CN114184596A - A Synchronous Thermogravimetric-Raman Characterization Method - Google Patents
A Synchronous Thermogravimetric-Raman Characterization Method Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention provides a synchronous thermogravimetry-Raman spectrum characterization method, which comprises the steps of weighing the mass change of a sample to be measured in the temperature rise process in real time through a chip with a self-heating function to obtain a thermogravimetry curve; meanwhile, laser is focused on the surface of the sample to be detected through a microscope so as to collect the Raman spectrum scattered by the sample to be detected in the temperature rising process and extract the structural change information of the sample to be detected in real time. The synchronous thermogravimetry-Raman spectrum characterization method provided by the invention can be used for characterizing the structure and object image evolution of the sample to be tested while acquiring the dynamic property of the sample to be tested through thermogravimetric analysis, and has the advantages of in-situ performance, no damage, rapidness, high precision, small sample consumption and the like.
Description
Technical Field
The invention belongs to the field of detection characterization, and relates to a synchronous thermogravimetry-Raman characterization method.
Background
Thermogravimetric analysis is an irreplaceable material characterization means in many scientific fields such as physics, chemistry and environment, and obtains information such as thermal stability, reaction kinetic characteristics and components of a material by measuring the mass change of the material in a heating process. The traditional thermogravimetric analyzer is huge in volume, and the core component of the traditional thermogravimetric analyzer is an electronic balance used for detecting the mass in the furnace. The acquisition of more information about the chemical reactions during heating is achieved by detecting the evolved gases during the reaction by expensive gas chromatography or mass spectrometry. Therefore, in the test thermogravimetric analysis process, the structure and phase evolution information of the material to be tested is analyzed in situ and in real time, and the traditional thermogravimetric analysis technology cannot be realized.
Raman (Raman) spectroscopy is a material characterization instrument that provides detailed information on chemical structures, phases and molecular interactions. In the Raman characterization process, laser needs to be focused on a material, a Raman spectrum is obtained by detecting scattered light of the material, and then material structure related information is extracted from the spectrum. Because the time of one spectral line tested by the Raman spectrum is often within a few seconds, the Raman spectrum is very suitable for representing real-time evolution information of a material structure under the influence of test conditions.
The synchronous combined characterization of the thermogravimetric analysis technology and the Raman spectrum technology can make up for the defect that the existing thermogravimetric analysis technology cannot carry out real-time characterization on the material structure. However, it is still difficult to introduce a laser beam of Raman spectroscopy into an existing conventional thermogravimetric analysis instrument such as a sample crucible in a furnace.
Therefore, the invention provides a synchronous thermogravimetric-Raman characterization method, which realizes high-precision thermogravimetric analysis and rapid and nondestructive spectrum characterization in situ and is actually necessary.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention aims to provide a synchronous thermogravimetric-raman characterization method for solving the problem of difficulty in the joint characterization of the thermogravimetric analysis technique and the raman spectroscopy technique in the prior art.
In order to achieve the above and other related objects, the present invention provides a characterization method for synchronous thermogravimetry-raman characterization, which includes providing a chip with a self-heating function, weighing the mass change of a sample to be measured in a heating process in real time by the chip to obtain a thermogravimetry curve, focusing laser on the surface of the sample to be measured by a microscope to collect a raman spectrum scattered by the sample to be measured in the heating process, and extracting the structural change information of the sample to be measured in real time to perform synchronous thermogravimetry-raman characterization.
Optionally, the method comprises the following steps:
s1: providing a resonant cantilever beam chip with a self-heating function, and placing the resonant cantilever beam chip in a test environment;
s2: carrying out baseline test operation, carrying out temperature programming on the resonant cantilever beam chip, and recording the change curve of the intrinsic resonant frequency of the cantilever beam along with the temperature;
s3: carrying out sample coating operation, and coating a sample to be detected on the free end of the cantilever beam;
s4: placing the cantilever coated with the sample to be tested in the same test environment as the step S2 again, and performing synchronous thermogravimetry and Raman characterization operation: testing the change curve of the resonant frequency of the cantilever beam loaded with the sample to be tested along with the temperature, simultaneously focusing laser on the sample to be tested by utilizing a Raman testing system, and collecting a Raman spectrum in the temperature programming heating process in real time;
s5: performing data processing, wherein the data processing comprises resonance frequency data processing and Raman spectrum data processing, and the resonance frequency data processing comprises:
obtaining a change relation curve of the resonance frequency variation delta f and the temperature by subtracting the resonance frequency values obtained in the step S2 and the step S4 at the same temperature, obtaining a residual mass percentage-temperature relation curve of the sample to be detected, namely a thermogram, by using the following relation,
wherein: f is the eigen-resonance frequency of the cantilever beam; delta f is the difference between the resonance frequency and the intrinsic resonance frequency of the cantilever beam measured in the sample coating and testing process; k is the Young modulus of the cantilever beam; m iseffIs the cantilever beamEffective mass of (a); Δ m is the mass of the residual sample on the cantilever;
the Raman spectrum data processing comprises the following steps:
and processing the Raman spectrum signal obtained in the step S4, wherein the processing comprises background subtraction and peak separation fitting, and a Raman spectrum image of the sample to be detected along with temperature change is obtained.
Optionally, the heating temperature range of the sample to be detected is 25 ℃ to 1200 ℃.
Optionally, in step S1, the test environment includes a gas environment condition and a temperature rise condition, the gas environment condition includes a vacuum condition and an atmosphere condition, the vacuum condition includes a vacuum degree, the atmosphere condition includes a gas type, a gas flow rate, and a gas pressure, and the temperature rise condition includes a temperature rise temperature and a temperature rise rate.
Optionally, the vacuum comprises 10-6mbar to 1 bar; the gas type comprises inert gas, air or reaction gas, the gas flow rate comprises 1 ml/min-100 ml/min, and the gas pressure comprises 1 bar.
Optionally, the heating rate comprises 1 ℃/min to 30000 ℃/min.
Optionally, the cantilever beam includes a driving resistor, a frequency detecting resistor, and a heating resistor.
Optionally, the heating resistor includes a platinum heating resistor with a heating temperature range of 25 ℃ to 600 ℃ or a molybdenum heating resistor with a heating temperature range of 25 ℃ to 1200 ℃.
Optionally, the mass range of the sample to be measured includes picogram level or nanogram level, and the mass measurement precision of the sample to be measured is picogram.
As described above, according to the synchronous thermogravimetry-Raman characterization method, the mass change of the sample to be measured in the temperature rise process is weighed in real time through the chip with the self-heating function, so that a thermogravimetry curve is obtained; meanwhile, laser is focused on the surface of the sample to be detected through a microscope so as to collect the Raman spectrum scattered by the sample to be detected in the temperature rising process and extract the structural change information of the sample to be detected in real time. The synchronous thermogravimetry-Raman spectrum characterization method provided by the invention can be used for characterizing the structure and object image evolution of the sample to be tested while acquiring the dynamic property of the sample to be tested through thermogravimetric analysis, and has the advantages of in-situ performance, no damage, rapidness, high precision, small sample consumption and the like.
Drawings
FIG. 1 is a flow chart of a synchronous thermogravimetric-Raman characterization method according to an embodiment of the present invention.
Fig. 2 is a schematic operation diagram of the synchronous thermogravimetric-raman characterization method in the embodiment of the present invention.
FIG. 3 is a thermogravimetric plot of molybdenum disulfide in an air atmosphere according to an example of the present invention.
Fig. 4 is a graph showing the results of the simultaneous raman characterization of fig. 3.
Fig. 5 is a thermogravimetric plot of graphene oxide under vacuum conditions in an embodiment of the present invention.
Fig. 6 is a graph showing the results of the simultaneous raman characterization of fig. 5.
Description of the element reference numerals
100 cantilever beam
200 chip substrate
201 heating resistor
202 drive resistor
203 frequency detection resistor
204 drive circuit
205 heating circuit
206 temperature measurement circuit
207 frequency detection circuit
208 heat-resistant groove
301 microscope
302 laser
303 raman signal
Sample A
S1-S5
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
As in the detailed description of the embodiments of the present invention, the cross-sectional views illustrating the device structures are not partially enlarged in general scale for convenience of illustration, and the schematic views are only examples, which should not limit the scope of the present invention. In addition, the three-dimensional dimensions of length, width and depth should be included in the actual fabrication.
For convenience in description, spatial relational terms such as "below," "beneath," "below," "under," "over," "upper," and the like may be used herein to describe one element or feature's relationship to another element or feature as illustrated in the figures. It will be understood that these terms of spatial relationship are intended to encompass other orientations of the device in use or operation in addition to the orientation depicted in the figures. Further, when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. As used herein, "between … …" is meant to include both endpoints.
In the context of this application, a structure described as having a first feature "on" a second feature may include embodiments in which the first and second features are formed in direct contact, and may also include embodiments in which additional features are formed in between the first and second features, such that the first and second features may not be in direct contact.
It should be noted that the drawings provided in the present embodiment are only for illustrating the basic idea of the present invention, and the drawings only show the components related to the present invention rather than being drawn according to the number, shape and size of the components in actual implementation, and the type, quantity and proportion of each component in actual implementation may be changed freely, and the layout of the components may be more complicated.
The embodiment provides a synchronous thermogravimetry-Raman characterization method, which comprises the steps of providing a chip with a self-heating function, and weighing the mass change of a sample to be measured in the temperature rise process in real time by the chip with the self-heating function to obtain a thermogravimetry curve; meanwhile, laser is focused on the surface of the sample to be measured through a microscope so as to collect Raman spectrum scattered by the sample to be measured in the temperature rising process, and the structural change information of the sample to be measured is extracted in real time so as to carry out synchronous thermogravimetry-Raman characterization.
The synchronous thermogravimetry-raman spectroscopy characterization method provided by the embodiment can be used for characterizing the structure and object image evolution of the sample to be tested while acquiring the dynamic property of the sample to be tested through thermogravimetric analysis, and has the advantages of being in situ, lossless, rapid, high in precision, small in sample consumption and the like.
In the following description, only the resonant cantilever chip with the self-heating function is taken as an example of the type of the chip with the self-heating function, but the type of the chip is not limited thereto.
As shown in fig. 1, the method specifically comprises the following steps:
step S1 is first executed: providing a resonant cantilever chip with a self-heating function, and placing the resonant cantilever chip in a test environment.
Specifically, as shown in fig. 2, the resonant cantilever chip with self-heating function provided in this embodiment is an MEMS sensor, and includes a chip substrate 200 and a cantilever 100, and can be used to accurately detect a small mass change by measuring a frequency offset. The chip substrate 200 includes a circuit lead, the cantilever beam 100 extends outward from the edge of the chip substrate 200, the cantilever beam 100 includes a driving resistor 202, a frequency detection resistor 203 and a heating resistor 201 connected to the corresponding circuit lead, further, preferably, the cantilever beam 100 further includes a heat resistance groove 208 penetrating the cantilever beam 100, the projection of the resistor on the heat resistance groove 208 is located in the range of the heat resistance groove 208, the heat resistance groove 208 is located between the frequency detection resistor 203 and the heating resistor 201, a sample a to be tested with synchronous thermogravimetry-raman characterization is loaded through the free end of the cantilever beam 100, the temperature of the sample a to be tested is controlled through the heating resistor 201, the heat transfer to the frequency detection resistor 203 is blocked through the heat resistance groove 208, so that while the sample a to be tested is heated, the influence on the frequency detection resistor 203 is reduced to improve the detection accuracy, and the change of the resonant frequency is detected through the frequency detection resistor 203.
The circuit lead comprises a driving circuit 204, a heating circuit 205, a temperature measuring circuit 206 and a frequency detecting circuit 207, wherein the driving circuit 204 is connected with the driving resistor 202 to realize the resonant driving of the cantilever beam 100; the heating circuit 205 and the temperature measuring circuit 206 are connected to the heating resistor 201, and are configured to heat the sample a to be measured coated on the free end of the cantilever beam 100, so as to implement a high-temperature heating function for the cantilever beam 100; the frequency detection circuit 207 is connected to the frequency detection resistor 203 to detect the resonant frequency, where the frequency detection resistor 203 employs a wheatstone bridge to achieve accurate resistance measurement, but the type of the frequency detection resistor 203 is not limited thereto.
The specific structure of the resonant cantilever chip is not limited herein.
As an example, the heating temperature range of the sample a to be measured may be 25 ℃ to 1200 ℃.
Specifically, the sample a to be measured can be heated through the heating resistor 201 on the cantilever beam 100, so as to realize the correlated thermogravimetric-raman characterization of the sample a to be measured. The heating temperature of the sample a to be tested may be 25 ℃, 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃, 600 ℃, 700 ℃, 1000 ℃, 1200 ℃ or the like, and may be specifically selected according to the test requirement, which is not limited herein. When the heating resistor 201 is a platinum heating resistor, the heating temperature range can be 25-600 ℃, and when the heating resistor 201 is a molybdenum heating resistor, the heating temperature range can be 25-1200 ℃.
As an example, in step S1, the test environment includes a gas environment condition and a temperature rise condition, the gas environment condition includes a vacuum condition and an atmosphere condition, the vacuum condition includes a vacuum degree, the atmosphere condition includes a gas type, a gas flow rate and a gas pressure, and the temperature rise condition includes a temperature rise temperature and a temperature rise rate.
Wherein the degree of vacuum comprises 10-6mbar-1 bar, e.g. 10-6mbar、10-3bar, 1bar, etc.; the gas species include inert gases such as Ar, N2Etc., or air, or a reactive gas such as H2S、H2Etc., the gas flow rate comprises 1ml/min to 100ml/min, such as 1ml/min, 10ml/min, 100ml/min, etc., and the gas pressure comprises 1 bar; the heating rate includes 1 deg.C/min-30000 deg.C/min, such as 1 deg.C/min, 100 deg.C/min, 500 deg.C/min, 1000 deg.C/min, 10000 deg.C/min, 20000 deg.C/min, 30000 deg.C/min, etc.
Step S2 is then executed: and (4) carrying out baseline test operation, carrying out temperature programming on the resonant cantilever chip, and recording the change curve of the intrinsic resonant frequency of the cantilever 100 along with the temperature.
Step S3 is then executed: and (4) carrying out sample coating operation, and coating the sample A to be detected on the free end of the cantilever beam 100.
As an example, the mass range of the sample a to be measured may include picogram or nanogram, and the mass measurement accuracy of the sample a to be measured is picogram.
Specifically, by using the synchronous thermogravimetric-raman characterization method in this embodiment, the usage amount of the sample a to be tested can be reduced, so that the structure and the object image evolution of the sample a to be tested can be characterized while the dynamic property of the sample a to be tested is obtained through thermogravimetric analysis, and the method has the advantages of in-situ performance, no damage, rapidness, high precision, less sample usage amount and the like.
In this embodiment, the mass range of the sample a to be measured can reach picogram level or nanogram level, and the mass measurement accuracy of the sample a to be measured can reach picogram.
Step S4 is then executed: placing the cantilever beam 100 coated with the sample A to be tested in the same test environment as the step S2 again, and performing simultaneous thermogravimetry and Raman characterization operations: testing the change curve of the resonant frequency of the cantilever beam 100 loaded with the sample A to be tested along with the temperature, simultaneously focusing the laser 302 on the sample A to be tested by utilizing a Raman testing system, and collecting the Raman spectrum in the programmed heating process in real time.
Specifically, in the test process, the sample A to be tested is coated at the free end of the cantilever beam 100, and the cantilever beam 100 has the functions of heating, temperature measurement and material quality change detection due to the design, so that the thermogravimetric analysis requirement of the material is met. The cantilever beam 100 can be operated directly under the microscope 301 of the raman testing system. In the process of raman spectroscopy characterization, the laser 302 directly irradiates the sample a to be tested at the free end of the cantilever beam 100 to obtain a raman spectroscopy signal 303 of the sample a to be tested. Meanwhile, the irradiation of the laser 302 has no influence on the functions of heating, temperature measurement and material quality change detection of the cantilever beam 100. Therefore, only by placing the cantilever beam 100 under the microscope 301 for Raman spectroscopy, the Raman spectrum of the material during heating can be measured simultaneously, and thus the material can be subjected to simultaneous thermogravimetric-Raman analysis. This analytical technique can be applied to many materials, including nanocrystals.
Step S5 is then executed: performing data processing, wherein the data processing comprises resonance frequency data processing and Raman spectrum data processing, and the resonance frequency data processing comprises:
obtaining a change relation curve of the resonance frequency variation delta f and the temperature by subtracting the resonance frequency values obtained in the step S2 and the step S4 at the same temperature, obtaining a residual mass percentage-temperature relation curve of the sample to be detected, namely a thermogram, by using the following relation,
wherein: f is the eigenresonance frequency of the cantilever beam 100; Δ f is the difference between the resonant frequency and the eigen-resonant frequency of the cantilever beam 100 measured during the sample application and testing process; k is the Young's modulus of the cantilever beam 100；meffIs the effective mass of the cantilever beam 100; Δ m is the mass of the residual sample on the cantilever beam 100;
the Raman spectrum data processing comprises the following steps:
and processing the Raman spectrum signal obtained in the step S4, wherein the processing comprises background subtraction and peak separation fitting, and a Raman spectrum image of the sample A to be detected along with temperature change is obtained.
In this embodiment, the same sample a to be detected located at the free end of the cantilever beam 100 can be subjected to synchronous thermogravimetry-raman characterization, so that the problem of compatibility between a thermogravimetry analyzer and a raman analyzer can be solved, the thermogravimetry technology and the raman technology can be combined, the heating temperature range of the sample a to be detected can be widened by the heating resistor 205, the application can be enlarged, the heat resistance groove 208 penetrating through the cantilever beam 100 and located between the heating resistor 201 and the frequency detection resistor 203 can also block the transfer of heat to the frequency detection resistor 203, so that the influence on the frequency detection resistor 203 is reduced while the heating of the sample a to be detected is ensured, and the detection characterization accuracy can be improved due to the fact that the same sample a to be detected is subjected to detection characterization. The method can represent the structure and the object image evolution of the sample A to be detected while obtaining the dynamic property of the sample A to be detected through thermogravimetric analysis, and has the advantages of being in situ, lossless, rapid, high in precision, small in sample using amount and the like.
The simultaneous thermogravimetric-raman characterization method is further explained by specific examples below.
Characterization of molybdenum disulfide (MoS) by thermogravimetry-Raman2) The oxidation process of the nanometer material in the air comprises the following steps:
the thermogravimetric characterization result of the molybdenum disulfide under the air atmosphere is shown in fig. 3, and the synchronous raman characterization result is shown in fig. 4. From the thermogravimetric analysis curve of fig. 3, it can be seen that: when the temperature is increased from room temperature to 400 ℃, the mass of the material is slowly changed, and the weight loss percentage of the material is only about 10 percent in the temperature interval; when the temperature is increased to above 400 ℃, the quality of the material is sharply reduced; when the temperature rises to 550 ℃, the residual mass percentage is reduced to 0Indicating that the material is completely absent and no material remains at the free end of the cantilever beam 100. From the simultaneous raman characterization results of fig. 4, it can be seen that: only MoS in Raman spectrum when temperature is raised from room temperature to 400 DEG C2Characteristic peak of (a); at the temperature of above 400 ℃, except MoS in Raman spectrum2Outside the characteristic peak of (A), molybdenum trioxide (MoO) appears3) Characteristic peak of (A), indicating MoS2A rapid oxidation process of; only MoO remains on the Raman spectrum at 500 DEG C3Characteristic peak of (A), indicating MoS2Complete oxidation of (2); at 550 ℃, only the characteristic peak of silicon is left on the raman spectrum, indicating that no sample has remained on the surface of the cantilever 100. Research has shown that: molybdenum trioxide readily sublimes at temperatures above 400 ℃. Thus, the combined thermogravimetric-raman characterization technique indicates that: MoS2The thermal weight loss process in the air is MoS2Oxidation to MoO3Then MoO3Heating for sublimation.
The method comprises the following steps of (1) utilizing synchronous thermogravimetry-Raman to characterize the reduction process of Graphene Oxide (GO) under vacuum:
the thermogravimetric characterization result of graphene oxide under the vacuum condition is shown in fig. 5, and the synchronous raman characterization result is shown in fig. 6. From the thermogravimetric analysis curve of fig. 5, it can be seen that: the thermal weight loss process of the graphene oxide under the vacuum condition can be divided into two stages. The first stage is a rapid weight loss stage before 250 ℃, and the second stage is a slow weight loss stage after 250 ℃. The thermal weight loss in the first stage can be attributed to the decomposition of oxygen-containing groups in the GO nanosheets. The second stage is the removal of hydrogen atoms from the aromatic ring. The raman test results of fig. 6 reflect the raman peak change of the material during thermal analysis. For graphene oxide, the intensity ratio of the D peak and the G peak of the raman spectrum reflects the degree of reduction and the degree of defects of graphene oxide. At temperatures below 300 ℃, the intensity ratio of the graphene oxide D and G peaks decreases with increasing temperature, reflecting an increase in the degree of reduction of the material, i.e., the decomposition of oxygen-containing groups. When the temperature is higher than 300 ℃, the intensity ratio of the D peak and the G peak is enhanced, indicating that the degree of defect is increased. This phenomenon is also consistent with the removal of hydrogen atoms from the second stage aromatic ring in thermogravimetric analysis.
In summary, according to the synchronous thermogravimetry-raman characterization method, the chip with the self-heating function is used for weighing the mass change of the sample to be measured in the temperature rise process in real time, so as to obtain the thermogravimetry curve; meanwhile, laser is focused on the surface of the sample to be detected through a microscope so as to collect the Raman spectrum scattered by the sample to be detected in the temperature rising process and extract the structural change information of the sample to be detected in real time. The synchronous thermogravimetry-Raman spectrum characterization method provided by the invention can be used for characterizing the structure and object image evolution of the sample to be tested while acquiring the dynamic property of the sample to be tested through thermogravimetric analysis, and has the advantages of in-situ performance, no damage, rapidness, high precision, small sample consumption and the like.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
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