Microfluidic chip with surface functional modification of substrate and crystallization control method
By functionalizing the substrate surface of the microfluidic chip and utilizing patterned SAMs and gas-liquid phase control, the problem of crystal nucleation orientation dispersion was solved, achieving precise control and efficient growth of crystals, and improving crystallization consistency and efficiency.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- WENZHOU KANGRUI BAIOU BIOTECHNOLOGY CO LTD
- Filing Date
- 2026-05-11
- Publication Date
- 2026-07-21
AI Technical Summary
In existing technologies, microfluidic chips exhibit dispersed crystal nucleation orientation, making it difficult to precisely control crystallization orientation, resulting in poor consistency in crystallization and difficulty in controlling morphology.
A microfluidic chip with functionalized substrate surface is used to achieve face-selective nucleation of crystals by printing patterned SAMs on the Au layer surface and combining gas-liquid phase control. High-density SAMs are formed by using PDMS stamp micro-contact printing technology to precisely define functional regions and achieve ordered array growth of crystals.
Precise control of crystal size, morphology, orientation and distribution has been achieved, improving crystallization consistency and efficiency. Crystal orientation consistency reaches 90%, crystallization uniformity is improved by 80%, growth cycle is shortened by 25%, and yield is increased to 95%.
Smart Images
Figure CN122164517B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of microfluidics and crystallization control, and more specifically, to a microfluidic chip with functionalized substrate surface and a crystallization control method. Background Technology
[0002] A microfluidic chip is a chip that enables various routine physical, chemical, or biological experiments on a micrometer-scale chip, handling minute amounts of fluids. Microfluidic chips have become a powerful tool for studying biological systems at single-cell resolution. Furthermore, microfluidic chips are widely used not only for manipulating droplet generation, microfluidic diffusion and sieving, and detecting protein-ligand interactions, but also for molecular assays in biochemistry.
[0003] In the precise preparation of crystal systems such as calcium carbonate crystals, drug crystals, and nanomaterials, precise control of the crystallization process (including size, morphology, polymorphism, and orientation) is a core requirement. The application of microfluidic chips in crystallization processes is one research direction. Currently, this process faces the following technical challenges: dispersed crystal nucleation orientation, making precise control of crystallization orientation difficult; poor consistency in crystallization results; and difficulty in controlling morphology. Therefore, how to precisely control the crystallization process to improve crystallization results is a technical problem that urgently needs to be solved by those skilled in the art. Summary of the Invention
[0004] This application aims to solve the technical problem of how to accurately control the crystallization process using microfluidic chips, and provides a microfluidic chip with functionalized substrate surface and a crystallization control method.
[0005] A first aspect of this disclosure provides a microfluidic chip with a substrate surface functionalized, comprising a substrate and a cover plate. The substrate has patterned SAMs (Surface Acrylic Atomics). The cover plate has a double-layer structure, comprising an upper layer and a lower layer bonded together. The bottom surface of the upper layer has a gas channel and a gas containment chamber. The upper layer has a gas input through-hole, a gas output through-hole, a liquid input through-hole, and a liquid output through-hole. The gas input through-hole communicates with the gas containment chamber through the gas channel, and the gas output through-hole communicates with the gas containment chamber through the gas channel. The bottom surface of the lower layer has a liquid channel and a reaction chamber. The lower layer has a liquid input through-hole and a liquid output through-hole. The liquid input through-hole communicates with the reaction chamber through the liquid channel, and the liquid output through-hole communicates with the reaction chamber through the liquid channel. The liquid input through-hole of the upper layer communicates with the liquid input through-hole of the lower layer, and the liquid output through-hole of the upper layer communicates with the liquid output through-hole of the lower layer. The gas containment chamber corresponds to the reaction chamber and is located above the reaction chamber. The lower layer of the cover plate is bonded to the substrate, and the patterned SAMs are located in the reaction chamber.
[0006] Preferably, the substrate is a composite substrate comprising glass, a Cr layer and an Au layer, wherein the Cr layer is located between the Au layer and the glass; the lower layer of the cover plate is bonded to the Au layer of the composite substrate.
[0007] More preferably, the surface roughness of the Au layer is ≤0.5nm.
[0008] Preferably, the upper layer of the cover plate is made of PDMS, and the lower layer of the cover plate is made of PDMS.
[0009] Preferably, in the radial direction, the gas-containing chamber is located at the center of the reaction chamber.
[0010] Preferably, the patterned SAMs are circular units distributed in a square array.
[0011] Preferably, there are multiple gas chambers connected in series via gas channels. A gas inlet is connected to the first gas chamber in the series of gas chambers via a gas channel, and a gas outlet is connected to the last gas chamber in the series of gas chambers via a gas channel. There are multiple reaction chambers connected in series via liquid channels. The liquid inlet hole on the lower layer of the cover plate is connected to the first reaction chamber in the series of multiple reaction chambers via liquid channels, and the liquid outlet hole on the lower layer of the cover plate is connected to the tail reaction chamber in the series of multiple reaction chambers via liquid channels. There are multiple sets of patterned SAMs on the substrate, and each reaction chamber contains one set of patterned SAMs.
[0012] Preferably, the reaction chamber is provided with a cylindrical array.
[0013] Preferably, the reaction chamber is circular, and the gas containing chamber is circular.
[0014] A second aspect of this disclosure provides a method for controlling the crystallization of a microfluidic chip using the above-described substrate surface functionalization modification, comprising the following steps: Step 1, preparation of the reaction system: Preparation of liquid phase; Preparation of gas phase; The second step is to adjust the microfluidic parameters: Liquid injection: Liquid is injected into the reaction chamber through the liquid inlet hole on the upper part of the cover plate. The liquid flows at a certain flow rate and flows out through the liquid outlet hole on the upper part of the cover plate. Gas injection: Gas is injected into the gas receiving chamber through the gas inlet through the upper part of the cover plate, and the gas flows out through the gas outlet through the upper part of the cover plate; the gas in the gas receiving chamber permeates into the reaction chamber and reacts with the liquid in the reaction chamber to grow crystals on the patterned SAMs.
[0015] Preferably, the microfluidic chip is placed under an inverted microscope to monitor the crystal growth process in real time.
[0016] Preferably, in the preparation of the reaction system in the first step, the liquid phase is a CaCl2 solution and the gas is a mixture of NH3 and CO2.
[0017] Patterned SAMs are formed on the surface of the Au layer by PDMS stamping. The contact area can be ω-terminated alkyl thiols (HS (CH2) nX, X=COOH, OH, SO3H), and the non-contact area can be methyl-terminated alkyl thiols (HS (CH2) 15CH3).
[0018] The beneficial effects of this disclosure are that the patterned SAMs based on PDMS stamp microcontact printing are of high quality, achieve precise definition of functional areas, and realize the ordered array growth of crystals.
[0019] The density of patterned SAMs formed by Au layers is more than 60% higher than that of glass substrates. By selecting different end-group functional groups (COOH, OH, SO3H), face-selective nucleation of CaCO3 crystals can be achieved (such as COOH / Au inducing calcite (015) face orientation, OH / Au inducing (104) face orientation), with an orientation consistency of up to 90%.
[0020] A crystallization control method, combined with the face-selective nucleation of patterned SAMs, enables precise control over the size, morphology, orientation, and distribution of crystals, achieving ordered array growth. This provides technical support for the large-scale fabrication of high-performance functional crystal materials by achieving multi-dimensional synergistic control over crystal size, morphology, orientation, and distribution.
[0021] It is suitable for the precise preparation of drug crystals, biomaterials, ceramic materials, nanomaterials and optical components, and can be widely used in pharmaceutical, biomedical engineering, advanced materials synthesis and other industries.
[0022] Further features and aspects of the present invention will be clearly described in the following detailed description with reference to the accompanying drawings. Attached Figure Description
[0023] Figure 1 In the figures (a), (b), (c), and (d), a square-circular array of red dye aqueous solution microprinting ink is shown on the surface of the Au layer. Figure 2 This is a schematic diagram of the upper-layer PDMS structure; Figure 3 This is a schematic diagram of the lower-level PDMS structure; Figure 4 This is a cross-sectional view of the lower-level PDMS; Figure 5 This is a schematic diagram showing the cylinder arrangement in the lower PDMS reaction chamber; Figure 6 This is a schematic diagram of the structure where the lower-layer PDMS and the lower-layer PDMS are bonded together; Figure 7 This is a top-down, vertical view showing the positional relationship between the gas containment chamber in the upper PDMS and the reaction chamber in the lower PDMS. Figure 8 This is a schematic diagram of the structure where the upper PDMS and the lower PDMS are bonded together; Figure 9 This is a schematic diagram of the structure in which a double-layer PDMS cover plate is bonded to a composite substrate; Figure 10 yes Figure 9 A magnified view of a section at point A in the middle; Figure 11 This is a schematic diagram of square array patterned SAMs; Figure 12 The figures (a), (b), (c), and (d) show the surface-selective nucleation of calcite crystals mediated by SAMs supported on gold:SO3H / Au. Figure 13 The microprinting ink shows that after adding 10 mm of HS(CH2)nX (X = CO2H) solution to ethanol, the substrate is placed in 1 mm of calcium chloride solution and left overnight in a closed desiccator containing a vial of ammonium carbonate (3 g), forming a square array of calcite on the gold surface. Figure 14 The microprinting ink shows that after adding 10 mm of HS(CH2)nX (X = CO2H) solution to ethanol, the substrate is placed in 1 mm of calcium chloride solution and left overnight in a closed desiccator containing a vial of ammonium carbonate (3 g), forming a square array of calcite on the gold surface. Figure 15 This is a high-magnification image of calcite, indicating that calcite preferentially crystallizes to the COOH end-group contact region; Figure 16 The image is a high-magnification image of calcite, indicating that calcite preferentially crystallizes to the COOH end-group contact region.
[0024] Explanation of symbols in the diagram: 1. Upper PDMS layer: 1-1. Gas inlet port, 1-2. Gas outlet port, 1-3. Gas channel, 1-4. Gas containment chamber, 1-5. Liquid inlet port, 1-6. Liquid outlet port; 2. Lower PDMS layer: 2-1. Liquid inlet port, 2-2. Liquid outlet port, 2-3. Liquid channel, 2-4. Reaction chamber, 2-5. Cylinder; 3. Composite substrate: 3-1. Glass, 3-2. Cr layer, 3-3. Au layer; 4. Patterned SAMs. Detailed Implementation
[0025] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
[0026] The specific embodiments described below are merely preferred embodiments of this application, and the scope of protection of this application is not limited thereto. Those skilled in the art can make modifications or variations based on the principles, concepts, and spirit of this application, and the resulting technical solutions should all be covered within the scope of protection of this application.
[0027] The key equipment involved includes the Edwards 306 Thermal Evaporator, the plasma treatment system: a conventional oxygen plasma generator, and the characterization equipment: an inverted microscope, a polarizing microscope, and a Raman spectroscopy system.
[0028] The fabrication process of microfluidic chips is as follows: Step 1, Substrate Pretreatment: The glass slide was immersed in a piranha solution (concentrated H2SO4:H2O2=3:1) for 2 hours to remove surface impurities. Using an Edwards 306 thermal evaporator, a 5nm Cr layer was first deposited on the glass slide by thermal evaporation, followed by a 50nm Au layer. The deposition rate was controlled at 0.1nm / s to ensure uniform film layer.
[0029] This forms a glass-Cr-Au composite substrate, with the Cr layer serving as a transition layer to enhance the adhesion between the gold film and the glass.
[0030] The Au layer serves as the growth substrate for subsequent SAMs, and its surface roughness is ≤0.5nm, which is beneficial for the dense and uniform growth of SAMs.
[0031] Step 2, PDMS stamp preparation: PDMS stamps are fabricated using soft lithography. The master mold is a silicon wafer with a circular bump array. After the PDMS monomer and crosslinking agent are mixed and degassed, the mixture is poured onto the master mold and baked at 65°C overnight. After peeling, a PDMS stamp with a relief structure is obtained. The surface humidity needs to be controlled before use (avoiding excessive dryness or moisture).
[0032] Step 3, fabrication of patterned SAMs: Step (1), "Inking" the stamp: Using alkyl thiol as "ink", immerse the PDMS stamp in a 10mM alkyl thiol ethanol solution to ensure that the circular raised area is uniformly adsorbed with ink; the alkyl thiol can be HS (CH2)15CO2H, HS (CH2)11OH or HS (CH2)11SO3H), with a purity ≥98%.
[0033] Step (2), Micro-contact printing: The PDMS stamp is brought into contact with the Au layer of the composite substrate, and uniform pressure (0.05-0.1MPa) is applied and held for 10s. Figure 1 The four photos show a square-circular array of microprinting ink produced by a red dye aqueous solution on the surface of an Au layer.
[0034] Step (3), passivation of non-contact areas: Immerse the composite substrate in an ethanol solution of 10mM HS (CH2) 15CH3 for 1 minute to seal the Au layer surface area that is not in contact with the PDMS stamp.
[0035] Step (4), cleaning and drying: Rinse the composite substrate with anhydrous ethanol and dry it with nitrogen to complete the preparation of SAMs and obtain a composite substrate with patterned SAMs. SAMs are self-assembled monolayers.
[0036] Patterned SAMs are used as functional layers. For example... Figure 11 As shown, patterned SAMs are circular functional units in a square array. The diameter d of the circular functional units can be 35 μm or 50 μm, and the spacing p between adjacent circular functional units can be 100 μm.
[0037] Step 4: Create the upper-layer PDMS and the lower-layer PDMS: Step (1), create the upper-layer PDMS: like Figure 2 As shown, the bottom surface of the upper PDMS1 is provided with gas channels 1-3 and gas chambers 1-4. There are multiple gas chambers 1-4, and adjacent gas chambers 1-4 are connected through gas channels 1-3. Multiple gas chambers 1-4 are connected in series through gas channels 1-3. The upper PDMS1 is provided with a gas inlet port 1-1 and a gas outlet port 1-2. The gas inlet port 1-1 is connected to the first gas chamber among the multiple gas chambers 1-4 connected in series through gas channels 1-3, and the gas outlet port 1-2 is connected to the last gas chamber among the multiple gas chambers 1-4 connected in series through gas channels 1-3. The upper PDMS1 is also provided with a liquid inlet port 1-5 and a liquid outlet port 1-6.
[0038] The specific manufacturing process can involve using PDMS material, which is produced by spin coating or casting, with a thickness of approximately 5mm. Gas inlets and outlets are reserved, and the gas passage surrounds the lower reaction chamber area to ensure uniform gas diffusion.
[0039] Step (2), create the lower-level PDMS: like Figure 3 and 4 As shown, the bottom surface of the lower PDMS2 is provided with a liquid channel 2-3 and a reaction chamber 2-4. There are multiple reaction chambers 2-4, and two adjacent reaction chambers 2-4 are connected through the liquid channel 2-3. Multiple reaction chambers 2-4 are connected in series through the liquid channel 2-3. The lower PDMS2 is provided with a liquid inlet through hole 2-1 and a liquid outlet through hole 2-2. The liquid inlet through hole 2-1 is connected to the first reaction chamber in the multiple reaction chambers 2-4 connected in series through the liquid channel 2-3. The liquid outlet through hole 2-2 is connected to the tail reaction chamber in the multiple reaction chambers 2-4 connected in series through the liquid channel 2-3.
[0040] The specific fabrication process can be as follows: Sylgard 184 PDMS monomer and crosslinking agent are mixed at a mass ratio of 10:1, degassed, and then poured onto a photolithographically prepared master substrate. The substrate is then baked at 65°C for 30 minutes to cure. After curing, the substrate is cut to form a structure containing multiple reaction chambers. The reaction chambers 2-4 are preferably circular, with a diameter of 120 μm, a height of 3 μm, and a volume of 23.3 pL. A liquid inlet through-hole 2-1 and a liquid outlet through-hole 2-2 are formed by punching holes using a 1 mm biopsy punch.
[0041] Multiple cylinders 2-5 can be produced in reaction chamber 2-4, such as Figure 5 As shown, multiple cylinders 2-5 form a cylindrical array. The diameter of cylinders 2-5 can be 3 μm, and the spacing between cylinders is 3 μm. The cylindrical array is used to control the crystal morphology.
[0042] Given that reaction chambers 2-4 are circular, a better design would be to also design gas-containing chambers 1-4 as circular.
[0043] Step 5, chip assembly: Step (1): The upper and lower PDMS layers are treated with oxygen plasma for 30 seconds (generating -Si-OH groups on the surface of the PDMS). After precise alignment of the upper and lower PDMS layers, they are bonded together and baked at 65°C for 30 minutes to achieve stable bonding and form a double-layer PDMS cover plate. Figure 6 , 7As shown in Figure 8, liquid inlet through-hole 1-5 is connected to liquid inlet through-hole 2-1, and liquid outlet through-hole 1-6 is connected to liquid outlet through-hole 2-2. One gas container chamber 1-4 corresponds to one reaction chamber 2-4, and the gas container chamber 1-4 is located above the reaction chamber 2-4. In the radial direction, the gas container chamber 1-4 is located at the center of the reaction chamber 2-4, which is conducive to uniform gas diffusion.
[0044] When both reaction chamber 2-4 and gas containment chamber 1-4 are circular, the cross-sectional area of gas containment chamber 1-4 is smaller than that of reaction chamber 2-4, which is conducive to uniform gas diffusion and also ensures that the crystallization location is in the central area of the reaction chamber, effectively preventing crystallization near the inlet and outlet and preventing channel blockage caused by crystallization.
[0045] Step (2), bonding the double-layer PDMS cover plate to the composite substrate: Align the double-layer PDMS cover plate with the composite substrate with patterned SAMs obtained in step 3 above, bond it after oxygen plasma treatment, bake it at 65°C overnight, and achieve irreversible bonding through Si-O-Si covalent bonds to ensure no leakage.
[0046] like Figure 9 and 10 As shown, the lower PDMS2 is bonded to the Au layer 3-3 of the composite substrate, and a set of patterned SAMs is located in a reaction chamber 2-4, with a set of patterned SAMs in each reaction chamber 2-4.
[0047] Crystallization control is achieved using the microfluidic chip described above: Step 1, preparation of the reaction system: The liquid phase is a CaCl2 solution (concentration: 5×10-3~10×10-3M), and MgCl2 (concentration: 5×10-3~15×10-3M) or polyacrylic acid (PAA, concentration 1μg / mL) can be added as additives; the concentration ratio of CaCl2 to MgCl2 can be 1:1~3:1.
[0048] The gas phase is a mixture of NH3 and CO2 produced by the decomposition of (NH4)2CO3 powder.
[0049] The second step is to adjust the microfluidic parameters: Liquid injection: CaCl2 solution is injected into reaction chamber 2-4 through liquid inlet port 1-5 at a flow rate of 10 μL / min using a syringe pump. After filling, the flow rate is reduced to 1 μL / h to maintain a stable liquid flow. The CaCl2 solution in the liquid path flows out through liquid outlet port 1-6.
[0050] Gas injection: An NH3+CO2 mixed gas is injected into the gas receiving chamber 1-4 at a flow rate of 1–10 μL / min through the gas inlet port 1-1 using another syringe pump. The NH3+CO2 mixed gas permeates through the PDMS membrane between the gas receiving chamber 1-4 and the reaction chamber 2-4 into the reaction chamber 2-4, where it reacts with the CaCl2 solution to generate CaCO3. The CaCO3 crystals grow only on the patterned SAMs, forming an ordered crystal array. The crystallization inhibition rate of non-functional regions reaches 100%, and the uniformity of crystal distribution is greatly improved, which is 80% higher than that of existing technologies. The NH3+CO2 mixed gas flows out from the gas outlet port 1-2.
[0051] The third step is monitoring the crystallization process: The microfluidic chip was placed under an inverted microscope to observe the crystal growth process in real time. The crystal orientation and polymorphism were characterized by polarization microscopy and Raman spectroscopy. The compactness of the surface SAMs of the Au layer was characterized by Raman spectroscopy, and the characteristic peak intensity was increased by 60% compared with that of SAMs on glass substrates. Using polarization microscopy and electron backscatter diffraction (EBSD) tests, 90% of the calcite crystals on the COOH / Au substrate showed (015) plane orientation, while 85% of the crystals on the OH / Au substrate showed (104) plane orientation, which is significantly better than the random orientation of the existing glass substrate.
[0052] Optical microscopy revealed that the COOH functionalized regions formed a regular circular array of CaCO3 crystals with diameters matching the size of the stamp protrusions (35 μm / 50 μm) and a spacing of 100 μm. The non-functional regions showed no crystallization.
[0053] Crystal orientation consistency is improved by 90%, and crystal uniformity is improved by 80%.
[0054] It ran continuously for 72 hours without leakage, the reaction chamber showed no deformation, and the crystallization process had a repeatability of 98%.
[0055] The gas-liquid mass transfer efficiency is improved by 50%, the crystal growth cycle is shortened from 24 hours in the existing technology to 18 hours, the growth cycle is shortened by 25%, and the crystallization yield is increased from 70% to 95%.
[0056] It is evident that the crystal size (21–50 μm), morphology (regular rhombohedrons, ordered arrays), orientation, and polymorphism (stable calcite phase) can be synergistically controlled by the type of functional groups, patterned SAMs parameters (size, spacing), gas-liquid flow rate, and additive type and concentration, thus meeting the preparation requirements of different functional materials.
[0057] Figure 13 , Figure 14 , Figure 15 and Figure 16These are microscopic images of crystal orientation induced by SAMs with different functional groups, optical microscopy. Figure 13 , Figure 14 The microprinting ink was shown to form a square array of calcite on a gold surface after adding 10 mm of HS(CH2)nX (X = CO2H) solution to ethanol, then placing the substrate in 1 mm of calcium chloride solution and incubating overnight in a closed desiccator containing a vial of ammonium carbonate (3 g). Figure 15 , Figure 16 The image shows a high-magnification image of calcite, indicating that calcite preferentially crystallizes to the cooh end-group contact region.
[0058] Using CaCO3 as a model system for verification, this method can be extended to the precise preparation of various crystal systems such as drug crystals (e.g., aspirin), ceramic precursors, and nanomaterials.
Claims
1. A microfluidic chip with functionalized substrate surface, characterized in that, The device includes a substrate and a cover plate. The substrate has patterned SAMs (Surface Acrylic Atomics). The cover plate has a double-layer structure, comprising an upper layer and a lower layer bonded together. The bottom surface of the upper layer has a gas channel and a gas receiving chamber. The upper layer also has a gas inlet, a gas outlet, a liquid inlet, and a liquid outlet. The gas inlet and outlet communicate with the gas receiving chamber through the gas channel. The bottom surface of the lower layer has a liquid channel and a reaction chamber. The lower layer also has a liquid inlet and a liquid outlet. The liquid inlet and outlet communicate with the reaction chamber through the liquid channel. The liquid inlet of the upper layer communicates with the liquid inlet of the lower layer, and the liquid outlet of the upper layer communicates with the liquid outlet of the lower layer. The gas receiving chamber corresponds to the reaction chamber and is located above the reaction chamber. The lower layer of the cover plate is bonded to the substrate, and the patterned SAMs are located in the reaction chamber; The upper layer of the cover plate is made of PDMS, and the lower layer of the cover plate is made of PDMS.
2. The microfluidic chip with functionalized substrate surface according to claim 1, characterized in that, The substrate is a composite substrate comprising glass, a Cr layer and an Au layer, wherein the Cr layer is located between the Au layer and the glass; the lower layer of the cover plate is bonded to the Au layer of the composite substrate.
3. The microfluidic chip with functionalized substrate surface according to claim 2, characterized in that, The surface roughness of the Au layer is ≤0.5nm.
4. The microfluidic chip with functionalized substrate surface according to claim 1, characterized in that, In the radial direction, the gas containment chamber is located at the center of the reaction chamber.
5. The microfluidic chip with functionalized substrate surface according to claim 1, characterized in that, The patterned SAMs are circular units distributed in a square array.
6. The microfluidic chip with functionalized substrate surface according to any one of claims 1-5, characterized in that, The gas containment chambers are multiple, and the multiple gas containment chambers are connected in series through gas channels. The gas inlet is connected to the first gas containment chamber in the series of multiple gas containment chambers through gas channels, and the gas outlet is connected to the tail gas containment chamber in the series of multiple gas containment chambers through gas channels. The reaction chambers are multiple and connected in series via liquid channels. The liquid inlet of the cover plate is connected to the first reaction chamber in the series of reaction chambers via liquid channels, and the liquid outlet of the cover plate is connected to the tail reaction chamber in the series of reaction chambers via liquid channels. The substrate has multiple sets of patterned SAMs, and each reaction chamber contains one set of patterned SAMs.
7. The microfluidic chip with functionalized substrate surface according to any one of claims 1-5, characterized in that, The reaction chamber is equipped with a cylindrical array.
8. The microfluidic chip with functionalized substrate surface according to any one of claims 1-5, characterized in that, The reaction chamber is circular, and the gas containing chamber is circular.
9. A method for controlling the crystallization of a microfluidic chip with a substrate surface functionalized according to any one of claims 1-8, characterized in that, Includes the following steps: Step 1, preparation of the reaction system: Preparation of liquid phase; Preparation of gas phase; The second step is to adjust the microfluidic parameters: Liquid injection: Liquid is injected into the reaction chamber through the liquid inlet hole on the upper part of the cover plate. The liquid flows at a certain flow rate and flows out through the liquid outlet hole on the upper part of the cover plate. Gas injection: Gas is injected into the gas receiving chamber through the gas inlet through the upper part of the cover plate, and the gas flows out through the gas outlet through the upper part of the cover plate; the gas in the gas receiving chamber permeates into the reaction chamber and reacts with the liquid in the reaction chamber to grow crystals on the patterned SAMs.
10. The crystallization control method according to claim 9, characterized in that, The microfluidic chip was placed under an inverted microscope to monitor the crystal growth process in real time.
11. The crystallization control method according to claim 9 or 10, characterized in that, In the preparation of the first step reaction system, the liquid phase is a CaCl2 solution, and the gas is a mixture of NH3 and CO2.