In-situ sample stage, in-situ infrared ATR testing device and method for thermochromic phase change thin film material

Abstract

The present invention discloses an in-situ sample stage, an in-situ infrared ATR testing device and method for thermochromic phase change thin film materials. An in-situ sample stage includes a base, a cooling box, a rapid temperature change module, a sample stage and a thermal insulation cover. The base is provided with a heat-insulating recessed portion, the cooling box is arranged in the recessed portion, a cooling water pipe is arranged on one side of the cooling box, the rapid temperature change module is closely arranged directly above the cooling box, the sample stage is arranged above the rapid temperature change module in a manner of closing the recessed portion, the sample stage is provided with a sample groove for placing the sample, and a thermal insulation cover is arranged on the top of the sample stage. The testing method proposed in the present invention realizes the new function of in-situ infrared spectroscopy characterization of the entire phase change process of thermochromic phase change thin film materials under different temperature conditions; it is easy to operate, does not require sample preparation and pre-treatment, maintains the integrity of the sample morphology, and avoids the influence of the film substrate at the same time, and has good data reproducibility.

Description

Technical field:

[0001] The invention relates to the technical field of infrared testing methods for phase change processes of thermochromic phase change thin film materials, and in particular to an in-situ sample stage, an in-situ infrared ATR testing device and method for thermochromic phase change thin film materials. Background technology:

[0002] Thermochromic phase change materials refer to temperature-sensitive phase change functional materials, which change color and structural phase when the temperature environment changes. The principle of attenuated total reflection infrared testing technology: the infrared light emitted from the light source passes through a crystal with a large refractive index and then projects onto the surface of the sample with a small refractive index. The light penetrates the sample to a certain depth and then returns. In this process, the sample selectively absorbs the incident light frequency region and the reflected light is weakened, thereby obtaining the structural information of the chemical composition of the sample surface. This technology is a widely used technology in infrared testing technology, which is convenient for testing and fast for sample preparation.

[0003] There is no good solution for real-time monitoring of the phase change process of thermochromic film samples in the existing technology. Summary of the invention:

[0004] In order to solve the problems existing in the prior art, the present invention provides an in-situ sample stage, an in-situ infrared ATR testing device and method for thermochromic phase change thin film materials. The method realizes the new function of in-situ infrared spectroscopy characterization of the entire phase change process of thermochromic phase change thin film materials under different temperature conditions. The operation is simple, no sample preparation and pretreatment are required, the integrity of the sample morphology is maintained, and the data reproducibility is good.

[0005] In order to achieve the above-mentioned purpose, the present invention adopts the following technical scheme: an in-situ sample stage, including a base, a cooling box, a rapid temperature change module and a sample stage, the base is provided with a heat-insulating recessed portion, the cooling box is arranged in the recessed portion, a cooling water pipe is arranged on one side of the cooling box, the rapid temperature change module is arranged closely above the cooling box, the sample stage is arranged above the rapid temperature change module in a manner of closing the recessed portion, the sample stage is provided with a sample groove for placing the sample, and a heat-insulating upper cover is arranged on the top of the sample stage. In the present invention, the cooling box is a cooling box composed of a fully enclosed metal box, the cooling box is in the shape of an internally hollow rectangular iron box, and one end of the cooling box is provided with a water inlet pipe and a water outlet pipe for the inlet and outlet of cooling water.

[0006] Preferably, the rapid temperature change module (Realplay / Realplay TCL-12706) is made of semiconductor materials, and the temperature change rate of the rapid temperature change module is 2-10°C / S. The rapid temperature change module can be heated and cooled, and the phase change process of thermochromic phase change thin film materials at high and low temperatures can be studied. When the rapid temperature change module is in conventional heating mode (surface temperature below 80°C), no cooling is required. When the electrodes are reversed and changed to cooling mode, the cooling system (cooling box) needs to be turned on for cooling. The temperature change rate of the rapid temperature change module can be as high as 2-10°C / S, and the effect of rapid temperature switching on thermochromic phase change thin film materials can be studied.

[0007] Preferably, the sample table is provided with a wire port and a cooling water pipe port, one end of the wire is connected to the rapid temperature change module, and the other end is connected to an external temperature controller through the wire port, and a cooling water inlet pipe and a cooling water outlet pipe are respectively provided on one side of the cooling box, and the cooling water inlet pipe and the cooling water outlet pipe are connected to the cooling box through the cooling water pipe port.

[0008] Preferably, a heat insulation plate for slowing down heat diffusion is provided above the sample groove, the heat insulation plate corresponds to the opening of the sample placement position, and the depth of the sample groove is greater than the thickness of the sample.

[0009] Preferably, the base is an integrally formed structure, and the base is made of a heat-insulating material, which is polytetrafluoroethylene, acrylic board or polyurethane.

[0010] The present invention also protects an in-situ infrared ATR testing device for thermochromic phase change thin film materials, comprising the above-mentioned in-situ sample stage, the objective lens wedge groove, the ATR objective lens, the first concave reflection objective lens, the second concave reflection objective lens, the first convex reflection objective lens and the second convex reflection objective lens. The ATR objective lens is arranged at a testing position directly above the in-situ sample stage through the objective lens wedge groove. The infrared incident light passes through the first convex reflection mirror and the first concave reflection mirror, enters the objective lens crystal of the ATR objective lens, and then is totally reflected and then passes through the second concave reflection mirror and the second convex reflection mirror before returning for ATR testing.

[0011] The present invention also protects an in-situ infrared ATR testing method for thermochromatic phase change thin film materials, wherein the thermochromatic phase change thin film sample is placed flat in a sample groove of an in-situ sample stage for program temperature control, so that the infrared ATR objective lens crystal is in effective contact with the thin film sample (i.e., the infrared ATR objective lens crystal is tightly pressed against the sample sheet, so that the crystal is in effective contact with the test surface with the thin film sample attached), and an attenuated total reflection infrared test is performed on the sample under different temperature conditions, wherein the program temperature control is performed through the in-situ sample stage; the in-situ infrared ATR testing method for thermochromatic phase change thin film materials is implemented through an in-situ infrared ATR testing device for thermochromatic phase change thin film materials, and specifically comprises the following steps:

[0012] S1. Install the in-situ sample stage onto the loading platform and lock the in-situ sample stage by rotation positioning;

[0013] S2. Place the film sample base downward and flat in the sample groove to locate the sample area to be tested;

[0014] S3, the loading platform is lowered to a suitable position, the ATR objective lens is inserted into the objective lens wedge groove and pushed to the test position;

[0015] S4. Lower the ATR objective lens and maintain a certain pressure. The test adopts the standard pressure mode to make the ATR objective lens crystal effectively contact with the thin film sample.

[0016] S5, the in-situ sample stage uniformly heats and cools the film sample through a programmed temperature control program;

[0017] S6. Perform infrared tests at different temperature points and collect infrared spectra.

[0018] The present invention can meet the heating requirements of thermochromic phase change film samples, especially film samples with glass or metal plates as substrates, during in-situ testing through a temperature-controllable in-situ sample stage. The base surface of the thermochromic phase change film sample is parallel to and in close contact with the bottom plane of the sample groove, and the side with the film sample attached faces upward. The thermochromic phase change film material in the present invention refers to a film sample with glass or metal plates as substrates.

[0019] The in-situ infrared ATR test method proposed by the present invention is composed of an in-situ sample stage capable of programmable temperature control, heating and cooling of thin film samples, and an attenuated total reflection infrared test method. It is used to measure thermochromatic phase change thin film samples, heat the thin film samples on the in-situ sample stage, and perform attenuated total reflection infrared test on them under the state of ATR objective lens pressurization.

[0020] The specific steps of step S1 are: installing the in-situ sample stage on the loading platform, the in-situ sample stage is provided with a fixing nut, and the in-situ sample stage is locked by rotation positioning, and the depth of the sample groove should be greater than the thickness of the film sample.

[0021] The heat-insulating upper cover of the in-situ sample stage is provided with a sample test area opening, and the film sample base faces downward, and the side with the film facing upward is placed in parallel in the sample groove.

[0022] Preferably, step S3 specifically includes the following steps:

[0023] S31, the loading platform is lowered to a suitable position to ensure that the height between the in-situ sample stage and the wedge-shaped groove of the objective lens on the top of the instrument is greater than the height of the ATR objective lens;

[0024] S32. Insert the ATR objective lens into the wedge groove of the objective lens and push it to the test position so that the top of the ATR objective lens crystal is directly above the opening of the sample test area of ​​the in-situ sample stage.

[0025] Preferably, step S4 specifically includes the following steps: lowering the ATR objective lens, maintaining a certain pressure between the ATR objective lens and the thin film sample, so that the objective lens crystal is effectively in contact with the sample, and ensuring that the sample morphology is intact. The test adopts a standard pressure mode, and a pressure value of 20 is preferably used. The infrared instrument model used in the present invention is: Nicolet iN 10, and the test software is: OMNIC Picta-Copyright2017.

[0026] Preferably, step S5 specifically includes the following steps: a heat-insulating upper cover with an opening for the sample detection area is arranged above the in-situ sample stage, and the sample is heated and cooled by a rapid temperature change module to achieve uniform heating and cooling of the thin film sample.

[0027] Compared with the prior art, the present invention has the following advantages:

[0028] 1. The in-situ sample stage proposed in the present invention realizes effective temperature control of the thin film sample through a rapid temperature change module, while also avoiding the influence of heat radiation or heat conduction of the heating component on the test instrument.

[0029] 2. The present invention can perform attenuated total reflection infrared testing under different temperature conditions during the programmed temperature control process, realizing the new function of in-situ infrared spectroscopy characterization of the entire phase change process of thermochromic phase change film materials under low temperature, high temperature, rapid temperature switching and other conditions, and can also study the influence of rapid temperature switching on thermochromic phase change film materials.

[0030] 3. The in-situ infrared ATR testing method proposed in the present invention is easy to operate, maintains the integrity of the sample morphology, avoids the influence of the film substrate, and has good sample reproducibility. Description of the drawings:

[0031] Figure 1 This is a flow chart of an in-situ infrared ATR testing method for a thermochromic phase change thin film material of the present invention;

[0032] Figure 2 A cross-sectional view of an in-situ infrared ATR testing device for a thermochromic phase change thin film material of the present invention;

[0033] Figure 3 It is a structural schematic diagram of the in-situ sample stage of the present invention;

[0034] Figure 4 It is a schematic diagram of the exploded structure of the in-situ sample stage of the present invention;

[0035] Figure 5 This is the in-situ temperature-variable infrared spectrum of the vanadium oxide composite film in Experimental Example 1;

[0036] Explanation of the reference numerals: 1. Loading platform; 2. Sample stage; 3. Temperature controller; 4. Sample groove; 5. Rapid temperature change module; 6. Base; 7. Detection area opening; 8. Wedge groove; 9. ATR objective lens; 10. Objective lens crystal; 11. First / second concave reflection objective lens; 12. First / second convex reflection objective lens; 13. Wire tube; 14. Fastener; 15. Cooling water pipe; 16. Wire port; 17. Insulation cover; 18. Cooling box; 19. Cooling water pipe port; 20. Thermocouple. Specific implementation method:

[0037] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0038] Unless otherwise specified, the equipment and reagents used in the present invention are conventional commercial products in the field of the present technology. The method is mainly used for film-shaped thermochromic phase change materials, but other sheet or film-shaped samples can also be tested under variable temperature conditions. In the following embodiments, the samples are preferably film samples.

[0039] Example 1

[0040] like Figure 1-4 As shown, the thermochromic phase change film sample is placed in parallel in the sample groove 4 of the sample stage 2 for programmed temperature control, so that the objective lens crystal 10 of the infrared ATR objective lens 9 is in effective contact with the film sample, and the attenuated total reflection infrared test is performed on it under different temperature conditions.

[0041] An in-situ infrared ATR testing method for a thermochromic phase change thin film material specifically comprises the following steps:

[0042] S1: The in-situ sample stage is mounted on the loading platform 1, and the in-situ sample stage is rotated and positioned and locked by the fastener 14;

[0043] S2: For the thin film sample, the sample base faces downward and the side with the film facing upward is placed parallel in the sample groove 4;

[0044] S3: The loading platform 1 is lowered to a suitable position, and the ATR objective lens 9 is inserted into the objective lens wedge groove 8 and pushed to the test position;

[0045] S4: lowering the ATR objective lens 9, which applies a certain pressure to the thin film sample, and the induction pressure value is preferably 20 (infrared instrument model: Nicolet IN 10, test software: OMNIC Picta–Copyright 2017), so that the objective lens crystal 10 is effectively in contact with the thin film sample;

[0046] S5: The sample stage 2 heats and cools the sample through the temperature controller 3 and the rapid temperature change module 5;

[0047] S6: Perform infrared tests at different temperature points and collect infrared spectra.

[0048] The in-situ sample stage in step S1 is formed by connecting the base 6, the cooling box 18, the rapid temperature change module 5, the sample stage 2 and the heat preservation cover 17 in sequence from bottom to top. The base 6 is made of polytetrafluoroethylene insulation material, is integrally formed, and has an insulating recessed portion; the cooling box 18 is directly laid in the middle of the base 6, and the cooling box 18 is composed of a group of fully enclosed square metal boxes. A cooling water pipe 15 is provided on one side of the cooling box, and the cooling water pipe 15 includes a cooling water inlet pipe and a cooling water outlet pipe. The cooling water inlet pipe and the cooling water outlet pipe are connected to the cooling box 18 through a cooling water pipe port 19 on the sample table 2; the rapid temperature change module 5 is located in the middle position directly above the cooling box 18, and its bottom surface is close to the cooling box 18. The rapid temperature change module is a semiconductor material for heating, and its shape can be square or round. There is a thermocouple 20 in the middle position for temperature detection; the bottom surface of the sample table 2 contacts the top surface of the rapid temperature change module 5, and is connected to the base 6 through a fastener 14, and is sealed by a seal; the fastener 14 can be a screw structure, and a threaded hole is opened on the base 6, and fixed by screwing the screw into the threaded hole.

[0049] The side length of the rapid temperature change module 5 should be smaller than the side length of the cooling box 18, while the side length of the cooling box 18 should be smaller than or equal to the radius of the base 6. The height of the rapid temperature change module 5 and the cooling box 18 overlapped is consistent with the height of the inner recess of the base. One end of the wire is connected to the rapid temperature change module, and the other end is connected to the temperature controller 3 through the wire port. The rapid temperature change module 5 is equipped with a thermocouple 20. The wiring of the temperature probe on the side wall is led out through the wire tube 13 on the side wall of the rapid temperature change module 5. The rapid temperature change module 5 adopts semiconductor heating. In the conventional heating mode, no cooling is required. When the electrode is reversed and it becomes the cooling mode, the cooling box needs to be turned on for cooling. The temperature change rate can reach 2-10℃ / S. In order to realize the program control of temperature, a wire port 16 and a cooling water pipe port 19 are provided on the sample stage 2, which can be used for the wire pipe 13 and the cooling water pipe 15 to enter and exit. In order to facilitate the placement of the sample to be tested, a sample groove 4 is provided on the surface of the sample stage 2. The shape of the sample groove 4 can be designed as needed.

[0050] In this embodiment, the sample in step S2 refers to a thin film sample with a glass or metal plate as a substrate. The substrate of the thin film sample faces downward, and the side with the thin film faces upward and is placed parallel to the sample groove 4. The sample stage 2 is provided with a sample groove 4 of a size and shape suitable for placing the thin film sample, and the depth of the sample groove 4 should not be less than the thickness of the thin film sample.

[0051] In this embodiment, in step S3, the loading platform 1 is lowered to a suitable position, and the height between the sample stage 2 and the wedge-shaped groove 8 on the top of the instrument should be greater than the height of the ATR objective lens 9 to ensure that the ATR objective lens is intact during the insertion process; the ATR objective lens 9 is inserted into the wedge-shaped groove 8 and pushed to the test position, so that the top of the objective lens crystal 10 at the top of the ATR objective lens 9 is located directly above the opening 7 of the detection area.

[0052] In this embodiment, the ATR objective lens 9 is lowered in step S4, and the objective lens crystal 10 is in effective contact with the thin film sample in the detection area opening 7 area, which means that a certain pressure is maintained between the ATR objective lens and the thin film sample and the sample morphology is not destroyed.

[0053] In this embodiment, in step S5, the sample stage 2 heats and cools the sample through the temperature controller 3, and the temperature controller 3 controls the rapid temperature change module 5 to perform program heating and cooling on the sample stage 2, and the temperature change rate can reach 2-10°C / S, achieving the effect of rapid heating and cooling. The base 6 is made of heat-insulating material, which can reduce the influence of heat radiation and heat conduction on the optical platform during the sample heating process. An insulating cover 17 with a sample detection area opening 7 is arranged above the sample stage 2, which can better ensure the insulation and temperature uniformity during the heating process; in order to more accurately detect the temperature of the sample, a temperature sensor can also be arranged on the surface of the sample stage 2, and the temperature sensor and the temperature probe of the rapid temperature change module 5 can be calibrated to obtain the phase change information of the sample corresponding to the absolute temperature.

[0054] In this embodiment, the specific infrared test in step S6 refers to the infrared light entering from above, and the incident light passes through the first convex reflection objective lens 12 and the first concave reflection objective lens 11 on the left side, enters the objective lens crystal 10, and then is totally reflected, and then returns through the second concave reflection objective lens 11 and the second convex reflection objective lens 12 on the right side to obtain an ATR spectrum.

[0055] Experimental Example 1

[0056] The in-situ infrared ATR testing method of the thermochromic phase change thin film material of Example 1 was used to test the vanadium oxide composite film on a glass substrate. The thickness of the vanadium oxide composite film was 80 nm. The in-situ sample stage was installed and locked by fasteners. The sample was placed into the sample slot of the in-situ sample stage with the side with the vanadium oxide composite film facing up. The loading platform was lowered to a suitable position, and the ATR objective lens was inserted into the wedge groove of the objective lens and pushed to the test position. The ATR objective lens was lowered to make the objective lens crystal effectively contact with the film, and the induction pressure value was preferably 20. The heating rate of the rapid temperature change module was set to 5°C / S, and the spectrum test of the vanadium oxide composite film under heating conditions was carried out.

[0057] Experimental comparative example 1

[0058] The conventional infrared ATR test method is used to test the vanadium oxide composite film on the glass substrate. The thickness of the vanadium oxide composite film is 80nm. The sample is placed with the vanadium oxide composite film side facing down into the sample slot of the sample table (because the sample slot is small, the area of ​​the sample needs to be manually reduced). The sample should cover the entire sample slot, and then the pressure touch rod is manually lowered to make the film sample effectively contact with the total reflection crystal below, and the spectrum test of the vanadium oxide composite film at room temperature is carried out.

[0059] like Figure 5 As shown, by comparing Experimental Example 1 with Comparative Example 1, it can be concluded that the method of the present invention can meet the heating of thermochromic phase change film samples, especially film samples with glass or metal plates as substrates, during the in-situ test, and realizes the attenuated total reflection infrared test under different temperature conditions during the program temperature control process. The method of the present invention is easy to operate, can effectively maintain the integrity of the sample morphology, and has good sample reproducibility.

[0060] The description of the above embodiments is only used to help understand the technical solution and core ideas of the present invention. It should be pointed out that for technicians in this technical field, several improvements and modifications can be made to the present invention without departing from the principles of the present invention. These improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. An in-situ sample stage, characterized in that: It includes a base, a cooling box, a rapid temperature change module, a sample table and a thermal insulation cover, wherein the base is provided with a thermal insulation recess, the cooling box is arranged in the recess, a cooling water pipe is provided on one side of the cooling box, the rapid temperature change module is closely arranged directly above the cooling box, the sample table is arranged above the rapid temperature change module in a manner of closing the recess, the sample table is provided with a sample groove for placing samples, and a thermal insulation cover is provided on the top of the sample table; the sample table is provided with a wire port and a cooling water pipe port, one end of the wire is connected to the rapid temperature change module, and the other end is connected to an external temperature controller through the wire port, a cooling water inlet pipe and a cooling water outlet pipe are respectively provided on one side of the cooling box, and the cooling water inlet pipe and the cooling water outlet pipe are connected to the cooling box through the cooling water pipe port.

2. The in-situ sample stage according to claim 1, characterized in that: The rapid temperature change module is made of semiconductor material, and the temperature change rate of the rapid temperature change module is as high as 2-10°C / S.

3. The in-situ sample stage according to claim 1, characterized in that: A heat insulation board for slowing down heat diffusion is also arranged above the sample groove, and the heat insulation board corresponds to the opening of the sample placement position. The depth of the sample groove is greater than the thickness of the sample.

4. The in-situ sample stage according to claim 1, characterized in that: The base is an integrally formed structure and is made of heat-insulating material.

5. An in-situ infrared ATR testing device for thermochromic phase change thin film materials, characterized in that: It includes the in-situ sample stage as described in claim 1, the objective lens wedge groove, the ATR objective lens, the first concave reflection objective lens, the second concave reflection objective lens, the first convex reflection objective lens and the second convex reflection objective lens. The ATR objective lens is set at the test position directly above the in-situ sample stage through the objective lens wedge groove. The infrared incident light passes through the first convex reflector and the first concave reflector and enters the objective lens crystal of the ATR objective lens, and then is totally reflected and returns after passing through the second concave reflector and the second convex reflector to perform the ATR test.

6. An in-situ infrared ATR testing method for thermochromic phase change thin film materials, characterized in that: The method is implemented by the in-situ infrared ATR testing device for the thermochromic phase change thin film material according to claim 5, comprising the following steps: S1. Install the in-situ sample stage onto the loading platform and lock the in-situ sample stage by rotation positioning; S2. Place the film sample base downward and flat in the sample groove to locate the sample area to be tested; S3, the loading platform is lowered to a suitable position, the ATR objective lens is inserted into the objective lens wedge groove and pushed to the test position; S4. Lower the ATR objective lens and maintain a certain pressure. The test adopts the standard pressure mode to make the ATR objective lens crystal effectively contact with the thin film sample. S5, the in-situ sample stage uniformly heats and cools the film sample through a programmed temperature control program; S6. Perform infrared tests at different temperature points and collect infrared spectra.

7. The in-situ infrared ATR testing method for thermochromic phase change thin film material according to claim 6, characterized in that: Step S3 specifically includes the following steps: S31, the loading platform is lowered to a suitable position to ensure that the height between the in-situ sample stage and the wedge-shaped groove of the objective lens on the top of the instrument is greater than the height of the ATR objective lens; S32. Insert the ATR objective lens into the wedge-shaped groove of the objective lens and push it to the test position so that the top of the ATR objective lens crystal is directly above the opening of the sample test area of ​​the in-situ sample stage.

8. The in-situ infrared ATR testing method for thermochromic phase change thin film materials according to claim 6, characterized in that: Step S4 specifically includes the following steps: lowering the ATR objective lens, maintaining a certain pressure between the ATR objective lens and the thin film sample, and testing using a standard pressure mode to make the objective lens crystal effectively contact with the sample and ensure that the sample morphology is intact.

9. The in-situ infrared ATR testing method for thermochromic phase change thin film material according to claim 6, characterized in that: Step S5 specifically includes the following steps: a heat-insulating upper cover with an opening for a sample detection area is arranged above the in-situ sample stage, and the sample is heated and cooled by a rapid temperature change module to achieve uniform heating and cooling of the thin film sample.

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