CN105445308B - A kind of heat analysis in situ-mass-spectrometer measurement method of thin-film material - Google Patents
A kind of heat analysis in situ-mass-spectrometer measurement method of thin-film material Download PDFInfo
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- CN105445308B CN105445308B CN201410432112.4A CN201410432112A CN105445308B CN 105445308 B CN105445308 B CN 105445308B CN 201410432112 A CN201410432112 A CN 201410432112A CN 105445308 B CN105445308 B CN 105445308B
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Abstract
The present invention relates to a kind of heat analysis in situ-mass-spectrometer measurement methods of thin-film material, which comprises 1) thin-film material presoma is coated in plate sample crucible, and using the plate sample crucible as the mass spectrometric sampling device of heat analysis-；2) heat analysis-Mass spectrometry experiments are carried out to the thin-film material presoma being coated in plate sample crucible to measure, the thermal analysis curve of thin-film material presoma is obtained, wherein the exclusion temperature of organic matter in thin-film material presoma can be obtained by heat analysis data；3) gained thin-film material presoma carries out heat analysis-mass-spectrometer measurement, while obtaining the mass spectrometry profile of thin-film material in air atmosphere.
Description
Technical field
The invention belongs to heat analysis-mass spectrometric hyphenated technique fields, more particularly to a kind of heat analysis-in situ of thin-film material
Mass-spectrometer measurement method.
Background technique
Heat analysis method can be used for characterizing the material of particle size in the micron-scale, can be also used for the material of characterization nano-scale
Material.For the material of various nano-sized powders and nano-dispersion, thermoanalysis technology can characterize its melting
Temperature, sintering process, is synthetically prepared and decomposes situation phase transition temperature.Film as one of most common form existing for substance,
In Material Field in occupation of increasingly consequence, much the film with various different function is widely used.
Film due to differences such as composition material, film build method, required functions, form, structure and in terms of there is very big difference.
Wherein, the post-processing of the thermal property and film of thin-film material and military service performance are closely related.The heat resistance of thin-film material is studied,
It is of great significance for the temperature range for determining that thin-film material uses.
The thermo-chemical model of most of thin-film materials concentrates on characterizing their phase transition temperature and sintering process etc., mainly
Using characterization methods such as thermogravimetric analysis (TGA), differential thermal analysis (DTA) or differential scanning calorimetries (DSC) to the film material of preparation
Material carries out THERMAL STABILITY, to optimize the technological parameter of material preparation, these methods have can the required measurement of Sensitive Detection
The thermal characteristics of material.But pass through the obtained analysis data of the methods of heat analysis, substantially institute in institute's measurement experiment crucible
There is the average value of both sample film plus substrates, cannot individually obtain the analysis data of thin-film material.Therefore, pass through these methods
Thin-film material with substrate is tested, many thermal characteristics of thin-film material can be covered by the signal of substrate.For
The Thermal characteristic analysis of thin-film material, especially micron, nanoscale has very big shadow for the grasp of the information of integral material
It rings.Currently, the heat analysis measuring method of the thin-film material of wet chemical method preparation, it generally can only be by peeling off film from substrate
It is tested, in-site detecting while sample after can not achieve thin film precursor pretreatment and forming a film.The problem of being primarily present is:
Crucible in heat analysis sampling device is smaller, it is difficult to realize bulk substrate and film sample introduction simultaneously, therefore also cannot achieve original
The thermal stability of position characterization thin-film material.In order to fully understand that the thermal decomposition process of thin-film material, research thin-film material are heating
Organic matter in the process excludes behavior, needs to carry out thin-film material heat analysis-mass spectrum in-situ characterization analysis, and the above demand is to grinding
Heat analysis-mass-spectrometer measurement the method for studying carefully thin-film material proposes an urgent demand.
Summary of the invention
The present invention is directed to make up the deficiency of existing heat analysis, mass-spectrometer measurement method, the present invention provides a kind of thin-film materials
Heat analysis-mass-spectrometer measurement method.
The present invention provides a kind of heat analysis in situ-mass-spectrometer measurement methods of thin-film material, which comprises
1) thin-film material presoma is coated in plate sample crucible, and using the plate sample crucible as heat
Analysis-mass spectrometric sampling device；
2) heat analysis-Mass spectrometry experiments are carried out to the thin-film material presoma being coated in plate sample crucible to measure, is obtained
The thermal analysis curve for obtaining thin-film material presoma, wherein organic matter in thin-film material presoma can be obtained by heat analysis data
Exclude temperature；
3) heat analysis-mass-spectrometer measurement is carried out to gained thin-film material presoma, while thin-film material can be obtained in air
Mass spectrometry profile under atmosphere.
Preferably, further including the microscopical compositon change in conjunction with mass-spectrometer measurement result measurement thin film precursor and/or thin-film material
Change.
Preferably, the thin-film material is composite organic-inorganic material.
Preferably, the material of the plate sample crucible is high-purity refractory oxide ceramics, preferably aluminium oxide ceramics
Crucible.
Preferably, the material of the plate sample crucible is refractory metal, preferably Mo, Nb, Au, Pt.
Beneficial effects of the present invention:
The heat analysis of in-situ study thin-film material pointed by the present invention-mass-spectrometer measurement method, by traditional sample crucible
Transform as it is plate, later on plate coated film presoma carry out heat analysis-mass spectrum Simultaneous Determination, so may be implemented thin
Sample is in situ incessantly in same primary experiment after film precursor pretreatment and film forming completes, and is really preparing close to material
Under application conditions, heat analysis process and organic matter decomposition behavior to thin-film material presoma carry out insitu analog dynamic and grind
Study carefully, improves the traditional method that previous material preparation process and analyte detection process are separated from each other.
Detailed description of the invention
Fig. 1 shows the comparison of the process between measurement method and traditional measurement method in an embodiment of the invention
Figure and the present invention in improved crucible schematic diagram；
Fig. 2 shows the heat analysis for using in-situ method to obtain thin-film material presoma in one embodiment of the present of invention is bent
Line；
It is bent that Fig. 3 shows the mass spectrum for obtaining thin-film material presoma using in-situ method in one embodiment of the present of invention
Line；
It is bent that Fig. 4 shows the heat analysis for obtaining thin-film material presoma using conventional method in a comparative example of the invention
Line；
It is bent that Fig. 5 shows the mass spectrum for obtaining thin-film material presoma using conventional method in a comparative example of the invention
Line.
Specific embodiment
The present invention is further illustrated below in conjunction with attached drawing and following embodiments, it should be appreciated that attached drawing and following embodiments
It is merely to illustrate the present invention, is not intended to limit the present invention.
For above-mentioned deficiency of the prior art, the object of the present invention is to provide a kind of new in-situ study film materials
The heat analysis of material-mass-spectrometer measurement method.The invention discloses a kind of heat analysis-mass-spectrometer measurement sides of in-situ characterization thin-film material
Method, comprising:
Existing heat analysis sampling device is improved, traditional heat analysis is transform as with crucible plate；
Then coated film presoma progress heat analysis-mass spectrum measures simultaneously on plate, before film may be implemented in this way
Sample in same primary experiment complete incessantly by original position after driving body pretreatment and film forming, so that it is thin that in-situ study also may be implemented
Thermal analysis curve of the membrane material in thermal histories determines the row of organic matter in thin-film material presoma in heat analysis-mass spectrogram
Except temperature, and mass spectrum is combined as a result, the micromechanism that analysis presoma converts；
Measurement method of the invention mainly carries out structure improvement by the sampling device to thermal-analysis instrumentation and optimization is set
Meter, in this way under the conditions of preparation process true close to material, to the heat analysis process and organic matter of thin-film material presoma
Decomposition behavior carries out insitu analog dynamic studies, improves the tradition that previous material preparation process and analyte detection process are separated from each other
Way.This for organic-inorganic hybrid film material preparation process and determine presoma to thin-film material transformation mechanism extremely
Close it is important, so that the screening for the packaging film material of semiconductor high-power device provides reliable foundation.
The thin-film material is composite organic-inorganic material.
The plate sample crucible is high-purity refractory oxide ceramics.Preferred oxide is aluminium oxide or oxidation
Zirconium substrate.
The plate sample crucible is refractory metal.Preferred metal is Mo, Nb, Au, Pt etc..
Enumerate some exemplary embodiments further below so that the present invention is better described.It should be understood that the present invention
The above embodiment and following embodiment of detailed description are only illustrative of the invention and is not intended to limit the scope of the invention, ability
Some nonessential modifications and adaptations that the technical staff in domain above content according to the present invention is made belong to guarantor of the invention
Protect range.In addition, specific proportion, time, the temperature etc. in following technological parameters are also merely exemplary, those skilled in the art
It can select suitably to be worth in the range of above-mentioned restriction.
Embodiment
Using the ethanol solution of butyl titanate as the aqueous solution of solution A and dehydrated alcohol as B solution, A and B are mixed
It closes, using acetylacetone,2,4-pentanedione as chelating agent, and the P25 nano titania of mass fraction 5% is added, is placed on constant temperature blender with magnetic force
Strong stirring 2h at 65 DEG C of oil bath, to obtain pale yellow gum aaerosol solution after the reaction was completed.Way in situ is will directly to suspend
Liquid is coated on plate crucible, is placed at room temperature for about after ten minutes, starts to test.Test condition are as follows: air atmosphere 30ml/min,
- 1000 DEG C of test temperature room temperature, heating rate are 10 DEG C/min.Fig. 2 is that in-situ method is used in one embodiment of the present of invention
Obtain the thermal analysis curve of thin-film material presoma.Fig. 3 is to obtain film using in-situ method in one embodiment of the present of invention
The mass spectrometry profile of material precursor.The weight loss that can be seen that entire sample from the data of TG has 51.53%.Wherein from room temperature
Occurs a step between to 200 DEG C, mass loss is about 11.57%, this shows to have a small amount of physical absorption in sample molten
Agent and water, in the desorption phenomenon that the temperature range occurs.Occur three weightless steps, mass loss between 200 DEG C -700 DEG C
Respectively 24.95%, 9.79%, 4.10% occur three maximum decomposition temperatures, summit temperature point on corresponding DTG curve
It Wei not be 314.5 DEG C, 490.7 DEG C, 583.7 DEG C.Show in this temperature range be mainly sample in organic matter oxygenolysis,
It may be accompanied by TiO in this course2The crystallization process changed from amorphous state to anatase.Simultaneously from Fig. 3 mass spectrometry profile
The upper sample that can be seen that occurs the positive ion mass spectrum peak of carbon dioxide: CO at 400 DEG C -700 DEG C or so2+(m/z=44), this
Illustrate that oxidation operation has decomposed to give off carbon dioxide gas in sample.TG curve is in flat trend after from 700 DEG C, shows sample
Organic matter thermal decomposition in product is complete.
Comparative example
Using the ethanol solution of butyl titanate as the aqueous solution of solution A and dehydrated alcohol as B solution, A and B are mixed
It closes, using acetylacetone,2,4-pentanedione as chelating agent, and the P25 nano titania of mass fraction 5% is added, is placed on constant temperature blender with magnetic force
Strong stirring 2h at 65 DEG C of oil bath, to obtain pale yellow gum aaerosol solution after the reaction was completed.For traditional method, will directly hang
Supernatant liquid applies
It is layed on silicon wafer, drying to constant weight in 40 DEG C of baking ovens, carries out the analysis of TG-DTA later.Test condition are as follows: empty
Gas atmosphere 30ml/min, -1000 DEG C of test temperature room temperature, heating rate are 10 DEG C/min.Fig. 4 is a comparative example of the invention
It is middle that the thermal analysis curve of thin-film material presoma is obtained using conventional method.Fig. 5 is in a comparative example of the invention using biography
System method obtains the mass spectrometry profile of thin-film material presoma.For using Si piece as the thin film of titanium oxide tradition characterizing method of substrate,
Whole process weight loss is seldom, and mass loss only has 1.13%, and without obvious fuel factor, this is mainly due to the quality of substrate Si
It is far longer than the quality of film layer, the fuel factor of entire thin-film material is covered by Si substrate, and Si is steady due to higher heat
Qualitative, oxidative phenomena during heat analysis is not obvious.Meanwhile it not being detected from Fig. 5 mass spectrometry profile corresponding yet
Carbon dioxide positive ion mass spectrum peak: CO2+(m/z=44).Therefore, we cannot get thin-film material from traditional analysis method
Thermal decomposition behavior,
Also the exclusion temperature of organic matter in thin-film material can not be determined.
Claims (2)
1. a kind of heat analysis in situ-mass-spectrometer measurement method of thin-film material, which is characterized in that the described method includes:
1) thin-film material presoma is coated in plate sample crucible, and using the plate sample crucible as heat point
Analysis-mass spectrometric sampling device, the material of the plate sample crucible are aluminium oxide, zirconium oxide, metal Mo, metal Nb, gold
Belong to one of Au, Pt metal；
2) heat analysis-Mass spectrometry experiments are carried out to the thin-film material presoma being coated in plate sample crucible to measure, is obtained thin
The thermal analysis curve of membrane material material precursor realizes thin film precursor pretreatment simultaneously and forms a film in same primary experiment incessantly
It is in situ to complete, wherein the exclusion temperature of organic matter in thin-film material presoma can be obtained by heat analysis data；
3) gained thin-film material presoma carries out heat analysis-mass-spectrometer measurement, while obtaining the matter of thin-film material in air atmosphere
Spectral curve；
The method also includes combining the microscopical compositon variation of mass-spectrometer measurement result measurement thin film precursor and/or thin-film material.
2. heat analysis according to claim 1-mass-spectrometer measurement method, which is characterized in that the thin-film material be it is organic-
Inorganic composite materials.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102830130A (en) * | 2011-06-16 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Method for quantitatively determining CO2 gas emitted from thermal analysis-mass spectrometry system |
| CN103245717A (en) * | 2012-02-10 | 2013-08-14 | 华中师范大学 | High-pressure formed substrate film assisted laser desorption dissociation mass spectrum quantitative analysis method |
| CN103822939A (en) * | 2014-02-28 | 2014-05-28 | 南京师范大学 | Thermal analysis method of TiO2 crystallization by water supporting at low temperature |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3949374B2 (en) * | 2000-07-17 | 2007-07-25 | 住友化学株式会社 | Titanium oxide, photocatalyst and photocatalyst coating using the same |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102830130A (en) * | 2011-06-16 | 2012-12-19 | 中国科学院上海硅酸盐研究所 | Method for quantitatively determining CO2 gas emitted from thermal analysis-mass spectrometry system |
| CN103245717A (en) * | 2012-02-10 | 2013-08-14 | 华中师范大学 | High-pressure formed substrate film assisted laser desorption dissociation mass spectrum quantitative analysis method |
| CN103822939A (en) * | 2014-02-28 | 2014-05-28 | 南京师范大学 | Thermal analysis method of TiO2 crystallization by water supporting at low temperature |
Non-Patent Citations (2)
| Title |
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| 混晶结构纳米Tio2薄膜制备及其光催化降解甲醛;孙召梅 等;《上海大学学报（自然科学版）》;20051031;第11卷(第5期);518-521 * |
| 稀土掺杂Tio2光催化抗菌材料的制备与性能研究;姜莉 等;《东北大学学报（自然科学版）》;20070930;第28卷(第9期);第1334页第1节、第1335页第2.2节，图4 * |
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Effective date of registration: 20211217 Address after: 215400 No.6 Liangfu Road, Taicang City, Suzhou City, Jiangsu Province Patentee after: Jiangsu Institute of advanced inorganic materials Address before: 200050 No. 1295 Dingxi Road, Shanghai, Changning District Patentee before: SHANGHAI INSTITUTE OF CERAMICS, CHINESE ACADEMY OF SCIENCES |