixing, solution blending, and melt blending. During mixing, the raw materials need to be mixed as evenly as possible.

[0041] In a second aspect, the present invention provides a device for detecting chemical bonds at the interface between an organic material and a substrate, the device comprising a memory and a processor, the memory storing a computer program, and the processor implementing the steps of the detection method described in the first aspect when executing the computer program.

[0042] Compared with the prior art, the present invention has the following beneficial effects:

[0043] After preparing the bonding interface between the organic material and the substrate, the present invention first performs Raman spectroscopy on the bulk of the organic material, the bulk of the substrate, and the bonding interface between the two. Based on the signal differences between the Raman spectra of the bonding interface and the bulk of the organic material and the bulk of the substrate, the chemical bond type of the bonding interface can be confirmed. Raman surface imaging of the region containing the bonding interface can then be performed to observe the density and distribution of chemical bonds in the bonding interface region, thereby assisting in the subsequent determination of the bond strength, etc. The detection method provided by the present invention achieves in-situ non-destructive testing of material interfaces and can provide guidance for the analysis of their interfacial bonding mechanisms. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 A schematic flow chart of a method for detecting chemical bonds at the bonding interface between a polymer composite material and a silicon material provided in Example 1 of the present invention;

[0045] Figure 2 Schematic diagram of a device for detecting chemical bonds at the bonding interface between a polymer composite material and a silicon material provided in Example 1 of the present invention;

[0046] Figure 3 Schematic diagram of the preparation process of the test sample provided in Example 1 of the present invention;

[0047] Figure 4 The test position marks of the test sample in step (3) of Example 1 of the present invention;

[0048] Figure 5 Raman spectra of the polymer composite material body, the silicon wafer body, and the bonding interface between the polymer composite material and the silicon wafer provided in Example 1 of the present invention;

[0049] Figure 6 This is a test area diagram (the area circled in red in the left figure) and a Raman surface scanning imaging test result diagram (right figure) in step (4) of Example 1 of the present invention. DETAILED DESCRIPTION

[0050] The technical solution of the present invention will be further described below with reference to the accompanying drawings and through specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0051] Example 1

[0052] In this embodiment, a method for detecting chemical bonds at the interface between a polymer composite material and a silicon material is provided, and the flow chart thereof is shown as follows: Figure 1 The schematic diagram of the detection device is shown in Figure 2 As shown, the detection method includes the following steps:

[0053] (1) Prepare a bonding interface between an organic material and a substrate to obtain a test sample.

[0054] Specifically, the organic material used in this embodiment is an underfill glue in a polymer composite material, and epoxy resin, filler, curing agent, coupling agent, and catalyst are mixed in a mass ratio of 20:70:5:4:1 to obtain a mixed glue solution;

[0055] Epoxy resin: bisphenol A epoxy resin, purchased from Hanson, USA, brand EPIKOTE 828;

[0056] Filler: epoxy-modified silica particles, purchased from Admatech Co., Ltd., brand FEB25A;

[0057] Curing agent: a mixture of methylhexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, with a mass ratio of 1:1;

[0058] Coupling agent: γ-aminopropyltriethoxysilane;

[0059] Catalyst: triphenyl phosphate.

[0060] The substrate used in this embodiment is a silicon wafer. After cleaning and preheating the silicon wafer, the mixed glue solution is defoamed and then dispensed onto the silicon wafer. The first curing is performed and the mold is removed. The cured sample is then inlaid with AB glue and cured for the second time. Then, it is polished to obtain the test sample (the preparation process of the test sample is shown in the figure). Figure 3 shown);

[0061] The first curing process was to set the oven program to heat up from room temperature to 125°C at a heating rate of 3.167°C / min, keep warm for 30 minutes, then heat up from 125°C to 165°C at a heating rate of 2.5°C / min, keep warm for 1.5 hours, and finally cool down from 165°C to room temperature at a cooling rate of 4.5°C / min.

[0062] The second curing was performed at 100°C for 3 h;

[0063] (2) Using a micro-Raman spectrometer, the main body of the organic material, the main body of the substrate, and the bonding interface between the organic material and the substrate are characterized and detected to obtain Raman spectrum data.

[0064] Specifically, the test sample is fixed on the sample stage of the Raman tester, and the bulk of the polymer composite material, the bulk of the silicon wafer, and the bonding interface between the polymer composite material and the silicon wafer are characterized using a micro-Raman spectrometer, such as Figure 4 As shown; the Raman spectral data of the polymer composite body, the silicon wafer body, and the bonding interface between the polymer composite and the silicon wafer obtained by the test are displayed in the form of images as shown below Figure 5shown.

[0065] (3) Analyzing the Raman spectrum data to obtain the signal difference of the Raman spectrum between the bonding interface and the main body of the organic material and the main body of the substrate, and confirming the chemical bond type of the bonding interface.

[0066] Specifically, in this embodiment, for the Raman spectrum data shown in the image, it can be seen that there is an additional 1000 cm -1 The characteristic peak at , which corresponds to the Si-OC chemical bond.

[0067] (4) Perform Raman surface scanning imaging on the area containing the bonding interface to detect the distribution of chemical bonds in the bonding interface area.

[0068] Specifically, such as Figure 6 As shown in the left figure, based on the signal difference, the area containing the bonding interface (the area circled in red) is subjected to Raman surface scanning imaging. The test results are as follows: Figure 6 As shown in the right figure, it can be seen that a horizontal yellow bright line appears in the figure, which corresponds to the distribution of chemical bonds detected in step (3);

[0069] In the Raman single spectrum detection process in step (3), the laser wavelength is set to 532 nm, the laser power is set to 6 mW, and the integration time is set to 20 s; in step (4), the area of ​​the Raman surface scan imaging region is set to 60 × 100 μm, the number of test points in each column is 30, the laser power is set to 6 mW, and the integration time is set to 7 s.

[0070] In summary, the present invention provides an in-situ, non-destructive, and non-contact method for directly detecting chemical bonds at the interface between organic materials and substrates using Raman spectroscopy. This detection method can be used to analyze the chemical bond formation mechanism at the interface between organic materials and substrates, and can observe the density and distribution of chemical bonds in the bonding interface area, etc., and can provide theoretical guidance for the interface chemical bonding mechanism of polymer composites (such as epoxy resin composites).

[0071] The applicant states that while the present invention uses the aforementioned embodiments to illustrate the method and apparatus for detecting chemical bonds at the interface between an organic material and a substrate, the present invention is not limited to the aforementioned embodiments, nor does it necessarily rely on the aforementioned embodiments for implementation. Those skilled in the art will appreciate that any improvements to the present invention, equivalent substitutions for the raw materials used, additions of auxiliary components, and selection of specific methods, etc., fall within the scope of protection and disclosure of the present invention.

Claims

1. A method for detecting chemical bonds at the interface between an organic material and a substrate, characterized in that: The detection method comprises the following steps: (1) preparing a bonding interface between an organic material and a substrate to obtain a test sample; (2) using a micro-Raman spectrometer to characterize and detect the bulk of the organic material, the bulk of the substrate, and the bonding interface between the organic material and the substrate to obtain Raman spectral data; (3) analyzing the Raman spectroscopy data to obtain signal differences between the Raman spectra of the bonding interface and the bulk of the organic material and the bulk of the substrate, thereby confirming the chemical bond type of the bonding interface; (4) Perform Raman surface scanning imaging on the area containing the bonding interface to detect the distribution of chemical bonds in the bonding interface area.

2. The detection method according to claim 1, wherein The organic material in step (1) includes any one of pure polymers and polymer composite materials.

3. The detection method according to claim 2, characterized in that The pure polymer includes any one of polyolefin polymers and polystyrene polymers, or a combination of at least two of them.

4. The detection method according to claim 2, characterized in that The components of the polymer composite material include resin, filler and auxiliary agent.

5. The detection method according to claim 4, characterized in that The resin includes any one of bisphenol F epoxy resin, bisphenol A epoxy resin, and phenolic resin, or a combination of at least two thereof; Preferably, the filler comprises any one of silicon dioxide, diamond, aluminum oxide, graphene, and boron nitride, or a combination of at least two thereof; Preferably, the auxiliary agent includes any one or a combination of at least two of a curing agent, a coupling agent, a catalyst, and an accelerator; Preferably, the curing agent includes any one of anhydride curing agent, amine curing agent, phenolic curing agent, or a combination of at least two thereof; Preferably, the coupling agent includes any one of an organosilicon coupling agent, a silane coupling agent, and a phthalate coupling agent, or a combination of at least two thereof; Preferably, based on 100% of the total weight of the polymer composite material, the content of the resin is 5% to 60%, the content of the filler is 40% to 70%, and the content of the auxiliary agent is 1% to 30%.

6. The detection method according to any one of claims 1 to 5, characterized in that The substrate includes silicon material.

7. The detection method according to any one of claims 1 to 6, characterized in that The laser wavelength in the characterization test using a micro-Raman spectrometer in step (2) and the Raman surface scanning imaging test in step (4) includes at least one of 488 nm, 514 nm, 532 nm, 633 nm, and 785 nm.

8. The detection method according to any one of claims 1 to 7, characterized in that In step (2), a micro-Raman spectrometer is used for characterization and detection, and the power of the laser is 1 mW to 25 mW; Preferably, in step (2), a micro-Raman spectrometer is used for characterization detection, and the integration time is 1s to 300s.

9. The detection method according to any one of claims 1 to 8, characterized in that The signal difference in step (3) includes at least one of the appearance of a new characteristic peak, a change in the intensity of the characteristic peak, a change in displacement, a change in half-peak width, and a change in relative peak intensity; Preferably, the area of ​​the region containing the bonding interface in step (4) is 50×80 μm to 70×120 μm; Preferably, in the Raman surface scanning imaging test in step (4), the power of the laser is 1 mW to 25 mW; Preferably, in the Raman surface scan imaging test in step (4), the integration time is 1s to 300s.

10. A device for detecting chemical bonds at the interface between an organic material and a substrate, characterized in that: The detection device includes a memory and a processor, the memory stores a computer program, and the processor implements the steps of the detection method according to any one of claims 1 to 9 when executing the computer program.

Images